Beneficiation of lithium-containing ores

Abstract

The present invention relates to the use of a collector composition for beneficiation of lithium-bearing minerals from ores, and a method for beneficiation of lithium-bearing minerals using the collector composition.

Description

Technical Field

[0001] The present invention relates to collector compositions for beneficiation of lithium-bearing minerals from ores, their use in flotation processes, and methods for beneficiation of lithium-bearing minerals using said collector compositions. Background Technology

[0002] Lithium is an important strategic resource, widely used in batteries, ceramics, glass, lubricants, refrigerants, nuclear industry, optoelectronics, and other emerging fields. It is also an indispensable raw material for modern high-tech products. In recent years, with the continuous development of high technology and the growth of lithium-ion battery-powered vehicles and mobile electronic products, the application of lithium and lithium salt products has become increasingly widespread, and international market demand for lithium products continues to grow.

[0003] Due to its reactivity, lithium does not exist naturally in elemental form. However, there are more than 100 known minerals that may contain lithium, although only a few are currently economically viable for mining. The most common lithium-bearing minerals found in economically viable deposits include spodumene, lepidolite, lepidolite, lepidolite, lepidolite, lepidolite, lepidolite, lepidolite, and jadarite. Among these, spodumene is considered the most important lithium ore mineral due to its high lithium content. Typical ore can contain 0.5% to 2% Li₂O, while typical spodumene concentrate suitable for lithium carbonate production contains 5.5% to 7% Li₂O (68% to 87% spodumene). High-grade concentrates with 7.6% Li₂O and low iron content are used in ceramics and other demanding industries.

[0004] Currently, global lithium resources are estimated at approximately 41 million tons, with Bolivia, Chile, Argentina, the United States, China, Brazil, Portugal, Zimbabwe, and Australia holding the largest reserves. Spodumene is essentially LiAlSi₂O₆, containing about 8% Li₂O, and is the most abundant lithium-bearing mineral. Spodumene occurs in association with other gangue minerals (such as feldspar, quartz, and muscovite), and must be separated from these gangue minerals before use in chemical and ceramic applications.

[0005] Currently, global lithium supply mainly comes from brine or hard rock deposits. In the former, lithium is concentrated into soluble salts through solar evaporation. Lithium produced from brine is typically of lower grade; although brine production requires higher capital investment, its operating costs are lower.

[0006] In the case of hard rock deposits, conventional mining and beneficiation techniques are used to produce high-grade spodumene concentrate or other mineral concentrates with grades higher than those of the parent rock. It is possible to obtain industrial-grade, battery-grade (99.5%) lithium chemicals from various acid roasting and lime roasting processes.

[0007] As is well known, existing technologies can separate valuable minerals from gangue minerals by using flotation.

[0008] Minerals (which can be dry-milled, but are preferably wet-milled) are first crushed and suspended in water for flotation. Collectors are typically added to the minerals, often in combination with frothers, and, where appropriate, with other auxiliary agents (e.g., regulators, deactivators, and / or enhancers, activators) to promote the separation of valuable minerals from unwanted gangue components in subsequent flotation. These agents typically allow the finely milled (slurry-conditioning) minerals to act for a period of time, after which air is blown into the suspension (flotation) to generate foam. In this case, the collector is responsible for hydrophobizing the mineral surfaces, causing these minerals to adhere to the bubbles formed during air blowing. The hydrophobization of the mineral components is selective, so that non-floating mineral components do not adhere to the bubbles. The foam containing the minerals is separated and then prepared. The goal of flotation is to separate valuable minerals from other minerals in the highest possible yield, while achieving the best possible enrichment in this case. Flotation includes different methods, such as direct flotation or reverse flotation. In direct flotation, the desired minerals are collected in the foam, while the unwanted minerals remain dispersed. In reverse flotation or reverse flotation, unwanted minerals are collected in the froth, while desired minerals remain dispersed in the bottom stream of the flotation cell.

[0009] Beneficiation of lithium-bearing minerals, such as spodumene, lepidolite, lepidolite, nepheline, lepidolite, lepidolite, lepidolite, lepidolite, lepidolite, lepidolite, lepidolite, lepidolite, lepidolite, and jadalite, from associated gangue minerals (e.g., quartz (SiO2) and iron oxides (Fe2O3, Fe3O4)) is difficult because they have similar surface chemical properties.

[0010] Given that most lithium deposits in the world also contain silicates, selectively separating lithium-bearing minerals from associated gangue minerals (e.g., quartz (SiO2) and iron oxides (Fe2O3, Fe3O4)) is a method that has been extensively studied.

[0011] In known lithium-bearing mineral beneficiation methods, anionic surfactants (such as fatty acids) are used as collectors.

[0012] Known anionic collectors include, for example, saturated and unsaturated fatty acids, oleic fatty acids, linoleic acid, linolenic acid, resinic acids, tall oil fatty acids, phosphate esters (especially optional alkoxylated phosphate esters derived from fatty alcohols or mixtures of fatty alcohols), alkyl sulfates (especially alkyl sulfates derived from fatty alcohols or mixtures of fatty alcohols), alkyl aryl sulfonates, alkyl sulfosuccinates, alkyl sulfosuccinimide salts, and acyl lactates.

[0013] WO2021038017 describes a collector composition for beneficiation of lithium silicates and magnesium silicates from ores containing various silicate minerals, the use of the collector composition in a flotation process, and a method for beneficiating lithium silicate and magnesium silicate minerals using the collector composition, the collector composition comprising at least one component a) selected from N-oleoylsarcosine; and at least one component b) selected from diisononyl phthalate, di(2-ethylhexyl) phthalate, di(2-propylheptyl) phthalate, diisononyl adipate, di(2-ethylhexyl) adipate, di(2-propylheptyl) adipate, and isotriadecyl alcohol.

[0014] The use of fatty acids as collectors / co-collectors in lithium ore beneficiation is known in the literature. However, high-dose collector compositions and long conditioning times are required. Several other flotation processes for lithium beneficiation are also disclosed in the literature.

[0015] However, the known technologies are insufficient to provide an economically viable solution for lithium ore beneficiation.

[0016] As can be seen from the current state of the prior art, there is still a need for improvement in the field of beneficiation of lithium-bearing minerals (such as lithium silicates, especially spodumene) from ores (wherein, collectors for beneficiation of lithium-bearing minerals from gangue minerals are used).

[0017] Therefore, the object of the present invention is to provide a collector composition that can be used to produce high-grade lithium-containing minerals, which can be separated in high yield and high recovery and have low iron content, good wettability, water dispersibility and suitable foaming properties. Summary of the Invention

[0018] The inventors unexpectedly discovered the use of collectors for the beneficiation of lithium-bearing minerals from ores containing both lithium-bearing and gangue minerals. These collectors can be used to separate lithium-bearing minerals, such as lithium silicates, from gangue minerals. These collectors allow for good efficiency and purity, as well as good wettability, water dispersibility, and suitable foaming properties.

[0019] Therefore, a first aspect of the present invention relates to the use of a collector composition for the beneficiation of lithium-bearing minerals (particularly lithium silicates) from ores containing lithium-bearing minerals and gangue minerals, wherein the collector composition comprises: a) at least one ether carboxylic acid or a salt thereof represented by formula (I) R1-OP-CH2-COOX (I) in, R1 is a straight-chain or branched alkyl or alkenyl chain having 4 to 30 carbon atoms; P consists of n -(CH2CH2O)- units, and / or m -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or q -(CH2CHR3O)- or -(CHR3CH2O)- units, where n, m, and / or q each independently represent a number from 0 to 25, and the sum of n+m+q is from 1 to 25; and X is H or a cation selected from alkali metals, alkaline earth metals, ammonium, and alkylammonium; and b) Fatty acids or mixtures of fatty acids.

[0020] Methods for preparing collector compositions as defined in the first aspect are also an object of the present invention.

[0021] A method for beneficiating lithium-bearing minerals from ores containing lithium-bearing minerals and gangue minerals is also part of the object of the present invention, wherein the collector composition according to the first aspect is used.

[0022] Another object of the present invention is a collector composition as defined in the first aspect, wherein the weight ratio between component a) and component b) is 99:1 to 1:99. Detailed Implementation

[0023] The term "lithium-bearing ore" refers to an ore containing one or more lithium minerals (e.g., lithium silicates). Typically, such ores are associated with various gangue minerals, which usually consist of varying amounts of silicates (SiO2) and iron oxides (Fe2O3 and Fe3O4). The amounts and types of lithium-bearing minerals and gangue present in the ore can vary considerably depending on the type of ore. Therefore, this invention applies to lithium-bearing ores regardless of the lithium content or properties of the lithium minerals or their gangue content.

[0024] The term "lithium-bearing mineral" refers to any mineral that contains lithium. Suitable examples of lithium-bearing minerals are spodumene (LiAlSi₂O₆) and petalite (LiAlSi₄O₂). 10 Lithium nepheline (LiAlSiO4), lepidolite (KLi2AlSi3O4) 10 (F,OH)2), lithium montmorillonite (Na) 0.3 (Mg,Li)3Si4O 10 (OH)2), lithium aluminum silicide (LiAlSi2O6·H2O), lithium iron phosphate (KLiFeAl2Si3O) 10 (F,OH)2) and lithium aluminum phosphate (LiAlPO4), with spodumene being preferred.

[0025] The term "ore" refers to an aggregate of rocks from which desired minerals are extracted.

[0026] In this context, the term "gangue" refers to mineral materials of low or no value that need to be separated from valuable minerals (i.e., lithium-bearing minerals). Examples of gangue minerals found in lithium ore include silicates (SiO2) and iron oxides (Fe3O3 and Fe3O4).

[0027] The term "mineral processing" in this article refers to the separation methods used to remove gangue minerals from ore to produce a higher-grade concentrate. For example, extracting lithium from lithium ore. Mineral processing includes crushing, grinding, gravity concentration, magnetic separation, and flotation concentration.

[0028] Collector composition: This invention discloses the use of a collector composition for the beneficiation of lithium-bearing minerals from ores containing lithium-bearing minerals and gangue minerals, wherein the collector composition comprises: a) at least one ether carboxylic acid or a salt thereof represented by formula (I) R1-OP-CH2-COOX (I) in, R1 is a straight-chain or branched alkyl or alkenyl chain having 4 to 30 carbon atoms; P is composed of n -(CH2CH2O)- units, and / or m -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or q -(CH2CHR3O)- or -(CHR3CH2O)- units, where n represents a number from 0 to 25, m represents a number from 0 to 25, and q represents a number from 0 to 25, and the sum of n+m+q represents a number from 1 to 25; R2 represents a -CH3 group; and R3 represents a -CH2CH3 group; X is H or a cation selected from alkali metals, alkaline earth metals, ammonium, and alkylammonium; and b) Fatty acids or mixtures of fatty acids.

[0029] According to a preferred embodiment of the present invention, the lithium-containing mineral, particularly the lithium silicate mineral, is selected from spodumene, petalite, lepidolite, lithium aluminum silicate, ferromagnetic mica, and lithium montmorillonite; more preferably selected from spodumene and petalite; and even more preferably, spodumene.

[0030] Compared to known collectors, the collector composition allows for improved recovery, yield, and higher purity of lithium-containing minerals, while also exhibiting stronger wettability and water dispersibility, as well as suitable foaming properties.

[0031] Ether carboxylic acids or their salts (a)

[0032] The collector composition according to the present invention comprises component (a), said component being at least one ether carboxylic acid of formula (I) or a salt thereof: R1-OP-CH2-COOX (I) in, R1 is a straight-chain or branched alkyl or alkenyl chain having 4 to 30 carbon atoms; P is composed of n -(CH2CH2O)- units, and / or m -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or q -(CH2CHR3O)- or -(CHR3CH2O)- units, where n represents a number from 0 to 25, m represents a number from 0 to 25, and q represents a number from 0 to 25, and the sum of n+m+q represents a number from 1 to 25; R2 represents a -CH3 group; and R3 represents a -CH2CH3 group; and X is H or a cation selected from alkali metals, alkaline earth metals, ammonium and alkylammonium.

[0033] In the context of this invention, the term "alkyl" refers to a straight or branched hydrocarbon chain containing a specified number of carbon atoms (e.g., 4 to 30 carbon atoms).

[0034] In the context of this invention, the term "alkenyl" refers to a straight-chain hydrocarbon chain containing a specified number of carbon atoms (e.g., 4 to 30 carbon atoms) and 1 to 3 double bonds.

[0035] In the context of this invention, the term "alkali metal" refers to any one of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs), preferably any one of sodium and potassium.

[0036] In the context of this invention, the term "alkaline earth metal" refers to any one of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba), preferably any one of magnesium and calcium.

[0037] In the context of this invention, the term "ammonium" refers to NH4. + .

[0038] In the context of this invention, the term "alkylammonium" refers to a quaternary ammonium substituted with one, two, or three alkyl groups as defined herein. Specifically, each alkyl group has one to 30 carbon atoms. Examples of alkylammoniums are dimethyl octylammonium, dimethyl decylammonium, dimethyl laurylammonium, dimethyl myristylammonium, dimethyl palmitylammonium, dimethyl hexadecylammonium, dimethyl stearylammonium, dimethyl behenylammonium, or mixtures thereof. Other suitable alkylammoniums are methyl dioctylammonium, methyl dialdecylammonium, methyl dilaurylammonium, methyl dimyristylammonium, methyl palmitylammonium, methyl dihexadecylammonium, methyl distearylammonium, methyl dibehenylammonium, or mixtures thereof.

[0039] As used herein, the term "salt" refers to the carboxylate anion (i.e., R1-OP-CH2COO) of a compound of formula (I) as defined herein. - ) and selected from alkali metals (e.g., Na) + and K + ), alkaline earth metals (e.g., Ca) 2+ and Mg 2+ Suitable cations of ammonium and alkylammonium. In a preferred embodiment of the invention, the salt of the ether carboxylic acid represented by formula (I) is a sodium or potassium salt of the ether carboxylic acid of the compound of formula (I), i.e., where X is Na. + or K + .

[0040] As used herein, the term "at least one" means at least one, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0041] According to one embodiment of the present invention, R1 is a straight-chain or branched alkyl group containing 4 to 30 carbon atoms, or a straight-chain or branched alkenyl group containing 4 to 30 carbon atoms and 1 to 3 double bonds; According to another embodiment of the present invention, R1 is a straight-chain or branched alkyl group containing 10 to 30 carbon atoms, or a straight-chain or branched alkenyl group containing 10 to 30 carbon atoms and 1 to 3 double bonds; preferably, the alkyl or alkenyl group contains 10 to 22 carbon atoms, more preferably 12 to 18 carbon atoms, even more preferably 12 to 16 carbon atoms, and even more preferably 12 to 14 carbon atoms.

[0042] In another embodiment of the invention, R1 is a straight-chain or branched alkyl or straight-chain alkenyl group 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 fats, such as fats, fish oil, their hydrogenated and semi-hydrolyzed oils, and mixtures thereof. In a preferred embodiment, R1 is a straight-chain or branched alkyl or straight-chain alkenyl group derived from palm oil or coconut oil.

[0043] In a specific embodiment of the invention, R1 is a straight-chain or branched alkyl group containing 10 to 30 carbon atoms, or a straight-chain alkenyl group containing 10 to 30 carbon atoms and 1 to 3 double bonds; preferably containing 10 to 22 carbon atoms, more preferably containing 12 to 18 carbon atoms, even more preferably containing 12 to 16 carbon atoms, and even more preferably containing 12 to 14 carbon atoms.

[0044] In another specific embodiment, R1 is a straight-chain alkyl group containing 10 to 30 carbon atoms; preferably containing 10 to 22 carbon atoms, more preferably containing 12 to 18 carbon atoms, even more preferably containing 12 to 16 carbon atoms, and even more preferably containing 12 to 14 carbon atoms.

[0045] In embodiments of the present invention, P is composed of n -(CH2CH2O)- units, and / or m -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or q -(CH2CHR3O)- or -(CHR3CH2O)- units, where n represents a number from 0 to 25; m represents a number from 0 to 25; and q represents a number from 0 to 25. When n is 0, the ether carboxylic acid or its salt of formula (I) does not contain an ethylene oxide unit. When m is 0, the ether carboxylic acid or its salt of formula (I) does not contain an propylene oxide unit. When q is 0, the ether carboxylic acid or its salt of formula (I) does not contain an ethylene oxide unit. In the ether carboxylic acid or its salt of formula (I), at least one alkylene oxide unit is present, wherein the alkylene oxide unit is ethylene oxide, propylene oxide, or ethylene oxide. The degree of alkoxylation is the sum of ethylene oxide, propylene oxide and butane oxide units present in the ether carboxylic acid or its salt of formula (I), i.e., the sum of n+m+q, and is preferably a number from 1 to 25.

[0046] In another embodiment of the invention, P is composed of n -(CH2CH2O)- units, and / or m -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or q -(CH2CHR3O)- or -(CHR3CH2O)- units, wherein n represents a number from 0 to 15, preferably 0 to 10, more preferably 0 to 6; m represents a number from 0 to 15, preferably 0 to 10, more preferably 0 to 6; and q represents a number from 0 to 15, preferably 0 to 10, more preferably 0 to 6. When n is 0, the ether carboxylic acid or its salt of formula (I) does not contain an ethylene oxide unit. When m is 0, the ether carboxylic acid or its salt of formula (I) does not contain an propylene oxide unit. When q is 0, the ether carboxylic acid or its salt of formula (I) does not contain an ethylene oxide unit. In the ether carboxylic acid or its salt of formula (I), at least one alkylene oxide unit is present, said alkylene oxide unit being ethylene oxide, propylene oxide, or ethylene oxide. The degree of alkoxylation is the sum of ethylene oxide, propylene oxide and butane oxide units present in the ether carboxylic acid or its salt of formula (I), i.e., the sum of n+m+q, and is a number from 1 to 15, preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3.

[0047] As described above, in this invention, the ether carboxylic acid or its salt according to formula (I) is ethoxylated and / or propoxylated and / or butoxylated, i.e., P is an ethoxylated and / or propoxylated and / or butoxylated group. The order of arrangement of ethylene oxide and / or propylene oxide and / or ethylene oxide groups is not important to this invention. Therefore, both the ether carboxylic acid or its salt according to formula (I) containing ethylene oxide groups and / or propylene oxide groups and / or butyl oxide groups in the form of independent blocks, and the ether carboxylic acid or its salt according to formula (I) containing randomly distributed ethylene oxide and / or propylene oxide and / or butyl oxide groups can be used in the compositions according to this invention.

[0048] In an embodiment of the present invention, P is composed of n -(CH2CH2O)- units, wherein n represents an integer from 1 to 15, preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3; m and q represent 0, and the sum of n+m+q represents a number from 1 to 15, preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3.

[0049] In one embodiment of the invention, P is composed of m -(CH2CHR2O)- or -(CHR2CH2O)- units, wherein m represents a number from 1 to 15, preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3; and n and q represent 0, and the sum of n+m+q represents a number from 1 to 15, preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3.

[0050] In one embodiment of the invention, P is composed of q -(CH2CHR3O)- or -(CHR3CH2O)- units, wherein q represents a number from 1 to 15, preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3; and n and m represent 0, and the sum of n+m+q represents a number from 1 to 12, preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3.

[0051] In another embodiment of the invention, P is composed of n -(CH2CH2O)- units and m -(CH2CHR2O)- or -(CHR2CH2O)- units, wherein n and m each independently represent an integer from 0 to 15, preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3; and q represents 0, and the sum of n+m+q represents a number from 1 to 15, preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3.

[0052] In one embodiment of the invention, the ether carboxylic acid of formula (I) or a salt thereof comprises ethylene oxide and propylene oxide groups. The ether carboxylic acid of formula (I) comprising ethylene oxide and propylene oxide groups in the form of independent blocks, and the ether carboxylic acid of formula (I) comprising randomly distributed ethylene oxide and propylene oxide groups, can be used in the compositions according to the invention.

[0053] In a preferred embodiment of the invention, the ether carboxylic acid of formula (I) or a salt thereof comprises ethylene oxide and a propylene oxide group. The ether carboxylic acid of formula (I) comprising ethylene oxide and a propylene oxide group in the form of independent blocks can be used in the compositions according to the invention.

[0054] In a particularly preferred embodiment, the ether carboxylic acid or its salt represented by formula (I) does not contain an epoxide butyl group, i.e., p=0.

[0055] In a particularly preferred embodiment, the ether carboxylic acid of formula (I) or its salts do not contain propylene oxide and butyl oxide, i.e., they contain only ethylene oxide units (m=0 and p=0).

[0056] In a more preferred embodiment, the ether carboxylic acid or a salt thereof is one of those shown in formula (Ia): R1-O-(CH2CH2O)n-CH2-COOX (Ia) in R1 is a straight-chain or branched alkyl or alkenyl chain having 10 to 18 carbon atoms; n is an integer from 1 to 6; and X is H or a cation selected from alkali metals, alkaline earth metals, ammonium and alkylammonium.

[0057] In a preferred embodiment, R1 is a straight-chain alkyl chain having 10 to 16 carbon atoms, and n is an integer from 1 to 6.

[0058] In a particularly preferred embodiment, R1 is a straight-chain alkyl chain having 12 to 14 carbon atoms, and n is an integer from 1 to 3.

[0059] Those skilled in the art know how to obtain ether carboxylic acids of formulas (I) and (Ia) according to the present invention. These ether carboxylic acids are typically obtained by methods comprising alkoxylation of an alcohol, followed by subsequent carboxymethylation of a mixture of alkoxylated fatty alcohols and non-alkoxylated fatty alcohols derived from carboxymethylation, as described by Meijer and Smid in *PolyetherCarboxylates; Anionic Surfactants; Surfactant Science Series, Vol. 56 (p. 313-361), edited by Helmut W. Stache, ISBN: 0-8247-9394-3*.

[0060] Commercially available ether carboxylates of formula (I) are AKYPO. ® LF 1, AKYPO ® LF 2, AKYPO ® LF 4 and AKYPO ® LF 6, AKYPO ® RLM 25, AKYPO ® RLM 45, AKYPO ® RLM 100, AKYPO ® RO 10 VG, AKYPO ® RO 20 VG, AKYPO ® RO 50 VG and AKYPO ® RO 90 VG, all sold by KaoChemicalsEurope. Among them, AKYPO, sold by KaoChemicalsEurope, is preferred. ® RLM 25, AKYPO ® RLM 45, AKYPO ® RLM 100, AKYPO ® RO 10 VG, AKYPO ® RO 20 VG, AKYPO ® RO 50 VG and AKYPO ® RO 90 VG.

[0061] In a particular embodiment, the amount of ether carboxylic acid (i.e. component (a)) of formula (I) in the collector composition of the present invention is from 0.05 wt% to 99.5 wt% based on the total weight of the composition, preferably from 3 wt% to 60 wt%, more preferably from 5 wt% to 50 wt%.

[0062] Each indicated quantity is expressed as a weight percentage of the mentioned component relative to the total weight of the composition.

[0063] Fatty acids (b)

[0064] The harvester composition according to the invention further comprises component (b), said component being a fatty acid or a mixture of fatty acids. In the context of the invention, said fatty acid or mixture of fatty acids has formula (II): R4-COOH (II) R4 is a straight-chain or branched alkyl or alkenyl chain having 3 to 29 carbon atoms and 1 to 3 double bonds, preferably having 7 to 25 carbon atoms, more preferably having 11 to 21 carbon atoms, and even more preferably having 11 to 17 carbon atoms.

[0065] Suitable C4-C 30 Fatty acids or mixtures thereof refer to those obtained from vegetable and animal oils and fats, such as castor oil, coconut oil, corn oil, mustard oil, olive oil, palm oil, peanut oil, rapeseed oil, sunflower oil, soybean oil, tall oil, and animal fats, which are ultimately completely or partially hydrogenated; as well as purified or synthetic fatty acids, such as hexanoic acid, caprylic acid, capric acid, isotretinoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, 2-ethylhexanoic acid, oleic acid, transoleic acid, petroselinic acid, linoleic acid, linolenic acid, linolenic acid, linolenic acid, ricinoleic acid, arachidic acid, gadolinic acid, behenic acid, erucic acid, or mixtures thereof. Tall oil, oleic acid, or mixtures thereof are preferred.

[0066] In another embodiment of the invention, component (b) is preferably C8-C. 26 Fatty acids or C8-C 26 A mixture of fatty acids; more preferably C 12 -C 22 Fatty acids or C 12 -C 22 A mixture of fatty acids.

[0067] In a preferred embodiment of the present invention, component (b) is C. 12 -C 22 Fatty acids or C 12- C 22 A mixture of fatty acids, preferably obtained from tall oil fatty acids, oleic acid, or mixtures thereof.

[0068] In a particularly preferred embodiment, component (b) is C. 12 -C 18 Fatty acids or mixtures of fatty acids, preferably oleic acid.

[0069] According to one embodiment of the present invention, the weight ratio between component (a) and component (b), i.e., a:b, is 1:99 to 99:1, preferably 3:97 to 60:40, and more preferably 5:95 to 50:50.

[0070] According to another embodiment of the invention, the weight ratio of component (a) to component (b), i.e., a:b, is 35:65 to 15:85 and / or 33:67 to 25:75.

[0071] In a particular embodiment, the amount of fatty acid or fatty acid mixture of formula (II) (i.e. component (b)) in the collector composition of the present invention is from 0.05 wt% to 99.5 wt%, preferably from 40 wt% to 97 wt%, more preferably from 50 wt% to 95 wt%.

[0072] Each indicated quantity is expressed as a weight percentage of the mentioned component relative to the total weight of the composition.

[0073] Ether carboxylic acids or their salts (c)

[0074] In a preferred embodiment, the collector composition according to the invention may further comprise component (c), which is an ether carboxylic acid or a salt thereof as defined below. In these preferred embodiments, R1 in the ether carboxylic acid or salt thereof of component (a) represents a straight-chain or branched alkyl or alkenyl chain as defined above, but having 10 to 30 carbon atoms, preferably 10 to 22 carbon atoms, more preferably 12 to 18 carbon atoms, even more preferably 12 to 16 carbon atoms, and even more preferably 12 to 14 carbon atoms. In these preferred embodiments, P, X, n, m, and q in the ether carboxylic acid or salt thereof of component (a) are as defined above.

[0075] Preferably, in these specific embodiments, n, m and q in the ether carboxylic acid or its salt 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.

[0076] Therefore, the collector composition according to the present invention (wherein R1 in the ether carboxylic acid or salt thereof of component (a) represents a straight-chain or branched alkyl or alkenyl chain as defined above, but having 10 to 30 carbon atoms, preferably 10 to 22 carbon atoms, more preferably 12 to 18 carbon atoms, even more preferably 12 to 16 carbon atoms, and even more preferably 12 to 14 carbon atoms) may also comprise component (c), said component being an ether carboxylic acid or salt thereof of formula (III): R5-OA-CH2-COOX (III) Wherein, R5 is a straight-chain or branched alkyl or alkenyl chain having 4 to 8 carbon atoms, preferably 6 to 8 carbon atoms, more preferably 8 carbon atoms; A is composed of r -(CH2CH2O)- units, and / or s -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or p -(CH2CHR3O)- or -(CHR3CH2O)- units, wherein r represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8; s represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8; p represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8, 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; R2 represents a -CH3 group; and R3 represents a -CH2CH3 group; and X is H or a cation selected from alkali metals, alkaline earth metals, ammonium, and alkylammonium; The condition is that components a) and c) are different.

[0077] As used herein, the term "alkyl" refers to a straight or branched hydrocarbon chain containing a specified number of carbon atoms (e.g., 4 to 8 carbon atoms).

[0078] As used herein, the term "alkenyl" refers to a straight-chain hydrocarbon chain containing a specified number of carbon atoms (e.g., 4 to 8 carbon atoms) and 1 to 3 double bonds.

[0079] In the context of this invention, the term "alkali metal" refers to any one of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs), preferably any one of sodium and potassium.

[0080] In the context of this invention, the term "alkaline earth metal" refers to any one of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba), preferably any one of magnesium and calcium.

[0081] In the context of this invention, the term "ammonium" refers to NH4. + .

[0082] In the context of this invention, the term "alkylammonium" refers to a quaternary ammonium substituted with one, two, or three alkyl groups as defined herein. Specifically, each alkyl group has one to 30 carbon atoms. Examples of alkylammoniums include dimethyl octylammonium, dimethyl decylammonium, dimethyl laurylammonium, dimethyl myristylammonium, dimethyl palmitylammonium, dimethyl hexadecylammonium, dimethyl stearylammonium, dimethyl behenylammonium, or mixtures thereof. Other suitable alkylammoniums are methyl dioctylammonium, methyl dialdecylammonium, methyl dilaurylammonium, methyl dimyristylammonium, methyl palmitylammonium, methyl dihexadecylammonium, methyl distearylammonium, methyl dibehenylammonium, or mixtures thereof.

[0083] As used herein, the term "salt" refers to the carboxylate anion (i.e., R5-OA-CH2COO) in the compound of formula (III) as defined herein. - ) and selected from alkali metals (e.g., Na) + and K + ), alkaline earth metals (such as Ca) 2+ and Mg 2+ Suitable cations of ammonium or alkylammonium. In a preferred embodiment of the invention, the salt of the ether carboxylic acid represented by formula (III) is a sodium or potassium salt of the ether carboxylic acid of the compound of formula (III), i.e., where X is Na. + or K + .

[0084] In another embodiment of the invention, R5 is a straight-chain or branched alkyl or straight-chain alkenyl group derived from natural fats and oils, as well as synthetically derived ones. Preferred fats include palm oil, coconut oil, sunflower oil, rapeseed oil, castor oil, olive oil, soybean oil; animal fats, such as animal fats, bone oil, fish oil, their hardened and semi-hardened oils, and mixtures thereof. As a result of their natural origin, the fats may contain a variety of straight-chain or branched, saturated or unsaturated alkyl and / or alkenyl groups.

[0085] In a specific embodiment of the invention, R5 is a straight-chain or branched alkyl chain having 4 to 8 carbon atoms, preferably 6 to 8 carbon atoms, and more preferably 8 carbon atoms.

[0086] In another specific embodiment of the invention, R5 is a straight-chain alkyl chain having 4 to 8 carbon atoms, preferably 6 to 8 carbon atoms, more preferably 8 carbon atoms.

[0087] In one embodiment of the invention, the ether carboxylic acid or its salt according to formula (III) may be ethoxylated and / or propoxylated and / or butoxylated, i.e., A is an ethoxylated and / or propoxylated and / or butoxylated group. The order of arrangement of ethylene oxide and / or propylene oxide and / or ethylene oxide groups is not important to the invention. Therefore, both the ether carboxylic acid or its salt according to formula (III) comprising ethylene oxide groups and / or propylene oxide groups and / or butyl oxide groups in the form of independent blocks, and the ether carboxylic acid or its salt according to formula (III) comprising randomly distributed ethylene oxide and / or propylene oxide and / or butyl oxide groups, can be used in the compositions according to the invention.

[0088] In an embodiment of the invention, A comprises r -(CH2CH2O)- units, and / or s -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or p -(CH2CHR3O)- or -(CHR3CH2O)- units, wherein r represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8; s represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8; and p represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8. When r is 0, the ether carboxylic acid or its salt of formula (III) does not contain an ethylene oxide unit. When s is 0, the ether carboxylic acid or its salt of formula (III) does not contain an propylene oxide unit. When p is 0, the ether carboxylic acid or its salt of formula (I) does not contain an ethylene oxide unit. In the ether carboxylic acid or its salt of formula (I), at least one alkylene oxide unit is present, said alkylene oxide unit being ethylene oxide, propylene oxide, or ethylene oxide. The degree of alkoxylation is expressed as the sum of the moles of ethylene oxide, and / or propylene oxide, and / or butane oxide present in the ether carboxylic acid or its salt of formula (III), i.e., the sum of r+s+p, and is independently a number from 1 to 20, preferably from 1 to 18, more preferably from 0 to 8.

[0089] As described above, in this invention, the ether carboxylic acid or its salt according to formula (III) is ethoxylated and / or propoxylated and / or butoxylated, i.e., A is an ethoxylated and / or propoxylated and / or butoxylated group. The order of ethylene oxide and / or propylene oxide and / or ethylene oxide groups is not important to this invention. Therefore, the ether carboxylic acid or its salt, as well as the sum of r+s+p, all represent the average degree of alkoxylation, which corresponds to a number from 1 to 20, preferably from 1 to 18, and more preferably from 1 to 8.

[0090] In one embodiment of the present invention, the ether carboxylic acid of formula (III) or a salt thereof may be ethoxylated and / or propoxylated and / or butoxylated. Both the ether carboxylic acid of formula (III) comprising ethylene oxide groups and / or propylene oxide groups and / or butyl oxide groups in the form of independent blocks, and the ether carboxylic acid of formula (III) comprising randomly distributed ethylene oxide and / or propylene oxide and / or butyl oxide groups, can be used in the compositions according to the present invention.

[0091] In an embodiment of the invention, A is composed of r -(CH2CH2O)- units, wherein s represents a number from 1 to 20, preferably from 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.

[0092] In an embodiment of the invention, A is composed of s -(CH2CHR2O)- or -(CHR2CH2O)- units, wherein s represents a number from 1 to 20, preferably from 1 to 18, more preferably from 1 to 8; and r and p represent 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.

[0093] According to one embodiment of the invention, A is composed of p -(CH2CHR3O)- or -(CHR3CH2O)- units, wherein p represents a number from 1 to 20, preferably from 1 to 18, more preferably from 1 to 8; and r and s represent 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.

[0094] In another embodiment of the invention, A is composed of r -(CH2CH2O)- units and an average of s -(CH2CHR2O)- or -(CHR2CH2O)- units, wherein r represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8; s represents a number from 0 to 20, preferably from 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.

[0095] In one embodiment of the invention, the ether carboxylic acid of formula (III) or a salt thereof comprises ethylene oxide and propylene oxide groups. Ether carboxylic acids of formula (III) comprising ethylene oxide and propylene oxide groups in the form of independent blocks, as well as ether carboxylic acids of formula (III) comprising randomly distributed ethylene oxide and propylene oxide groups, can be used in the compositions according to the invention.

[0096] In a preferred embodiment of the invention, the ether carboxylic acid of formula (III) comprises ethylene oxide and propylene oxide groups. The ether carboxylic acid of formula (III) comprising ethylene oxide and propylene oxide groups in the form of independent blocks can be used in the compositions according to the invention.

[0097] In a particularly preferred embodiment, the ether carboxylic acid represented by formula (III) is free of epoxide butane, i.e., p=0.

[0098] In a particular embodiment, the ether carboxylic acid of formula (III) or its salts do not contain propylene oxide and butyl oxide, i.e., they contain only ethylene oxide units.

[0099] In a more preferred embodiment, the ether carboxylic acid or a salt thereof is one of those shown in formula (IIIa): R5-O-(CH2CH2O) r -CH2-COOX (IIIa) in R5 is a straight-chain or branched alkyl or alkenyl chain having 4 to 8 carbon atoms; r is an integer from 1 to 8; and X is H or a cation selected from alkali metals, alkaline earth metals, ammonium and alkylammonium.

[0100] In a particularly preferred embodiment, R5 is a straight-chain alkyl chain having 6 to 8 carbon atoms, and r is an integer from 1 to 6.

[0101] The method for obtaining the ether carboxylic acid or its salt according to formula (III) is the same as that previously described for obtaining the compound of formula (I).

[0102] A commercially available example of a formula (III) ether carboxylate is AKYPO. ® LF 1, AKYPO ® LF 2, AKYPO ® LF 4 and AKYPO ® LF 6 is sold by Kao Chemicals Europe.

[0103] In one embodiment of the invention, the weight ratio between component a) and component c) is 99:1 to 1:99, preferably 99:1 to 25:75, and more preferably 99:1 to 30:70.

[0104] In another embodiment of the invention, the weight ratio between the sum of components a) and c) and component b), i.e. ((a+c):(b)), is 1:99 to 99:1, preferably 3:97 to 60:40, and more preferably 5:95 to 50:50.

[0105] In one embodiment of the invention, the weight ratio between the sum of components a) and c) and component b), i.e. ((a+c):(b)), is 10:90 to 40:60.

[0106] In another embodiment of the invention, the weight ratio between the sum of components a) and c) and component b), i.e. ((a+c):(b)), is 35:65 to 15:85 and / or 33:67 to 25:75.

[0107] In a particular embodiment, the amount of ether carboxylic acid of formula (III) in the collector composition of the present invention is from 0.05 wt% to 50 wt% based on the total weight of the composition, preferably from 0.05 wt% to 30 wt% based on the total weight of the composition, and more preferably from 0.05 wt% to 20 wt% based on the total weight of the composition.

[0108] Each indicated quantity is expressed as a weight percentage of the mentioned component relative to the total weight of the composition.

[0109] Fatty alcohols (d)

[0110] The collector composition according to the invention may further comprise component (d), said component being a fatty alcohol or a mixture of fatty alcohols containing 4 to 30 carbon atoms.

[0111] C4-C 30 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, and soybean oil; animal fats, such as animal fats, bone oil, fish oil, their hardened and semi-hardened oils, and mixtures thereof. As a result of their natural source, alkoxylated alcohols may contain a variety of alkyl and alkenyl groups, which may be straight-chain or branched, saturated or unsaturated.

[0112] Optional, C4-C 30 Fatty alcohols are ethoxylated and / or propoxylated, with an average degree of alkoxylation ranging from 1 to 25.

[0113] In embodiments according to the invention, the fatty alcohol (d) or mixture thereof is represented by formula (IV) and / or formula (IVa) or mixture thereof: R1-ODH (IV) R5-OEH (IVa) R1 and R5 are defined as described above for component (a) in equation (I) and component (c) in equation (III), respectively.

[0114] D consists of t -(CH2CH2O)- units, and / or u -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or v -(CH2CHR3O)- or -(CHR3CH2O)- units, where t represents a number from 0 to 15, u represents a number from 0 to 15, v represents a number from 0 to 15, and the sum of t+u+v represents a number from 0 to 15, and

[0115] E is composed of x -(CH2CH2O)- units, and / or y -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or z -(CH2CHR3O)- or -(CHR3CH2O)- units; wherein x represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8; y represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8; and z represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8; and the sum of x+y+z represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 10.

[0116] Suitable fatty alcohols according to formula (IV) and / or formula (IVa) are n-butanol, n-hexanol, n-octanol, 2-ethylbutanol, 2-methylpentanol, 2-ethylhexanol, 2-methylheptanol, n-decanol, 2-methyl-4-nonanol, 3,7-dimethyl-3-octanol, 3,7-dimethyl-1-octanol, 3,6-dimethyl-3-octanol, lauryl alcohol (1-dodecanol), myristol (1-tetradecanol), cetyl alcohol (1-hexadecanol), palmitol (cis-9-hexadecan-1-ol), stearyl alcohol (1-octadecanol), isostearyl alcohol (16-methylheptadecan-1-ol), trans-oleyl alcohol. (9E-octadecene-1-ol), oleyl alcohol (cis-9-octadecene-1-ol), linoleyl alcohol (9Z,12Z-octadecadien-1-ol), trans-linoleyl alcohol (9E,12E-octadecadien-1-ol), linolenic acid alcohol (9Z,12Z,15Z-octadectrien-1-ol), trans-linolenic acid alcohol (9E,12E,15-E-octadectrien-1-ol), castor oil alcohol (12-hydroxy-9-octadecene-1-ol), arachidonic acid alcohol (1-eicosanool), behenol (1-dococosanool), mustard alcohol (cis-13-dococosanool), or mixtures thereof.

[0117] In another embodiment of the invention, the fatty alcohol (d) is derived from natural fats and oils as well as synthetic sources. Preferred fats and oils include palm oil, coconut oil, sunflower oil, rapeseed oil, castor oil, olive oil, and soybean oil; animal fats, such as animal fats, bone oil, fish oil, their hardened and semi-hardened oils, and mixtures thereof. As a result of their natural source, the fats and oils may contain a variety of alkyl and / or alkenyl groups, which may be straight-chain or branched, saturated or unsaturated.

[0118] In an embodiment of the present invention, the fatty alcohol (d) is represented by formula (IV): R1-ODH (IV) R1 and D are as defined above.

[0119] The fatty alcohols of formula (IV) may be ethoxylated and / or propoxylated and / or butoxylated or non-alkoxylated. As described with respect to compounds of formula (I), the ethylene oxide unit, propylene oxide unit, and butane oxide unit may exist as independent blocks or be randomly distributed.

[0120] In embodiments of the present invention, R1 is a straight-chain or branched alkyl group containing 4 to 30 carbon atoms, or a straight-chain alkenyl group containing 4 to 30 carbon atoms and 1 to 3 double bonds.

[0121] In another embodiment of the invention, R1 is a straight-chain or branched alkyl group containing 10 to 30 carbon atoms, or a straight-chain alkenyl group containing 10 to 30 carbon atoms and 1 to 3 double bonds, preferably containing 10 to 22 carbon atoms, more preferably containing 12 to 18 carbon atoms, even more preferably containing 12 to 16 carbon atoms, and even more preferably containing 12 to 14 carbon atoms.

[0122] In an embodiment of the invention, D is composed of t -(CH2CH2O)- units, and / or u -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or v -(CH2CHR3O)- or -(CHR3CH2O)- units, wherein t represents a number from 0 to 15, preferably 0 to 10, more preferably 0 to 6, and even more preferably 0 to 3; u represents a number from 0 to 15, preferably 0 to 10, more preferably 0 to 6, and even more preferably 0 to 3; v represents a number from 0 to 15, preferably 0 to 10, more preferably 0 to 6, and even more preferably 0 to 3.

[0123] The compounds of formula (IV) can be non-alkoxylated (i.e., t=u=v=0) or alkoxylated. The degree of alkoxylation of the fatty alcohols of formula (IV) is expressed by the sum of t+u+v, where t, u, and v are each independently a number from 1 to 15, preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3.

[0124] In one embodiment of the invention, the fatty alcohol of formula (IV) comprises ethylene oxide and propylene oxide groups. Fatty alcohols of formula (IV) comprising ethylene oxide and propylene oxide groups in the form of independent blocks, as well as fatty alcohols of formula (IV) comprising randomly distributed ethylene oxide and propylene oxide groups, can be used in the compositions according to the invention.

[0125] In a preferred embodiment of the invention, the fatty alcohol of formula (IV) can be ethoxylated and propoxylated. Fatty alcohols of formula (IV) comprising ethylene oxide and propylene oxide groups in independent blocks can be used in the compositions according to the invention.

[0126] In a particularly preferred embodiment of the invention, the fatty alcohol of formula (IV) can be ethoxylated (i.e., u and v are 0).

[0127] In one embodiment of the invention, component (d) of formula (IV) corresponds to the non-alkoxylated fatty alcohol of formula (IV) (i.e., t, u, v are all 0), which is derived from the preparation of the ether carboxylic acid of formula (I).

[0128] In one embodiment of the invention, component (d) of formula (IV) corresponds to a mixture of alkoxylated and non-alkoxylated fatty alcohols of the general formula (IV), said mixture being derived from the preparation of ether carboxylic acid (a) of formula (I).

[0129] In another embodiment of the invention, a component (d) comprising one or more fatty alcohols of formula (IV) is intentionally added to the composition as a blend or mixture.

[0130] In another embodiment of the invention, the fatty alcohol is represented by formula (IVa): R5-OEH (IVa) R5 and D are as defined above.

[0131] The fatty alcohols of formula (IVa) can be ethoxylated and / or propoxylated and / or butoxylated or non-alkoxylated. As described with respect to compounds of formula (IVa), the ethylene oxide unit, propylene oxide unit, and butane oxide unit can exist in the form of independent blocks or in a random distribution.

[0132] In one embodiment of the present invention, R5 is a straight-chain or branched alkyl group containing 4 to 8 carbon atoms, or a straight-chain alkenyl group containing 4 to 8 carbon atoms and 1 to 3 double bonds; preferably containing 6 to 8 carbon atoms, more preferably containing 8 carbon atoms.

[0133] According to one embodiment of the present invention, E is composed of x -(CH2CH2O)- units, and / or y -(CH2CHR6O)- or -(CHR2CH6O)- units, and / or z -(CH2CHR7O)- or -(CHR7CH2O)- units, wherein x represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8; y represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8; and z represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8.

[0134] The degree of alkoxylation of the fatty alcohol of formula (IVa) is represented by the sum of x + y + z, where x, y and z are each independently numbers from 0 to 20, preferably from 0 to 18, and more preferably from 0 to 8.

[0135] In one embodiment of the invention, the fatty alcohol of formula (IVa) comprises ethylene oxide and propylene oxide groups. Both fatty alcohols (IVa) comprising ethylene oxide and propylene oxide groups in the form of independent blocks, and fatty alcohols of formula (IVa) comprising randomly distributed ethylene oxide and propylene oxide groups, can be used in the compositions of the invention.

[0136] In a preferred embodiment of the invention, the fatty alcohol of formula (IV) can be ethoxylated and propoxylated. Fatty alcohols (IVa) comprising ethylene oxide and propylene oxide groups in independent blocks can be used in the compositions of the invention.

[0137] In a particularly preferred embodiment of the invention, the fatty alcohol of formula (IV) can be ethoxylated (i.e., where y and z are 0).

[0138] In one embodiment of the present invention, component (c) of formula (IVa) corresponds to the non-alkoxylated fatty alcohol of formula (IVa) (i.e., where x, y, z are 0), which can be obtained as a byproduct of the preparation process of ether carboxylic acid (c) of formula (III).

[0139] According to one embodiment of the present invention, component (c) of formula (IVa) corresponds to a mixture of alkoxylated and non-alkoxylated fatty alcohols of formula (IVa), said mixture being obtained as a byproduct in the preparation process of ether carboxylic acid (c) of formula (III).

[0140] In another embodiment of the invention, a component (d) comprising one or more fatty alcohols of formula (IVa) is intentionally added to the composition as a blend or mixture.

[0141] Alkoxylated fatty alcohols according to formulas (IV) and (IVa) can be prepared by methods well known in the art, i.e., by reacting a suitable starting fatty alcohol with ethylene oxide and / or propylene oxide and / or butane oxide in the presence of a suitable catalyst, such as, for example, a conventional basic catalyst like KOH, or a so-called narrow-distribution catalyst (see, for example, 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 butane oxide are used, the alkoxides can be added as blocks in any order or randomly.

[0142] In another embodiment of the invention, the fatty alcohol (d) comprises a mixture of fatty alcohols of formula (IV) and (IVa) as defined above.

[0143] In another embodiment of the invention, the fatty alcohols of formula (IV) and / or formula (IVa) include non-alkoxylated fatty alcohols corresponding to formula (IV) and / or formula (IVa) (i.e., where t, u, v, x, y and z are all 0).

[0144] In another embodiment of the invention, component (d) corresponds to a mixture of alkoxylated and non-alkoxylated fatty alcohols of formulas (IV) and (IVa).

[0145] In one embodiment of the invention, components (d) of formulas (IV) and (IVa) are intentionally added to the composition as blends or mixtures.

[0146] In one embodiment of the invention, the weight ratio between component (a) and component (d), i.e., a:d, is 99.99:0.001 to 1:50, preferably 99.99:0.001 to 25:25, and more preferably 99.99:0 to 50:10.

[0147] In one embodiment of the invention, the weight ratio of component (c) to component (d), i.e., c:d, is 99.99:0.001 to 99.99:50, preferably 99.99:0.001 to 25:25, and more preferably 99.99:0.001 to 50:10.

[0148] In the collector composition of the present invention, the amount of fatty alcohol (d) is no more than 50 wt% based on the total weight of the composition, preferably from 0 wt% to 25 wt% based on the total dosage of the composition, and more preferably from 0 wt% to 10 wt%.

[0149] Each indicated quantity is expressed as a weight percentage of the mentioned component relative to the total weight of the composition.

[0150] Fatty acid esters (e)

[0151] The collector composition of the present invention may further comprise component (e), said component being a fatty acid ester or a mixture of fatty acid esters, wherein said fatty acid ester has the formula (V): R6-COO-R7(V) in R6 is selected from: R1-OP-CH2-, where R1 and P are as defined in formula (I); R5-OA-CH2-, where R5 and A are as defined in formula (III); and R4, which is as defined in formula (II); R7 is selected from: -D-R1, where R1 and D are as defined above for component (d) of formula (IV); and -E-R5, where R5 and E are as defined above for component (d) of formula (IVa).

[0152] According to another embodiment of the invention, R6 is R1-OP-, where R1 and P are as defined by formula (I).

[0153] According to another embodiment of the invention, R6 is R5-OA-; wherein R5 and A are as defined by formula (III).

[0154] According to another embodiment of the invention, R6 is R4- as defined above for component (b) in formula (II).

[0155] According to another embodiment of the invention, R7 is -D-R1, wherein R1 and D are as defined above for component (d) of formula (IV).

[0156] According to another embodiment of the invention, R7 is -E-R5, wherein R5 and E are as defined above for component (d) of formula (IVa).

[0157] According to one embodiment of the invention, the fatty acid portion of component (e) is derived from the same fatty acid or a mixture thereof of component (b).

[0158] According to one embodiment of the invention, component (e) present in the composition is intentionally added.

[0159] In embodiments of the invention, component (e) can be obtained as a byproduct of the reaction of the ether carboxylic acid (a) of formula (I) present in the composition with the free fatty alcohol (d) of formula (IV). According to this embodiment of component (d) of formula (V), R6 represents R1-OP-CH2-, wherein R1 and P are as defined in formula (I); and R7 represents -D-R1, wherein R1 and D are as defined above for component (d) of formula (IV). The fatty acid ester according to this embodiment is represented by general formula (VI): R1-OP-CH2-COO-D-R1 (VI) The definitions of R1, P, and D are as described above.

[0160] In an embodiment of the present invention, component (e) of formula (VI) can be obtained as a byproduct of the reaction of ether carboxylic acid (a) of formula (I) with free fatty alcohol (d) of formula (IV), wherein component (d) of formula (IV) corresponds to the non-alkoxylated fatty alcohol of formula (IV) (i.e., t, u, v are all 0) from the preparation of ether carboxylic acid (a) of formula (I).

[0161] In an embodiment of the invention, component (e) fatty acid ester or a mixture of fatty acid esters of formula (VI) can be obtained as a byproduct of the reaction of ether carboxylic acid (a) of formula (I) with free fatty alcohol (d) of formula (IV), wherein component (d) of formula (IV) corresponds to a mixture of alkoxylated and non-alkoxylated fatty alcohols of general formula (IV), wherein the mixture is derived from the preparation of ether carboxylic acid (a) of formula (I).

[0162] In embodiments of the invention, component (e), a fatty acid ester or mixture of fatty acid esters, can be obtained as a byproduct of the reaction of the ether carboxylic acid (a) of formula (I) present in the composition with the free fatty alcohol (d) of formula (IVa). According to this embodiment of component (d) of formula (V), R6 represents R1-OP-CH2-, wherein R1 and P are as defined in formula (I); and R7 represents -E-R5, wherein R5 and E are as defined above for component (d) of formula (IVa). The fatty acid ester or mixture of fatty acid esters (e) according to this embodiment is represented by general formula (V-II): R1-OP-CH2-COO-E-R5 (V-II) The definitions of R1, R5, P, and E are as described above.

[0163] In an embodiment of the present invention, component (e) of formula (V-II), a fatty acid ester or a mixture of fatty acid esters, can be obtained as a byproduct of the reaction of ether carboxylic acid (a) of formula (I) with free fatty alcohol (d) of formula (IVa), wherein component (d) of formula (IVa) corresponds to the non-alkoxylated fatty alcohol of formula (IVa) obtained in the preparation of ether carboxylic acid (a) of formula (I) (i.e., x, y, z are all 0).

[0164] In one embodiment of the invention, component (e) fatty acid ester or a mixture of fatty acid esters of formula (V-II) can be obtained as a byproduct of the reaction of ether carboxylic acid (a) of formula (I) with 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), wherein the mixture is produced during the preparation of ether carboxylic acid (a) of formula (I).

[0165] In one embodiment of the invention, a fatty acid ester or mixture of fatty acid esters (e) can be obtained as a byproduct of the reaction of an ether carboxylic acid (c) of formula (III) with a free fatty alcohol (d) of formula (IV). According to this embodiment of component (d) of formula (V), R6 represents R5-OA-CH2-, wherein R5 and A are as defined in formula (III); and R7 is -D-R1, wherein R1 and D are as defined above for component (d) of formula (IV). The fatty acid ester or mixture of fatty acid esters (e) according to this embodiment is represented by the general formula (V-III): R5-OA-CH2-COO-D-R1 (V-III) The definitions of R1, R5, A, and D are as described above.

[0166] In one embodiment of the invention, the fatty acid ester or mixture of fatty acid esters of formula (V-III) (e) can be obtained as a byproduct of the reaction of the ether carboxylic acid (c) of formula (III) with the free fatty alcohol (d) of formula (IV), wherein the component (d) of formula (IV) corresponds to the non-alkoxylated fatty alcohol of formula (IV) obtained in the preparation of the ether carboxylic acid (a) of formula (I) (i.e., t, u, v are all 0).

[0167] In one embodiment of the invention, a mixture (e) of fatty acid esters or fatty acid esters of formula (V-III) can be obtained as a byproduct of the reaction of ether carboxylic acid (c) of formula (III) with free fatty alcohol (d) of formula (IV), wherein component (d) of formula (IV) corresponds to a mixture of alkoxylated and non-alkoxylated fatty alcohols of general formula (IV), wherein the mixture is produced during the preparation of ether carboxylic acid (a) of formula (I).

[0168] In one embodiment of the invention, a fatty acid ester or mixture of fatty acid esters (e) can be obtained as a byproduct of the reaction of an ether carboxylic acid (c) of formula (III) with a free fatty alcohol (d) of formula (IVa). According to this embodiment of component (d) of formula (V), R6 represents R5-OA-CH2-, wherein R5 and A are as defined in formula (III); and R7 is -E-R5, wherein R5 and E are as defined above for component (d) of formula (IVa). The fatty acid ester or mixture of fatty acid esters (e) according to this embodiment is represented by the general formula (V-IV): R5-OA-CH2-COO-E-R5 (V-IV) R5, A, and E are as defined above.

[0169] In one embodiment of the invention, the fatty acid ester or mixture of fatty acid esters of formula (V-IV) can be obtained as a byproduct of the reaction of the ether carboxylic acid (c) of formula (III) with the free fatty alcohol (d) of formula (IVa), wherein the component (d) of formula (IVa) corresponds to the non-alkoxylated fatty alcohol of formula (IVa) obtained in the preparation of the ether carboxylic acid (c) of formula (III) (i.e., x, y, z are all 0).

[0170] In one embodiment of the invention, a mixture (e) of fatty acid esters or fatty acid esters of formula (V-IV) can be obtained as a byproduct of the reaction of ether carboxylic acid (c) of formula (III) with 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 formula (IVa), wherein the mixture is produced during the preparation of ether carboxylic acid (c) of formula (III).

[0171] In one embodiment of the invention, a fatty acid ester or mixture of fatty acid esters (e) can be obtained by reacting a fatty acid or mixture of fatty acids of formula (II) (b) with a free fatty alcohol of formula (IV) (d). According to this embodiment of component (d) of formula (V), R6 represents R4 as defined in formula (II), and R7 is -D-R1, wherein R1 and D are as defined above for component (d) of formula (IV). The fatty acid ester or mixture of fatty acid esters according to this embodiment is represented by the general formula (VV): R4-COO-D-R1 (VV) R1, R4, and D are defined as described above.

[0172] In one embodiment of the invention, the ester (d) of formula (VV) is obtained by reacting the fatty acid (b) of formula (II) with the fatty alcohol (d) of formula (IV), wherein the component (d) of formula (IV) corresponds to the non-alkoxylated fatty alcohol of the general formula (IV), which is produced during the preparation of the ether carboxylic acid (a) of formula (I).

[0173] In one embodiment of the invention, a fatty acid ester or mixture of fatty acid esters of formula (VV) (e) can be obtained by reacting a fatty acid or mixture of fatty acids of formula (II) (b) with a free fatty alcohol of formula (IV) (d), wherein component (d) of formula (IV) corresponds to a mixture of alkoxylated and non-alkoxylated fatty alcohols of the general formula (IV) present in the reaction mixture, wherein the reaction mixture is generated during the preparation of an ether carboxylic acid of formula (I) (a).

[0174] In one embodiment of the invention, a fatty acid ester or mixture of fatty acid esters (e) is obtained by reacting a fatty acid or mixture of fatty acids of formulas (II) and (III) (b) with a free fatty alcohol of formula (IVa) (d). According to this embodiment of component (d) of formula (V), R6 represents R4, wherein R4 is as defined in formula (II), and R7 is -E-R5, wherein R5 and E are as defined above for component (d) of formula (IVa). The fatty acid ester or mixture of fatty acid esters (e) according to this embodiment is represented by general formulas (V-VI): R4-COO-E-R5 (V-VI) R4, R5, and E are as defined above.

[0175] In one embodiment of the invention, a fatty acid ester or mixture of fatty acid esters of formula (V-VI) is obtained by reacting a fatty acid or mixture of fatty acids of formula (II) with a fatty alcohol of formula (IVa) (d), wherein component (d) of formula (IVa) corresponds to a non-alkoxylated fatty alcohol of general formula (IVa), which is produced during the preparation of ether carboxylic acid (c) of formula (III).

[0176] In one embodiment of the invention, a fatty acid ester (e) of formula (V-VI) can be obtained by reacting a fatty acid or a mixture of fatty acids of formula (II) (b) with a free fatty alcohol of formula (IVa) (d), wherein component (d) of formula (IV) corresponds to a mixture of alkoxylated and non-alkoxylated fatty alcohols of the general formula (IVa) present in the reaction mixture, wherein the reaction mixture is generated during the preparation of an ether carboxylic acid (c) of formula (III).

[0177] In one embodiment of the invention, the amount of fatty acid ester (e) is from 0% wt to 50% wt, based on the total weight of the composition; preferably from 0% wt to 25% wt; more preferably from 0% wt to 10% wt.

[0178] Each indicated quantity is expressed as a weight percentage of the mentioned component relative to the total weight of the composition.

[0179] The collector composition of the present invention

[0180] In an embodiment, the present invention relates to the use of a collector composition for the beneficiation of lithium-bearing minerals, said lithium-bearing minerals being contained in an ore containing lithium-bearing minerals and gangue minerals, wherein said composition comprises: (a) at least one ether carboxylic acid of formula (I) above or a salt thereof, and (b) Fatty acids or mixtures of fatty acids according to formula (II) above; The characteristic is that the weight ratio between component a) and component b) is 99:1 to 1:99, preferably 3:97 to 60:40, and more preferably 5:95 to 50:50.

[0181] In another embodiment of the invention, the weight ratio between component (a) and component (b), i.e., a:b, is 35:65 to 15:85, and / or 33:67 to 25:75.

[0182] Other components of the collector composition used in this invention are at least one ether carboxylic acid or its salt (c), a fatty alcohol (d), a fatty acid ester or a mixture of fatty acid esters (e), and / or water, as defined above.

[0183] In a specific embodiment, the collector composition comprises component (a), component (b), and component (c). Unexpectedly, the addition of the second ether carboxylic acid (c) resulted in a synergistic effect between the two components, thereby significantly improving the purity of Li₂O.

[0184] According to specific embodiments of the invention, the use of a collector composition for the beneficiation of lithium-containing minerals (e.g., lithium silicates, preferably spodumene) contained in ore is described.

[0185] In a particular embodiment, the collector composition used in this invention comprises an ether carboxylic acid of formula (I) or a salt thereof (component (a)) and a fatty acid or mixture of fatty acids of formula (II) (component (b)). In a particular embodiment, the amount of the ether carboxylic acid of formula (I) or a salt thereof in the composition used in this invention is at least 99.5 wt%, preferably 3 wt% to 60 wt%, more preferably 5 wt% to 50 wt%; and the amount of the fatty acid or mixture of fatty acids in the collector composition used in this invention is at least 99.5 wt%, preferably 40 wt% to 97 wt%, more preferably 50 wt% to 95 wt%. The amount of the ether carboxylic acid of formula (I) or a salt thereof and the amount of fatty acid (b) are selected such that the total amount does not exceed 100 wt%. Preferably, the weight ratio between the ether carboxylic acid of formula (I) or a salt thereof (a) and the fatty acid (b) of formula (II), i.e., a:b, is 1:99 to 99:1, preferably 3:97 to 60:40, more preferably 5:95 to 50:50.

[0186] In another specific embodiment, the collector composition used in this invention comprises one or more ether carboxylic acids of formula (I) or salts thereof (component (a)), fatty acids of formula (II) or mixtures thereof (component (b)), and at least one ether carboxylic acid of formula (III) or salt thereof (component (c)). Preferably, in the collector composition of this invention, the total weight content of components (a) and (c) does not exceed 95 wt%, and the indicated amount is expressed as a percentage per weight relative to the total weight of the composition, preferably from 3 wt% to 60 wt%, more preferably from 5 wt% to 50 wt%, and the content of fatty acid (b) is from 0.05 wt% to 99.5 wt%, preferably from 40 wt% to 97 wt%, more preferably from 50 wt% to 95 wt%, based on the total weight of the composition.

[0187] According to another embodiment of the invention, the weight ratio (a+c):b between the ether carboxylic acid of formula (I) or its salt (a) and the ether carboxylic acid of formula (III) or its salt (c) relative to the fatty acid of formula (II), is 1:99 to 99:1, preferably 3:97 to 60:40, more preferably 5:95 to 50:50. In a particularly preferred embodiment, the weight ratio (a+c):b is 35:65 to 15:85, more preferably 33:67 to 25:75.

[0188] In another specific embodiment, the collector composition used in this invention comprises at least an ether carboxylic acid of formula (I) (component (a)), a fatty acid of formula (II) (component (b)), and a fatty alcohol of formula (IV) (component (d)), wherein component (d) corresponds to an alkoxylated fatty alcohol and a non-alkoxylated fatty alcohol produced during the preparation of the ether carboxylic acid (a), wherein the components are as defined above. According to one embodiment of the use of this composition, the ether carboxylic acid of formula (I) in the collector composition used in this invention has a weight content of not more than 99.5 wt%; a weight content of fatty acid (b) of 0.05 wt% to 99.5 wt%; and a weight content of fatty alcohol (d) of 0.05 wt% to 50 wt% in the collector composition, wherein the weight percentages are based on the total weight of the composition. Preferably, in the collector composition used in this invention, the weight content of the ether carboxylic acid (a) of formula (I) is 3 wt% to 60 wt%; the weight content of the fatty acid (b) in the collector composition is 40 wt% to 97 wt%; and the weight content of the fatty alcohol (d) is 0.05 wt% to 25 wt%, wherein the weight percentages are based on the total weight of the composition. Preferably, the weight ratio between the ether carboxylic acid of formula (I) or its salt (a) and the fatty alcohol (d) of formula (III), i.e., a:d, is 99:1 to 1:50, more preferably 99:1 to 25:25, and more preferably 99:1 to 50:10.

[0189] In another specific embodiment, the collector composition used in this invention comprises at least an ether carboxylic acid of formula (I) or a salt thereof (component (a)), a fatty acid of formula (II) or a mixture thereof (component (b)), and a fatty acid ester or a mixture of fatty acid esters of formula (V) (component (e)), wherein the components are as defined above. Preferably, the weight content of at least one ether carboxylic acid of formula (I) or a salt thereof in the collector composition does not exceed 99.5 wt%; the weight content of fatty acid (b) is from 0.05 wt% 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.

[0190] In another specific embodiment, the collector composition used in this invention comprises at least an ether carboxylic acid of formula (I) or a salt thereof (component (a)), a fatty acid or a mixture of fatty acids of formula (II) (component (b)), at least an ether carboxylic acid of formula (III) or a salt thereof (component (c)), and a fatty acid ester or a mixture of fatty acid esters of formula (V) (e), as defined above, wherein components (a) and (c) are different, the sum of the weight contents of the ether carboxylic acids of formula (I) and the salt thereof of formula (III), the indicated amount being expressed as a weight percentage relative to the total weight of the collector composition, and the sum of the weights of (a) and (c) in the collector composition not exceeding 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 wt% to 99.5 wt%, and wherein the weight content of the fatty acid ester (e) in the collector composition is from 0 wt% to 50 wt%; preferably from 0 wt% to 25 wt%; more preferably from 0 wt% to 10 wt%. wt%, wherein the weight percentage is based on the total weight of the composition. Preferably, the weight ratio between at least one ether carboxylic acid of formula (I) or its salt and the fatty acid or mixture of fatty acids, i.e., a:b, is 1:99 to 99:1, preferably 3:97 to 60:40, more preferably 5:95 to 50:50. More preferably, the weight ratio between at least one ether carboxylic acid or its salt (a) and the sum of component (c) relative to the fatty acid or mixture of fatty acids (b), i.e., ((a)+(c)):(b), is 1:99 to 99:1, preferably 3:97 to 60:40, more preferably 5:95 to 50:50.

[0191] In another specific embodiment, the collector composition used in this invention comprises one or more ether carboxylic acids of formula (I) or salts thereof (component (a)), fatty acids or mixtures of fatty acids of formula (II) (component (b)), and fatty alcohols of formula (IV) (component (d)), wherein the components are as defined above, and wherein component (d) corresponds to a mixture (e) of non-carboxymethylated substances (alkoxylated fatty alcohols and / or non-alkoxylated fatty alcohols) produced during the preparation of ether carboxylic acids (a) and fatty acid esters of formula (V), wherein the weight content of the ether carboxylic acid of formula (I) or salts thereof in the collector composition does not exceed 99.5% wt; wherein the weight content of the fatty acid or mixture of fatty acids in the collector is from 0.05 wt% to 99.5 wt%; wherein the weight content of the fatty alcohol of formula (d) in the collector composition does not exceed 50 wt%, preferably from 1 wt% to 25 wt%, more preferably from 1 wt% to 10 wt%, and wherein the weight content of the fatty acid ester (e) in the collector composition is from 0 wt% to 50 wt%, preferably from 0 wt% to 25 wt%. wt%; more preferably 0 wt% to 10 wt%, wherein the weight percentage is based on the total weight of the composition. Preferably, the weight ratio between at least the ether carboxylic acid of formula (I) or its salt and the fatty acid or mixture of fatty acids, i.e., a:b, is 1:99 to 99:1, preferably 3:97 to 60:40, more preferably 5:95 to 50:50. The weight ratio between the ether carboxylic acid or its salt (a) and the fatty alcohol (d), i.e., a:d, is 99:0.001 to 0.001:50, preferably 99:0.001 to 25:25, more preferably 99:0.001 to 50:10.

[0192] In another specific embodiment, the collector composition used in this invention comprises one or more ether carboxylic acids of formula (I) or salts thereof (component (a)), a fatty acid or mixture of fatty acids of formula (II) (component (b)), at least one ether carboxylic acid of formula (III) or salts thereof (component (c)), and component (d), wherein component (d) corresponds to a mixture of non-carboxymethylated substances (alkoxylated fatty alcohols and / or non-alkoxylated fatty alcohols) generated during the preparation of ether carboxylic acids (a) and (c), wherein components (a) and (c) correspond to formulas (IV) and (IVa), respectively, provided that components (a) and (c) are different, wherein the sum of the weight contents of the ether carboxylic acid of formula (I) or salts thereof and component (c) of formula (III) in the collector composition does not exceed 99.5 wt%; wherein the weight content of the fatty acid or mixture of fatty acids in the collector is at least 99.5 wt%, and wherein the weight content of the fatty alcohol (d) in the collector composition is from 0 wt% to 50 wt%, preferably from 1 wt% to 25 wt%, more preferably from 1 wt% to 10 wt%. wt%, wherein the weight percentage is based on the total weight of the composition. Preferably, the weight ratio between at least one ether carboxylic acid of formula (I) or its salt and the fatty acid or mixture of fatty acids, i.e., a:b, is 1:99 to 99:1, preferably 3:97 to 60:40, more preferably 5:95 to 50:50. More preferably, the weight ratio between the sum of at least one ether carboxylic acid or its salt (a) and component (c) relative to the fatty acid or mixture of fatty acids (b), i.e., ((a)+(c)):(b), is 1:99 to 99:1, preferably 3:97 to 60:40, more preferably 5:95 to 50:50.

[0193] In another embodiment of the invention, the weight ratio between at least one ether carboxylic acid or its salt (a) and component (c) relative to the fatty alcohol (d), i.e. ((a)+(c)):(d), is 99:0.001 to 0.001:50, preferably 99:0.001 to 25:25, more preferably 99:0.001 to 50:10, wherein the fatty alcohol is a mixture of fatty alcohols as defined above.

[0194] In another specific embodiment, the collector composition used in this invention comprises at least an ether carboxylic acid of formula (I) or a salt thereof (component (a)), a fatty acid or a mixture of fatty acids of formula (II) (component (b)), at least an ether carboxylic acid of formula (III) or a salt thereof (component (c)), a mixture of fatty alcohols of formulas (IV) and (IVa) (component (d)), and a fatty acid ester or a mixture of fatty acid esters of formula (V) (component (e)), wherein component (d) corresponds to a mixture of non-carboxymethylated substances (alkoxylated fatty alcohols and non-alkoxylated fatty alcohols) generated during the preparation of ether carboxylic acids (a) and (c), wherein all said components are as defined above, provided that components (a) and components (c) are different, and wherein the sum of the total weight contents of the ether carboxylic acid of formula (I) or a salt thereof and the components of formula (III) in the collector composition does not exceed 99.5 wt%; wherein the weight content of the fatty acid or mixture of fatty acids in the collector is at least 99.5 wt%; wherein the weight content of the fatty alcohol (d) in the collector composition does not exceed 50 wt%, preferably from 1 wt% to 25 wt%. The weight percentage is preferably 1 wt% to 10 wt%, and the fatty acid ester (e) in the collector composition is 0 wt% to 50 wt%, preferably 0 wt% to 25 wt%, more preferably 0 wt% to 10 wt%, wherein the weight percentage is based on the total weight of the composition. Preferably, the weight ratio between at least one ether carboxylic acid of formula (I) or its salt and the fatty acid or mixture of fatty acids, i.e., a:b, is 1:99 to 99:1, preferably 3:97 to 60:40, more preferably 5:95 to 50:50. More preferably, the weight ratio of at least one ether carboxylic acid or its salt (a) to the sum of component (c) relative to fatty acid or fatty acid mixture (b), i.e. ((a)+(c)):(b), is 1:99 to 99:1, preferably 3:97 to 60:40, more preferably 5:95 to 50:50; and the weight ratio of at least one ether carboxylic acid or its salt (a) to fatty alcohol (d), i.e. a:d, is 99:0.001 to 0.001:50, preferably 99:0.001 to 25:25, more preferably 99:0.001 to 50:10.

[0195] In addition, the collector composition of the present invention may also contain one or more of the following additives, which is not a limiting list and other components may also be present: nonionic surfactants, anionic surfactants and cationic surfactants, foaming agents, foam control agents, pH adjusters, activators (i.e., CaCl2) for obtaining minerals in foam or deactivators for foam in which minerals are not needed, dispersants, etc.

[0196] Method for obtaining a collector composition

[0197] Another aspect of the invention relates to a method for preparing a collector composition comprising a component (a) and a component (b), wherein the component (a) comprises at least one ether carboxylic acid of formula (I) or a salt thereof, and the component (b) comprises a fatty acid or a mixture of fatty acids, the method being carried out by mixing the components (a) and (b), preferably under continuous stirring, particularly for 10 minutes to 1 hour (preferably 10 to 20 minutes, more preferably 15 minutes), and more preferably at a temperature of 20°C to 25°C.

[0198] According to another embodiment of the invention, the collector composition obtained by this method may further comprise component (c), said component (c) comprising at least one ether carboxylic acid or a salt thereof represented by formula (III) as defined above, provided that components (a) and (c) are different.

[0199] In one embodiment of the invention, the collector composition used in the invention is obtained by mixing component (a), component (b), and component (d) of formula (IV), wherein component (d) is as defined above and preferably corresponds to the non-carboxymethylated substance (alkoxylated fatty alcohol and / or non-alkoxylated fatty alcohol) produced during the preparation of ether carboxylic acid (a). Preferably, the mixing of the components is carried out under continuous stirring, particularly for 10 minutes to 1 hour (preferably 10 to 20 minutes, more preferably 15 minutes), and more preferably at a temperature of 20°C to 25°C.

[0200] In one embodiment of the invention, the collector composition used in the invention is obtained by mixing component (a), component (b), and component (e). Preferably, the mixing of components is carried out under continuous stirring, particularly for 10 minutes to 1 hour (preferably 10 to 20 minutes, more preferably 15 minutes), and more preferably at a temperature of 20°C to 25°C.

[0201] In another specific embodiment, the collector composition used in this invention is obtained by mixing at least one ether carboxylic acid of formula (I) or a salt thereof (component (a)), a fatty acid or a mixture of fatty acids of formula (II) (component (b)), a fatty alcohol of formula (IV) (component (d)), and a fatty acid ester (component (e)), wherein component (d) corresponds to a mixture of non-carboxymethylated substances (alkoxylated fatty alcohols and / or non-alkoxylated fatty alcohols) produced during the preparation of ether carboxylic acid (a). Preferably, the mixing of said components is preferably carried out under continuous stirring, particularly continuous stirring for 10 minutes to 1 hour (preferably 10 to 20 minutes, more preferably 15 minutes), and more preferably at a temperature of 20°C to 25°C.

[0202] In another specific embodiment, the collector composition used in this invention is obtained by mixing at least one ether carboxylic acid of formula (I) or a salt thereof (component (a)), a fatty acid of formula (II) or a mixture of fatty acids (component (b)), a fatty alcohol of formula (IV) (component (d)), and a fatty acid ester (component (e)), wherein component (d) corresponds to a mixture of non-carboxymethylated substances (alkoxylated fatty alcohols and / or non-alkoxylated fatty alcohols) produced during the preparation of ether carboxylic acid (a). Preferably, the mixing of components is carried out under continuous stirring, particularly for 10 minutes to 1 hour (preferably 10 to 20 minutes, more preferably 15 minutes), and more preferably at a temperature of 20°C to 25°C.

[0203] In another specific embodiment, the collector composition used in this invention is obtained by mixing an ether carboxylic acid of formula (I) or a salt thereof (component (a)), a fatty acid or a mixture of fatty acids of formula (II) (component (b)), at least one ether carboxylic acid of formula (III) or a salt thereof (component (c)), and a fatty alcohol (d), wherein component (d) corresponds to a mixture of non-carboxymethylated substances (alkoxylated fatty alcohols and / or non-alkoxylated fatty alcohols) of formulas (IV and IVa) produced during the preparation of ether carboxylic acids (a) and (c). Preferably, the mixing of components is carried out under continuous stirring, particularly for 10 minutes to 1 hour (preferably 10 to 20 minutes, more preferably 15 minutes), and more preferably at a temperature of 20°C to 25°C.

[0204] In another specific embodiment, the mixture is obtained by mixing at least one ether carboxylic acid of formula (I) or a salt thereof (component (a)), a fatty acid or a mixture of fatty acids of formula (II) (component (b)), at least one ether carboxylic acid of formula (III) or a salt thereof (component (c)), and a fatty acid ester component (component (e)). Preferably, the mixing is carried out under continuous stirring, particularly for 10 minutes to 1 hour (preferably 10 to 20 minutes, more preferably 15 minutes), and more preferably at a temperature of 20°C to 25°C.

[0205] In another specific embodiment, the collector composition used in this invention is obtained by mixing at least one ether carboxylic acid of formula (I) or a salt thereof (component (a)), a fatty acid or a mixture of fatty acids of formula (II) (component (b)), at least one ether carboxylic acid of formula (III) or a salt thereof (component (c)), a fatty alcohol of formula (IV and IVa) (d), and a fatty acid ester of formula (V) according to formulas V-VI to V-VIII (component (e)), wherein component (d) corresponds to a mixture of non-carboxymethylated substances (alkoxylated fatty alcohols and / or non-alkoxylated fatty alcohols) generated during the preparation of ether carboxylic acids (a) and (c). Preferably, the mixing of components is preferably carried out under continuous stirring, particularly continuous stirring for 10 minutes to 1 hour (preferably 10 to 20 minutes, more preferably 15 minutes), and more preferably at a temperature of 20°C to 25°C.

[0206] flotation process

[0207] Another object of the present invention is a method for beneficiating lithium-bearing minerals from ores comprising lithium-bearing minerals and gangue minerals, wherein a collector composition as defined above is used.

[0208] In a particular embodiment, the lithium-containing mineral is a lithium silicate, preferably but not limited to spodumene.

[0209] This invention relates to a method for beneficiating lithium-bearing minerals (e.g., lithium silicates) from ores comprising lithium-bearing minerals and gangue minerals, wherein the method comprises the following steps: a) Mixing an ore containing lithium-bearing minerals and gangue minerals with water to obtain an aqueous mixture. b) Add the collector composition as described above to the aqueous mixture obtained in step a). c) Stir the mixture obtained in step b) (conditioning step), d) Introducing air into mixture c to generate foam, and e) Collect lithium-containing minerals, such as lithium silicates, from the foam.

[0210] In a particular implementation, the method includes additional optional steps b) and / or c), such that the method comprises the following steps: a1) Mixing an ore containing lithium-bearing minerals and gangue minerals with water to obtain an aqueous mixture. b1) Optionally adjust the pH of the aqueous mixture obtained in step a) to obtain a pH-adjusted aqueous mixture. c1) Optionally, the ore is slurry-conditioned with inhibitors and / or activators. d1) Adding the collector composition as described above to the aqueous mixture obtained in step a1) (when steps b1) and c1) are not performed), adding it to the aqueous mixture obtained in step b1) (when step b1) is performed but step c1) is not performed), or adding it to the aqueous mixture obtained in step c1) (when step c1) is performed. e1) Stir the mixture obtained in step d1 (slurry preparation step). f1) Introducing air injection to generate foam, and g1) Collect lithium-containing minerals, such as lithium silicates, from foam.

[0211] Steps a) and a1) involve mixing the ore containing lithium-bearing minerals and gangue minerals with water to form an aqueous mixture. Preferably, the lithium-bearing mineral is spodumene (LiAlSi2O6). The main components of the ore containing lithium-bearing minerals are as defined above, specifically spodumene, quartz, plagioclase, feldspar, muscovite, and other silicate minerals.

[0212] In one embodiment of the invention, during step b1), the pH is adjusted with a pH-adjusting substance such as NaOH, Na2CO3, KOH, K2CO3, HCl, H2SO4, H3PO4, or HNO3.

[0213] In one embodiment of the invention, during step b1), the adjusted pH value is 6 to 10; preferably 7 to 9.

[0214] If the pH of the suspension obtained in steps a) and / or a1) has reached the desired value, then step b1 is unnecessary.

[0215] Step c1) is optional, and the ore is slurryed with inhibitors and / or activators.

[0216] The term "inhibitor" refers to a reagent that inhibits the flotation of unwanted minerals, allowing for the selective recovery of lithium-containing minerals. In lithium flotation, inhibitors are used to suppress the flotation of minerals such as quartz or feldspar, as these minerals interfere with the separation process. Sodium silicate is a commonly used inhibitor in lithium flotation, used to inhibit the flotation of quartz and other silicate minerals.

[0217] The term "activator" refers to a chemical compound typically added to promote the interaction between collector molecules and the mineral surface. Examples include Na₂CO₃, NaOH, Na₂S, CaOH, CaCO₃, and CaCl₂, with CaCl₂ being preferred.

[0218] The next step, namely steps b and d1), is to add the previously described collector composition to the aqueous suspension obtained in steps a), a1), b1), or c1). When steps b1) and c1) are not performed, the collector composition is added to the aqueous suspension obtained in step a) or a1). When step b1) is performed but step c1) is not performed, the collector composition is added to the aqueous mixture obtained in step b1). When step c1) is performed, the collector composition is added to the aqueous mixture obtained in step c1).

[0219] According to one embodiment of the present invention, in steps b) and d1), components (a) and (b) of the collector composition are added as a blend, or alternatively, components (a) and (b) of the collector composition are added separately.

[0220] According to another embodiment of the present invention, in steps b) and d1), components (a), (b) and (c) of the collector composition are added as a blend, or alternatively, components (a), (b) and (c) of the collector composition are added separately.

[0221] According to another embodiment of the invention, in steps b) and d1), components (a), (b), and (d) are added as a blend, or alternatively, components (a), (b), and (d) of the collector composition are added separately, wherein component (d) corresponds to a mixture of non-carboxymethylated substances (alkoxylated fatty alcohols and non-alkoxylated fatty alcohols) generated during the preparation of ether carboxylic acid (a).

[0222] According to another embodiment of the present invention, in steps b) and d1), components (a), (b) and (e) are added as a blend, or optionally, components (a), (b) and (e) of the collector composition are added separately.

[0223] In another embodiment of the invention, in steps b) and d1), components (a), (b), (d), and (e) are added as a blend, or alternatively, components (a), (b), (d), and (e) of the collector composition are added separately, wherein component (d) corresponds to a mixture of non-carboxymethylated substances (alkoxylated fatty alcohols and non-alkoxylated fatty alcohols) generated during the preparation of ether carboxylic acid (a).

[0224] According to another embodiment of the invention, in steps b) and d1), components (a), (b), (c), and (d) are added as a blend, or alternatively, components (a), (b), (c), and (e) of the collector composition are added separately, wherein component (d) corresponds to a mixture of non-carboxymethylated substances (alkoxylated fatty alcohols and non-alkoxylated fatty alcohols) generated during the preparation of ether carboxylic acid (a).

[0225] In another embodiment of the invention, in steps b) and d1), components (a), (b), (c) and (e) are added as a blend, or alternatively, components (a), (b), (c), (d) and (e) of the collector composition are added separately.

[0226] In another embodiment of the invention, in steps b) and d1), components (a), (b), (c), (d), and (e) are added as a blend, or alternatively, components (a), (b), (c), (d), and (e) of the collector composition are added separately, wherein component (d) corresponds to a mixture of non-carboxymethylated substances (alkoxylated fatty alcohols and non-alkoxylated fatty alcohols) generated during the preparation of ether carboxylic acid (a).

[0227] In another embodiment, the flotation process includes the addition of one or more modifiers prior to step b) or d1).

[0228] The term "modifier" refers to a reagent used to modify the action of a collector on a mineral surface, thereby altering the interaction between the mineral and the collector. In some cases, this is done by promoting the interaction; in others, by preventing it from occurring. Examples of modifiers are sodium silicate, sodium metaphosphate, polybasic organic acids, starch, sodium fluorosilicate, sagebrush, and tannins.

[0229] Steps d) and f1) involve agitating the mixture obtained in step d) and injecting air to generate foam. This can be achieved by injecting air into the aqueous mixture in the form of bubbles.

[0230] Steps e) and g1) involve collecting lithium silicates from the foam. This can be done in a flotation cell.

[0231] The flotation process can be completed in one cycle, or optionally, in multiple cycles to maximize the recovery of lithium concentrate.

[0232] In a particularly preferred embodiment of the invention, in order to maximize the recovery of the desired lithium-containing minerals, such as lithium silicates, especially spodumene, the flotation process may further include a second cycle comprising the following steps: i) Mix the flotation minerals obtained during step e) or g1) with water to form an aqueous mixture. ii) Agitate the aqueous suspension obtained in step i) under air injection to generate foam, and iii) Collect lithium-containing minerals from the foam.

[0233] According to one embodiment of the present invention, the flotation process is a single-cycle process, carried out according to steps a) to e) or a1) to g1) as defined above, to achieve high Li2O.

[0234] In another embodiment, the flotation process is carried out in two cycles, including steps a) to e) and i) to iii), or a1) to g1) and i) to iii), with the aim of obtaining high purity.

[0235] In another preferred embodiment, the amount of the collector composition added in steps b) and d1) is 5 g to 5000 g per ton of ore provided in step a) or a1), preferably 10 g to 3000 g per ton of ore, and more preferably 40 g to 2000 g per ton of ore.

[0236] The following examples are intended to provide a sufficiently clear and complete description of the invention for those skilled in the art, but should not be construed as limiting the basic aspects of the subject matter described above in this specification.

[0237] Example

[0238] The first part of the Examples section relates to the preparation of the collector compositions of the present invention.

[0239] The second part of the Examples section relates to flotation tests of collector combinations, and the determination of mass recovery (yield) and Li2O content (%) in flotation concentrate.

[0240] Example 1. Preparation of the collector composition

[0241] Preparation of collector combination 1 (according to the present invention): At 25°C, 33 g of polyoxyethylene C12-14 ether carboxylic acid (component a) with an average of 3 ethylene oxide units and 67 g of oleic fatty acid (component b) were mixed for 10 minutes.

[0242] Preparation of collector combination 2 (according to the present invention): At 25°C, 16.5 g of C12-14 alkyl ether carboxylic acid with an average degree of ethoxylation of 3 ethylene oxide units (component a), 67 g of oil fatty acid (component b) and 16.5 g of C8 alkyl ether carboxylic acid with an average degree of ethoxylation of 5 were mixed for 10 minutes.

[0243] Example 2. Flotation Tests and Collector Evaluation

[0244] flotation test

[0245] In all embodiments, an ore containing spodumene (LiAlSi2O6) as a lithium-bearing mineral and other silicate minerals as gangue minerals is used. The main components of the ore include spodumene, quartz, plagioclase, feldspar, muscovite, and other silicate minerals.

[0246] ICP-OES analysis showed that the ore containing spodumene and other silicates (gangue minerals) had a Li2O content of 1.2%.

[0247] The particle size distribution of spodumene ore was characterized by laser diffraction using a Malvern Mastersizer 2000 laser particle size analyzer with 2-propanol as solvent at 22℃. The results are shown in Table 1.

[0248] Table 1: Particle size distribution of spodumene ore

[0249] d(0.1): indicates that particles with a diameter smaller than this size account for 10% of the volume.

[0250] d(0.5): indicates that particles with a diameter smaller than this size account for 50% of the volume.

[0251] d(0.9): indicates that particles with a diameter smaller than this size account for 90% of the volume.

[0252] Spodumene is flotated (direct flotation) from silicate mineral-containing ores to enrich it for Li₂O content. The spodumene is then recovered in a frothy concentrate.

[0253] A Denver D-12 laboratory flotation system was used. Experiments were conducted in 1.2 L flotation cells at 1000 rpm and at room temperature. Tap water with a hardness of 10 °HF to 20 °HF was used.

[0254] The experiment consisted of two flotation steps: a roughing flotation and a cleaning flotation.

[0255] In the roughing flotation, NaOH is used as a pH adjuster, and the minerals are conditioned at pH 8 for 5 minutes. Afterwards, a collector composition is added in the required dosage. The roughing flotation ore is used as feedstock for the cleaning flotation. The cleaning flotation ore is the final concentrate.

[0256] The target figure is the highest possible Li2O content, preferably, Li2O content (%) > 5.5%.

[0257] Evaluation of harvesting agents

[0258] The dosage of the added collector ranged from 400 g / ton to 2000 g / ton. The flotation results are shown in Table 1. The percentage of Li₂O was analyzed by ICP-OES. Numbers 1 and 2 represent embodiments according to the present invention, while C1 and C2 are comparative references.

[0259] Table 1. Evaluation of collectors

[0260] As can be seen from the above results, the embodiments of the present invention exhibit good % yield and high Li2O content (above 5.5%), while the comparative embodiments failed to meet both requirements simultaneously. Compared with other collectors (Comparative 1 and 2), the collector compositions of the present invention (Examples 1 and 2) allow for the use of less collector composition (collector dosage) to obtain the same % yield and higher Li2O content.

Claims

1. The use of a collector composition for the beneficiation of lithium-bearing minerals from an ore comprising lithium-bearing minerals and gangue minerals, wherein the collector composition comprises: a) at least one ether carboxylic acid of formula (I) or a salt thereof R1-OP-CH2-COOX (I) in, R1 is a straight-chain or branched alkyl or alkenyl chain having 4 to 30 carbon atoms; P is composed of n -(CH2CH2O)- units, and / or m -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or q -(CH2CHR3O)- or -(CHR3CH2O)- units, where n represents a number from 0 to 25, m represents a number from 0 to 25, q represents a number from 0 to 25, and the sum of n+m+q represents a number from 1 to 25; R2 represents a -CH3 group, and R3 represents a -CH2CH3 group; and X is H or a cation selected from alkali metals, alkaline earth metals, ammonium, and alkylammonium; and b) Fatty acids or mixtures of fatty acids.

2. The use according to claim 1, wherein component b) is a C4-C30 fatty acid or a mixture of C4-C30 fatty acids, preferably a C8-C26 fatty acid or a mixture of C8-C26 fatty acids, more preferably a C12-C22 fatty acid or a mixture of C12-C22 fatty acids.

3. The use according to any one of claims 1 or 2, wherein the weight ratio between component a) and component b) is 1:99 to 99:1, preferably 3:97 to 60:40, more preferably 5:95 to 50:

50.

4. The use according to any one of claims 1 to 3, wherein R1 represents a straight-chain or branched alkyl or alkenyl chain having 10 to 30 carbon atoms, preferably 10 to 22 carbon atoms, more preferably 12 to 18 carbon atoms.

5. The use according to any one of claims 1 to 4, wherein n, m and q 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.

6. The use according to any one of claims 4 or 5, wherein the collector composition further comprises: c) at least one ether carboxylic acid or a salt thereof represented by formula (III) R5-OA-CH2-COOX (III) in, R5 is a straight-chain or branched alkyl or alkenyl chain having 4 to 8 carbon atoms, preferably 6 to 8 carbon atoms, more preferably 8 carbon atoms; A is composed of r -(CH2CH2O)- units, and / or s -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or p -(CH2CHR3O)- or -(CHR3CH2O)- units, wherein r represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8; s represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8; and p represents a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8; and the sum of r+s+p represents a number from 1 to 20, preferably from 1 to 18, more preferably from 1 to 10; R2, R3 and X are as defined in any of the preceding claims.

7. The use according to any one of claims 4 to 6, wherein the weight ratio between component a) and component c) is 99:1 to 1:99, preferably 99:1 to 25:75, more preferably 100:0 to 50:

50.

8. The use according to claim 6 or 7, wherein the weight ratio between component a), component c) and component b), i.e. ((a+c):(b)), is 1:99 to 99:1, preferably 3:97 to 60:40, more preferably 5:95 to 50:

50.

9. The use according to any one of claims 4 to 8, wherein the composition further comprises component (d), said component (d) comprising a fatty alcohol of formula (IV), a fatty alcohol of formula (IVa), or a mixture thereof: R1-ODH (IV) R5-OEH (IVa) in D is composed of t -(CH2CH2O)- units, and / or u -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or v -(CH2CHR3O)- or -(CHR3CH2O)- units, wherein t represents a number from 0 to 15, preferably 0 to 10, more preferably 0 to 6; u represents a number from 0 to 15, preferably 0 to 10, more preferably 0 to 6; v represents a number from 0 to 15, preferably 0 to 10, more preferably 0 to 6; and the sum of t+u+v represents a number from 0 to 15, preferably 0 to 10, more preferably 0 to 6. E is composed of x -(CH2CH2O)- units, and / or y -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or z -(CH2CHR3O)- or -(CHR3CH2O)- units; wherein x represents a number from 0 to 20, preferably 0 to 18, more preferably 0 to 8; y represents a number from 0 to 20, preferably 0 to 18, more preferably 0 to 8; and z represents a number from 0 to 20, preferably 0 to 18, more preferably 0 to 8; and the sum of x+y+z represents a number from 0 to 20, preferably 0 to 18, more preferably 0 to 10; and R1, R2, R3 and R5 are as defined in any of the preceding claims.

10. The use according to claim 9, wherein the weight ratio between component a) and component d) is 99:1 to 1:50, preferably 99:1 to 25:25, more preferably 99:1 to 50:

10.

11. The use according to claim 9 or 10, wherein the weight ratio between components a), b) and d), i.e. ((a+d):b), is 1:99 to 99:1, preferably 3:97 to 60:40, more preferably 5:95 to 50:

50.

12. A method for preparing a collector composition as defined in any one of claims 1 to 11, comprising mixing, under stirring, a) component as defined in any one of claims 1, 4 or 5, b) component as defined in claim 1 or 2, c) component as defined in claim 6 when present, and d component as defined in claim 9 when present.

13. A method for beneficiating lithium-bearing minerals from an ore containing lithium-bearing minerals and gangue minerals, comprising: a) Mix the ore containing lithium-bearing minerals and gangue minerals with water to obtain an aqueous mixture. b) Add the collector composition according to the present invention to the aqueous mixture obtained in a). c) Stir the aqueous mixture obtained in b). d) Introducing air into mixture c) to generate foam, and e) Collect the lithium-containing minerals from the foam.

14. The method of claim 13, wherein for each ton of ore in step a), 5 g to 5000 g of the collector composition according to any one of claims 1 to 11 is added in step b).

15. A collector composition for beneficiating lithium-bearing minerals from an ore comprising lithium-bearing minerals and gangue minerals, wherein the collector composition comprises: a) at least one ether carboxylic acid or a salt thereof represented by formula (I) R1-OP-CH2-COOX (I) in, R1 is a straight-chain or branched alkyl or alkenyl chain having 4 to 30 carbon atoms; P is composed of n -(CH2CH2O)- units, and / or m -(CH2CHR2O)- or -(CHR2CH2O)- units, and / or q -(CH2CHR3O)- or -(CHR3CH2O)- units, where n represents a number from 0 to 25, m represents a number from 0 to 25, and q represents a number from 0 to 25, and the sum of n+m+q represents a number from 1 to 25; R2 represents a -CH3 group; and R3 represents a -CH2CH3 group; and X is H or a cation selected from alkali metals, alkaline earth metals, ammonium, and alkylammonium. b) Fatty acids or mixtures of fatty acids; The characteristic is that the weight ratio of component a) to component b) is 99:1 to 1:99.

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