Collector composition for ore beneficiation

Abstract

Disclosed herein are collector compositions comprising fatty acids and / or fatty acid derivatives, sulfonate compounds and hydroxamic acids or hydroxamates, which can be used for the beneficiation of industrial minerals.

Description

FIELD OF THE INVENTION

[0001] This invention relates generally to a collector composition (may also be referred to as a "collector") for the beneficiation of ores, preferably industrial minerals, more preferably a phosphate, lithium or rare earth collector composition, further preferably a lithium collector composition. The collector is also suitable for the selective flotation (aka froth flotation) and separation of rare earth metals.BACKGROUND OF THE INVENTION

[0002] Citing the Society for Mining, Metallurgy and Exploration, as of 2019, the industrial minerals mining industry in the US alone is a $58.2 (USD) billion industry. Examples of industrial minerals includes but is not limited to sand, phosphate, lithium, and rare earths. Given the current emphasis on the use of lithium, the application is written terms of lithium but is equally applicable to the general field of mining and beneficiation of industrial minerals including but not limited to sand, phosphate, lithium, and rare earths.

[0003] Improved beneficiation processes will help with the production of lithium in support of the demand for Li-ion battery operated products. Froth flotation is a widely practiced technique in mineral beneficiation, which is a process where valuable constituents of an ore are concentrated via physical separation. In froth flotation, the valuable minerals (or unwanted gangue materials in reverse flotation) are hydrophobized with the flotation collectors and then attached to the surface of the bubbles to be floated out from the unwanted gangue materials (or valuable minerals in reverse flotation). The ability of the flotation collectors in differentiating the surface hydrophobicity between the valuable minerals and unwanted gangue materials is the key to a successful and efficient froth flotation separation. Since gas bubbles attachment capacity of the different types of minerals in the ore is also important to the separation efficiency, frothers are commonly used in froth flotation and have desirable bubble properties, e.g., bubble stability. Bubbles with weak stability may have limited capability collecting the solid particles, while bubbles too stable may cause excess foaming affecting the operation efficiency and safety.

[0004] Efficient beneficiation of the lithium containing ores such as but not limited to lepidolite, petalite, lithium containing pegmatite and spodumene is critical for supplying high-grade lithium concentrate to produce lithium-ion batteries. Spodumene, as a pyroxene mineral consisting of lithium aluminum inosilicate with the formula of Li 2 O·Al 2 O 3 ·4SiO 2 , is an important natural source of lithium. There are many other types of unwanted minerals such as feldspar, mica, carbonate, quartz and iron minerals, which co-exist within the spodumene ore. In order to utilize spodumene ore for lithium production, the grade of spodumene needs to be upgraded with the removal of the undesired impurities.

[0005] Collectors for lithium flotation have been disclosed in many patents. US3028008 disclosed fatty acid as flotation collector for obtaining high purity spodumene from beryl. Dispersant and beryl retarding agent like quebracho, sodium sulfide, starch, and lignin sulfonate were used along with the fatty acid collector. US2748938 taught the use of water-insoluble sulfonated oils as collectors for concentrating spodumene. Unsulfonated oils can be used to boost the collecting efficiency of the sulfonated oils. The sulfonated oils include fatty acids and hydrocarbons. US3710934 taught the use of a C9 to C11 aliphatic primary beta-amine for concentrating spodumene ores. The process is a reverse flotation with the siliceous and iron impurities floated away by the claimed collector. CN110369146B described a mixture comprised of sodium hydroxide saponified vegetable oleic acid and dodecyl dimethyl tertiary amine as the spodumene ore flotation collector. CN102600987B disclosed a lithium oxide collector made of oxidized paraffin soap, sulfonated soap, naphthenic acid, and an activation agent. The activation agent is selected from sodium dodecyl sulfate, sodium hexadecanesulfate, or dodecyltrimethylammonium chloride. CN105013620A disclosed a spodumene beneficiation collector comprising of oxidized paraffin wax soap, sodium naphthenate, ethoxylated sodium carboxylates, and quaternary ammonium salt.

[0006] Though there are numerous patents on the collectors for lithium flotation, especially from China in the recent years, a few patents involved the use of hydroxamic acid or its salt, which actively chelates with specific minerals for efficient separation. The use of hydroxamic acid or its salt as flotation collectors has been reported in some prior art. US4629556 disclosed the use of alkyl hydroxamate or alkyl hydroxamic acid as collector in removing the colored titaniferous impurities from kaolin clay. US6200377 taught the use of hydroxamate or hydroxamic acid and fatty acid for the selective separation of minerals, which chelate with hydroxamate from the unwanted gangue materials. A silicon-containing compound can be used as conditioner to boost the separation efficiency. US 10478829 described the solution of hydroxamic acid and / or a salt of hydroxamic acid in water-soluble organic solvent as flotation reagents for the beneficiation of oxide and / or sulfide containing ores. The hydroxamic acid is a C6-C22 fatty hydroxamic acid, or a mixture of C8-C12 fatty hydroxamic acid. The patent also taught the method preparing the hydroxamic acid and the salt of the hydroxamic acid. US5237079 claimed a method making alkyl or alkaryl hydroxamic acid and / or salt as collector for the beneficiation of non-sulfide minerals. US7007805 disclosed the fatty hydroxamate with a carbon chain length of 6 to 14 carbon atoms as the froth flotation collector. The collector may also contain less than 1% hydroxylamine and 5% fatty acid. The above patents didn't mention the beneficiation of lithium containing ores.

[0007] It is desirable to provide more efficient collectors than those in the prior art to separate the desired mineral in the spodumene, petalite, amblygonite, lithium or rare earth containing pegmatites, lepidolite, dolomite, bastnasite, monazite, xenotime, ancylite, calcio-ancylite, doverite, parisite, synchysite, fluocerite, fluorite, gagarinite, pyrochlore, yttofluorite, anatase, brannerite, cerianite, euxenite, fergusonite, loparite, perovskite, samarskite, uraninte, britholite, brockite, chevkinite, churchite, crandallite, florencite, fluorapatite, gorceixite, goyazite, phabdophane, vitusite, allanite, cerite, cheralite, eudialyte, gadolinite, hingganite, limorlite, kainosite, rinkite, sphene, steenstrupine, thalenite, thorite, zicon or the like, from the unwanted impurities.

[0008] It is further desirable for the newly developed collector to generate much higher Li 2 O concentrate recovery (or other classes of oxide minerals such as but not limited to rare earth oxides) with good selectivity as compared to commonly used collectors.

[0009] It is further desirable to provide collectors with controlled viscosity, and in particular reduced viscosity at low temperature. The adsorption of the collector composition on minerals surface is an important factor affecting the flotation performance. Prior to adsorption, collectors need to disperse into the slurry comprising the mixture of minerals and water. High viscosity makes collectors difficult to disperse into a slurry. The temperature of a slurry is typically not controlled; in other words, the slurry temperature is more or less dependent on ambient conditions. Because of seasonal variation of ambient conditions, slurry temperature can be as low as near the freezing point. The viscosity of a collector composition can be typically increased significantly as the slurry temperature decreases. Thus, benefits of controlling the viscosity may include easier processability, more efficient / responsible production, more efficient collector composition usage, better processability and / or less energy usage.BRIEF DESCRIPTION

[0010] The below embodiments and other of the present disclosure will become apparent in light of the following disclosure.

[0011] One embodiment disclosed herein is a collector composition for industrial minerals, preferably a phosphate, lithium or rare earth collector composition, more preferably a lithium collector composition. The composition may include (1) at least one fatty acid, fatty acid derivative and combinations thereof; (2) at least one hydroxamic acid or hydroxamate; (3) a sulfonate compound, wherein (a) the sulfonate may comprise at least about 0.5 wt% to about 75 wt% of the collector composition, preferably the collector composition comprised of the sulfonate compound in an amount: (i) of at least about 0.5 wt% to about 2 wt%, or about 2 wt% to about 5 wt%, or about 5 wt% to about 15 wt%, or about 15 wt% to about 25 wt%, or about 25 wt% to about 35 wt%, or about 35 wt% to about 45 wt%, or about 45 wt% to about 55 wt%, or about 55 wt% to about 65 wt%, or about 65 wt% to about 75 wt% or / and combinations thereof or (ii) more than about 5 wt% to less than about 70 wt%, at least about 10 wt%, to up to about 65 wt%, at least about 15 wt% to up to about 55 wt%, at least about 18 wt% up to about 55 wt%, at least about 20 wt% up to about 50 wt%, more than 20 wt% up to about 50 wt%; and / or (b) a weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof to the sulfonate compound comprises about 12:1 to about 1:2.5, preferably, at least one of no more than about 8:1, or no more than about 4:1, or no more than about 3: 1, or no more than about 2:1, no more than about 1:1, or about 1:1, or less than about 1:2 or combinations thereof.

[0012] Another embodiment disclosed herein is also a collector composition for industrial minerals, preferably a phosphate, lithium or rare earth collector composition, more preferably a lithium collector composition. The composition may include (1) at least one fatty acid, fatty acid derivative and combinations thereof; and (2) at least one hydroxamic acid or hydroxamate. The at least one fatty acid, fatty acid derivative and combinations thereof may comprise between about 0.5 % to about 20% of a mixture of C16:0 (hexadecanoic acid) and C18:0 (octadecanoic acid) fatty acids and / or fatty acid derivatives. Preferably an amount of the mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives comprises less than the about 20 wt%, more preferably less than about 15 wt%, further preferably less than 14 wt%, even further preferably less than about 10 wt%, even more preferably less than about 5 wt%, or preferably the collector composition comprised of the mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives in the amount of about 0.5 wt% to about 4 wt%, or about 4 wt% to about 8 wt%, or about 8 wt% to about 12 wt%, or about 12 wt% to 14 wt%, or 14 wt% to about 16 wt% or about 16 wt% to no more than about 20 wt% or combinations thereof.

[0013] Advantages of the claimed subject matter includes the disclosure of embodiments of compositions having an appropriate viscosity to function as a collector composition, e.g., compositions having a viscosity of less than about 5000 cP at a given temperature, preferably having a viscosity of no more than about 3000 cP at a given temperature, more preferably no more than about 2000 cP at a given temperature, further preferably no more than about 1000 cP at a given temperature, even more preferably at less than about 1000 cP at a given temperature.

[0014] Another advantage includes the collector compositions are suitable for use at temperatures of less than "room" temperature, less than about 23°C.

[0015] A further advantage of the collector compositions disclosed herein is the compositions maintain a suitable viscosity over a wide range of temperatures.DESCRIPTION OF FIGURES

[0016] Figure 1 is a chart of the viscosity of a mixture as a function of wt% of petroleum sulfonate in the mixture at 15.6°C (60°F).DETAILED DESCRIPTION OF THE INVENTION

[0017] The description herein is merely illustrative of specific manners in which to make and use this invention and are not to be interpreted as limiting in scope. In addition, it is understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting.

[0018] Unless otherwise defined herein, technical terms used in connection with the present disclosure shall have the meanings that are commonly understood by those of ordinary skill in the art. Further, unless otherwise required by context, singular terms shall include pluralities and plural terms shall include the singular.

[0019] All patents, published patent applications, and non-patent publications mentioned in the specification are indicative of the level of skill of those skilled in the art to which the present disclosure pertains. All patents, published patent applications, and non-patent publications referenced in any portion of this application are herein expressly incorporated by reference in their entirety to the same extent as if each individual patent or publication was specifically and individually indicated to be incorporated by reference.

[0020] All of the articles and / or methods disclosed herein can be made and executed without undue experimentation in light of the present disclosure. While the articles and methods of the present disclosure have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations can be applied to the articles and / or methods and in the steps or in the sequence of steps of the method(s) described herein without departing from the concept, spirit and scope of the present disclosure. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the present disclosure.

[0021] While the collector compositions have been described with a certain degree of particularity, it is to be noted that many modifications may be made in the details of the components without departing from the spirit and scope of this disclosure. It is understood that the compositions are not limited to the embodiments set forth herein for purposes of exemplification.

[0022] The term "at least one" refers to one as well as any quantity more than one, including but not limited to, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc. The term "at least one" can extend up to 100 or 1000 or more depending on the term to which it is attached.

[0023] All percentages, parts, proportions, and ratios as used herein are by weight of the total composition, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and therefore do not include solvents or byproducts that can be included in commercially available materials, unless otherwise specified.

[0024] All references to singular characteristics or limitations of the present invention shall include the corresponding plural characteristics or limitations, and vice-versa, unless otherwise specified or clearly implied to the contrary by the context in which the reference is made.

[0025] Numerical ranges as used herein are intended to include every number and subset of numbers contained within that range, whether specifically disclosed or not. Further, these numerical ranges should be construed as providing support for a claim directed to any number or subset of numbers in that range.

[0026] As used herein, the words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include") or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. The terms "or combinations thereof, "and / or combinations thereof' "and combinations thereof, and "combinations thereof' as used herein refer to all permutations and combinations of the listed items preceding the term. For example, "A, B, C, or combinations thereof' is intended to include at least one of: A, B, C, AB, AC, BC, or ABC and, if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more items or terms, such as BB, AAA, AAB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context.

[0027] For purposes of the following detailed description, other than in any operating examples, or where otherwise indicated, numbers that express, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". The numerical parameters set forth in the specification and attached claims are approximations that can vary depending upon the desired properties to be obtained in carrying out the invention.Collector composition

[0028] In general, the invention relates to a novel collector for use in a flotation process for the beneficiation of lithium containing ores as well as other industrial minerals. The collector may be a combination of chemicals, including (1) one or more fatty acids, and / or fatty acid derivatives; (2) one or more hydroxamic acids or hydroxamates; and (3) one or more optional sulfonate compounds. An optional fourth (4) component may be one or more amines, e.g., fatty (poly)amine, fatty amido (poly)amine, fatty imidazoline, fatty imidazo (poly)amine, fatty (poly) ester amine, fatty (poly) quaternized ammonium salt, alkanolamine, and combinations thereof. If so desired, the composition may include one or more frothers. These components may be mixed together as one product or may be added separately but preferably at the same time. The separate addition may be either simultaneous or sequential, preferably at the conditioning step prior to flotation. The collector may be emulsified by adding water and suitable emulsifiers before applying to froth flotation.

[0029] In the present disclosure, the fatty acid(s) and / or fatty acid derivative(s) is(are) different from the hydroxamic acid(s) or hydroxamate(s) in the collector composition.

[0030] The collector composition of the invention is preferably a collector for industrial minerals. More preferably, the collector composition of the invention is a phosphate, lithium or rare earth collector composition, even more preferably a lithium collector composition.

[0031] The composition may include fatty acids, fatty acid derivatives such as but not limited to fatty acid salts and / or esters of fatty acids, and combinations thereof. Preferable fatty acids may include straight-chain fatty acids, branched chain fatty acids, cycle containing fatty acids, saturated, unsaturated, aromatic containing fatty acids containing from 6 to 24 carbon atoms. The fatty acid may contain from 6 to 8 carbon atoms, or from 8 to 10 carbon atoms, or from 10 to 12 carbon atoms, or from 12 to 14 carbon atoms, or from 14 to 16 carbon atoms, or from 16 to 18 carbon atoms, or from 18 to 20 carbon atoms, or from 20 to 22 carbon atoms, or from 22 to 24 carbon atoms. The fatty acid is not limited to a linear compound; it may be nonlinear. Typical sources for the fatty acids may be vegetable or animal fats and oils. Vegetable based fatty acids are a preferred type of fatty acid. Tall oil fatty acid, oleic fatty acid (also referred to as oleic acid), soya oil fatty acid, palmitic acid, stearic acid, linoleic acid, linolenic acid, canola fatty acid and their combinations are examples of preferred fatty acids that may be suitable in the collector compositions. The fatty acids may be present in salt form (as fatty acid derivatives).

[0032] Advantageously, the fatty acid derivatives according to the disclosure are selected from fatty acid salts, esters of fatty acids, and combinations thereof. Preferably, the fatty acid derivatives are based on fatty acids as described above (such as tall oil fatty acid, oleic fatty acid, soya oil fatty acid, palmitic acid, stearic acid, linoleic acid, linolenic acid, canola fatty acid and combinations thereof).

[0033] Preferably, the at least one fatty acid, fatty acid derivative or combinations thereof comprise, or is, at least one vegetable fatty acid.

[0034] Preferred amounts of the fatty acid in the composition may range from about 51% to 99% by weight, preferably about 55% to 98% by weight, preferably about 60% to 97% by weight, preferably about 65% to 96% by weight, more preferably about 70% to 95% by weight and even more preferably about 80 to 90% by weight. In the case the fatty acid contains a blend of the aforementioned fatty acids, the amount of the particular fatty acid in the composition may range from no more than 70% by weight to 0.5% by weight, preferably at least about 5% by weight (such as from at least about 5% by weight to no more than 70% by weight).

[0035] An acid number of particular components that make up the fatty acids, fatty acid derivatives and combinations thereof comprises about 100 up to about 280. Typical units for the acid number is milligrams of KOH / gram (of test specimen) (e.g., the type of fatty acid: tall oil fatty acid, canola fatty acid, soya fatty acid, oleic fatty acid, etc.). The titration test may be used to determine the acid number. In some embodiments, the fatty acids, fatty acid derivatives and combinations thereof of the collector composition of the disclosure have an acid number of about 100 to about 280 mg of KOH / g. In particular, the fatty acids, fatty acid derivatives and combinations thereof may have an acid number of from about 100 to about 120 mg of KOH / g, or from about 120 to about 140 mg of KOH / g, or from about 140 to about 160 mg of KOH / g, or from about 160 to about 180 mg of KOH / g, or from about 180 to about 200 mg of KOH / g, or from about 200 to about 220 mg of KOH / g, or from about 220 to about 240 mg of KOH / g, or from about 240 to about 260 mg of KOH / g, or from about 260 to about 280 mg of KOH / g.

[0036] Particular fatty acids and fatty acid derivatives (and combinations thereof), in particular fatty acids, that may be used herein include or are fatty acids having a viscosity of greater than 1000 cP at 60°F (15°C). Examples of suitable viscosities may include at least 1500 cP, at least about 2000 cP, at least about 2500 cP, or at least about 3000 cP.

[0037] The composition may include hydroxamic acids, hydroxamates and combinations thereof. Hydroxamate as used herein includes at least hydroxamic salts and esters. Examples of non-polar hydrocarbon chains of the hydroxamic acids or hydroxamates are straight or branched C6 to C24 alk(en)yl, aryl or alk(en)ylaryl groups (for example, C6 to C10, or C10 to C14, or C14 to C16, or C16 to C18, or C18 to C20, or C20 to C24 alk(en)yl, aryl or alk(en)ylaryl groups).

[0038] In one embodiment, a concentration of the hydroxamic acids or hydroxamates in the composition may range from about 0.5% to 20% by weight, or from about 1% to 10% by weight, or from more than about 1.5% by weight to less than 10% by weight.

[0039] The collector composition may preferably comprise the hydroxamic acid or hydroxamate in an amount of no more than 10 wt% of the collector composition, preferably the collector composition comprises the hydroxamic acid or hydroxamate in an amount of no more than about 4 wt% based on the weight of the collector composition, preferably less than about 4 wt%, more preferably less than about 3 wt%, further preferably less than about 2.5 wt%, even more preferably at least about 1 wt%, even further preferably at least about 1.5 wt%.

[0040] The collector composition may for example comprise the hydroxamic acid or hydroxamate in an amount from about 1 to about 10 wt%, or from about 1 to about 4 wt%, or from about 1 to less than about 4 wt%, or from about 1 to less than about 3 wt%, or from about 1 to less than about 2.5 wt%, or from about 1.5 to about 10 wt%, or from about 1.5 to about 4 wt%, or from about 1.5 to less than about 4 wt%, or from about 1.5 to less than about 3 wt%, or from about 1.5 to less than about 2.5 wt%. In some embodiments, the amount of hydroxamic acid or hydroxamate in the composition may be about 0.5 wt% to about 1.0 wt%, or about 1.0 wt% to about 2.0 wt%, or about 2.0 wt% to about 3.0 wt%, or about 3.0 wt% to less than about 4.0 wt%, or about 3.0 wt% to about 4.0 wt%.

[0041] Preferably, the hydroxamic acid or hydroxamate comprises, or is, an aliphatic compound.

[0042] Preferably, the hydroxamic acid has an acid number of at least about 5 to about 100, preferably about 25 to about 90, more preferably about 40 to about 80, further preferably about 50 to about 70. In some embodiments, the acid number may comprise, or be, at least one from about 5 to about 15, about 15 to about 25, about 25 to about 35, about 35 to about 45, about 45 to about 55, about 55 to about 65, about 65 to about 75, about 75 to about 85, and about 85 to about 95, the acid number being determined by a titration test and having the units of mg KOH / g (of test specimen).

[0043] Preferably the hydroxamic acid or hydroxamate has the formula:         (RC(=O)NH-O) n M wherein R is an alkyl, alkenyl, aryl, alkylaryl or alkenylaryl group having 6 to 24 carbon atoms, preferably 8 to 24 carbon atoms, and M represents a hydrogen, alkali metal, or alkaline earth metal with n being charge of valence of M, preferably the hydroxamic acid comprises or is an aliphatic compound and / or preferably the hydroxamic acid has an acid number of at least about 5 to about 100, preferably about 25 to about 90, more preferably about 40 to about 80, further preferably about 50 to about 70; or the acid number can be from about 5 to about 15, or about 15 to about 25, or about 25 to about 35, or about 35 to about 45, or about 45 to about 55, or about 55 to about 65, or about 65 to about 75, or about 75 to about 85, or about 85 to about 95, the acid number being determined by the titration test and having the units of mg KOH / g.

[0044] In embodiments of the collector composition of the disclosure, the weight ratio of the fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate may be at least about 5:1 or more than about 5:1, preferably at least about 10:1 or more than about 10:1, preferably at least about 15:1, preferably more than about 20:1, preferably more than about 22:1, more preferably more than about 25:1, further preferably at least about 27:1, even more preferably at least about 30:1. In some embodiments, the weight ratio of the fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate may be up to about 60:1.

[0045] In certain embodiments, the weight ratio of the fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate may be more than about 5:1 to about 10:1, or about 10:1 to about 15: 1, or about 15: 1 to about 20:1, or about 20.1 to about 22:1, or about 22:1 to about 25:1, or about 25: 1 to about 27: 1, or about 27:1 to about 30:1, or about 30:1 to about 35:1, or about 35:1 to about 40:1, or about 40:1 to about 45:1, or about 45:1 to about 50:1, or about 50:1 to about 55:1 or about 55:1 to about 60:1.

[0046] In other embodiments, the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate may be at least about 5:1, preferably at least about 10:1, more preferably at least about 20:1, even more preferably up to about60: 1, further preferably up to about 50: 1, even further preferably up to about 40: 1, and most preferably no more than about 30:1.

[0047] In other embodiments, the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate may be more than about 5:1, preferably at least about 10:1, more preferably no more than about 20:1 (such as from more than about 5:1 to no more than about 20:1 or from at least about 10:1 to no more than about 20:1). In particular, the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate may be from more than about 5:1 to about 10:1, or about 10:1 to about 15:1, or about 15:1 to no more than about 20:1, or combinations thereof In some embodiments, the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate may be from more than about 5:1 to about 60:1, or from about 10:1 to about 60:1, or from about 20:1 to about 60:1, or from more than about 5:1 to about 50:1, or from about 10:1 to about 50:1, or from about 20:1 to about 50:1, or from more than about 5:1 to about 40:1, or from about 10:1 to about 40:1, or from about 20:1 to about 40:1, or from more than about 5:1 to about 30:1, or from about 10:1 to about 30:1, or from about 20:1 to about 30:1.

[0048] The composition may inlcude a sulfonate compound. The sulfonate compound may comprise a compound having, or the sulfonate compound may have, a viscosity of greater than 1000 cP at 60°F (15°C), preferably a viscosity of greater than about 5000 cP.

[0049] The sulfonate compound may be formed by the sulfonation of an aromatic compound. An example of suitable compounds may be an alk(en)yl(aryl)sulfonate and their salts. Typically, the alk(en)yl(aryl) may include moieties having carbon numbers ranging from about 8 carbon atoms to about 100 carbon atoms, preferably, from about 10 to about 80 carbon atoms, more preferred from about 14 to about 60 carbon atoms. Examples of suitable sulfonate compounds include but are not limited to sodium sulfonates, natural petroleum sulfonate or alkylbenzene derived synthetic petroleum sulfonate. Preferably, the sulfonate compound comprises, or is, at least one selected from sodium sulfonates, petroleum sulfonates and its derivatives, sulfonated fatty acids and its derivatives, and combinations thereof. Preferred examples of petroleum sulfonates may include natural petroleum sulfonates and synthetic petroleum sulfonates, further preferred petroleum sulfonates include at least one of alkyl sulfonates, alkyl aryl sulfonates, alkyl xylene sulfonates, α-olefin sulfonates and combinations thereof. Preferably the sodium sulfonate comprises sodium alkylbenzenesulfonate, comprising a straight-chain alkylbenzenesulfonic acid.

[0050] In one embodiment, the sulfonate compound may comprise a petroleum sulfonate. The petroleum sulfonates may be classified as low (L) equivalent weight petroleum sulfonates typically having an equivalent weight of about 410-440 g / mole, as medium equivalent weight petroleum sulfonates (HL, referred to in this fashion because it was typically supplied as a blend of low and high equivalent weight petroleum sulfonates) having an equivalent weight of about 450-480 g / mole and high (H) equivalent weight petroleum sulfonates typically having an equivalent weight of about 490-520 g / mole. A preferred sulfonate compound is either a medium or a high equivalent weight petroleum sulfonate, more preferably the medium equivalent weight petroleum sulfonate.

[0051] These general equivalent weight ranges apply to both synthetic and natural petroleum sulfonates.

[0052] The equivalent weight is measured and calculated according to ASTM D3712.

[0053] In another embodiment, a preferred range of equivalent weight of petroleum sulfonates, either natural or synthetic is from about 390 to 600, more preferable from 390 to 420, or from 420 to 450, or from 450 to 480, or from 480 to 510, or from 510 to 540, or from 540 to 570, or from 570 to 600.

[0054] Optionally, the collector composition disclosed herein may comprise at least one amine. In particular, the composition may comprise at least one alkanolamine. In advantageous embodiments, the alkanolamines used in the collector composition of the disclosure contain both hydroxyl and amino functional groups. Preferably, the alkanolamines may be water soluble or miscible with water. More preferably, the at least one alkanolamine is selected from aminoethylethanolamine, ethanolamine, diethanol amine, methyldiethanolamine, triethanolamine, hydroxyethylpiperazine and combinations thereof. Preferably concentrations of alkanolamines range from more than trace amounts (for example, from more than about 0.001 % by weight) to less than about 5% by weight, preferably no more than about 3% by weight, even more preferably no more than about 2.5% by weight and even further preferred no more than about 2% by weight (such as from more than about 0.001 to less than about 5 % by weight, or from more than about 0.001 to no more than about 3% by weight, or from more than about 0.001 to no more than about 2.5% by weight, or from more than about 0.001 to no more than about 2% by weight).

[0055] Additionally or alternatively, the composition may comprise at least one amine selected from fatty (poly)amine, fatty amido (poly)amine, fatty imidazoline, fatty imidazo (poly)amine, fatty (poly) ester amine, fatty (poly) quaternized ammonium salt, and combination thereof. The fatty (poly)amine, fatty amido (poly)amine, fatty imidazoline, fatty imidazo (poly)amine, fatty (poly) ester amine, fatty (poly) quaternized ammonium salt may include 4-24 carbon atoms in the fatty chain. Preferred fatty chains may include straight-chains, branched chains, cycles containing chains, saturated, unsaturated, aromatic containing chains, or chains with at least 6 carbon atoms containing at least one pendant hydroxyl group, preferably containing from 6 to 24 carbon atoms. Preferably, concentrations of fatty (poly)amine, fatty amido (poly)amine, fatty imidazoline, fatty imidazo (poly)amine, fatty (poly) ester amine, fatty (poly) quaternized ammonium salt (and the combinations therefore) range from more than trace amounts (for example, from more than about 0.001 % by weight) to less than about 5% by weight, preferably no more than about 3% by weight, even more preferably no more than about 2.5% and even further preferred no more than about 2% by weight (such as from more than about 0.001 to less than about 5 % by weight, or from more than about 0.001 to no more than about 3% by weight, or from more than about 0.001 to no more than about 2.5% by weight, or from more than about 0.001 to no more than about 2% by weight).

[0056] Preferably, the amine may comprise, or be, at least one selected from the group of a fatty (poly)amine, fatty amido (poly)amine, fatty imidazoline, fatty imidazo (poly)amine, fatty (poly) ester amine, fatty (poly) quaternized ammonium salt, aminoethylethanolamine, methanolamine, ethanolamine, N-methylethanolamine, dimethylethanolamine, ethylethanolamine, diethylethanolamine, propylethanolamine, dipropylethanolamine, butylethanolamine, dibutylethanolamine, diethanolamine, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, triethanolamine, isobutanol-2-amine, valinol, alaninol, hydroxyethylpiperazine and combinations thereof.

[0057] The composition may include at least one frother. Frothers can be any commonly used frothers like pine oil, methylisobutyl carbinol, alcohols, alkoxylated alcohols, alkoxylated methylisobutyl carbinol, polyglycols, or combination therefore, to improve the froth properties such as stability and density. Preferably, the amount of frothers in the composition ranges from 0.5 to 10% by weight.

[0058] The collector composition may comprise a defoamer, preferably at a concentration of up to about 5 wt%, preferably less than about 5 wt%, more preferably at least about 1 wt%, further preferably at least about 1.5 wt%, based on the weight of the collector composition (such as from about 1 to about 5 wt%, or from about 1 to less than about 5 wt%, or from about 1.5 to about 5 wt%, or from about 1.5 to less than about 5 wt%).

[0059] If so desired, the composition may be devoid of an effective amount of silicon to boost separation efficiency.

[0060] If so desired, the composition may be devoid of any more than trace amounts of any of alkyne compounds, alkylbenzene compounds and combinations thereof. For example, the composition can comprise alkyne compounds, alkylbenzene compounds or combinations thereof in an amount of at most 0.001 % by weight (including about 0 % by weight).

[0061] In some aspects of the disclosure, if so desired, the composition may be devoid of an effective amount of sulfonated compounds that function as a collector (for example, the composition may be devoid of sulfonated compounds or may comprise sulfonated compounds in an amount of at most 2 % by weight, or at most 1 % by weight, or at most 0.5 % by weight, or at most 0.1 % by weight).

[0062] If so desired, the composition may be devoid of an effective amount of a separate lithium depressant (for example, the composition may be devoid of lithium depressant or may comprise lithium depressant in an amount of at most 2 % by weight or at most 1 % by weight, or at most 0.5 % by weight, or at most 0.1 % by weight) An advantage of the disclosed collector is that it may be used to routinely concentrate lithium (Li 2 O) from mined spodumene ores having at least about 1% Li 2 O into a concentration having at least about 4.5% of Li 2 O by a single flotation, preferably greater than about 5.0% and have a recovery of at least about 70% of the Li 2 O, preferably greater than about 70%, even more preferably at least about 75%.

[0063] A further advantage includes that the disclosed collector can improve lithium recovery by more than about 5% over known collectors, preferably about 10% or more.First variant of collector composition

[0064] According to a first variant of the disclosure, the collector composition comprises: a. at least one fatty acid, fatty acid derivative and combinations thereof; b. at least one hydroxamic acid or hydroxamate; c. a sulfonate compound, wherein the collector composition comprises the sulfonate compound in an amount of at least about 0.5 wt% to about 75 wt% based on the total weight of the collector composition.

[0065] What is described above can apply to this first variant of the disclosure, unless specified otherwise.

[0066] Preferably, the collector composition comprises the sulfonate compound in an amount of more than about 5 wt% to less than about 70 wt%, preferably at least 10 wt%, or more than about 10 wt%, to up to about 65 wt%, more preferably at least about 15 wt%, or more than 15 wt % to up to about 55 wt%. In an advantageous embodiment, the amount of the sulfonate compound in the composition can at least about 20 wt% to about 75 wt%.

[0067] In some embodiments, the collector composition comprises the sulfonate compound in an amount of at least about 0.5 wt% to about 2 wt%, or about 2 wt% to about 5 wt%, or about 5 wt% to about 7 wt% or about 7 wt% to about 10 wt%, or about 10 wt% to about 15 wt%, or about 15 wt% to about 20 wt%, or about 20 wt% to about 25 wt%, or about 25 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to about 55 wt%, or about 55 wt% to about 65 wt%, or about 65 wt% to about 75 wt% or combinations thereof.

[0068] In one embodiment, the sulfonate compound may be included in the composition within a range of about 0.5 wt% to about 10 wt%, preferably about 0.5 wt% to about 7 wt%. The wt% are based on the weight of the collector composition.

[0069] The fatty acid, fatty acid derivative or combinations thereof may comprise a soya oil fatty acid.

[0070] Preferably the composition comprises the soya oil fatty acid in an amount of at least about 5 wt% based on the weight of the collector composition, further preferably at least about 10 wt%, even more preferably at least about 15 wt%, even further preferably at least about 20 wt%, and most preferably no more than about 50 wt%.

[0071] The composition may comprise the soya oil fatty acid in an amount of from about 5 to 50 wt%, or from about 10 to 50 wt%, or from about 15 to 50 wt%, or from about 20 to 50 wt%. In some embodiments, the collector composition can comprise the soya oil fatty acid in the amount of at least about 5 wt% to about 15 wt%, or about 15 wt% to about 25 wt%, or about 25 wt% to about 35 wt%, or about 35 wt% to about 45 wt%, or about 45 wt% to no more than about 50 wt%, or combinations thereof.

[0072] In some embodiments, the collector composition comprise a soya oil fatty acid and the weight ratio of the soya oil fatty acid to the sulfonate compound is about 12:1 to about 1:2.5, preferably at least one of no more than about 8:1, or no more than about 4:1, or no more than about 3:1, or no more than about 2:1, no more than about 1:1, or about 1:1, or less than about 1:2, or combinations thereof.

[0073] The fatty acid, fatty acid derivative or combinations thereof may comprise a canola fatty acid.

[0074] Preferably the composition comprises the canola fatty acid in an amount of at least about 5 wt% based on the weight of the collector composition, further preferably at least about 15 wt%, even more preferably at least about 20 wt%, even further preferably at least about 30 wt%, and most preferably no more than about 60 wt% (such as from about 5 to 60 wt%, or from about 15 to 60 wt%, or from about 20 to 60 wt%, or from about 30 to 60 wt%). In some embodiments, the collector composition can comprise the canola fatty acid in the amount of at least about 5 wt% to 10 wt%, 10 wt% to 15 wt%, 15 wt% to 20 wt%, 20 wt% to 25 wt%, 25 wt% to 30 wt%, 30 wt% to 35 wt%, 35 wt% to 40 wt%, 40 wt% to 45 wt%, 45 wt% to 50 wt%, 50 wt% to 55 wt%, or 55 wt% to less than 60 wt%, or combinations thereof.

[0075] In some embodiments, the collector composition comprise a canola fatty acid and the weight ratio of the canola fatty acid to the sulfonate compound is about 12:1 to about 1:2.5, preferably at least one of no more than about 8:1, no more than about 4:1, or no more than about 3:1, or no more than about 1:1, or about 1:1, or less than about 1:2, or combinations thereof.

[0076] In one embodiment, the fatty acid, the fatty acid derivative or the combinations thereof have a viscosity of greater than 1000 cP at 60°F (15°C). Nonlimiting examples of such fatty acids include but, is not limited to soya oil fatty acid and canola fatty acid. Preferably such fatty acids have an acid number of at least about 100 up to about 280 mg KOH / g. Typically such fatty acids have an acid number of at least about 150, further at least about 170, even further at least about 180, optionally no more than about 260, furthermore no more than about 220, preferentially no more than about 210 mg KOH / g (such as from about 150 to 260 mg KOH / g, preferably from about 150 to 220 mg KOH / g, more preferably from 170 to 210 mg KOH / g).

[0077] The collector composition may comprise a fatty acid comprising 60 wt% or more of C18: 1 (oleic fatty acid), preferably 65 wt% or more, even more preferably 70 wt% or more, based on the weight of the collector composition. The fatty acid may be from a bio-source, distilled / concentrated as is known in art.

[0078] Alternatively, the collector composition may comprise less than 70 wt% of the C18: 1 (oleic fatty acid) fatty acid, preferably less than about 60 wt%, more preferably less than about 50 wt%, further preferably less than about 40 wt%, even more preferably less than about 30 wt%, even further preferred less than about 20 wt% based on the weight of the collector composition.

[0079] In other embodiments, the collector composition may comprise the C18:1 (oleic fatty acid) fatty acid in the amount of at least about 20 wt% to about 25 wt%, or about 25 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to about 50 wt%, or about 50 wt% to about 55 wt%, or about 55 wt% to about 60 wt%, or about 60 wt% to about 65 wt%, or about 65 wt% to about 70 wt% or combinations thereof.

[0080] The collector composition may comprise tall oil fatty acid. The collector composition may comprise less than 70 wt% of tall oil fatty acid, preferably less than about 50 wt%, more preferably less than about 25 wt%, further preferably less than about 19 wt%, even more preferably less than about 15 wt%, even further preferred less than about 1 wt% based on the weight of the collector composition. In some embodiments, the collector composition may comprise tall oil fatty acid in the amount of at least about 0.5 wt% to about 4.0 wt%, about 4.0 wt% to about 8 wt%, about 8 wt% to about 12 wt%, about 12 wt% to about 16 wt%, about 16 wt% to about 20 wt%, about 20 wt% to about 24 wt%, about 24 wt% to about 28 wt%, about 28 wt% to about 32 wt%, about 32 wt% to about 36 wt%, about 36 wt% to about 40 wt%, about 40 wt% to about 44 wt%, about 44 wt% to about 48 wt%, about 48 wt% to about 52 wt%, about 52 wt% to about 56 wt%, about 56wt% to about 59 wt%, about 59 wt% to about 62 wt%, about 62 wt% to about 65 wt%, or about 65 wt% to 70 wt%, or combinations thereof.

[0081] In some embodiments, the collector composition comprise tall oil fatty acid and the weight ratio of the tall oil fatty acid to the sulfonate compound is about 12:1 to about 1:2.5, preferably at least one of no more than about 8:1, or no more than about 4:1, or no more than about 3:1, or no more than about 1: 1, or about 1:1, or less than about 1:2, or combinations thereof.

[0082] The tall oil fatty acid in the collector composition may comprise C16:0 or C18:0 fatty acid or fatty acid derivative, or a mixture of C16:0 and C18:0 fatty acid and / or fatty acid derivative. The tall oil fatty acid may comprise no more than about 20 wt% of a mixture of C16:0 and C18:0 fatty acid and / or fatty acid derivative, preferably no more than about 14 wt%, preferably no more than about 10 wt%, more preferably no more than about 5 wt%, further preferably no more than about 2.5 wt%. The tall oil fatty acid may comprise the mixture of C16:0 and C18:0 in fatty acid and fatty acid derivative in the amount of about 0.5 wt% to about 4 wt%, or about 4 wt% to about 8 wt%, or about 8 wt% to about 12 wt%, or about 12 wt% to about 16 wt%, or about 16 wt% to about 20 wt% and combinations thereof.

[0083] The fatty acid, fatty acid derivative and combinations thereof in the collector composition may comprise a blend of the aforementioned fatty acids in any combination thereof. In one embodiment, the blend of fatty acids may comprise at least about 10 wt% of oleic fatty acid based on the weight of the collector composition, preferably at least about 15 wt%, more preferably at least 20 wt%, further preferably at least about 25 wt%, even more preferably at least about 30 wt%, even further preferably no more than about 50 wt% (such as from about 10 to no more than about 50 wt%, or from about 15 to no more than about 50 wt%, or from about 20 to no more than about 50 wt%, or from about 25 to no more than about 50 wt%, or from about 30 to no more than about 50 wt%). In some embodiments, the at least one fatty acid, fatty acid derivative or combinations thereof comprises oleic fatty acid, preferably the collector composition comprises the oleic fatty acid in the amount of about 1 wt% to about 5 wt%, about 5 wt% to about 10 wt%, about 10 wt% to about 15 wt%, about 15 wt% to about 20 wt%, about 20 wt% to about 25 wt%, about 25 wt%, to about 30 wt%, about 30 wt% to about 35 wt%, about 35 wt% to about 40 wt%, about 40 wt% to about 45 wt%, about 45 wt% to no more than about 50 wt%, or combinations thereof.

[0084] The collector composition advantageously has a viscosity at 60°F (15°C) of less than 3500 cP, preferably less than 2000 cP, preferably less than 1000 cP, preferably less than about 850 cP, more preferably less than about 700 cP, further preferably less than about 600 cP, even more preferably less than about 200 cP, further preferably less than about 125 cP, and most preferably less than about 80 cP.

[0085] The collector composition of the disclosure may comprise: a. from 15 to 99 wt% of at least one fatty acid, fatty acid derivative and combinations thereof; b. from of 0.5 to 10 wt% of at least one hydroxamic acid or hydroxamate; c. from about 0.5 wt% to about 75 wt% of a sulfonate compound, based on the total weight of the collector composition.Second variant of collector composition

[0086] According to a second variant of the disclosure, the collector composition comprises: a. at least one fatty acid, fatty acid derivative and combinations thereof; and b. at least one hydroxamic acid or hydroxamate, wherein the at least one fatty acid, fatty acid derivative and combinations thereof comprise from about 0.5 % to about 20% of a mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives.

[0087] Preferably an amount of the mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives is less than about 20 wt%, more preferably less than about 15 wt%, further preferably less than about 14 wt%, even further preferably less than about 10 wt%, even more preferably less than about 5 wt% (such as from about 0.5 % to less than about 20 wt%, or from about 0.5 % to less than about 15 wt%, or from about 0.5 % to less than about 14 wt%, or from about 0.5 % to less than about 10 wt%, or from about 0.5 % to less than about 5 wt%).

[0088] In some embodiments, the collector composition comprises the mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives in the amount of about 0.5 wt% to about 4 wt%, or about 4 wt% to about 8 wt%, or about 8 wt% to about 12 wt%, or about 12 wt% to 14 wt%, or 14 wt% to about 16 wt%, or about 16 wt% to no more than about 20 wt% or combinations thereof.

[0089] What is described above can apply to this first variant of the disclosure, unless specified otherwise.

[0090] Preferably, the fatty acid, fatty acid derivative or combinations thereof comprise at least one of soya oil fatty acid, canola fatty acid, tall oil fatty acid, oleic fatty acid and combinations thereof, preferably at least 2 selected from the group of the soya oil fatty acid, the canola fatty acid, the oleic fatty acid and the tall oil fatty acid.

[0091] The collector composition may comprise tall oil fatty acid.

[0092] The collector composition may comprise no more than 95 wt% of tall oil fatty acid, preferably less than about 55 wt%, more preferably less than about 19 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt%, based on the amount of the fatty acid, fatty acid derivative or combinations thereof in the collector composition.

[0093] In some embodiments, the collector composition may comprise tall oil fatty acid in the amount of about 1 wt% to about 5 wt%, about 5 wt% to about 10 wt%, about 10 wt% to about 15 wt%, about 15 wt% to less than about 19%, about 19 wt% to about 23 wt%, about 23 wt% to about 27 wt%, about 27 wt% to about 30 wt%, about 30 wt% to about 35 wt%, about 35 wt% to about 40 wt%, about 40 wt% to about 45 wt%, about 45 wt% to about 50 wt%, about 50 wt% to about 55 wt%, about 55 wt% to about 58 wt%, about 58 wt% to about 61 wt%, about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or about 70 wt% to about 75 wt%, or about 75 wt% to about 80 wt%, or about 80 wt% to about 85 wt%, or about 85 wt% to about 90 wt%, or about 90 wt% to about 95 wt%, or combinations thereof, based on the amount of the fatty acid, fatty acid derivative or combinations thereof in the collector composition.

[0094] In some embodiments, the collector composition may comprise the tall oil fatty acid and the weight ratio of the tall oil fatty acid to a sulfonate compound is about 20:1 to about 1:2.5, preferably at least one of no more than about 15:1, no more than about 10:1, no more than about 8:1, or no more than about 4:1, or no more than about 3: 1, or no more than about 1: 1, or about 1:1, or less than about 1:2, or combinations thereof.

[0095] In other embodiments, the at least one fatty acid, fatty acid derivative and combinations thereof consists essentially of tall oil fatty acid.

[0096] In other embodiments, the at least one fatty acid, fatty acid derivative and combinations thereof consists of tall oil fatty acid.

[0097] In other embodiments, the collector composition may be devoid of tall oil fatty acid.

[0098] The fatty acid, fatty acid derivative or combinations thereof in the collector composition may comprise oleic fatty acid.

[0099] The fatty acid, fatty acid derivative or combinations thereof may comprise less than 70 wt% of oleic fatty acid, preferably less than about 55 wt%, more preferably less than about 30 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt% based on the amount of the fatty acid, fatty acid derivative or combinations thereof in the collector composition.

[0100] In some embodiments, the fatty acid, fatty acid derivative or combinations thereof comprises oleic fatty acid in an amount of about 1 wt% to about 5 wt%, about 5 wt% to about 10 wt%, about 10 wt% to about 15 wt%, about 15 wt% to about 19, about 19 wt% to about 23 wt%, about 23 wt% to about 27 wt%, about 27 wt% to about 30 wt%, about 30 wt% to about 35 wt%, about 35 wt% to about 40 wt%, about 40 wt% to about 45 wt%, about 45 wt% to about 50 wt%, about 50 wt% to about 55 wt%, about 55 wt% to about 58 wt%, about 58 wt% to about 61 wt%, about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or combinations thereof.

[0101] The fatty acid, fatty acid derivative or combinations thereof in the collector composition may comprise canola fatty acid.

[0102] The fatty acid, fatty acid derivative or combinations thereof may comprise less than 70 wt% of canola fatty acid, preferably less than about 55 wt%, more preferably less than about 30 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt% based on the amount of the fatty acid, fatty acid derivative or combinations thereof in the collector composition.

[0103] In some embodiments, the fatty acid, fatty acid derivative or combinations thereof comprises the canola fatty acid in an amount of about 1 wt% to about 5 wt%, about 5 wt% to about 10 wt%, about 10 wt% to about 15 wt%, about 15 wt% to about 19, about 19 wt% to about 23 wt%, about 23 wt% to about 27 wt%, about 27 wt% to about 30 wt%, about 30 wt% to about 35 wt%, about 35 wt% to about 40 wt%, about 40 wt% to about 45 wt%, about 45 wt% to about 50 wt%, about 50 wt% to about 55 wt%, about 55 wt% to about 58 wt%, about 58 wt% to about 61 wt%, about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or combinations thereof.

[0104] The fatty acid, fatty acid derivative or combinations thereof in the collector composition may comprise soya oil fatty acid.

[0105] The fatty acid, fatty acid derivative or combinations thereof may comprise less than 70 wt% of soya oil fatty acid, preferably less than about 55 wt%, more preferably less than about 30 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt% based on the amount of the fatty acid, fatty acid derivative or combinations thereof in the collector composition.

[0106] In some embodiments, the fatty acid, fatty acid derivative or combinations thereof comprises the soya oil fatty acid in an amount of about 1 wt% to about 5 wt%, about 5 wt% to about 10 wt%, about 10 wt% to about 15 wt%, about 15 wt% to about 19, about 19 wt% to about 23 wt%, about 23 wt% to about 27 wt%, about 27 wt% to about 30 wt%, about 30 wt% to about 35 wt%, about 35 wt% to about 40 wt%, about 40 wt% to about 45 wt%, about 45 wt% to about 50 wt%, about 50 wt% to about 55 wt%, about 55 wt% to about 58 wt%, about 58 wt% to about 61 wt%, about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or combinations thereof.

[0107] The collector composition can comprise a sulfonate compound, in particular as described above. A concentration of the sulfonate compound (for example of sodium sulfonate and / or petroleum sulfonate) in the composition may range from 0 (preferably at least 0.1 % by weight) to 15 % by weight.

[0108] In other embodiments, the collector composition may comprise the sulfonate compound in an amount of more than about 5 wt% to less than about 70 wt%, preferably at least 10 wt% , or more than about 10 wt%, to up to about 65 wt%, more preferably at least about 15 wt% to up to about 55 wt%, further preferably at least about 18 wt% up to about 55 wt%, further preferably at least about 20 wt% up to about 50 wt%, further preferably more than 20 wt% up to about 50 wt%.

[0109] In some embodiments, the collector composition may comprise the sulfonate compound in an amount of at least about 0.5 wt% to about 2 wt%, or about 2 wt% to about 5 wt%, or about 5 wt% to about 15 wt%, or about 15 wt% to about 25 wt%, or about 25 wt% to about 35 wt%, or about 35 wt% to about 45 wt%, or about 45 wt% to about 55 wt%, or about 55 wt% to about 65 wt%, or about 65 wt% to about 75 wt% or combinations thereof.

[0110] The collector composition of the disclosure may comprise: a. from 51 to 99.5 wt% of at least one fatty acid, fatty acid derivative and combinations thereof comprising from about 0.5 % to about 20% of a mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives; and b. from of 0.5 to 10 wt% of at least one hydroxamic acid or hydroxamate; c. optionally an amine; d. optionally a sulfonate compound; e. optionally other additives as described herein, based on the total weight of the collector composition.Third variant of collector composition

[0111] According to a third variant of the disclosure, the collector composition comprises: a. at least one fatty acid, fatty acid derivative and combinations thereof; b.at least one hydroxamic acid or hydroxamate; c.a sulfonate compound, wherein the collector composition comprises the sulfonate compound such that the weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof to the sulfonate compound is about 12:1 to about 1:2.5.

[0112] The weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof to the sulfonate compound is preferably about 12:1 to about 1:2.5, preferably about 8:1 to about 1:2.5, further preferably about 4:1 to about 1:2, even further preferably about 3:1 to about 1: 1.5, more preferably about 2:1 to about 1: 1.5, such as about 1:1 or from about 2:1 to about 1:1. In some embodiment, the weight ratio may be about 5:1 to about 1:2.5, for example from about 1:2 to about 1:2.5.

[0113] In some embodiments, the weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof to the sulfonate compound may be about 12:1 to about 10:1, or about 10:1 to about 8:1, or about 8:1 to about 6:1, or about 6:1 to about 4:1, or about 4:1 to about 3.5:1, or about 3.5:1 to about 3: 1, or about 3:1 to about 2.5:1, or about 2.5:1 to about 2:1, or about 2:1 to about 1.5:1, or about 1.5:1 to about 1:1, or about 1:1 to about 1:1.5, or about 1:1.5 to about 1:2, or about 1:2 to about 1:2.5, or combinations thereof.

[0114] What is described above can apply to third first variant of the disclosure, unless specified otherwise. In particular, all embodiments described in relation to the first variant can apply to this third variant.Uses and processes

[0115] The disclosure also relates to the use of a collector composition as described above, for the beneficiation of industrial minerals, preferably any one of phosphate, lithium, and rare earths.

[0116] The disclosure also relates to a beneficiation process for separating impurities from any one of lithium containing ore, rare earth containing ore or phosphate containing ore. The process includes pulping the ore to produce an ore slurry; reagentizing the ore slurry to produce a reagentized slurry by adding a composition as described above. The process may also include separating at least some of the impurities from the lithium and collecting the lithium in the form of a concentrate.

[0117] In the case of lithium beneficiation, preferably, the reagentizing step does not include introducing a separate lithium depressant. Preferably, the step of reagentizing the ore slurry further comprises adding a pH modifier.

[0118] In some embodiments, the reagentizing step further comprises separately adding at least one of the components of the collector composition (such as the fatty acid and / or fatty acid derivative, the hydroxamic acid or hydroxamate, the sulfonate compound, the optional amine).

[0119] The process further may comprise combining at least two of the fatty acid and / or fatty acid derivative, the hydroxamic acid or hydroxamate, the sulfonate compound, and the optional amine prior to being added to the ore slurry.

[0120] The disclosure also relates to a flotation method for removing gangue from lithium containing ores. The method includes producing an ore slurry comprising lithium containing ore and a collector composition as described above. The method also includes subjecting the ore slurry to flotation. Preferably, the ore slurry further comprises a pH modifier.

[0121] The step of subjecting the ore slurry to flotation preferably produces an underflow and an overflow, the method further comprising: separating one of the overflows or the underflow as the gangue; and collecting the other of the underflow or the overflow as lithium concentrate.ASPECTS

[0122] A first aspect of the invention includes a collector composition, preferably a phosphate, lithium or rare earth collector composition, more preferably a lithium collector composition, comprising: a. at least one fatty acid, fatty acid derivative and combinations thereof; b. at least one hydroxamic acid or hydroxamate; c. a sulfonate compound, wherein i. the sulfonate compound is in an amount of at least about 0.5 wt% to about 75 wt% of the collector composition, preferably the collector composition comprises the sulfonate compound in an amount 1. of at least about 0.5 wt% to about 2 wt%, or about 2 wt% to about 5 wt%, or about 5 wt% to about 15 wt%, or about 15 wt% to about 25 wt%, or about 25 wt% to about 35 wt%, or about 35 wt% to about 45 wt%, or about 45 wt% to about 55 wt%, or about 55 wt% to about 65 wt%, or about 65 wt% to about 75 wt% or combinations thereof; or 2. more than about 5 wt% to less than about 70 wt%, more preferably more than about 10 wt%, to up to about 65 wt%, more preferably more than about 15 wt% to up to about 55 wt%, even further preferably more than 20 wt% to up to about 50 wt%; ii. alternatively instead of in terms of wt% (or additionally), the collector composition may comprise a weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof to the sulfonate compound of about 12:1 to about 1 :2.5, preferably at least one of no more than about 8:1, or no more than about 4:1, or no more than about 3:1, or no more than about 2:1, or no more than about 1:1, or about 1:1, or less than about 1:2 or combinations thereof (such as from less than about 10:1 to about 1:2.5, or from no more than about 8:1 to about 1:2.5, or from no more than about 4:1 to about 1:2.5, or from no more than about 3:1 to about 1:2.5, or from no more than about 2:1 to about 1:2.5, or from about 1:1 to about 1:2.5, or from less than about 1:2 to about 1:2.5).

[0123] In a second aspect applicable to the first aspect, the sulfonate compound comprises a compound having a viscosity of greater than 1000 cP at 60°F (15°C), preferably a viscosity of greater than about 5000 cP.

[0124] In a third aspect applicable to aspects 1-2, the sulfonate compound comprises at least one selected from sodium sulfonates, petroleum sulfonates and its derivatives, sulfonated fatty acids and its derivatives, and combinations thereof, preferred examples of petroleum sulfonates may include natural petroleum sulfonates and synthetic petroleum sulfonates, further preferred petroleum sulfonates include at least one of alkyl sulfonates, alkyl aryl sulfonates, alkyl xylene sulfonates and α-olefin sulfonates and combinations thereof, preferably the sodium sulfonate comprises sodium alkylbenzenesulfonate comprising a straight-chain alkylbenzenesulfonic acid.

[0125] In a fourth aspect applicable to aspects 1-3, the at least one fatty acid, fatty acid derivative and combinations thereof have a viscosity of greater than 1000 cP at 60°F (15°C) and an acid number of at least about 100 up to about 280 mg KOH / g, under a titration test, preferably the acid number comprises (or is) at least about 170, more preferably at least about 180, optionally no more than about 260, further preferably no more than about 220, even further preferably no more than about 210 (for example the acid number is from about 170 to about 260, in particular from about 170 to about 220, more particularly from about 180 to about 210).

[0126] In a fifth aspect applicable to aspects 1-4, the at least one fatty acid, fatty acid derivative and combinations thereof comprises a soya oil fatty acid, preferably a. the collector composition comprises the soya oil fatty acid in an amount of at least 5 wt% based on the weight of the collector composition, further preferably at least about 10 wt%, even more preferably at least about 15 wt%, even further preferably at least about 20 wt%, and most preferably no more than about 50 wt%; or b. the collector composition comprises the soya oil fatty acid in the amount of at least about 5 wt% to about 15 wt%, or about 15 wt% to about 25 wt%, or about 25 wt% to about 35 wt%, or about 35 wt% to about 45 wt%, or about 45 wt% to no more than about 50 wt% or combinations thereof; and / or c. a weight ratio of the soya oil fatty acid to the sulfonate compound comprises (or is) about 12:1 to about 1:2.5, preferably at least one of no more than about 8:1, or no more than about 4:1, or no more than about 3:1, or no more than about 2:1, or no more than about 1:1, or about 1:1, or less than about 1:2, or combinations thereof (such as from no more than about 8:1 to about 1:2.5, or from no more than about 4:1 to about 1:2.5, or from no more than about 3:1 to about 1:2.5, or from no more than about 2:1 to about 1:2.5, or from about 1:1 to about 1:2.5, or from less than about 1:2 to about 1:2.5).

[0127] In a sixth aspect applicable to aspects 1-5, the at least one fatty acid, fatty acid derivative and combinations thereof comprises a canola fatty acid, preferably a. the collector composition comprises the canola fatty acid in an amount of at least 5 wt% based on the weight of the collector composition, further preferably at least about 15 wt%, even more preferably at least about 20 wt%, even further preferably at least about 30 wt%, and most preferably no more than about 60 wt% or b. the collector composition comprises the canola fatty acid in the amount of at least about 5 wt% to 10 wt%, or 10 wt% to 15 wt%, or 15 wt% to 20 wt%, or 20 wt% to 25 wt%, or 25 wt% to 30 wt%, or 30 wt% to 35 wt%, or 35 wt% to 40 wt%, or 40 wt% to 45 wt%, or 45 wt% to 50 wt%, or 50 wt% to 55 wt%, or 55 wt% to less than 60 wt%, or combinations thereof; and / or c. a weight ratio of the canola fatty acid to the sulfonate compound comprises (or is) about 12:1 to about 1:2.5, preferably at least one of no more than about 8:1, or no more than about 4:1, or no more than about 3:1, or no more than about 2:1, or no more than about 1:1, or about 1:1, or less than about 1:2, or combinations thereof (such as from no more than about 8:1 to about 1:2.5, or from no more than about 4:1 to about 1:2.5, or from no more than about 3:1 to about 1:2.5, or from no more than about 2:1 to about 1:2.5, or from about 1:1 to about 1:2.5, or from less than about 1:2 to about 1:2.5).

[0128] In a seventh aspect applicable to aspects 1-6, the collector composition comprises hydroxamic acid or hydroxamate in an amount of no more than 10 wt% of the collector composition, preferably the collector composition comprised of the at least one hydroxamic acid or hydroxamate in an amount of i. no more than about 4 wt% based on the weight of the collector composition, preferably less than about 4 wt%, more preferably less than about 3 wt%, further preferably less than about 2.5 wt%, even more preferably at least about 1 wt%, even further preferably at least about 1.5 wt% or ii. about 0.5 wt% to about 1.0 wt%, or about 1.0 wt% to about 2.0 wt%, or about 2.0 wt% to about 3.0 wt%, or about 3.0 wt% to less than about 4.0 wt%; and / or iii. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) at least about 5:1, preferably at least about 10:1, more preferably at least 20:1, even more preferably up to about 60:1, further preferably up to about 50:1, even further preferably up to about 40:1, and most preferably up to about 30:1; or iv. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) from more than about 5:1 to about 10.1, or from about 10:1 to about 15:1, or about 15:1 to about 20:1, or about 20:1 to about 25:1, or about 25:1 to about 30:1, or about 30:1 to about 35:1, or about 35:1 to about 40:1, or about 40:1 to about 45:1, or about 45:1 to about 50:1, or about 50:1 to about 55:1, or about 55:1 to about 60:1, or combinations thereof; or v. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) more than about 5:1, preferably at least about 10:1, more preferably no more than about 20:1; or vi. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) more than about 5:1 to about 10:1, or about 10:1 to about 15:1, or about 15: 1 to no more than about 20:1, or combinations thereof; wherein: a. preferably the at least one hydroxamic acid or hydroxamate comprises an aliphatic compound, and / or b. preferably the hydroxamic acid has an acid number of at least about 5 to about 100, preferably about 25 to about 90, more preferably about 40 to about 80, further preferably about 50 to about 70; or the acid number is from about 5 to about 15, or about 15 to about 25, or about 25 to about 35, or about 35 to about 45, or about 45 to about 55, or about 55 to about 65, or about 65 to about 75, or about 75 to about 85, or about 85 to about 95; the acid number being determined by the titration test and having the units of mg KOH / g of test specimen.

[0129] In an eighth aspect applicable to aspects 1-7, a weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof (having preferably a viscosity of greater than 1000 cP at 60°F (15°C) and an acid number of at least about 100 up to about 220 mg KOH / g) to the at least one hydroxamic acid or hydroxamate comprises more than about 5:1, preferably at least about 10:1, more preferably no more than about 20:1.

[0130] In a nineth aspect applicable to aspects 1-8, the collector composition comprises a. less than 70 wt% of tall oil fatty acid, preferably less than about 50 wt%, more preferably less than about 25 wt%, further preferably less than about 19 wt%, even more preferably less than about 15 wt%, even further preferred less than about 1 wt%, based on the weight of the collector composition; or b. the collector composition comprises the tall oil fatty acid in the amount of at least about 0.5 wt% to about 4.0 wt%, or about 4.0 wt% to about 8 wt%, or about 8 wt% to about 12 wt%, or about 12 wt% to about 16 wt%, or about 16 wt% to about 20 wt%, or about 20 wt% to about 24 wt%, or about 24 wt% to about 28 wt%, or about 28 wt% to about 32 wt%, or about 32 wt% to about 36 wt%, or about 36 wt% to about 40 wt%, or about 40 wt% to about 44 wt%, or about 44 wt% to about 48 wt%, or about 48 wt% to about 52 wt%, or about 52 wt% to about 56 wt%, or about 56wt% to about 59 wt%, or about 59 wt% to about 62 wt%, or about 62 wt% to about 65 wt%, or about 65 wt% to 70 wt% or combinations thereof; and / or c. a weight ratio of the tall oil fatty acid to the sulfonate compound comprises about 12:1 to about 1 :2.5, preferably at least one of no more than about 8:1, no more than about 4: 1, or no more than about 3:1, or no more than about 2:1, or no more than about 1:1, or about 1:1, or less than about 1:2, or combinations thereof (such as from no more than about 8:1 to about 1:2.5, or from no more than about 4:1 to about 1:2.5, or from no more than about 3:1 to about 1:2.5, or from no more than about 2:1 to about 1:2.5, or from about 1:1 to about 1:2.5, or from less than about 1:2 to about 1:2.5); d. preferably the tall oil fatty acid comprises no more than about 20 wt% of a mixture of C16:0 and C18:0 fatty acid and / or fatty acid derivative, preferably no more than about 14 wt%, preferably no more than about 10 wt%, further preferably no more than about 5 wt%, even further preferably no more than about 2.5 wt%.

[0131] In a tenth aspect applicable to aspects 1-9, a. the at least one fatty acid, fatty acid derivative and combinations thereof comprises a blend of fatty acids and the blend of fatty acids comprises at least about 10 wt% of oleic fatty acid based on the weight of the collector composition, preferably at least about 15 wt%, more preferably at least 20 wt%, further preferably at least about 25 wt%, even more preferably at least about 30 wt%, even further preferably no more than about 50 wt%; or b. the at least one fatty acid, fatty acid derivative and combinations thereof comprises oleic fatty acid, preferably the collector composition comprises the oleic fatty acid in the amount of about 1 wt% to about 5 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 15 wt%, or about 15 wt% to about 20 wt%, or about 20 wt% to about 25 wt%, or about 25 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to no more than about 50 wt% or combinations thereof.

[0132] In an eleventh aspect applicable to aspects 1-10, the collector composition at 60°F (15°C) has a viscosity of less than 3500 cP, preferably less than 2000 cP, preferably less than 1000 cP, preferably less than about 850 cP, more preferably less than about 700 cP, further preferably less than about 600 cP, even more preferably less than about 200 cP, further preferably less than about 125 cP, and most preferably less than about 80 cP.

[0133] In a twelve aspect applicable to aspects 1-11, the collector composition further comprises at least one amine, preferably the amine comprises both hydroxyl and amino functional groups, or preferably the amine comprises at least one selected from the group of a fatty (poly)amine, fatty amido (poly)amine, fatty imidazoline, fatty imidazo (poly)amine, fatty (poly) ester amine, fatty (poly) quaternized ammonium salt, aminoethylethanolamine, methanolamine, ethanolamine, N-methylethanolamine, dimethylethanolamine, ethylethanolamine, diethylethanolamine, propylethanolamine, dipropylethanolamine, butylethanolamine, dibutylethanolamine, diethanolamine, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, triethanolamine, isobutanol-2-amine, valinol, alaninol, hydroxyethylpiperazine and combinations thereof.

[0134] In a thirteenth aspect applicable to aspects 1-12, the collector composition further comprises a defoamer, preferably at a concentration of up to about 5 wt, preferably less than about 5 wt%, more preferably at least about 1 wt%, further preferably at least about 1.5 wt% based on the weight of the collector composition.

[0135] In a fourteenth aspect applicable to aspects 1-13, a weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof to the at least one hydroxamic acid or hydroxamate comprises more than about 20:1, preferably more than about 22:1, more preferably more than about 25:1, further preferably at least about 27:1, even more preferably at least about 30:1.

[0136] In a fifteenth aspect applicable to aspects 1-14, the at least one fatty acid, fatty acid derivative and combinations thereof comprises a vegetable fatty acid;

[0137] In a sixteenth aspect applicable to aspects 1-15, the at least one fatty acid, fatty acid derivative and combinations thereof comprise, consist essentially of, or consist of, tall oil fatty acid.

[0138] A seventeenth aspect includes a collector composition, preferably for industrial minerals, more preferably a phosphate, lithium or rare earth collector composition, further preferably a lithium collector composition, comprising a. at least one fatty acid, fatty acid derivative and combinations thereof; and b. at least one hydroxamic acid or hydroxamate wherein the at least one fatty acid, fatty acid derivative and combinations thereof comprise from about 0.5 % to about 20% of a mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives, preferably an amount of the mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives comprises less than about 20 wt%, more preferably less than about 15 wt%, further preferably less than 14 wt%, even further preferably less than about 10 wt%, even more preferably less than about 5 wt%; or preferably the collector composition comprises the mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives in the amount of about 0.5 wt% to about 4 wt%, or about 4 wt% to about 8 wt%, or about 8 wt% to about 12 wt%, or about 12 wt% to 14 wt%, or 14 wt% to about 16 wt%, or about 16 wt% to no more than about 20 wt% or combinations thereof.

[0139] In an eighteenth aspect applicable to aspects 17, the at least one fatty acid, fatty acid derivative and combinations thereof comprises at least one of soya oil fatty acid, canola fatty acid, tall oil fatty acid, oleic fatty acid and combinations thereof, preferably comprising at least 2 selected from the group of the soya oil fatty acid, the canola fatty acid, the oleic fatty acid and the tall oil fatty acid.

[0140] In a nineteenth aspect applicable to aspects 1-18, a. an amount of the hydroxamic acid or hydroxamate comprises (or is) no more than about 4 wt% of the collector composition, preferably less than about 4 wt%, more preferably less than about 3 wt%, further preferably less than about 2.5 wt%, even more preferably at least about 1 wt%, even further preferably at least about 1.5 wt% or b. the collector composition comprises the at least one hydroxamic acid or hydroxamate in an amount of about 0.5 wt% to about 1.0 wt%, about 1.0 wt% to about 2.0 wt%, about 2.0 wt% to about 3.0 wt%, about 3.0 wt% to about 4.0 wt% and / or c. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) at least about 5:1, preferably at least about 10:1, more preferably at least 20:1, even more preferably up to about 60:1, further preferably up to about 50:1, even further preferably up to about 40:1, and most preferably up to about 30:1; or d. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) from more than about 5:1 to about 10.1, or from about 10:1 to about 15:1, or about 15:1 to about 20:1, or about 20:1 to about 25:1, or about 25:1 to about 30:1, or about 30:1 to about 35: 1, or about 35:1 to about 40:1, or about 40:1 to about 45:1, or about 45: 1 to about 50:1, or about 50:1 to about 55:1, or about 55:1 to about 60:1, or combinations thereof; or e. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) more than about 5:1, preferably at least about 10:1, more preferably no more than about 20:1; or f. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) more than about 5:1 to about 10:1, or about 10:1 to about 15:1, or about 15:1 to no more than about 20:1, or combinations thereof; wherein g. preferably the at least one hydroxamic acid or hydroxamate comprises an aliphatic compound and / or the hydroxamic acid has an acid number of at least about 5 to about 100, preferably about 25 to about 90, more preferably about 40 to about 80, further preferably about 50 to about 70 or the acid number comprises at least one from about 5 to about 15, about 15 to about 25, about 25 to about 35, about 35 to about 45, about 45 to about 55, about 55 to about 65, about 65 to about 75, about 75 to about 85, about 85 to about 95, the acid number determined by the titration test and having the units of mg KOH / g.

[0141] In a twentieth aspect applicable to aspects 17-19, a. the fatty acid, fatty acid derivative and combinations thereof comprises no more than 95 wt% of tall oil fatty acid, preferably less than about 55 wt%, more preferably less than about 19 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt% based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition; or b. the collector composition comprises the tall oil fatty acid in an amount of about 1 wt% to about 5 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 15 wt%, or about 15 wt% to less than about 19%, or about 19 wt% to about 23 wt%, or about 23 wt% to about 27 wt%, or about 27 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to about 50 wt%, or about 50 wt% to about 55 wt%, or about 55 wt% to about 58 wt%, or about 58 wt% to about 61 wt%, or about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or about 70 wt% to about 75 wt%, or about 75 wt% to about 80 wt%, or about 80 wt% to about 85 wt%, or about 85 wt% to about 90 wt%, or about 90 wt% to about 95 wt% or combinations thereof, based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition; and / or c. the collector composition comprises a tall oil fatty acid and the weight ratio of the tall oil fatty acid to a sulfonate compound is about 20:1 to about 1:2.5, preferably at least one of no more than about 15: 1, no more than about 10:1, no more than about 8:1, or no more than about 4:1, or no more than about 3:1, or no more than about 1:1, or about 1:1, or less than about 1:2, or combinations thereof (such as from no more than about 15:1 to about 1:2.5, or from no more than about 10:1 to about 1:2.5, or from no more than about 8:1 to about 1:2.5, or from no more than about 4:1 to about 1:2.5, or from no more than about 3:1 to about 1:2.5, or from no more than about 2:1 to about 1:2.5, or from about 1:1 to about 1:2.5, or from less than about 1:2 to about 1:2.5).

[0142] In a twenty-first aspect applicable to aspects 17-20, the collector composition is devoid of tall oil fatty acid.

[0143] In a twenty-second aspect applicable to aspects 17-21, a. the fatty acid, fatty acid derivative and combinations thereof comprises less than 70 wt% of oleic fatty acid, preferably less than about 55 wt%, more preferably less than about 30 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt% based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition; or b. the collector composition comprises the oleic fatty acid in an amount of about 1 wt% to about 5 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 15 wt%, or about 15 wt% to about 19, or about 19 wt% to about 23 wt%, or about 23 wt% to about 27 wt%, or about 27 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to about 50 wt%, or about 50 wt% to about 55 wt%, or about 55 wt% to about 58 wt%, or about 58 wt% to about 61 wt%, or about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or combinations thereof, based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition.

[0144] In a twenty-third aspect applicable to aspects 17-22, a. the fatty acid, fatty acid derivative and combinations thereof comprises less than 70 wt% of canola fatty acid, preferably less than about 55 wt%, more preferably less than about 30 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt% based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition; or b. the collector composition comprises the canola fatty acid in an amount of about 1 wt% to about 5 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 15 wt%, or about 15 wt% to about 19, or about 19 wt% to about 23 wt%, or about 23 wt% to about 27 wt%, or about 27 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to about 50 wt%, or about 50 wt% to about 55 wt%, or about 55 wt% to about 58 wt%, or about 58 wt% to about 61 wt%, or about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or combinations thereof, based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition.

[0145] In a twenty-fourth aspect applicable to aspects 17-23, a. the fatty acid, fatty acid derivative and combinations thereof comprises less than 70 wt% of soya oil fatty acid, preferably less than about 55 wt%, more preferably less than about 30 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt% based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition; or b. the collector composition comprises the soya oil fatty acid in an amount of about 1 wt% to about 5 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 15 wt%, or about 15 wt% to about 19, about 19 wt% to about 23 wt%, or about 23 wt% to about 27 wt%, or about 27 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to about 50 wt%, or about 50 wt% to about 55 wt%, or about 55 wt% to about 58 wt%, or about 58 wt% to about 61 wt%, or about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or combinations thereof, based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition.

[0146] In a twenty-fifth aspect applicable to aspects 17-24, an acid number of the at least one fatty acid, fatty acid derivative and combinations thereof is at least about 100 up to about 280, preferably about 170 to about 210, more preferably about 180 to about 205.

[0147] In a twenty-sixth aspect applicable to aspects 17-25, the collector composition further comprises a sulfonate compound, preferably the sulfonate compound comprises at least one selected from sodium sulfonates, petroleum sulfonates and its derivatives, sulfonated fatty acids and its derivatives, and combinations thereof, preferred examples of petroleum sulfonates may include natural petroleum sulfonates and synthetic petroleum sulfonates, further preferred petroleum sulfonates include at least one of alkyl sulfonates, alkyl aryl sulfonates, alkyl xylene sulfonates and α-olefin sulfonates and combinations thereof, preferably the sodium sulfonate comprises sodium alkylbenzenesulfonate comprising a straight-chain alkylbenzenesulfonic acid; and / or a. the collector composition comprises the sulfonate compound in an amount of at least about 0.5 wt% to about 2 wt%, about 2 wt% to about 5 wt%, about 5 wt% to about 15 wt%, about 15 wt% to about 25 wt%, about 25 wt% to about 35 wt%, about 35 wt% to about 45 wt%, about 45 wt% to about 55 wt%, about 55 wt% to about 65 wt%, about 65 wt% to about 75 wt% and combinations thereof; or b. the collector composition comprises more than about 5 wt% to less than about 70 wt%, preferably at least about 10 wt%, to up to about 65 wt%, more preferably at least about 15 wt% to up to about 55 wt%, further preferably more than 20 wt% to up to about 50 wt%, of the sulfonate compound; and / or c. wherein the collector composition comprises a tall oil fatty acid and the weight ratio of the tall oil fatty acid to a sulfonate compound is about 20:1 to about 1:2.5, preferably at least one of no more than about 15:1, no more than about 10:1, no more than about 8:1, or no more than about 4:1, or no more than about 3:1, or no more than about 1:1, or about 1:1, or less than about 1:2, or combinations thereof (such as from no more than about 15:1 to about 1:2.5, or from no more than about 10:1 to about 1:2.5, or from no more than about 8:1 to about 1:2.5, or from no more than about 4:1 to about 1:2.5, or from no more than about 3:1 to about 1:2.5, or from no more than about 2:1 to about 1:2.5, or from about 1:1 to about 1:2.5, or from less than about 1:2 to about 1:2.5).

[0148] In a twenty-seventh aspect applicable to aspects 17-26, a weight ratio of the fatty acid, fatty acid derivative and combinations thereof to hydroxamic acid or hydroxamate a. comprises more than about 10:1, preferably at least about 15:1, further preferably at least about 20:1, more preferably at least about 22:1, even more preferably at least about 25:1; or b. comprises more than about 10:1 to about 15:1, or about 15:1 to about 20:1, or about 20.1 to about 22:1, or about 22:1 to about 25:1.

[0149] In a twenty-eighth aspect applicable to aspects 17-27, the at least one fatty acid, fatty acid derivative and combinations thereof comprises tall oil fatty acid.

[0150] In a twenty-nineth aspect applicable to aspects 17-28, the at least one fatty acid, fatty acid derivative and combinations thereof consists essentially of tall oil fatty acid.

[0151] In a thirtieth aspect applicable to aspects 17-29, the at least one fatty acid, fatty acid derivative and combinations thereof consists of tall oil fatty acid.

[0152] A thirty-first aspect includes a beneficiation process for separating impurities from lithium containing ore. The process includes pulping the ore to produce an ore slurry; reagentizing the ore slurry to produce a reagentized slurry by adding: a collector of aspects 1 to 30. The process may also include separating at least some of the impurities from the lithium and collecting the lithium in the form of a concentrate.

[0153] Regarding a thirty-second aspect applicable to aspect 31, the reagentizing of the eleventh aspect does not include introducing a separate lithium depressant.

[0154] In a thirty-third aspect, applicable to either of aspect 31 or 32, the reagentizing the ore slurry further comprises adding a pH modifier.

[0155] In a thirty-fourth aspect, applicable to anyone of aspects 31-33, the reagentizing further comprises separately adding at least one of (a) the fatty acid or fatty acid derivative (b) the hydroxamic acid or hydroxamate and (c) optionally the sulfonate compound.

[0156] In a thirty-fifth aspect, applicable to anyone of aspects 31-34 the process further comprises combining at least two of (a) the fatty acid or fatty acid derivative, (b) the hydroxamic acid or hydroxamate and (c) optionally the sulfonate compound prior to being added to the ore slurry.

[0157] A thirty-sixth includes a flotation method for removing gangue from lithium containing ores. The method includes producing an ore slurry comprising lithium containing ore and a collector. The collector may be a collector of any one of aspect 1 to 30. The method also includes subjecting the ore slurry to flotation.

[0158] In a thirty-seventh aspect, the ore slurry of aspect 36 further comprises a pH modifier.

[0159] In a thirty-eighth aspect, applicable to either one of aspects 36 or 37 wherein the subjecting the ore slurry to flotation produces an underflow and an overflow, the method further comprising: separating one of the overflows or the underflow as the gangue; and collecting the other of the underflow or the overflow as lithium concentrate.

[0160] In a thirty-nineth aspect, the composition of any one of aspects 1-30, the composition is used for the beneficiation of a rare earth.Examples

[0161] The present invention is further illustrated by the following examples. In order that those skilled in the field may better understand how the present invention can be practiced, the following examples are given by way of illustration only and not necessarily by way of limitation.

[0162] The viscosities were taken using an AMETEK Brookfield DV1 Digital Viscometer (Model: DV1MRVTJO) with a small sample adapter. The temperature was controlled using a Brookfield TC-650MX-115 circulating refrigerated bath. The spindle used was the SC4-21 inside the CS4-13R sample chamber. The highest RPM level on the viscometer was used to the point that the machine would not report errors. Maximum RPMs is 100 RPM, and the minimum is 0.5 RPM. In the case the reported value is NA, the viscosity was too high to measure.

[0163] Tables 1-3 and Figure 1 illustrate the effect of petroleum sulfonate with canola fatty acid and soya fatty acid (AKA soya oil fatty acid) in adjusting the fatty acids for use in collector compositions. As illustrated in the Tables, petroleum sulfonate is very thick in its native form. Likewise, canola fatty acid and soya fatty acid have high viscosities (greater than 1000 cP) at temperatures of 15.6°C or below. Surprisingly it is illustrated below in Tables 1-3 and Figure 1 how the addition of petroleum sulfonate to canola fatty acid, soya fatty acid and combinations thereof, may reduce the viscosity of mixture.

[0164] Preferred C16:0 + C18:0 fatty acids are fatty acids having a GC area% of less than 14%. Preferred examples have a viscosity of less than about 3000 cP across the temperature range shown in Table 5, preferably less than about 1500 cP, more preferably less than about 1000 cP. The GC area % represents the wt% of the compound(s) in the sample.

[0165] Table 4 shows that the addition of hydroxamic acid has little effect on viscosity of fatty acid. The hydroxamic acid used in this example is an alkyl hydroxamic acid having a C6-C16 straight chain.

[0166] Tables 1-3 illustrate the effect the sulfonate compound has on soya oil fatty acid and canola fatty acid in reducing the viscosity of either fatty acid alone or both as a 50 / 50 mixture of the fatty acids. Table 1 illustrates the addition of up to 50 wt% of the sulfonate compound and the canola fatty acid has reduced viscosity at temperatures of up to at least about 15.6°C. Table 2 illustrates the benefit of using the sulfonate compound with soya oil fatty acid. The mixtures of soya oil fatty acid and the sulfonate compound exhibited reduced viscosity at all temperatures up to at least about 15.6°C. Regarding mixtures of canola fatty acid, soya oil fatty acid and the sulfonate compound, the mixtures had a reduced viscosity for all mixtures at temperatures up to at least about 15.6°C. Table 4 illustrates how minimizing the total amount of C16:0 and C18:0 reduces the viscosity of the mixture as well as the combination of hydroxamic acid with the C16:0 and C18:0 fatty acids does not increase the viscosity of the mixture to a level which the mixture is unsuitable for use as a collector composition.

[0167] While this invention has been described in detail with reference to certain preferred embodiments, it should be appreciated that the present disclosure is not limited to those precise embodiments. Rather, in view of the present disclosure, many modifications and variations would present themselves to those skilled in the art without departing from the scope and spirit of this invention. Table 1Viscosity (cP) Measured at various temperature (°C)Temperature (°C) ((°F))4.4°C ((40°F))10.0°C ((50°F))15.6°C ((60°F))Petroleum sulfonateNANANACanola fatty acid100000854001080Soya fatty acidNA92005420Canola fatty acid + petroleum sulfonate (75:25)11310594Canola fatty acid + petroleum sulfonate (50:50)73502160590Canola fatty acid + petroleum sulfonate (25:75)NANA16640 Table 2 Viscosity (cP) Measured at various temperature (°C)Temperature (°C) ((°F))4.4°C ((40°F))10.0°C ((50°F))15.6 °C ((60°F))Petroleum sulfonateNANANACanola fatty acid100000854001080Soya fatty acidNA92005420Soya fatty acid + petroleum sulfonate (75:25)14270307206Soya fatty acid + petroleum sulfonate (50:50)972050801075Soya fatty acid + petroleum sulfonate (25:75)835052903190 Table 3 Viscosity (cP) Measured at various temperature (°C)Temperature (°C) ((°F))4.4°C ((40°F))10.0°C ((50°F))15.6°C ((60°F))Petroleum sulfonateNANANACanola fatty acid100000854001080Soya fatty acidNA92005420Canola fatty acid + soya fatty acid (50:50)NANA2890Mixture of canola fatty acid + soya fatty acid (50:50) + petroleum sulfonate (75:25)459001118277Mixture of canola fatty acid + soya fatty acid (50:50) + petroleum sulfonate (50:50)73502160590Mixture of canola fatty acid + soya fatty acid (50:50) + petroleum sulfonate (25:75)740043202675 Table 4 Effect of C16:0 (palmitic acid) + C18:0 (stearic acid) on viscosityViscosity (cP) Measured at various temperature (°C)Temperature (°C) ((°F))4.4°C ((40°F))10.0°C ((50°F))15.6°C ((60°F))Fatty acid acid number: 1971775543C16:0 + C18:0 = 3.5 GC area%Fatty acid acid number: 1973166448C16:0 + C18:0 = 3.5 GC area% + 4% hydroxamic acid *Fatty acid acid number: 2084665845C16:0 + C18:0 = 6.1 GC area%Fatty acid acid number: 2012075347109C16:0 + C18:0 = 9.5 GC area%Fatty acid acid number: 202NA4650257C16:0 + C18:0 = 14.4 GC area%Fatty acid acid number: 198NA92005420C16:0 + C18:0 = 18.0 GC area%(*) Effect of hydroxamic acid on fatty acid

Examples

examples

Examples

[0161]The present invention is further illustrated by the following examples. In order that those skilled in the field may better understand how the present invention can be practiced, the following examples are given by way of illustration only and not necessarily by way of limitation.

[0162]The viscosities were taken using an AMETEK Brookfield DV1 Digital Viscometer (Model: DV1MRVTJO) with a small sample adapter. The temperature was controlled using a Brookfield TC-650MX-115 circulating refrigerated bath. The spindle used was the SC4-21 inside the CS4-13R sample chamber. The highest RPM level on the viscometer was used to the point that the machine would not report errors. Maximum RPMs is 100 RPM, and the minimum is 0.5 RPM. In the case the reported value is NA, the viscosity was too high to measure.

[0163]Tables 1-3 and Figure 1 illustrate the effect of petroleum sulfonate with canola fatty acid and soya fatty acid (AKA soya oil fatty acid) in adjusting the fatty acids for ...

FIELD OF THE INVENTION

[0001] This invention relates generally to a collector composition (may also be referred to as a "collector") for the beneficiation of ores, preferably industrial minerals, more preferably a phosphate, lithium or rare earth collector composition, further preferably a lithium collector composition. The collector is also suitable for the selective flotation (aka froth flotation) and separation of rare earth metals.BACKGROUND OF THE INVENTION

[0002] Citing the Society for Mining, Metallurgy and Exploration, as of 2019, the industrial minerals mining industry in the US alone is a $58.2 (USD) billion industry. Examples of industrial minerals includes but is not limited to sand, phosphate, lithium, and rare earths. Given the current emphasis on the use of lithium, the application is written terms of lithium but is equally applicable to the general field of mining and beneficiation of industrial minerals including but not limited to sand, phosphate, lithium, and rare earths.

[0003] Improved beneficiation processes will help with the production of lithium in support of the demand for Li-ion battery operated products. Froth flotation is a widely practiced technique in mineral beneficiation, which is a process where valuable constituents of an ore are concentrated via physical separation. In froth flotation, the valuable minerals (or unwanted gangue materials in reverse flotation) are hydrophobized with the flotation collectors and then attached to the surface of the bubbles to be floated out from the unwanted gangue materials (or valuable minerals in reverse flotation). The ability of the flotation collectors in differentiating the surface hydrophobicity between the valuable minerals and unwanted gangue materials is the key to a successful and efficient froth flotation separation. Since gas bubbles attachment capacity of the different types of minerals in the ore is also important to the separation efficiency, frothers are commonly used in froth flotation and have desirable bubble properties, e.g., bubble stability. Bubbles with weak stability may have limited capability collecting the solid particles, while bubbles too stable may cause excess foaming affecting the operation efficiency and safety.

[0004] Efficient beneficiation of the lithium containing ores such as but not limited to lepidolite, petalite, lithium containing pegmatite and spodumene is critical for supplying high-grade lithium concentrate to produce lithium-ion batteries. Spodumene, as a pyroxene mineral consisting of lithium aluminum inosilicate with the formula of Li 2 O·Al 2 O 3 ·4SiO 2 , is an important natural source of lithium. There are many other types of unwanted minerals such as feldspar, mica, carbonate, quartz and iron minerals, which co-exist within the spodumene ore. In order to utilize spodumene ore for lithium production, the grade of spodumene needs to be upgraded with the removal of the undesired impurities.

[0005] Collectors for lithium flotation have been disclosed in many patents. US3028008 disclosed fatty acid as flotation collector for obtaining high purity spodumene from beryl. Dispersant and beryl retarding agent like quebracho, sodium sulfide, starch, and lignin sulfonate were used along with the fatty acid collector. US2748938 taught the use of water-insoluble sulfonated oils as collectors for concentrating spodumene. Unsulfonated oils can be used to boost the collecting efficiency of the sulfonated oils. The sulfonated oils include fatty acids and hydrocarbons. US3710934 taught the use of a C9 to C11 aliphatic primary beta-amine for concentrating spodumene ores. The process is a reverse flotation with the siliceous and iron impurities floated away by the claimed collector. CN110369146B described a mixture comprised of sodium hydroxide saponified vegetable oleic acid and dodecyl dimethyl tertiary amine as the spodumene ore flotation collector. CN102600987B disclosed a lithium oxide collector made of oxidized paraffin soap, sulfonated soap, naphthenic acid, and an activation agent. The activation agent is selected from sodium dodecyl sulfate, sodium hexadecanesulfate, or dodecyltrimethylammonium chloride. CN105013620A disclosed a spodumene beneficiation collector comprising of oxidized paraffin wax soap, sodium naphthenate, ethoxylated sodium carboxylates, and quaternary ammonium salt.

[0006] Though there are numerous patents on the collectors for lithium flotation, especially from China in the recent years, a few patents involved the use of hydroxamic acid or its salt, which actively chelates with specific minerals for efficient separation. The use of hydroxamic acid or its salt as flotation collectors has been reported in some prior art. US4629556 disclosed the use of alkyl hydroxamate or alkyl hydroxamic acid as collector in removing the colored titaniferous impurities from kaolin clay. US6200377 taught the use of hydroxamate or hydroxamic acid and fatty acid for the selective separation of minerals, which chelate with hydroxamate from the unwanted gangue materials. A silicon-containing compound can be used as conditioner to boost the separation efficiency. US 10478829 described the solution of hydroxamic acid and / or a salt of hydroxamic acid in water-soluble organic solvent as flotation reagents for the beneficiation of oxide and / or sulfide containing ores. The hydroxamic acid is a C6-C22 fatty hydroxamic acid, or a mixture of C8-C12 fatty hydroxamic acid. The patent also taught the method preparing the hydroxamic acid and the salt of the hydroxamic acid. US5237079 claimed a method making alkyl or alkaryl hydroxamic acid and / or salt as collector for the beneficiation of non-sulfide minerals. US7007805 disclosed the fatty hydroxamate with a carbon chain length of 6 to 14 carbon atoms as the froth flotation collector. The collector may also contain less than 1% hydroxylamine and 5% fatty acid. The above patents didn't mention the beneficiation of lithium containing ores.

[0007] It is desirable to provide more efficient collectors than those in the prior art to separate the desired mineral in the spodumene, petalite, amblygonite, lithium or rare earth containing pegmatites, lepidolite, dolomite, bastnasite, monazite, xenotime, ancylite, calcio-ancylite, doverite, parisite, synchysite, fluocerite, fluorite, gagarinite, pyrochlore, yttofluorite, anatase, brannerite, cerianite, euxenite, fergusonite, loparite, perovskite, samarskite, uraninte, britholite, brockite, chevkinite, churchite, crandallite, florencite, fluorapatite, gorceixite, goyazite, phabdophane, vitusite, allanite, cerite, cheralite, eudialyte, gadolinite, hingganite, limorlite, kainosite, rinkite, sphene, steenstrupine, thalenite, thorite, zicon or the like, from the unwanted impurities.

[0008] It is further desirable for the newly developed collector to generate much higher Li 2 O concentrate recovery (or other classes of oxide minerals such as but not limited to rare earth oxides) with good selectivity as compared to commonly used collectors.

[0009] It is further desirable to provide collectors with controlled viscosity, and in particular reduced viscosity at low temperature. The adsorption of the collector composition on minerals surface is an important factor affecting the flotation performance. Prior to adsorption, collectors need to disperse into the slurry comprising the mixture of minerals and water. High viscosity makes collectors difficult to disperse into a slurry. The temperature of a slurry is typically not controlled; in other words, the slurry temperature is more or less dependent on ambient conditions. Because of seasonal variation of ambient conditions, slurry temperature can be as low as near the freezing point. The viscosity of a collector composition can be typically increased significantly as the slurry temperature decreases. Thus, benefits of controlling the viscosity may include easier processability, more efficient / responsible production, more efficient collector composition usage, better processability and / or less energy usage.BRIEF DESCRIPTION

[0010] The below embodiments and other of the present disclosure will become apparent in light of the following disclosure.

[0011] One embodiment disclosed herein is a collector composition for industrial minerals, preferably a phosphate, lithium or rare earth collector composition, more preferably a lithium collector composition. The composition may include (1) at least one fatty acid, fatty acid derivative and combinations thereof; (2) at least one hydroxamic acid or hydroxamate; (3) a sulfonate compound, wherein (a) the sulfonate may comprise at least about 0.5 wt% to about 75 wt% of the collector composition, preferably the collector composition comprised of the sulfonate compound in an amount: (i) of at least about 0.5 wt% to about 2 wt%, or about 2 wt% to about 5 wt%, or about 5 wt% to about 15 wt%, or about 15 wt% to about 25 wt%, or about 25 wt% to about 35 wt%, or about 35 wt% to about 45 wt%, or about 45 wt% to about 55 wt%, or about 55 wt% to about 65 wt%, or about 65 wt% to about 75 wt% or / and combinations thereof or (ii) more than about 5 wt% to less than about 70 wt%, at least about 10 wt%, to up to about 65 wt%, at least about 15 wt% to up to about 55 wt%, at least about 18 wt% up to about 55 wt%, at least about 20 wt% up to about 50 wt%, more than 20 wt% up to about 50 wt%; and / or (b) a weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof to the sulfonate compound comprises about 12:1 to about 1:2.5, preferably, at least one of no more than about 8:1, or no more than about 4:1, or no more than about 3: 1, or no more than about 2:1, no more than about 1:1, or about 1:1, or less than about 1:2 or combinations thereof.

[0012] Another embodiment disclosed herein is also a collector composition for industrial minerals, preferably a phosphate, lithium or rare earth collector composition, more preferably a lithium collector composition. The composition may include (1) at least one fatty acid, fatty acid derivative and combinations thereof; and (2) at least one hydroxamic acid or hydroxamate. The at least one fatty acid, fatty acid derivative and combinations thereof may comprise between about 0.5 % to about 20% of a mixture of C16:0 (hexadecanoic acid) and C18:0 (octadecanoic acid) fatty acids and / or fatty acid derivatives. Preferably an amount of the mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives comprises less than the about 20 wt%, more preferably less than about 15 wt%, further preferably less than 14 wt%, even further preferably less than about 10 wt%, even more preferably less than about 5 wt%, or preferably the collector composition comprised of the mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives in the amount of about 0.5 wt% to about 4 wt%, or about 4 wt% to about 8 wt%, or about 8 wt% to about 12 wt%, or about 12 wt% to 14 wt%, or 14 wt% to about 16 wt% or about 16 wt% to no more than about 20 wt% or combinations thereof.

[0013] Advantages of the claimed subject matter includes the disclosure of embodiments of compositions having an appropriate viscosity to function as a collector composition, e.g., compositions having a viscosity of less than about 5000 cP at a given temperature, preferably having a viscosity of no more than about 3000 cP at a given temperature, more preferably no more than about 2000 cP at a given temperature, further preferably no more than about 1000 cP at a given temperature, even more preferably at less than about 1000 cP at a given temperature.

[0014] Another advantage includes the collector compositions are suitable for use at temperatures of less than "room" temperature, less than about 23°C.

[0015] A further advantage of the collector compositions disclosed herein is the compositions maintain a suitable viscosity over a wide range of temperatures.DESCRIPTION OF FIGURES

[0016] Figure 1 is a chart of the viscosity of a mixture as a function of wt% of petroleum sulfonate in the mixture at 15.6°C (60°F).DETAILED DESCRIPTION OF THE INVENTION

[0017] The description herein is merely illustrative of specific manners in which to make and use this invention and are not to be interpreted as limiting in scope. In addition, it is understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting.

[0018] Unless otherwise defined herein, technical terms used in connection with the present disclosure shall have the meanings that are commonly understood by those of ordinary skill in the art. Further, unless otherwise required by context, singular terms shall include pluralities and plural terms shall include the singular.

[0019] All patents, published patent applications, and non-patent publications mentioned in the specification are indicative of the level of skill of those skilled in the art to which the present disclosure pertains. All patents, published patent applications, and non-patent publications referenced in any portion of this application are herein expressly incorporated by reference in their entirety to the same extent as if each individual patent or publication was specifically and individually indicated to be incorporated by reference.

[0020] All of the articles and / or methods disclosed herein can be made and executed without undue experimentation in light of the present disclosure. While the articles and methods of the present disclosure have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations can be applied to the articles and / or methods and in the steps or in the sequence of steps of the method(s) described herein without departing from the concept, spirit and scope of the present disclosure. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the present disclosure.

[0021] While the collector compositions have been described with a certain degree of particularity, it is to be noted that many modifications may be made in the details of the components without departing from the spirit and scope of this disclosure. It is understood that the compositions are not limited to the embodiments set forth herein for purposes of exemplification.

[0022] The term "at least one" refers to one as well as any quantity more than one, including but not limited to, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc. The term "at least one" can extend up to 100 or 1000 or more depending on the term to which it is attached.

[0023] All percentages, parts, proportions, and ratios as used herein are by weight of the total composition, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and therefore do not include solvents or byproducts that can be included in commercially available materials, unless otherwise specified.

[0024] All references to singular characteristics or limitations of the present invention shall include the corresponding plural characteristics or limitations, and vice-versa, unless otherwise specified or clearly implied to the contrary by the context in which the reference is made.

[0025] Numerical ranges as used herein are intended to include every number and subset of numbers contained within that range, whether specifically disclosed or not. Further, these numerical ranges should be construed as providing support for a claim directed to any number or subset of numbers in that range.

[0026] As used herein, the words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include") or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. The terms "or combinations thereof, "and / or combinations thereof' "and combinations thereof, and "combinations thereof' as used herein refer to all permutations and combinations of the listed items preceding the term. For example, "A, B, C, or combinations thereof' is intended to include at least one of: A, B, C, AB, AC, BC, or ABC and, if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more items or terms, such as BB, AAA, AAB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context.

[0027] For purposes of the following detailed description, other than in any operating examples, or where otherwise indicated, numbers that express, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". The numerical parameters set forth in the specification and attached claims are approximations that can vary depending upon the desired properties to be obtained in carrying out the invention.Collector composition

[0028] In general, the invention relates to a novel collector for use in a flotation process for the beneficiation of lithium containing ores as well as other industrial minerals. The collector may be a combination of chemicals, including (1) one or more fatty acids, and / or fatty acid derivatives; (2) one or more hydroxamic acids or hydroxamates; and (3) one or more optional sulfonate compounds. An optional fourth (4) component may be one or more amines, e.g., fatty (poly)amine, fatty amido (poly)amine, fatty imidazoline, fatty imidazo (poly)amine, fatty (poly) ester amine, fatty (poly) quaternized ammonium salt, alkanolamine, and combinations thereof. If so desired, the composition may include one or more frothers. These components may be mixed together as one product or may be added separately but preferably at the same time. The separate addition may be either simultaneous or sequential, preferably at the conditioning step prior to flotation. The collector may be emulsified by adding water and suitable emulsifiers before applying to froth flotation.

[0029] In the present disclosure, the fatty acid(s) and / or fatty acid derivative(s) is(are) different from the hydroxamic acid(s) or hydroxamate(s) in the collector composition.

[0030] The collector composition of the invention is preferably a collector for industrial minerals. More preferably, the collector composition of the invention is a phosphate, lithium or rare earth collector composition, even more preferably a lithium collector composition.

[0031] The composition may include fatty acids, fatty acid derivatives such as but not limited to fatty acid salts and / or esters of fatty acids, and combinations thereof. Preferable fatty acids may include straight-chain fatty acids, branched chain fatty acids, cycle containing fatty acids, saturated, unsaturated, aromatic containing fatty acids containing from 6 to 24 carbon atoms. The fatty acid may contain from 6 to 8 carbon atoms, or from 8 to 10 carbon atoms, or from 10 to 12 carbon atoms, or from 12 to 14 carbon atoms, or from 14 to 16 carbon atoms, or from 16 to 18 carbon atoms, or from 18 to 20 carbon atoms, or from 20 to 22 carbon atoms, or from 22 to 24 carbon atoms. The fatty acid is not limited to a linear compound; it may be nonlinear. Typical sources for the fatty acids may be vegetable or animal fats and oils. Vegetable based fatty acids are a preferred type of fatty acid. Tall oil fatty acid, oleic fatty acid (also referred to as oleic acid), soya oil fatty acid, palmitic acid, stearic acid, linoleic acid, linolenic acid, canola fatty acid and their combinations are examples of preferred fatty acids that may be suitable in the collector compositions. The fatty acids may be present in salt form (as fatty acid derivatives).

[0032] Advantageously, the fatty acid derivatives according to the disclosure are selected from fatty acid salts, esters of fatty acids, and combinations thereof. Preferably, the fatty acid derivatives are based on fatty acids as described above (such as tall oil fatty acid, oleic fatty acid, soya oil fatty acid, palmitic acid, stearic acid, linoleic acid, linolenic acid, canola fatty acid and combinations thereof).

[0033] Preferably, the at least one fatty acid, fatty acid derivative or combinations thereof comprise, or is, at least one vegetable fatty acid.

[0034] Preferred amounts of the fatty acid in the composition may range from about 51% to 99% by weight, preferably about 55% to 98% by weight, preferably about 60% to 97% by weight, preferably about 65% to 96% by weight, more preferably about 70% to 95% by weight and even more preferably about 80 to 90% by weight. In the case the fatty acid contains a blend of the aforementioned fatty acids, the amount of the particular fatty acid in the composition may range from no more than 70% by weight to 0.5% by weight, preferably at least about 5% by weight (such as from at least about 5% by weight to no more than 70% by weight).

[0035] An acid number of particular components that make up the fatty acids, fatty acid derivatives and combinations thereof comprises about 100 up to about 280. Typical units for the acid number is milligrams of KOH / gram (of test specimen) (e.g., the type of fatty acid: tall oil fatty acid, canola fatty acid, soya fatty acid, oleic fatty acid, etc.). The titration test may be used to determine the acid number. In some embodiments, the fatty acids, fatty acid derivatives and combinations thereof of the collector composition of the disclosure have an acid number of about 100 to about 280 mg of KOH / g. In particular, the fatty acids, fatty acid derivatives and combinations thereof may have an acid number of from about 100 to about 120 mg of KOH / g, or from about 120 to about 140 mg of KOH / g, or from about 140 to about 160 mg of KOH / g, or from about 160 to about 180 mg of KOH / g, or from about 180 to about 200 mg of KOH / g, or from about 200 to about 220 mg of KOH / g, or from about 220 to about 240 mg of KOH / g, or from about 240 to about 260 mg of KOH / g, or from about 260 to about 280 mg of KOH / g.

[0036] Particular fatty acids and fatty acid derivatives (and combinations thereof), in particular fatty acids, that may be used herein include or are fatty acids having a viscosity of greater than 1000 cP at 60°F (15°C). Examples of suitable viscosities may include at least 1500 cP, at least about 2000 cP, at least about 2500 cP, or at least about 3000 cP.

[0037] The composition may include hydroxamic acids, hydroxamates and combinations thereof. Hydroxamate as used herein includes at least hydroxamic salts and esters. Examples of non-polar hydrocarbon chains of the hydroxamic acids or hydroxamates are straight or branched C6 to C24 alk(en)yl, aryl or alk(en)ylaryl groups (for example, C6 to C10, or C10 to C14, or C14 to C16, or C16 to C18, or C18 to C20, or C20 to C24 alk(en)yl, aryl or alk(en)ylaryl groups).

[0038] In one embodiment, a concentration of the hydroxamic acids or hydroxamates in the composition may range from about 0.5% to 20% by weight, or from about 1% to 10% by weight, or from more than about 1.5% by weight to less than 10% by weight.

[0039] The collector composition may preferably comprise the hydroxamic acid or hydroxamate in an amount of no more than 10 wt% of the collector composition, preferably the collector composition comprises the hydroxamic acid or hydroxamate in an amount of no more than about 4 wt% based on the weight of the collector composition, preferably less than about 4 wt%, more preferably less than about 3 wt%, further preferably less than about 2.5 wt%, even more preferably at least about 1 wt%, even further preferably at least about 1.5 wt%.

[0040] The collector composition may for example comprise the hydroxamic acid or hydroxamate in an amount from about 1 to about 10 wt%, or from about 1 to about 4 wt%, or from about 1 to less than about 4 wt%, or from about 1 to less than about 3 wt%, or from about 1 to less than about 2.5 wt%, or from about 1.5 to about 10 wt%, or from about 1.5 to about 4 wt%, or from about 1.5 to less than about 4 wt%, or from about 1.5 to less than about 3 wt%, or from about 1.5 to less than about 2.5 wt%. In some embodiments, the amount of hydroxamic acid or hydroxamate in the composition may be about 0.5 wt% to about 1.0 wt%, or about 1.0 wt% to about 2.0 wt%, or about 2.0 wt% to about 3.0 wt%, or about 3.0 wt% to less than about 4.0 wt%, or about 3.0 wt% to about 4.0 wt%.

[0041] Preferably, the hydroxamic acid or hydroxamate comprises, or is, an aliphatic compound.

[0042] Preferably, the hydroxamic acid has an acid number of at least about 5 to about 100, preferably about 25 to about 90, more preferably about 40 to about 80, further preferably about 50 to about 70. In some embodiments, the acid number may comprise, or be, at least one from about 5 to about 15, about 15 to about 25, about 25 to about 35, about 35 to about 45, about 45 to about 55, about 55 to about 65, about 65 to about 75, about 75 to about 85, and about 85 to about 95, the acid number being determined by a titration test and having the units of mg KOH / g (of test specimen).

[0043] Preferably the hydroxamic acid or hydroxamate has the formula:         (RC(=O)NH-O) n M wherein R is an alkyl, alkenyl, aryl, alkylaryl or alkenylaryl group having 6 to 24 carbon atoms, preferably 8 to 24 carbon atoms, and M represents a hydrogen, alkali metal, or alkaline earth metal with n being charge of valence of M, preferably the hydroxamic acid comprises or is an aliphatic compound and / or preferably the hydroxamic acid has an acid number of at least about 5 to about 100, preferably about 25 to about 90, more preferably about 40 to about 80, further preferably about 50 to about 70; or the acid number can be from about 5 to about 15, or about 15 to about 25, or about 25 to about 35, or about 35 to about 45, or about 45 to about 55, or about 55 to about 65, or about 65 to about 75, or about 75 to about 85, or about 85 to about 95, the acid number being determined by the titration test and having the units of mg KOH / g.

[0044] In embodiments of the collector composition of the disclosure, the weight ratio of the fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate may be at least about 5:1 or more than about 5:1, preferably at least about 10:1 or more than about 10:1, preferably at least about 15:1, preferably more than about 20:1, preferably more than about 22:1, more preferably more than about 25:1, further preferably at least about 27:1, even more preferably at least about 30:1. In some embodiments, the weight ratio of the fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate may be up to about 60:1.

[0045] In certain embodiments, the weight ratio of the fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate may be more than about 5:1 to about 10:1, or about 10:1 to about 15: 1, or about 15: 1 to about 20:1, or about 20.1 to about 22:1, or about 22:1 to about 25:1, or about 25: 1 to about 27: 1, or about 27:1 to about 30:1, or about 30:1 to about 35:1, or about 35:1 to about 40:1, or about 40:1 to about 45:1, or about 45:1 to about 50:1, or about 50:1 to about 55:1 or about 55:1 to about 60:1.

[0046] In other embodiments, the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate may be at least about 5:1, preferably at least about 10:1, more preferably at least about 20:1, even more preferably up to about60: 1, further preferably up to about 50: 1, even further preferably up to about 40: 1, and most preferably no more than about 30:1.

[0047] In other embodiments, the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate may be more than about 5:1, preferably at least about 10:1, more preferably no more than about 20:1 (such as from more than about 5:1 to no more than about 20:1 or from at least about 10:1 to no more than about 20:1). In particular, the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate may be from more than about 5:1 to about 10:1, or about 10:1 to about 15:1, or about 15:1 to no more than about 20:1, or combinations thereof In some embodiments, the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate may be from more than about 5:1 to about 60:1, or from about 10:1 to about 60:1, or from about 20:1 to about 60:1, or from more than about 5:1 to about 50:1, or from about 10:1 to about 50:1, or from about 20:1 to about 50:1, or from more than about 5:1 to about 40:1, or from about 10:1 to about 40:1, or from about 20:1 to about 40:1, or from more than about 5:1 to about 30:1, or from about 10:1 to about 30:1, or from about 20:1 to about 30:1.

[0048] The composition may inlcude a sulfonate compound. The sulfonate compound may comprise a compound having, or the sulfonate compound may have, a viscosity of greater than 1000 cP at 60°F (15°C), preferably a viscosity of greater than about 5000 cP.

[0049] The sulfonate compound may be formed by the sulfonation of an aromatic compound. An example of suitable compounds may be an alk(en)yl(aryl)sulfonate and their salts. Typically, the alk(en)yl(aryl) may include moieties having carbon numbers ranging from about 8 carbon atoms to about 100 carbon atoms, preferably, from about 10 to about 80 carbon atoms, more preferred from about 14 to about 60 carbon atoms. Examples of suitable sulfonate compounds include but are not limited to sodium sulfonates, natural petroleum sulfonate or alkylbenzene derived synthetic petroleum sulfonate. Preferably, the sulfonate compound comprises, or is, at least one selected from sodium sulfonates, petroleum sulfonates and its derivatives, sulfonated fatty acids and its derivatives, and combinations thereof. Preferred examples of petroleum sulfonates may include natural petroleum sulfonates and synthetic petroleum sulfonates, further preferred petroleum sulfonates include at least one of alkyl sulfonates, alkyl aryl sulfonates, alkyl xylene sulfonates, α-olefin sulfonates and combinations thereof. Preferably the sodium sulfonate comprises sodium alkylbenzenesulfonate, comprising a straight-chain alkylbenzenesulfonic acid.

[0050] In one embodiment, the sulfonate compound may comprise a petroleum sulfonate. The petroleum sulfonates may be classified as low (L) equivalent weight petroleum sulfonates typically having an equivalent weight of about 410-440 g / mole, as medium equivalent weight petroleum sulfonates (HL, referred to in this fashion because it was typically supplied as a blend of low and high equivalent weight petroleum sulfonates) having an equivalent weight of about 450-480 g / mole and high (H) equivalent weight petroleum sulfonates typically having an equivalent weight of about 490-520 g / mole. A preferred sulfonate compound is either a medium or a high equivalent weight petroleum sulfonate, more preferably the medium equivalent weight petroleum sulfonate.

[0051] These general equivalent weight ranges apply to both synthetic and natural petroleum sulfonates.

[0052] The equivalent weight is measured and calculated according to ASTM D3712.

[0053] In another embodiment, a preferred range of equivalent weight of petroleum sulfonates, either natural or synthetic is from about 390 to 600, more preferable from 390 to 420, or from 420 to 450, or from 450 to 480, or from 480 to 510, or from 510 to 540, or from 540 to 570, or from 570 to 600.

[0054] Optionally, the collector composition disclosed herein may comprise at least one amine. In particular, the composition may comprise at least one alkanolamine. In advantageous embodiments, the alkanolamines used in the collector composition of the disclosure contain both hydroxyl and amino functional groups. Preferably, the alkanolamines may be water soluble or miscible with water. More preferably, the at least one alkanolamine is selected from aminoethylethanolamine, ethanolamine, diethanol amine, methyldiethanolamine, triethanolamine, hydroxyethylpiperazine and combinations thereof. Preferably concentrations of alkanolamines range from more than trace amounts (for example, from more than about 0.001 % by weight) to less than about 5% by weight, preferably no more than about 3% by weight, even more preferably no more than about 2.5% by weight and even further preferred no more than about 2% by weight (such as from more than about 0.001 to less than about 5 % by weight, or from more than about 0.001 to no more than about 3% by weight, or from more than about 0.001 to no more than about 2.5% by weight, or from more than about 0.001 to no more than about 2% by weight).

[0055] Additionally or alternatively, the composition may comprise at least one amine selected from fatty (poly)amine, fatty amido (poly)amine, fatty imidazoline, fatty imidazo (poly)amine, fatty (poly) ester amine, fatty (poly) quaternized ammonium salt, and combination thereof. The fatty (poly)amine, fatty amido (poly)amine, fatty imidazoline, fatty imidazo (poly)amine, fatty (poly) ester amine, fatty (poly) quaternized ammonium salt may include 4-24 carbon atoms in the fatty chain. Preferred fatty chains may include straight-chains, branched chains, cycles containing chains, saturated, unsaturated, aromatic containing chains, or chains with at least 6 carbon atoms containing at least one pendant hydroxyl group, preferably containing from 6 to 24 carbon atoms. Preferably, concentrations of fatty (poly)amine, fatty amido (poly)amine, fatty imidazoline, fatty imidazo (poly)amine, fatty (poly) ester amine, fatty (poly) quaternized ammonium salt (and the combinations therefore) range from more than trace amounts (for example, from more than about 0.001 % by weight) to less than about 5% by weight, preferably no more than about 3% by weight, even more preferably no more than about 2.5% and even further preferred no more than about 2% by weight (such as from more than about 0.001 to less than about 5 % by weight, or from more than about 0.001 to no more than about 3% by weight, or from more than about 0.001 to no more than about 2.5% by weight, or from more than about 0.001 to no more than about 2% by weight).

[0056] Preferably, the amine may comprise, or be, at least one selected from the group of a fatty (poly)amine, fatty amido (poly)amine, fatty imidazoline, fatty imidazo (poly)amine, fatty (poly) ester amine, fatty (poly) quaternized ammonium salt, aminoethylethanolamine, methanolamine, ethanolamine, N-methylethanolamine, dimethylethanolamine, ethylethanolamine, diethylethanolamine, propylethanolamine, dipropylethanolamine, butylethanolamine, dibutylethanolamine, diethanolamine, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, triethanolamine, isobutanol-2-amine, valinol, alaninol, hydroxyethylpiperazine and combinations thereof.

[0057] The composition may include at least one frother. Frothers can be any commonly used frothers like pine oil, methylisobutyl carbinol, alcohols, alkoxylated alcohols, alkoxylated methylisobutyl carbinol, polyglycols, or combination therefore, to improve the froth properties such as stability and density. Preferably, the amount of frothers in the composition ranges from 0.5 to 10% by weight.

[0058] The collector composition may comprise a defoamer, preferably at a concentration of up to about 5 wt%, preferably less than about 5 wt%, more preferably at least about 1 wt%, further preferably at least about 1.5 wt%, based on the weight of the collector composition (such as from about 1 to about 5 wt%, or from about 1 to less than about 5 wt%, or from about 1.5 to about 5 wt%, or from about 1.5 to less than about 5 wt%).

[0059] If so desired, the composition may be devoid of an effective amount of silicon to boost separation efficiency.

[0060] If so desired, the composition may be devoid of any more than trace amounts of any of alkyne compounds, alkylbenzene compounds and combinations thereof. For example, the composition can comprise alkyne compounds, alkylbenzene compounds or combinations thereof in an amount of at most 0.001 % by weight (including about 0 % by weight).

[0061] In some aspects of the disclosure, if so desired, the composition may be devoid of an effective amount of sulfonated compounds that function as a collector (for example, the composition may be devoid of sulfonated compounds or may comprise sulfonated compounds in an amount of at most 2 % by weight, or at most 1 % by weight, or at most 0.5 % by weight, or at most 0.1 % by weight).

[0062] If so desired, the composition may be devoid of an effective amount of a separate lithium depressant (for example, the composition may be devoid of lithium depressant or may comprise lithium depressant in an amount of at most 2 % by weight or at most 1 % by weight, or at most 0.5 % by weight, or at most 0.1 % by weight) An advantage of the disclosed collector is that it may be used to routinely concentrate lithium (Li 2 O) from mined spodumene ores having at least about 1% Li 2 O into a concentration having at least about 4.5% of Li 2 O by a single flotation, preferably greater than about 5.0% and have a recovery of at least about 70% of the Li 2 O, preferably greater than about 70%, even more preferably at least about 75%.

[0063] A further advantage includes that the disclosed collector can improve lithium recovery by more than about 5% over known collectors, preferably about 10% or more.First variant of collector composition

[0064] According to a first variant of the disclosure, the collector composition comprises: a. at least one fatty acid, fatty acid derivative and combinations thereof; b. at least one hydroxamic acid or hydroxamate; c. a sulfonate compound, wherein the collector composition comprises the sulfonate compound in an amount of at least about 0.5 wt% to about 75 wt% based on the total weight of the collector composition.

[0065] What is described above can apply to this first variant of the disclosure, unless specified otherwise.

[0066] Preferably, the collector composition comprises the sulfonate compound in an amount of more than about 5 wt% to less than about 70 wt%, preferably at least 10 wt%, or more than about 10 wt%, to up to about 65 wt%, more preferably at least about 15 wt%, or more than 15 wt % to up to about 55 wt%. In an advantageous embodiment, the amount of the sulfonate compound in the composition can at least about 20 wt% to about 75 wt%.

[0067] In some embodiments, the collector composition comprises the sulfonate compound in an amount of at least about 0.5 wt% to about 2 wt%, or about 2 wt% to about 5 wt%, or about 5 wt% to about 7 wt% or about 7 wt% to about 10 wt%, or about 10 wt% to about 15 wt%, or about 15 wt% to about 20 wt%, or about 20 wt% to about 25 wt%, or about 25 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to about 55 wt%, or about 55 wt% to about 65 wt%, or about 65 wt% to about 75 wt% or combinations thereof.

[0068] In one embodiment, the sulfonate compound may be included in the composition within a range of about 0.5 wt% to about 10 wt%, preferably about 0.5 wt% to about 7 wt%. The wt% are based on the weight of the collector composition.

[0069] The fatty acid, fatty acid derivative or combinations thereof may comprise a soya oil fatty acid.

[0070] Preferably the composition comprises the soya oil fatty acid in an amount of at least about 5 wt% based on the weight of the collector composition, further preferably at least about 10 wt%, even more preferably at least about 15 wt%, even further preferably at least about 20 wt%, and most preferably no more than about 50 wt%.

[0071] The composition may comprise the soya oil fatty acid in an amount of from about 5 to 50 wt%, or from about 10 to 50 wt%, or from about 15 to 50 wt%, or from about 20 to 50 wt%. In some embodiments, the collector composition can comprise the soya oil fatty acid in the amount of at least about 5 wt% to about 15 wt%, or about 15 wt% to about 25 wt%, or about 25 wt% to about 35 wt%, or about 35 wt% to about 45 wt%, or about 45 wt% to no more than about 50 wt%, or combinations thereof.

[0072] In some embodiments, the collector composition comprise a soya oil fatty acid and the weight ratio of the soya oil fatty acid to the sulfonate compound is about 12:1 to about 1:2.5, preferably at least one of no more than about 8:1, or no more than about 4:1, or no more than about 3:1, or no more than about 2:1, no more than about 1:1, or about 1:1, or less than about 1:2, or combinations thereof.

[0073] The fatty acid, fatty acid derivative or combinations thereof may comprise a canola fatty acid.

[0074] Preferably the composition comprises the canola fatty acid in an amount of at least about 5 wt% based on the weight of the collector composition, further preferably at least about 15 wt%, even more preferably at least about 20 wt%, even further preferably at least about 30 wt%, and most preferably no more than about 60 wt% (such as from about 5 to 60 wt%, or from about 15 to 60 wt%, or from about 20 to 60 wt%, or from about 30 to 60 wt%). In some embodiments, the collector composition can comprise the canola fatty acid in the amount of at least about 5 wt% to 10 wt%, 10 wt% to 15 wt%, 15 wt% to 20 wt%, 20 wt% to 25 wt%, 25 wt% to 30 wt%, 30 wt% to 35 wt%, 35 wt% to 40 wt%, 40 wt% to 45 wt%, 45 wt% to 50 wt%, 50 wt% to 55 wt%, or 55 wt% to less than 60 wt%, or combinations thereof.

[0075] In some embodiments, the collector composition comprise a canola fatty acid and the weight ratio of the canola fatty acid to the sulfonate compound is about 12:1 to about 1:2.5, preferably at least one of no more than about 8:1, no more than about 4:1, or no more than about 3:1, or no more than about 1:1, or about 1:1, or less than about 1:2, or combinations thereof.

[0076] In one embodiment, the fatty acid, the fatty acid derivative or the combinations thereof have a viscosity of greater than 1000 cP at 60°F (15°C). Nonlimiting examples of such fatty acids include but, is not limited to soya oil fatty acid and canola fatty acid. Preferably such fatty acids have an acid number of at least about 100 up to about 280 mg KOH / g. Typically such fatty acids have an acid number of at least about 150, further at least about 170, even further at least about 180, optionally no more than about 260, furthermore no more than about 220, preferentially no more than about 210 mg KOH / g (such as from about 150 to 260 mg KOH / g, preferably from about 150 to 220 mg KOH / g, more preferably from 170 to 210 mg KOH / g).

[0077] The collector composition may comprise a fatty acid comprising 60 wt% or more of C18: 1 (oleic fatty acid), preferably 65 wt% or more, even more preferably 70 wt% or more, based on the weight of the collector composition. The fatty acid may be from a bio-source, distilled / concentrated as is known in art.

[0078] Alternatively, the collector composition may comprise less than 70 wt% of the C18: 1 (oleic fatty acid) fatty acid, preferably less than about 60 wt%, more preferably less than about 50 wt%, further preferably less than about 40 wt%, even more preferably less than about 30 wt%, even further preferred less than about 20 wt% based on the weight of the collector composition.

[0079] In other embodiments, the collector composition may comprise the C18:1 (oleic fatty acid) fatty acid in the amount of at least about 20 wt% to about 25 wt%, or about 25 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to about 50 wt%, or about 50 wt% to about 55 wt%, or about 55 wt% to about 60 wt%, or about 60 wt% to about 65 wt%, or about 65 wt% to about 70 wt% or combinations thereof.

[0080] The collector composition may comprise tall oil fatty acid. The collector composition may comprise less than 70 wt% of tall oil fatty acid, preferably less than about 50 wt%, more preferably less than about 25 wt%, further preferably less than about 19 wt%, even more preferably less than about 15 wt%, even further preferred less than about 1 wt% based on the weight of the collector composition. In some embodiments, the collector composition may comprise tall oil fatty acid in the amount of at least about 0.5 wt% to about 4.0 wt%, about 4.0 wt% to about 8 wt%, about 8 wt% to about 12 wt%, about 12 wt% to about 16 wt%, about 16 wt% to about 20 wt%, about 20 wt% to about 24 wt%, about 24 wt% to about 28 wt%, about 28 wt% to about 32 wt%, about 32 wt% to about 36 wt%, about 36 wt% to about 40 wt%, about 40 wt% to about 44 wt%, about 44 wt% to about 48 wt%, about 48 wt% to about 52 wt%, about 52 wt% to about 56 wt%, about 56wt% to about 59 wt%, about 59 wt% to about 62 wt%, about 62 wt% to about 65 wt%, or about 65 wt% to 70 wt%, or combinations thereof.

[0081] In some embodiments, the collector composition comprise tall oil fatty acid and the weight ratio of the tall oil fatty acid to the sulfonate compound is about 12:1 to about 1:2.5, preferably at least one of no more than about 8:1, or no more than about 4:1, or no more than about 3:1, or no more than about 1: 1, or about 1:1, or less than about 1:2, or combinations thereof.

[0082] The tall oil fatty acid in the collector composition may comprise C16:0 or C18:0 fatty acid or fatty acid derivative, or a mixture of C16:0 and C18:0 fatty acid and / or fatty acid derivative. The tall oil fatty acid may comprise no more than about 20 wt% of a mixture of C16:0 and C18:0 fatty acid and / or fatty acid derivative, preferably no more than about 14 wt%, preferably no more than about 10 wt%, more preferably no more than about 5 wt%, further preferably no more than about 2.5 wt%. The tall oil fatty acid may comprise the mixture of C16:0 and C18:0 in fatty acid and fatty acid derivative in the amount of about 0.5 wt% to about 4 wt%, or about 4 wt% to about 8 wt%, or about 8 wt% to about 12 wt%, or about 12 wt% to about 16 wt%, or about 16 wt% to about 20 wt% and combinations thereof.

[0083] The fatty acid, fatty acid derivative and combinations thereof in the collector composition may comprise a blend of the aforementioned fatty acids in any combination thereof. In one embodiment, the blend of fatty acids may comprise at least about 10 wt% of oleic fatty acid based on the weight of the collector composition, preferably at least about 15 wt%, more preferably at least 20 wt%, further preferably at least about 25 wt%, even more preferably at least about 30 wt%, even further preferably no more than about 50 wt% (such as from about 10 to no more than about 50 wt%, or from about 15 to no more than about 50 wt%, or from about 20 to no more than about 50 wt%, or from about 25 to no more than about 50 wt%, or from about 30 to no more than about 50 wt%). In some embodiments, the at least one fatty acid, fatty acid derivative or combinations thereof comprises oleic fatty acid, preferably the collector composition comprises the oleic fatty acid in the amount of about 1 wt% to about 5 wt%, about 5 wt% to about 10 wt%, about 10 wt% to about 15 wt%, about 15 wt% to about 20 wt%, about 20 wt% to about 25 wt%, about 25 wt%, to about 30 wt%, about 30 wt% to about 35 wt%, about 35 wt% to about 40 wt%, about 40 wt% to about 45 wt%, about 45 wt% to no more than about 50 wt%, or combinations thereof.

[0084] The collector composition advantageously has a viscosity at 60°F (15°C) of less than 3500 cP, preferably less than 2000 cP, preferably less than 1000 cP, preferably less than about 850 cP, more preferably less than about 700 cP, further preferably less than about 600 cP, even more preferably less than about 200 cP, further preferably less than about 125 cP, and most preferably less than about 80 cP.

[0085] The collector composition of the disclosure may comprise: a. from 15 to 99 wt% of at least one fatty acid, fatty acid derivative and combinations thereof; b. from of 0.5 to 10 wt% of at least one hydroxamic acid or hydroxamate; c. from about 0.5 wt% to about 75 wt% of a sulfonate compound, based on the total weight of the collector composition.Second variant of collector composition

[0086] According to a second variant of the disclosure, the collector composition comprises: a. at least one fatty acid, fatty acid derivative and combinations thereof; and b. at least one hydroxamic acid or hydroxamate, wherein the at least one fatty acid, fatty acid derivative and combinations thereof comprise from about 0.5 % to about 20% of a mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives.

[0087] Preferably an amount of the mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives is less than about 20 wt%, more preferably less than about 15 wt%, further preferably less than about 14 wt%, even further preferably less than about 10 wt%, even more preferably less than about 5 wt% (such as from about 0.5 % to less than about 20 wt%, or from about 0.5 % to less than about 15 wt%, or from about 0.5 % to less than about 14 wt%, or from about 0.5 % to less than about 10 wt%, or from about 0.5 % to less than about 5 wt%).

[0088] In some embodiments, the collector composition comprises the mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives in the amount of about 0.5 wt% to about 4 wt%, or about 4 wt% to about 8 wt%, or about 8 wt% to about 12 wt%, or about 12 wt% to 14 wt%, or 14 wt% to about 16 wt%, or about 16 wt% to no more than about 20 wt% or combinations thereof.

[0089] What is described above can apply to this first variant of the disclosure, unless specified otherwise.

[0090] Preferably, the fatty acid, fatty acid derivative or combinations thereof comprise at least one of soya oil fatty acid, canola fatty acid, tall oil fatty acid, oleic fatty acid and combinations thereof, preferably at least 2 selected from the group of the soya oil fatty acid, the canola fatty acid, the oleic fatty acid and the tall oil fatty acid.

[0091] The collector composition may comprise tall oil fatty acid.

[0092] The collector composition may comprise no more than 95 wt% of tall oil fatty acid, preferably less than about 55 wt%, more preferably less than about 19 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt%, based on the amount of the fatty acid, fatty acid derivative or combinations thereof in the collector composition.

[0093] In some embodiments, the collector composition may comprise tall oil fatty acid in the amount of about 1 wt% to about 5 wt%, about 5 wt% to about 10 wt%, about 10 wt% to about 15 wt%, about 15 wt% to less than about 19%, about 19 wt% to about 23 wt%, about 23 wt% to about 27 wt%, about 27 wt% to about 30 wt%, about 30 wt% to about 35 wt%, about 35 wt% to about 40 wt%, about 40 wt% to about 45 wt%, about 45 wt% to about 50 wt%, about 50 wt% to about 55 wt%, about 55 wt% to about 58 wt%, about 58 wt% to about 61 wt%, about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or about 70 wt% to about 75 wt%, or about 75 wt% to about 80 wt%, or about 80 wt% to about 85 wt%, or about 85 wt% to about 90 wt%, or about 90 wt% to about 95 wt%, or combinations thereof, based on the amount of the fatty acid, fatty acid derivative or combinations thereof in the collector composition.

[0094] In some embodiments, the collector composition may comprise the tall oil fatty acid and the weight ratio of the tall oil fatty acid to a sulfonate compound is about 20:1 to about 1:2.5, preferably at least one of no more than about 15:1, no more than about 10:1, no more than about 8:1, or no more than about 4:1, or no more than about 3: 1, or no more than about 1: 1, or about 1:1, or less than about 1:2, or combinations thereof.

[0095] In other embodiments, the at least one fatty acid, fatty acid derivative and combinations thereof consists essentially of tall oil fatty acid.

[0096] In other embodiments, the at least one fatty acid, fatty acid derivative and combinations thereof consists of tall oil fatty acid.

[0097] In other embodiments, the collector composition may be devoid of tall oil fatty acid.

[0098] The fatty acid, fatty acid derivative or combinations thereof in the collector composition may comprise oleic fatty acid.

[0099] The fatty acid, fatty acid derivative or combinations thereof may comprise less than 70 wt% of oleic fatty acid, preferably less than about 55 wt%, more preferably less than about 30 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt% based on the amount of the fatty acid, fatty acid derivative or combinations thereof in the collector composition.

[0100] In some embodiments, the fatty acid, fatty acid derivative or combinations thereof comprises oleic fatty acid in an amount of about 1 wt% to about 5 wt%, about 5 wt% to about 10 wt%, about 10 wt% to about 15 wt%, about 15 wt% to about 19, about 19 wt% to about 23 wt%, about 23 wt% to about 27 wt%, about 27 wt% to about 30 wt%, about 30 wt% to about 35 wt%, about 35 wt% to about 40 wt%, about 40 wt% to about 45 wt%, about 45 wt% to about 50 wt%, about 50 wt% to about 55 wt%, about 55 wt% to about 58 wt%, about 58 wt% to about 61 wt%, about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or combinations thereof.

[0101] The fatty acid, fatty acid derivative or combinations thereof in the collector composition may comprise canola fatty acid.

[0102] The fatty acid, fatty acid derivative or combinations thereof may comprise less than 70 wt% of canola fatty acid, preferably less than about 55 wt%, more preferably less than about 30 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt% based on the amount of the fatty acid, fatty acid derivative or combinations thereof in the collector composition.

[0103] In some embodiments, the fatty acid, fatty acid derivative or combinations thereof comprises the canola fatty acid in an amount of about 1 wt% to about 5 wt%, about 5 wt% to about 10 wt%, about 10 wt% to about 15 wt%, about 15 wt% to about 19, about 19 wt% to about 23 wt%, about 23 wt% to about 27 wt%, about 27 wt% to about 30 wt%, about 30 wt% to about 35 wt%, about 35 wt% to about 40 wt%, about 40 wt% to about 45 wt%, about 45 wt% to about 50 wt%, about 50 wt% to about 55 wt%, about 55 wt% to about 58 wt%, about 58 wt% to about 61 wt%, about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or combinations thereof.

[0104] The fatty acid, fatty acid derivative or combinations thereof in the collector composition may comprise soya oil fatty acid.

[0105] The fatty acid, fatty acid derivative or combinations thereof may comprise less than 70 wt% of soya oil fatty acid, preferably less than about 55 wt%, more preferably less than about 30 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt% based on the amount of the fatty acid, fatty acid derivative or combinations thereof in the collector composition.

[0106] In some embodiments, the fatty acid, fatty acid derivative or combinations thereof comprises the soya oil fatty acid in an amount of about 1 wt% to about 5 wt%, about 5 wt% to about 10 wt%, about 10 wt% to about 15 wt%, about 15 wt% to about 19, about 19 wt% to about 23 wt%, about 23 wt% to about 27 wt%, about 27 wt% to about 30 wt%, about 30 wt% to about 35 wt%, about 35 wt% to about 40 wt%, about 40 wt% to about 45 wt%, about 45 wt% to about 50 wt%, about 50 wt% to about 55 wt%, about 55 wt% to about 58 wt%, about 58 wt% to about 61 wt%, about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or combinations thereof.

[0107] The collector composition can comprise a sulfonate compound, in particular as described above. A concentration of the sulfonate compound (for example of sodium sulfonate and / or petroleum sulfonate) in the composition may range from 0 (preferably at least 0.1 % by weight) to 15 % by weight.

[0108] In other embodiments, the collector composition may comprise the sulfonate compound in an amount of more than about 5 wt% to less than about 70 wt%, preferably at least 10 wt% , or more than about 10 wt%, to up to about 65 wt%, more preferably at least about 15 wt% to up to about 55 wt%, further preferably at least about 18 wt% up to about 55 wt%, further preferably at least about 20 wt% up to about 50 wt%, further preferably more than 20 wt% up to about 50 wt%.

[0109] In some embodiments, the collector composition may comprise the sulfonate compound in an amount of at least about 0.5 wt% to about 2 wt%, or about 2 wt% to about 5 wt%, or about 5 wt% to about 15 wt%, or about 15 wt% to about 25 wt%, or about 25 wt% to about 35 wt%, or about 35 wt% to about 45 wt%, or about 45 wt% to about 55 wt%, or about 55 wt% to about 65 wt%, or about 65 wt% to about 75 wt% or combinations thereof.

[0110] The collector composition of the disclosure may comprise: a. from 51 to 99.5 wt% of at least one fatty acid, fatty acid derivative and combinations thereof comprising from about 0.5 % to about 20% of a mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives; and b. from of 0.5 to 10 wt% of at least one hydroxamic acid or hydroxamate; c. optionally an amine; d. optionally a sulfonate compound; e. optionally other additives as described herein, based on the total weight of the collector composition.Third variant of collector composition

[0111] According to a third variant of the disclosure, the collector composition comprises: a. at least one fatty acid, fatty acid derivative and combinations thereof; b.at least one hydroxamic acid or hydroxamate; c.a sulfonate compound, wherein the collector composition comprises the sulfonate compound such that the weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof to the sulfonate compound is about 12:1 to about 1:2.5.

[0112] The weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof to the sulfonate compound is preferably about 12:1 to about 1:2.5, preferably about 8:1 to about 1:2.5, further preferably about 4:1 to about 1:2, even further preferably about 3:1 to about 1: 1.5, more preferably about 2:1 to about 1: 1.5, such as about 1:1 or from about 2:1 to about 1:1. In some embodiment, the weight ratio may be about 5:1 to about 1:2.5, for example from about 1:2 to about 1:2.5.

[0113] In some embodiments, the weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof to the sulfonate compound may be about 12:1 to about 10:1, or about 10:1 to about 8:1, or about 8:1 to about 6:1, or about 6:1 to about 4:1, or about 4:1 to about 3.5:1, or about 3.5:1 to about 3: 1, or about 3:1 to about 2.5:1, or about 2.5:1 to about 2:1, or about 2:1 to about 1.5:1, or about 1.5:1 to about 1:1, or about 1:1 to about 1:1.5, or about 1:1.5 to about 1:2, or about 1:2 to about 1:2.5, or combinations thereof.

[0114] What is described above can apply to third first variant of the disclosure, unless specified otherwise. In particular, all embodiments described in relation to the first variant can apply to this third variant.Uses and processes

[0115] The disclosure also relates to the use of a collector composition as described above, for the beneficiation of industrial minerals, preferably any one of phosphate, lithium, and rare earths.

[0116] The disclosure also relates to a beneficiation process for separating impurities from any one of lithium containing ore, rare earth containing ore or phosphate containing ore. The process includes pulping the ore to produce an ore slurry; reagentizing the ore slurry to produce a reagentized slurry by adding a composition as described above. The process may also include separating at least some of the impurities from the lithium and collecting the lithium in the form of a concentrate.

[0117] In the case of lithium beneficiation, preferably, the reagentizing step does not include introducing a separate lithium depressant. Preferably, the step of reagentizing the ore slurry further comprises adding a pH modifier.

[0118] In some embodiments, the reagentizing step further comprises separately adding at least one of the components of the collector composition (such as the fatty acid and / or fatty acid derivative, the hydroxamic acid or hydroxamate, the sulfonate compound, the optional amine).

[0119] The process further may comprise combining at least two of the fatty acid and / or fatty acid derivative, the hydroxamic acid or hydroxamate, the sulfonate compound, and the optional amine prior to being added to the ore slurry.

[0120] The disclosure also relates to a flotation method for removing gangue from lithium containing ores. The method includes producing an ore slurry comprising lithium containing ore and a collector composition as described above. The method also includes subjecting the ore slurry to flotation. Preferably, the ore slurry further comprises a pH modifier.

[0121] The step of subjecting the ore slurry to flotation preferably produces an underflow and an overflow, the method further comprising: separating one of the overflows or the underflow as the gangue; and collecting the other of the underflow or the overflow as lithium concentrate.ASPECTS

[0122] A first aspect of the invention includes a collector composition, preferably a phosphate, lithium or rare earth collector composition, more preferably a lithium collector composition, comprising: a. at least one fatty acid, fatty acid derivative and combinations thereof; b. at least one hydroxamic acid or hydroxamate; c. a sulfonate compound, wherein i. the sulfonate compound is in an amount of at least about 0.5 wt% to about 75 wt% of the collector composition, preferably the collector composition comprises the sulfonate compound in an amount 1. of at least about 0.5 wt% to about 2 wt%, or about 2 wt% to about 5 wt%, or about 5 wt% to about 15 wt%, or about 15 wt% to about 25 wt%, or about 25 wt% to about 35 wt%, or about 35 wt% to about 45 wt%, or about 45 wt% to about 55 wt%, or about 55 wt% to about 65 wt%, or about 65 wt% to about 75 wt% or combinations thereof; or 2. more than about 5 wt% to less than about 70 wt%, more preferably more than about 10 wt%, to up to about 65 wt%, more preferably more than about 15 wt% to up to about 55 wt%, even further preferably more than 20 wt% to up to about 50 wt%; ii. alternatively instead of in terms of wt% (or additionally), the collector composition may comprise a weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof to the sulfonate compound of about 12:1 to about 1 :2.5, preferably at least one of no more than about 8:1, or no more than about 4:1, or no more than about 3:1, or no more than about 2:1, or no more than about 1:1, or about 1:1, or less than about 1:2 or combinations thereof (such as from less than about 10:1 to about 1:2.5, or from no more than about 8:1 to about 1:2.5, or from no more than about 4:1 to about 1:2.5, or from no more than about 3:1 to about 1:2.5, or from no more than about 2:1 to about 1:2.5, or from about 1:1 to about 1:2.5, or from less than about 1:2 to about 1:2.5).

[0123] In a second aspect applicable to the first aspect, the sulfonate compound comprises a compound having a viscosity of greater than 1000 cP at 60°F (15°C), preferably a viscosity of greater than about 5000 cP.

[0124] In a third aspect applicable to aspects 1-2, the sulfonate compound comprises at least one selected from sodium sulfonates, petroleum sulfonates and its derivatives, sulfonated fatty acids and its derivatives, and combinations thereof, preferred examples of petroleum sulfonates may include natural petroleum sulfonates and synthetic petroleum sulfonates, further preferred petroleum sulfonates include at least one of alkyl sulfonates, alkyl aryl sulfonates, alkyl xylene sulfonates and α-olefin sulfonates and combinations thereof, preferably the sodium sulfonate comprises sodium alkylbenzenesulfonate comprising a straight-chain alkylbenzenesulfonic acid.

[0125] In a fourth aspect applicable to aspects 1-3, the at least one fatty acid, fatty acid derivative and combinations thereof have a viscosity of greater than 1000 cP at 60°F (15°C) and an acid number of at least about 100 up to about 280 mg KOH / g, under a titration test, preferably the acid number comprises (or is) at least about 170, more preferably at least about 180, optionally no more than about 260, further preferably no more than about 220, even further preferably no more than about 210 (for example the acid number is from about 170 to about 260, in particular from about 170 to about 220, more particularly from about 180 to about 210).

[0126] In a fifth aspect applicable to aspects 1-4, the at least one fatty acid, fatty acid derivative and combinations thereof comprises a soya oil fatty acid, preferably a. the collector composition comprises the soya oil fatty acid in an amount of at least 5 wt% based on the weight of the collector composition, further preferably at least about 10 wt%, even more preferably at least about 15 wt%, even further preferably at least about 20 wt%, and most preferably no more than about 50 wt%; or b. the collector composition comprises the soya oil fatty acid in the amount of at least about 5 wt% to about 15 wt%, or about 15 wt% to about 25 wt%, or about 25 wt% to about 35 wt%, or about 35 wt% to about 45 wt%, or about 45 wt% to no more than about 50 wt% or combinations thereof; and / or c. a weight ratio of the soya oil fatty acid to the sulfonate compound comprises (or is) about 12:1 to about 1:2.5, preferably at least one of no more than about 8:1, or no more than about 4:1, or no more than about 3:1, or no more than about 2:1, or no more than about 1:1, or about 1:1, or less than about 1:2, or combinations thereof (such as from no more than about 8:1 to about 1:2.5, or from no more than about 4:1 to about 1:2.5, or from no more than about 3:1 to about 1:2.5, or from no more than about 2:1 to about 1:2.5, or from about 1:1 to about 1:2.5, or from less than about 1:2 to about 1:2.5).

[0127] In a sixth aspect applicable to aspects 1-5, the at least one fatty acid, fatty acid derivative and combinations thereof comprises a canola fatty acid, preferably a. the collector composition comprises the canola fatty acid in an amount of at least 5 wt% based on the weight of the collector composition, further preferably at least about 15 wt%, even more preferably at least about 20 wt%, even further preferably at least about 30 wt%, and most preferably no more than about 60 wt% or b. the collector composition comprises the canola fatty acid in the amount of at least about 5 wt% to 10 wt%, or 10 wt% to 15 wt%, or 15 wt% to 20 wt%, or 20 wt% to 25 wt%, or 25 wt% to 30 wt%, or 30 wt% to 35 wt%, or 35 wt% to 40 wt%, or 40 wt% to 45 wt%, or 45 wt% to 50 wt%, or 50 wt% to 55 wt%, or 55 wt% to less than 60 wt%, or combinations thereof; and / or c. a weight ratio of the canola fatty acid to the sulfonate compound comprises (or is) about 12:1 to about 1:2.5, preferably at least one of no more than about 8:1, or no more than about 4:1, or no more than about 3:1, or no more than about 2:1, or no more than about 1:1, or about 1:1, or less than about 1:2, or combinations thereof (such as from no more than about 8:1 to about 1:2.5, or from no more than about 4:1 to about 1:2.5, or from no more than about 3:1 to about 1:2.5, or from no more than about 2:1 to about 1:2.5, or from about 1:1 to about 1:2.5, or from less than about 1:2 to about 1:2.5).

[0128] In a seventh aspect applicable to aspects 1-6, the collector composition comprises hydroxamic acid or hydroxamate in an amount of no more than 10 wt% of the collector composition, preferably the collector composition comprised of the at least one hydroxamic acid or hydroxamate in an amount of i. no more than about 4 wt% based on the weight of the collector composition, preferably less than about 4 wt%, more preferably less than about 3 wt%, further preferably less than about 2.5 wt%, even more preferably at least about 1 wt%, even further preferably at least about 1.5 wt% or ii. about 0.5 wt% to about 1.0 wt%, or about 1.0 wt% to about 2.0 wt%, or about 2.0 wt% to about 3.0 wt%, or about 3.0 wt% to less than about 4.0 wt%; and / or iii. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) at least about 5:1, preferably at least about 10:1, more preferably at least 20:1, even more preferably up to about 60:1, further preferably up to about 50:1, even further preferably up to about 40:1, and most preferably up to about 30:1; or iv. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) from more than about 5:1 to about 10.1, or from about 10:1 to about 15:1, or about 15:1 to about 20:1, or about 20:1 to about 25:1, or about 25:1 to about 30:1, or about 30:1 to about 35:1, or about 35:1 to about 40:1, or about 40:1 to about 45:1, or about 45:1 to about 50:1, or about 50:1 to about 55:1, or about 55:1 to about 60:1, or combinations thereof; or v. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) more than about 5:1, preferably at least about 10:1, more preferably no more than about 20:1; or vi. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) more than about 5:1 to about 10:1, or about 10:1 to about 15:1, or about 15: 1 to no more than about 20:1, or combinations thereof; wherein: a. preferably the at least one hydroxamic acid or hydroxamate comprises an aliphatic compound, and / or b. preferably the hydroxamic acid has an acid number of at least about 5 to about 100, preferably about 25 to about 90, more preferably about 40 to about 80, further preferably about 50 to about 70; or the acid number is from about 5 to about 15, or about 15 to about 25, or about 25 to about 35, or about 35 to about 45, or about 45 to about 55, or about 55 to about 65, or about 65 to about 75, or about 75 to about 85, or about 85 to about 95; the acid number being determined by the titration test and having the units of mg KOH / g of test specimen.

[0129] In an eighth aspect applicable to aspects 1-7, a weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof (having preferably a viscosity of greater than 1000 cP at 60°F (15°C) and an acid number of at least about 100 up to about 220 mg KOH / g) to the at least one hydroxamic acid or hydroxamate comprises more than about 5:1, preferably at least about 10:1, more preferably no more than about 20:1.

[0130] In a nineth aspect applicable to aspects 1-8, the collector composition comprises a. less than 70 wt% of tall oil fatty acid, preferably less than about 50 wt%, more preferably less than about 25 wt%, further preferably less than about 19 wt%, even more preferably less than about 15 wt%, even further preferred less than about 1 wt%, based on the weight of the collector composition; or b. the collector composition comprises the tall oil fatty acid in the amount of at least about 0.5 wt% to about 4.0 wt%, or about 4.0 wt% to about 8 wt%, or about 8 wt% to about 12 wt%, or about 12 wt% to about 16 wt%, or about 16 wt% to about 20 wt%, or about 20 wt% to about 24 wt%, or about 24 wt% to about 28 wt%, or about 28 wt% to about 32 wt%, or about 32 wt% to about 36 wt%, or about 36 wt% to about 40 wt%, or about 40 wt% to about 44 wt%, or about 44 wt% to about 48 wt%, or about 48 wt% to about 52 wt%, or about 52 wt% to about 56 wt%, or about 56wt% to about 59 wt%, or about 59 wt% to about 62 wt%, or about 62 wt% to about 65 wt%, or about 65 wt% to 70 wt% or combinations thereof; and / or c. a weight ratio of the tall oil fatty acid to the sulfonate compound comprises about 12:1 to about 1 :2.5, preferably at least one of no more than about 8:1, no more than about 4: 1, or no more than about 3:1, or no more than about 2:1, or no more than about 1:1, or about 1:1, or less than about 1:2, or combinations thereof (such as from no more than about 8:1 to about 1:2.5, or from no more than about 4:1 to about 1:2.5, or from no more than about 3:1 to about 1:2.5, or from no more than about 2:1 to about 1:2.5, or from about 1:1 to about 1:2.5, or from less than about 1:2 to about 1:2.5); d. preferably the tall oil fatty acid comprises no more than about 20 wt% of a mixture of C16:0 and C18:0 fatty acid and / or fatty acid derivative, preferably no more than about 14 wt%, preferably no more than about 10 wt%, further preferably no more than about 5 wt%, even further preferably no more than about 2.5 wt%.

[0131] In a tenth aspect applicable to aspects 1-9, a. the at least one fatty acid, fatty acid derivative and combinations thereof comprises a blend of fatty acids and the blend of fatty acids comprises at least about 10 wt% of oleic fatty acid based on the weight of the collector composition, preferably at least about 15 wt%, more preferably at least 20 wt%, further preferably at least about 25 wt%, even more preferably at least about 30 wt%, even further preferably no more than about 50 wt%; or b. the at least one fatty acid, fatty acid derivative and combinations thereof comprises oleic fatty acid, preferably the collector composition comprises the oleic fatty acid in the amount of about 1 wt% to about 5 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 15 wt%, or about 15 wt% to about 20 wt%, or about 20 wt% to about 25 wt%, or about 25 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to no more than about 50 wt% or combinations thereof.

[0132] In an eleventh aspect applicable to aspects 1-10, the collector composition at 60°F (15°C) has a viscosity of less than 3500 cP, preferably less than 2000 cP, preferably less than 1000 cP, preferably less than about 850 cP, more preferably less than about 700 cP, further preferably less than about 600 cP, even more preferably less than about 200 cP, further preferably less than about 125 cP, and most preferably less than about 80 cP.

[0133] In a twelve aspect applicable to aspects 1-11, the collector composition further comprises at least one amine, preferably the amine comprises both hydroxyl and amino functional groups, or preferably the amine comprises at least one selected from the group of a fatty (poly)amine, fatty amido (poly)amine, fatty imidazoline, fatty imidazo (poly)amine, fatty (poly) ester amine, fatty (poly) quaternized ammonium salt, aminoethylethanolamine, methanolamine, ethanolamine, N-methylethanolamine, dimethylethanolamine, ethylethanolamine, diethylethanolamine, propylethanolamine, dipropylethanolamine, butylethanolamine, dibutylethanolamine, diethanolamine, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, triethanolamine, isobutanol-2-amine, valinol, alaninol, hydroxyethylpiperazine and combinations thereof.

[0134] In a thirteenth aspect applicable to aspects 1-12, the collector composition further comprises a defoamer, preferably at a concentration of up to about 5 wt, preferably less than about 5 wt%, more preferably at least about 1 wt%, further preferably at least about 1.5 wt% based on the weight of the collector composition.

[0135] In a fourteenth aspect applicable to aspects 1-13, a weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof to the at least one hydroxamic acid or hydroxamate comprises more than about 20:1, preferably more than about 22:1, more preferably more than about 25:1, further preferably at least about 27:1, even more preferably at least about 30:1.

[0136] In a fifteenth aspect applicable to aspects 1-14, the at least one fatty acid, fatty acid derivative and combinations thereof comprises a vegetable fatty acid;

[0137] In a sixteenth aspect applicable to aspects 1-15, the at least one fatty acid, fatty acid derivative and combinations thereof comprise, consist essentially of, or consist of, tall oil fatty acid.

[0138] A seventeenth aspect includes a collector composition, preferably for industrial minerals, more preferably a phosphate, lithium or rare earth collector composition, further preferably a lithium collector composition, comprising a. at least one fatty acid, fatty acid derivative and combinations thereof; and b. at least one hydroxamic acid or hydroxamate wherein the at least one fatty acid, fatty acid derivative and combinations thereof comprise from about 0.5 % to about 20% of a mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives, preferably an amount of the mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives comprises less than about 20 wt%, more preferably less than about 15 wt%, further preferably less than 14 wt%, even further preferably less than about 10 wt%, even more preferably less than about 5 wt%; or preferably the collector composition comprises the mixture of C16:0 and C18:0 fatty acids and / or fatty acid derivatives in the amount of about 0.5 wt% to about 4 wt%, or about 4 wt% to about 8 wt%, or about 8 wt% to about 12 wt%, or about 12 wt% to 14 wt%, or 14 wt% to about 16 wt%, or about 16 wt% to no more than about 20 wt% or combinations thereof.

[0139] In an eighteenth aspect applicable to aspects 17, the at least one fatty acid, fatty acid derivative and combinations thereof comprises at least one of soya oil fatty acid, canola fatty acid, tall oil fatty acid, oleic fatty acid and combinations thereof, preferably comprising at least 2 selected from the group of the soya oil fatty acid, the canola fatty acid, the oleic fatty acid and the tall oil fatty acid.

[0140] In a nineteenth aspect applicable to aspects 1-18, a. an amount of the hydroxamic acid or hydroxamate comprises (or is) no more than about 4 wt% of the collector composition, preferably less than about 4 wt%, more preferably less than about 3 wt%, further preferably less than about 2.5 wt%, even more preferably at least about 1 wt%, even further preferably at least about 1.5 wt% or b. the collector composition comprises the at least one hydroxamic acid or hydroxamate in an amount of about 0.5 wt% to about 1.0 wt%, about 1.0 wt% to about 2.0 wt%, about 2.0 wt% to about 3.0 wt%, about 3.0 wt% to about 4.0 wt% and / or c. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) at least about 5:1, preferably at least about 10:1, more preferably at least 20:1, even more preferably up to about 60:1, further preferably up to about 50:1, even further preferably up to about 40:1, and most preferably up to about 30:1; or d. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) from more than about 5:1 to about 10.1, or from about 10:1 to about 15:1, or about 15:1 to about 20:1, or about 20:1 to about 25:1, or about 25:1 to about 30:1, or about 30:1 to about 35: 1, or about 35:1 to about 40:1, or about 40:1 to about 45:1, or about 45: 1 to about 50:1, or about 50:1 to about 55:1, or about 55:1 to about 60:1, or combinations thereof; or e. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) more than about 5:1, preferably at least about 10:1, more preferably no more than about 20:1; or f. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate comprises (or is) more than about 5:1 to about 10:1, or about 10:1 to about 15:1, or about 15:1 to no more than about 20:1, or combinations thereof; wherein g. preferably the at least one hydroxamic acid or hydroxamate comprises an aliphatic compound and / or the hydroxamic acid has an acid number of at least about 5 to about 100, preferably about 25 to about 90, more preferably about 40 to about 80, further preferably about 50 to about 70 or the acid number comprises at least one from about 5 to about 15, about 15 to about 25, about 25 to about 35, about 35 to about 45, about 45 to about 55, about 55 to about 65, about 65 to about 75, about 75 to about 85, about 85 to about 95, the acid number determined by the titration test and having the units of mg KOH / g.

[0141] In a twentieth aspect applicable to aspects 17-19, a. the fatty acid, fatty acid derivative and combinations thereof comprises no more than 95 wt% of tall oil fatty acid, preferably less than about 55 wt%, more preferably less than about 19 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt% based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition; or b. the collector composition comprises the tall oil fatty acid in an amount of about 1 wt% to about 5 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 15 wt%, or about 15 wt% to less than about 19%, or about 19 wt% to about 23 wt%, or about 23 wt% to about 27 wt%, or about 27 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to about 50 wt%, or about 50 wt% to about 55 wt%, or about 55 wt% to about 58 wt%, or about 58 wt% to about 61 wt%, or about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or about 70 wt% to about 75 wt%, or about 75 wt% to about 80 wt%, or about 80 wt% to about 85 wt%, or about 85 wt% to about 90 wt%, or about 90 wt% to about 95 wt% or combinations thereof, based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition; and / or c. the collector composition comprises a tall oil fatty acid and the weight ratio of the tall oil fatty acid to a sulfonate compound is about 20:1 to about 1:2.5, preferably at least one of no more than about 15: 1, no more than about 10:1, no more than about 8:1, or no more than about 4:1, or no more than about 3:1, or no more than about 1:1, or about 1:1, or less than about 1:2, or combinations thereof (such as from no more than about 15:1 to about 1:2.5, or from no more than about 10:1 to about 1:2.5, or from no more than about 8:1 to about 1:2.5, or from no more than about 4:1 to about 1:2.5, or from no more than about 3:1 to about 1:2.5, or from no more than about 2:1 to about 1:2.5, or from about 1:1 to about 1:2.5, or from less than about 1:2 to about 1:2.5).

[0142] In a twenty-first aspect applicable to aspects 17-20, the collector composition is devoid of tall oil fatty acid.

[0143] In a twenty-second aspect applicable to aspects 17-21, a. the fatty acid, fatty acid derivative and combinations thereof comprises less than 70 wt% of oleic fatty acid, preferably less than about 55 wt%, more preferably less than about 30 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt% based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition; or b. the collector composition comprises the oleic fatty acid in an amount of about 1 wt% to about 5 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 15 wt%, or about 15 wt% to about 19, or about 19 wt% to about 23 wt%, or about 23 wt% to about 27 wt%, or about 27 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to about 50 wt%, or about 50 wt% to about 55 wt%, or about 55 wt% to about 58 wt%, or about 58 wt% to about 61 wt%, or about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or combinations thereof, based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition.

[0144] In a twenty-third aspect applicable to aspects 17-22, a. the fatty acid, fatty acid derivative and combinations thereof comprises less than 70 wt% of canola fatty acid, preferably less than about 55 wt%, more preferably less than about 30 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt% based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition; or b. the collector composition comprises the canola fatty acid in an amount of about 1 wt% to about 5 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 15 wt%, or about 15 wt% to about 19, or about 19 wt% to about 23 wt%, or about 23 wt% to about 27 wt%, or about 27 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to about 50 wt%, or about 50 wt% to about 55 wt%, or about 55 wt% to about 58 wt%, or about 58 wt% to about 61 wt%, or about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or combinations thereof, based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition.

[0145] In a twenty-fourth aspect applicable to aspects 17-23, a. the fatty acid, fatty acid derivative and combinations thereof comprises less than 70 wt% of soya oil fatty acid, preferably less than about 55 wt%, more preferably less than about 30 wt%, further preferably less than about 15 wt%, even more preferably less than about 10 wt%, even further preferred less than about 1 wt% based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition; or b. the collector composition comprises the soya oil fatty acid in an amount of about 1 wt% to about 5 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 15 wt%, or about 15 wt% to about 19, about 19 wt% to about 23 wt%, or about 23 wt% to about 27 wt%, or about 27 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to about 50 wt%, or about 50 wt% to about 55 wt%, or about 55 wt% to about 58 wt%, or about 58 wt% to about 61 wt%, or about 61 wt% to about 65 wt%, or about 65 wt% to about 70 wt%, or combinations thereof, based on an amount of the fatty acid, fatty acid derivative and combinations thereof in the collector composition.

[0146] In a twenty-fifth aspect applicable to aspects 17-24, an acid number of the at least one fatty acid, fatty acid derivative and combinations thereof is at least about 100 up to about 280, preferably about 170 to about 210, more preferably about 180 to about 205.

[0147] In a twenty-sixth aspect applicable to aspects 17-25, the collector composition further comprises a sulfonate compound, preferably the sulfonate compound comprises at least one selected from sodium sulfonates, petroleum sulfonates and its derivatives, sulfonated fatty acids and its derivatives, and combinations thereof, preferred examples of petroleum sulfonates may include natural petroleum sulfonates and synthetic petroleum sulfonates, further preferred petroleum sulfonates include at least one of alkyl sulfonates, alkyl aryl sulfonates, alkyl xylene sulfonates and α-olefin sulfonates and combinations thereof, preferably the sodium sulfonate comprises sodium alkylbenzenesulfonate comprising a straight-chain alkylbenzenesulfonic acid; and / or a. the collector composition comprises the sulfonate compound in an amount of at least about 0.5 wt% to about 2 wt%, about 2 wt% to about 5 wt%, about 5 wt% to about 15 wt%, about 15 wt% to about 25 wt%, about 25 wt% to about 35 wt%, about 35 wt% to about 45 wt%, about 45 wt% to about 55 wt%, about 55 wt% to about 65 wt%, about 65 wt% to about 75 wt% and combinations thereof; or b. the collector composition comprises more than about 5 wt% to less than about 70 wt%, preferably at least about 10 wt%, to up to about 65 wt%, more preferably at least about 15 wt% to up to about 55 wt%, further preferably more than 20 wt% to up to about 50 wt%, of the sulfonate compound; and / or c. wherein the collector composition comprises a tall oil fatty acid and the weight ratio of the tall oil fatty acid to a sulfonate compound is about 20:1 to about 1:2.5, preferably at least one of no more than about 15:1, no more than about 10:1, no more than about 8:1, or no more than about 4:1, or no more than about 3:1, or no more than about 1:1, or about 1:1, or less than about 1:2, or combinations thereof (such as from no more than about 15:1 to about 1:2.5, or from no more than about 10:1 to about 1:2.5, or from no more than about 8:1 to about 1:2.5, or from no more than about 4:1 to about 1:2.5, or from no more than about 3:1 to about 1:2.5, or from no more than about 2:1 to about 1:2.5, or from about 1:1 to about 1:2.5, or from less than about 1:2 to about 1:2.5).

[0148] In a twenty-seventh aspect applicable to aspects 17-26, a weight ratio of the fatty acid, fatty acid derivative and combinations thereof to hydroxamic acid or hydroxamate a. comprises more than about 10:1, preferably at least about 15:1, further preferably at least about 20:1, more preferably at least about 22:1, even more preferably at least about 25:1; or b. comprises more than about 10:1 to about 15:1, or about 15:1 to about 20:1, or about 20.1 to about 22:1, or about 22:1 to about 25:1.

[0149] In a twenty-eighth aspect applicable to aspects 17-27, the at least one fatty acid, fatty acid derivative and combinations thereof comprises tall oil fatty acid.

[0150] In a twenty-nineth aspect applicable to aspects 17-28, the at least one fatty acid, fatty acid derivative and combinations thereof consists essentially of tall oil fatty acid.

[0151] In a thirtieth aspect applicable to aspects 17-29, the at least one fatty acid, fatty acid derivative and combinations thereof consists of tall oil fatty acid.

[0152] A thirty-first aspect includes a beneficiation process for separating impurities from lithium containing ore. The process includes pulping the ore to produce an ore slurry; reagentizing the ore slurry to produce a reagentized slurry by adding: a collector of aspects 1 to 30. The process may also include separating at least some of the impurities from the lithium and collecting the lithium in the form of a concentrate.

[0153] Regarding a thirty-second aspect applicable to aspect 31, the reagentizing of the eleventh aspect does not include introducing a separate lithium depressant.

[0154] In a thirty-third aspect, applicable to either of aspect 31 or 32, the reagentizing the ore slurry further comprises adding a pH modifier.

[0155] In a thirty-fourth aspect, applicable to anyone of aspects 31-33, the reagentizing further comprises separately adding at least one of (a) the fatty acid or fatty acid derivative (b) the hydroxamic acid or hydroxamate and (c) optionally the sulfonate compound.

[0156] In a thirty-fifth aspect, applicable to anyone of aspects 31-34 the process further comprises combining at least two of (a) the fatty acid or fatty acid derivative, (b) the hydroxamic acid or hydroxamate and (c) optionally the sulfonate compound prior to being added to the ore slurry.

[0157] A thirty-sixth includes a flotation method for removing gangue from lithium containing ores. The method includes producing an ore slurry comprising lithium containing ore and a collector. The collector may be a collector of any one of aspect 1 to 30. The method also includes subjecting the ore slurry to flotation.

[0158] In a thirty-seventh aspect, the ore slurry of aspect 36 further comprises a pH modifier.

[0159] In a thirty-eighth aspect, applicable to either one of aspects 36 or 37 wherein the subjecting the ore slurry to flotation produces an underflow and an overflow, the method further comprising: separating one of the overflows or the underflow as the gangue; and collecting the other of the underflow or the overflow as lithium concentrate.

[0160] In a thirty-nineth aspect, the composition of any one of aspects 1-30, the composition is used for the beneficiation of a rare earth.Examples

[0161] The present invention is further illustrated by the following examples. In order that those skilled in the field may better understand how the present invention can be practiced, the following examples are given by way of illustration only and not necessarily by way of limitation.

[0162] The viscosities were taken using an AMETEK Brookfield DV1 Digital Viscometer (Model: DV1MRVTJO) with a small sample adapter. The temperature was controlled using a Brookfield TC-650MX-115 circulating refrigerated bath. The spindle used was the SC4-21 inside the CS4-13R sample chamber. The highest RPM level on the viscometer was used to the point that the machine would not report errors. Maximum RPMs is 100 RPM, and the minimum is 0.5 RPM. In the case the reported value is NA, the viscosity was too high to measure.

[0163] Tables 1-3 and Figure 1 illustrate the effect of petroleum sulfonate with canola fatty acid and soya fatty acid (AKA soya oil fatty acid) in adjusting the fatty acids for use in collector compositions. As illustrated in the Tables, petroleum sulfonate is very thick in its native form. Likewise, canola fatty acid and soya fatty acid have high viscosities (greater than 1000 cP) at temperatures of 15.6°C or below. Surprisingly it is illustrated below in Tables 1-3 and Figure 1 how the addition of petroleum sulfonate to canola fatty acid, soya fatty acid and combinations thereof, may reduce the viscosity of mixture.

[0164] Preferred C16:0 + C18:0 fatty acids are fatty acids having a GC area% of less than 14%. Preferred examples have a viscosity of less than about 3000 cP across the temperature range shown in Table 5, preferably less than about 1500 cP, more preferably less than about 1000 cP. The GC area % represents the wt% of the compound(s) in the sample.

[0165] Table 4 shows that the addition of hydroxamic acid has little effect on viscosity of fatty acid. The hydroxamic acid used in this example is an alkyl hydroxamic acid having a C6-C16 straight chain.

[0166] Tables 1-3 illustrate the effect the sulfonate compound has on soya oil fatty acid and canola fatty acid in reducing the viscosity of either fatty acid alone or both as a 50 / 50 mixture of the fatty acids. Table 1 illustrates the addition of up to 50 wt% of the sulfonate compound and the canola fatty acid has reduced viscosity at temperatures of up to at least about 15.6°C. Table 2 illustrates the benefit of using the sulfonate compound with soya oil fatty acid. The mixtures of soya oil fatty acid and the sulfonate compound exhibited reduced viscosity at all temperatures up to at least about 15.6°C. Regarding mixtures of canola fatty acid, soya oil fatty acid and the sulfonate compound, the mixtures had a reduced viscosity for all mixtures at temperatures up to at least about 15.6°C. Table 4 illustrates how minimizing the total amount of C16:0 and C18:0 reduces the viscosity of the mixture as well as the combination of hydroxamic acid with the C16:0 and C18:0 fatty acids does not increase the viscosity of the mixture to a level which the mixture is unsuitable for use as a collector composition.

[0167] While this invention has been described in detail with reference to certain preferred embodiments, it should be appreciated that the present disclosure is not limited to those precise embodiments. Rather, in view of the present disclosure, many modifications and variations would present themselves to those skilled in the art without departing from the scope and spirit of this invention. Table 1Viscosity (cP) Measured at various temperature (°C)Temperature (°C) ((°F))4.4°C ((40°F))10.0°C ((50°F))15.6°C ((60°F))Petroleum sulfonateNANANACanola fatty acid100000854001080Soya fatty acidNA92005420Canola fatty acid + petroleum sulfonate (75:25)11310594Canola fatty acid + petroleum sulfonate (50:50)73502160590Canola fatty acid + petroleum sulfonate (25:75)NANA16640 Table 2 Viscosity (cP) Measured at various temperature (°C)Temperature (°C) ((°F))4.4°C ((40°F))10.0°C ((50°F))15.6 °C ((60°F))Petroleum sulfonateNANANACanola fatty acid100000854001080Soya fatty acidNA92005420Soya fatty acid + petroleum sulfonate (75:25)14270307206Soya fatty acid + petroleum sulfonate (50:50)972050801075Soya fatty acid + petroleum sulfonate (25:75)835052903190 Table 3 Viscosity (cP) Measured at various temperature (°C)Temperature (°C) ((°F))4.4°C ((40°F))10.0°C ((50°F))15.6°C ((60°F))Petroleum sulfonateNANANACanola fatty acid100000854001080Soya fatty acidNA92005420Canola fatty acid + soya fatty acid (50:50)NANA2890Mixture of canola fatty acid + soya fatty acid (50:50) + petroleum sulfonate (75:25)459001118277Mixture of canola fatty acid + soya fatty acid (50:50) + petroleum sulfonate (50:50)73502160590Mixture of canola fatty acid + soya fatty acid (50:50) + petroleum sulfonate (25:75)740043202675 Table 4 Effect of C16:0 (palmitic acid) + C18:0 (stearic acid) on viscosityViscosity (cP) Measured at various temperature (°C)Temperature (°C) ((°F))4.4°C ((40°F))10.0°C ((50°F))15.6°C ((60°F))Fatty acid acid number: 1971775543C16:0 + C18:0 = 3.5 GC area%Fatty acid acid number: 1973166448C16:0 + C18:0 = 3.5 GC area% + 4% hydroxamic acid *Fatty acid acid number: 2084665845C16:0 + C18:0 = 6.1 GC area%Fatty acid acid number: 2012075347109C16:0 + C18:0 = 9.5 GC area%Fatty acid acid number: 202NA4650257C16:0 + C18:0 = 14.4 GC area%Fatty acid acid number: 198NA92005420C16:0 + C18:0 = 18.0 GC area%(*) Effect of hydroxamic acid on fatty acid

Examples

examples

Examples

[0161]The present invention is further illustrated by the following examples. In order that those skilled in the field may better understand how the present invention can be practiced, the following examples are given by way of illustration only and not necessarily by way of limitation.

[0162]The viscosities were taken using an AMETEK Brookfield DV1 Digital Viscometer (Model: DV1MRVTJO) with a small sample adapter. The temperature was controlled using a Brookfield TC-650MX-115 circulating refrigerated bath. The spindle used was the SC4-21 inside the CS4-13R sample chamber. The highest RPM level on the viscometer was used to the point that the machine would not report errors. Maximum RPMs is 100 RPM, and the minimum is 0.5 RPM. In the case the reported value is NA, the viscosity was too high to measure.

[0163]Tables 1-3 and Figure 1 illustrate the effect of petroleum sulfonate with canola fatty acid and soya fatty acid (AKA soya oil fatty acid) in adjusting the fatty acids for ...

Claims

1. A collector composition, preferably a phosphate, lithium or rare earth collector composition, more preferably a lithium collector composition comprising a. at least one fatty acid, fatty acid derivative and combinations thereof; b. at least one hydroxamic acid or hydroxamate; c. a sulfonate compound, wherein i. the sulfonate compound is in an amount of at least about 0.5 wt% to about 75 wt% of the collector composition, preferably 1. the collector composition comprises the sulfonate compound in an amount of at least about 0.5 wt% to about 2 wt%, or about 2 wt% to about 5 wt%, or about 5 wt% to about 15 wt%, or about 15 wt% to about 25 wt%, or about 25 wt% to about 35 wt%, or about 35 wt% to about 45 wt%, or about 45 wt% to about 55 wt%, or about 55 wt% to about 65 wt%, or about 65 wt% to about 75 wt% or combinations thereof; or 2. the collector composition comprises the sulfonate compound in an amount more than about 5 wt% to less than about 70 wt%, more preferably more than about 10 wt% to about 65 wt%, further preferably more than about 15 wt% to about 55 wt%, even further preferably more than 20 wt% to about 50 wt%; and / or ii. a weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof to the sulfonate compound is about 12:1 to about 1:2.5, preferably the weight ratio is at least one of no more than about 8:1, no more than about 4:1, or no more than about 3:1, or no more than about 2:1, or no more than about 1:1, or about 1:1, or less than about 1:2.

2. The collector composition of claim 1 wherein the sulfonate compound comprises a compound having a viscosity of greater than 1000 cP at 60°F (15°C), preferably a viscosity of greater than about 5000 cP.

3. The collector composition of claim 1 or 2 wherein the sulfonate compound comprises at least one selected from sodium sulfonates, petroleum sulfonates and its derivatives, sulfonated fatty acids and its derivatives, and combinations thereof, preferred examples of petroleum sulfonates may include natural petroleum sulfonates and synthetic petroleum sulfonates, further preferred petroleum sulfonates include at least one of alkyl sulfonates, alkyl aryl sulfonates, alkyl xylene sulfonates and α-olefin sulfonates and combinations thereof, preferably the sodium sulfonate comprises sodium alkylbenzenesulfonate, comprising a straight-chain alkylbenzenesulfonic acid.

4. The collector composition of any one of the preceding claims wherein the at least one fatty acid, fatty acid derivative and combinations thereof have a viscosity of greater than 1000 cP at 60°F (15°C) and an acid number of at least about 100 up to about 280 mg KOH / g, under a titration test, preferably the acid number comprises at least about 170, more preferably at least about 180, further preferably no more than about 220, even further preferably no more than about 210.

5. The collector composition of any one of the preceding claims wherein the at least one fatty acid, fatty acid derivative and combinations thereof comprises a soya oil fatty acid, preferably a. the collector composition comprises the soya oil fatty acid in an amount of at least 5 wt% based on the weight of the collector composition, further preferably at least about 10 wt%, even more preferably at least about 15 wt%, even further preferably at least about 20 wt%, and most preferably no more than about 50 wt%; or b. the collector composition comprises the soya oil fatty acid in the amount of at least about 5 wt% to about 15 wt%, or about 15 wt% to about 25 wt%, or about 25 wt% to about 35 wt%, or about 35 wt% to about 45 wt%, or about 45 wt% to no more than about 50 wt% or combinations thereof; and / or c. a weight ratio of the soya oil fatty acid to the sulfonate compound is about 12:1 to about 1:2.5, preferably at least one of no more than about 8:1, no more than about 4:1, or no more than about 3:1, or no more than about 2:1, or no more than about 1:1, or about 1:1, or less than about 1:2.

6. The collector composition of any one of the preceding claims wherein the at least one fatty acid, fatty acid derivative and combinations thereof comprises a canola fatty acid, preferably a. the collector composition comprises the canola fatty acid in an amount of at least 5 wt% based on the weight of the collector composition, further preferably at least about 15 wt%, even more preferably at least about 20 wt%, even further preferably at least about 30 wt%, and most preferably no more than about 60 wt% or b. the collector composition comprises the canola fatty acid in the amount of at least about 5 wt% to 10 wt%, or 10 wt% to 15 wt%, or 15 wt% to 20 wt%, or 20 wt% to 25 wt%, or 25 wt% to 30 wt%, or 30 wt% to 35 wt%, or 35 wt% to 40 wt%, or 40 wt% to 45 wt%, or 45 wt% to 50 wt%, or 50 wt% to 55 wt%, or 55 wt% to less than 60 wt%, or combinations thereof; and / or c. a weight ratio of the canola fatty acid to the sulfonate compound is about 12:1 to about 1:2.5, preferably at least one of no more than about 8:1, no more than about 4:1, or no more than about 3:1, or no more than about 2:1, or no more than about 1:1, or about 1:1, or less than about 1:2.

7. The collector composition of any one the preceding claims, comprising hydroxamic acid or hydroxamate in an amount of no more than 10 wt% of the collector composition, preferably the collector composition comprises the at least one hydroxamic acid or hydroxamate in either an amount (in wt%) or a weight ratio such that: i. the amount of hydroxamic acid or hydroxamate is no more than about 4 wt% based on the weight of the collector composition, preferably less than about 4 wt%, more preferably less than about 3 wt%, further preferably less than about 2.5 wt%, even more preferably at least about 1 wt%, even further preferably at least about 1.5 wt% or ii. the amount of hydroxamic acid or hydroxamate is about 0.5 wt% to about 1.0 wt%, or about 1.0 wt% to about 2.0 wt%, or about 2.0 wt% to about 3.0 wt%, or about 3.0 wt% to less than about 4.0 wt%; and / or iii. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate is at least about 5:1, preferably at least about 10:1, more preferably at least 20:1, even more preferably up to about 60:1, further preferably up to about 50: 1, even further preferably up to about 40: 1, and most preferably up to about 30:1; or iv. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate is from more than about 5:1 to about 10.1, or from about 10:1 to about 15:1, or about 15:1 to about 20:1, or about 20:1 to about 25:1, or about 25:1 to about 30: 1, or about 30:1 to about 35:1, or about 35:1 to about 40:1, or about 40:1 to about 45:1, or about 45:1 to about 50:1, or about 50:1 to about 55:1 or about 55:1 to about 60:1, or combinations thereof; or v. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate is more than about 5:1, preferably at least about 10:1, more preferably no more than about 20:1; or vi. the weight ratio of the at least one fatty acid, fatty acid derivative or combinations thereof to the hydroxamic acid or hydroxamate is more than about 5:1 to about 10:1, or about 10:1 to about 15:1, or about 15:1 to no more than about 20:1, or combinations thereof; wherein: a. preferably the at least one hydroxamic acid or hydroxamate comprises an aliphatic compound, and / or b. preferably the hydroxamic acid has an acid number of at least about 5 to about 100, preferably about 25 to about 90, more preferably about 40 to about 80, further preferably about 50 to about 70; or the acid number is from about 5 to about 15, or about 15 to about 25, or about 25 to about 35, or about 35 to about 45, or about 45 to about 55, or about 55 to about 65, or about 65 to about 75, or about 75 to about 85, or about 85 to about 95 or combinations thereof; the acid number being determined by the titration test and having the units of mg KOH / g of test specimen.

8. The collector composition of any one of preceding claims 4-7, wherein a weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof, having a viscosity of greater than 1000 cP at 60°F (15°C) and an acid number of at least about 100 up to about 220 mg KOH / g, to the at least one hydroxamic acid or hydroxamate is more than about 5:1, preferably at least about 10:1, more preferably no more than about 20:1.

9. The collector composition of any one of the preceding claims comprising a. less than 70 wt% of tall oil fatty acid, preferably less than about 50 wt%, more preferably less than about 25 wt%, further preferably less than about 19 wt%, even more preferably less than about 15 wt%, even further preferred less than about 1 wt%, based on the weight of the collector composition; or b. the collector composition comprises the tall oil fatty acid in the amount of at least about 0.5 wt% to about 4.0 wt%, or about 4.0 wt% to about 8 wt%, or about 8 wt% to about 12 wt%, or about 12 wt% to about 16 wt%, or about 16 wt% to about 20 wt%, or about 20 wt% to about 24 wt%, or about 24 wt% to about 28 wt%, or about 28 wt% to about 32 wt%, or about 32 wt% to about 36 wt%, or about 36 wt% to about 40 wt%, or about 40 wt% to about 44 wt%, or about 44 wt% to about 48 wt%, or about 48 wt% to about 52 wt%, or about 52 wt% to about 56 wt%, or about 56wt% to about 59 wt%, or about 59 wt% to about 62 wt%, or about 62 wt% to about 65 wt%, or about 65 wt% to 70 wt% or combinations thereof; and / or c. a weight ratio of the tall oil fatty acid to the sulfonate compound comprises about 12:1 to about 1:2.5, preferably at least one of no more than about 8:1, no more than about 4: 1, or no more than about 3: 1, or no more than about 2: 1, or no more than about 1: 1, or about 1:1, or less than about 1:2, or combinations thereof; d. preferably the tall oil fatty acid comprises no more than about 20 wt% of a mixture of C16:0 and C18:0 fatty acid and / or fatty acid derivative, preferably no more than 14 wt%, more preferably no more than about 10 wt%, further preferably no more than about 5 wt%, even further preferably no more than about 2.5 wt%.

10. The collector composition of any one of the preceding claims wherein a. the at least one fatty acid, fatty acid derivative and combinations thereof comprises a blend of fatty acids and the blend of fatty acids comprises at least about 10 wt% of oleic fatty acid based on the weight of the collector composition, preferably at least about 15 wt%, more preferably at least 20 wt%, further preferably at least about 25 wt%, even more preferably at least about 30 wt%, even further preferably no more than about 50 wt%; or b. the at least one fatty acid, fatty acid derivative and combinations thereof comprises oleic fatty acid, preferably the collector composition comprises the oleic fatty acid in the amount of about 1 wt% to about 5 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 15 wt%, or about 15 wt% to about 20 wt%, or about 20 wt% to about 25 wt%, or about 25 wt% to about 30 wt%, or about 30 wt% to about 35 wt%, or about 35 wt% to about 40 wt%, or about 40 wt% to about 45 wt%, or about 45 wt% to no more than about 50 wt% or combinations thereof.

11. The collector composition of any one of the preceding claims wherein the collector composition at 60°F (15°C) having a viscosity of less than 1000 cP, preferably less than about 850 cP, more preferably less than about 700 cP, further preferably less than about 600 cP, even more preferably less than about 200 cP, further preferably less than about 125 cP, and most preferably less than about 80 cP.

12. The collector composition of any one of the preceding claims further comprising at least one amine, preferably the amine comprises both hydroxyl and amino functional groups, or preferably the amine comprises at least one selected from the group of a fatty (poly)amine, fatty amido (poly)amine, fatty imidazoline, fatty imidazo (poly)amine, fatty (poly) ester amine, fatty (poly) quaternized ammonium salt, aminoethylethanolamine, methanolamine, ethanolamine, N-methylethanolamine, dimethylethanolamine, ethylethanolamine, diethylethanolamine, propylethanolamine, dipropylethanolamine, butylethanolamine, dibutylethanolamine, diethanolamine, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, triethanolamine, isobutanol-2-amine, valinol, alaninol, hydroxyethylpiperazine and combinations thereof.

13. The collector composition of any one of the preceding claims further comprising a defoamer, preferably at a concentration of up to about 5 wt, preferably less than about 5 wt%, more preferably at least about 1 wt%, further preferably at least about 1.5 wt% based on the weight of the collector composition.

14. The collector composition of any one of the preceding claims wherein a weight ratio of the at least one fatty acid, fatty acid derivative and combinations thereof to the at least one hydroxamic acid or hydroxamate comprises more than about 20:1, preferably more than about 22:1, more preferably more than about 25: 1, further preferably at least about 27: 1, even more preferably at least about 30:1.

15. The collector composition of any one of the preceding claims wherein the at least one fatty acid, fatty acid derivative and combinations thereof comprises a vegetable fatty acid; preferably the at least one fatty acid, fatty acid derivative and combinations thereof comprise, consist essentially of, or consist of, tall oil fatty acid.

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