Compositions and methods for froth modification

Abstract

Modifier compositions, improved sparge compositions for froth flotation separation containing the modifier compositions, and improved methods of froth flotation using the modifier compositions have been developed, as well as kits including the modifier composition for industrial use. The modifier compositions obtain both improved yield and a higher grade of a targeted mineral product in froth flotation of one or more phosphate, lithium, and / or iron ores, while avoiding excess foam formation during the flotation.

Description

COMPOSITIONS AND METHODS FOR FROTH MODIFICATIONBACKGROUND(00011 Many minerals and other materials are obtained from mining and other resource recovery operations as an intimate mixture that is difficult to separate into its constituents. For example, ores as mined are often multimineralic, and contain at least one desired component, a beneficiary, and one or more other less valuable and / or desirable materials, a gangue.

[0002] hi a beneficiation process, two or more materials that coexist in a mixture are separated from each other to obtain a beneficiary in a more concentrated form than that which exi sted in the mix ture. One form of beneficiation is froth flotation separation.

[0003] In froth flotation separation of a mineral ore, the ore is finely ground (comminuted) to form a comminuted ore in the form of a paniculate. The comminuted ore is slurried in a liquid medium, typically water, to make a slurry that is a sparge composition. Other components that assist in the separation of beneficiary from gangue can be included in the sparge composition, components such as collectors, modifiers, depressants, frothers (frothing agents), and / or activators.

[0004] In a process known as sparging, a gas, typically air, is bubbled through the sparge composition, and a froth forms at the surface of the sparge composition. During sparging, some materials from the ore such as targeted particles are carried up with the gas bubbles (i.e. floated) and concentrate in the froth, whereas other materials concentrate in the body of the liquid, the underflow.

[0005] The role of a collector is to assist the flotation of targeted particles in the sparge composition. The role of a depressant is to hinder or prevent the flotation of untargeted particles in the sparge composition.| WM16] When the sparge composition is sparged, bubbles associate with the more hydrophobic particles present in the ore, and rise up out of the slurry; and the associated bubble-particle composite forms a layer, referred to as a “froth” or “overflow”. The overflow is accordingly partitioned from and situated above an underflow. The underflow includes ore solids that are less hydrophobic than the particles that form the froth. The overflow may bedeposited on a launder. The less hydrophobic material remains behind in the underflow, thereby accomplishing the froth flotation separation.1'0007] Two common forms of flotation separation processes are direct flotation and reverse flotation. In direct flotation processes the froth comprises the beneficiary or concentrate, while in reverse flotation processes the froth comprises gangue or tailings. The object of the flotation in both forms of froth flota tion is to separa te and recover as much as possible of the beneficiary’ from the particulate material in as high a concentration of that beneficiary as possible. In froth flotation, a sparge composition is sparged to form a froth layer and an underflow. In a direct froth flotation, the froth layer comprises a concentrated beneficiary (a concentrate), and the underflow comprises tailings (concentrated gangue), in reverse froth flotation, the froth layer comprises tailings and the underflow comprises a concentrated beneficiary. In direct froth flotation, the froth can comprise more beneficiary than gangue, and the tailings can comprise more gangue than beneficiary. In reverse froth flotation, the froth can comprise more gangue than beneficiary and the tailings can comprise more beneficiary than gangue.10008] Froth flotation separation can be used to separate solids from solids (such as the constituents of mine ore), and liquids or semi-solids front solids (such as the separation of bitumen from oil sands).

[0009] A prerequisite for flotation separation is the liberation of particles. For flotation of mineral ores, therefore, comminuting (grinding the solids up by such techniques as drygrinding, wet-grinding, and the like) is required io liberate minerals. Extensive grinding or comminution can result in better liberation of particles for foe separation of beneficiary and gangue in a froth flotation process.

[0010] Although the object of froth flotation is to separate and recover as much as possible of the beneficiary in as high a concentration as possible, in such processes there is a compromise between purity of concentrate and yield of the beneficiary. Adjustment of froth flotation conditions and / or materials can produce an improvement of purity at the expense of yield or visa-versa. Further, changes to foe chemistry or cell size used for the froth flotation process can cause excessive frothing during the froth flotation process, which has been observed to correlate to reduced grade and / or recovery (yield) of beneficiary, in addition to froth handling issues.[00.11] Further, over the past few decades, the need to process more minerals while lowering capital costs has led io an increase in the size of flotation cells, for example 0.03 n? to 1000 nr. This increase has created new challenges in the operation of industrial flotation cells, particularly in terms of froth removal, because the distance the froth must travel increases with an increase in the flotation cell diameter, which negatively impacts recovery.[0012| Accordingly, there is an ongoing need to provide improved compositions and methods of froth flotation that can be implemented in existing froth flotation installations for separation of beneficiaries from ores, it would be an advantage to provide improved methods and materials therefor for obtaining better yields and beter purity of beneficiaries. It would be an advantage to provide improved methods and / or compositions for froth flotation which do not cause excessive frothing during the froth flotation process accompanied by reduced grade and / or recovery (yield) of beneficiary and froth handling issues.SUMMARY

[0013] Disclosed in first embodiments herein are modifier compositions comprising, consisting essentially of or consisting of a mixture of one or more fatty acid triglycerides with one or more alkoxylated fatty alcohols. In some first embodiments, the weight proportion of the one or more fatty acid triglycerides to the one or more alkoxylated fatty alcohols in the mixture is between 100: 1 and 1 : 100.[0014| In any one or more modifier compositions of first embodiments, at least one of the one or more alkoxylated faty alcohols has a structure according to the formulaR'-O4CHR?-CHRs-Ok[CHR4>CHR*-OkR3whereinR’ is a linear, branched, or alicyclic C6-C30 saturated or unsaturated moiety,R\ R3, R\ R and Rsare independently selected from H or a C 1 -C5 linear or branched alkyl moiety, n is 0 or an integer between I and 100, m is 0 or an integer between I and 100, and the sum of n + m is at least 2.

[0015] In any one or more modifier compositions of first embodiments, the one or more alkoxyla ted faty alcohols comprises, consists essentially of, or consists of a first alkoxylated faty alcohol comprising R1that is a linear or branched C10-C20 moiety; and a secondaikoxylated fatty alcohol comprising R* that is a linear or branched C6-CI4 moiety. In some such embodiments, the first aikoxylated fatty alcohol comprises R7R\ and R!each of which is H, R5that is CH?, n that is between 1 and 35, and m that is between I and 35; and the second aikoxylated fatty alcohol comprises R3R\ and R* each of which is H, Rsthat is CH>, n that is between I and 35, and m that is between 1 and 35. In embodiments, the weight proportion of the first aikoxylated fatty alcohol to the second aikoxylated fatty alcohol in the mixture is 100: 1 to 1 : 100.

[0016] In any one or more modifier compositions of first embodiments, each of the one or more fatty acid triglycerides independently has a structure according to the formulawherein R7, Rs, and R3are independently selected from saturated or unsaturated C6-C30 linear, branched, or alicyclic moieties. In any one or more modifier compositions of first embodiments, one or more of R\ R\ and R3are C10-C20 moieties. In any one or more modifier compositions of first embodiments, one or more of R\ R% and Rsare linear. In any one or more modifier compositions of first embodiments, each of Rr, Rs, and R* are linear. In any one or more modifier compositions of first embodiments, one or more of R\ Rfi and R3are unsaturated. In any one or more modifier compositions of first embodiments, each of R’, Rs, and .R3are unsaturated. hr any one or more modifier compositions of first embodiments, one or more of R7, Rs, and R* are monounsaturated, in any one or more modifier compositions of first embodiments, one or more of R’, R\ and R'1include two or three unsaturated moieties.10017 ] In any one or more modifi er compositions of first embodiments, at least one of the one or more fatty acid triglycerides is derived from a plant source. Suitable plant sources include whole plants, seeds, stems, flowers, roots, or two or more thereof from cotton, flax, grape, hemp, safflower, olive, palm, peanut, rice, avocado, canola, coconut, com, sesame, soybean, sunflower, walnut, or any combination thereof.|0018j In any one or more modifier cornpositions of first embodiments, the modifier composition further includes a solvent. In any one or more modifier compositions of firstembodiments, the solvent comprises, consists essentially of, or consists of a hydrocarbon or mixture thereof. In any one or more modifier compositions of first embodiments, the solvent comprises, consists essentially of, or consists of water. In any one or more modifier compositions of first embodiments, the mixture of one or more fatty acid triglycerides with one or more alkoxylated fatty alcohols is present at 0.1 wt% to 99.9 wi% in a solvent.

[0019] Disclosed in second embodiments herein are sparge compositions comprising, consisting essentially of, or consisting of a mixture of: a medium comprising water; a mineral ore comprising a beneficiary and a gangue; a collector; and a modifier composition of any of first embodiments. In any one or more sparge compositions of second embodiments, the waler is fresh water or sea water. In any one or more sparge compositions of second embodiments, the mineral ore is a phosphate ore, a lithium ore, or an iron ore. In any one or more sparge compositions of second embodiments, the phosphate ore comprises an apatite, such as an apatite is selected from the group consisting of fluorapatite, hydroxyapatite, chlorapatite, or any combination thereof. In any one or more sparge compositions of second embodiments, the gangue comprises calcite, dolomite, a silicate, silica, a seashell or seashell portion, or any combination thereof. In any one or more sparge compositions of second embodiments, the weight proportion of the mineral ore to the modifier composition of any of first embodiments in the sparge composition is about 1000: 1 to 2:1 .10020] In any one or more sparge compositions of second embodiments, the sparge composition further includes a pH adjustment agent such as an acid selected from phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, citric acid, a polymeric acid, or any combination thereof; or a base selected from sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, or any combination thereof. Accordingly, in some sparge compositions of second embodiments, the sparge composition includes, is present at, or is adjusted to have a pH between 2.5 and 7; in other second embodiments, the sparge composition includes, is present at, or is adjusted to have a pH between 7 and 12.

[0021] In any one or more sparge compositions of second embodiments, the collector comprises, consists essentially of, or consists of one or more sulfonated fatty acids, one or more sulfonated fatty acid salts, or any combination thereof. In any one or more sparge compositions of second embodiments, the collector comprises, consists essentially of, or consists of a sulfonated oleic acid, a sulfonated oleic acid salt, sulfonated linoleic acid, a sulfonated linoleic acid salt, a sulfonated linolenic acid, a sulfonated linolenic acid salt, a sulfonated ricinoleicacid, a sulfonated ricmolcic add salt, a sulfonated palmitoleic acid, a sulfonated palmitoleic acid salt, a sulfonated 11 -eicosenoic acid, a sulfonated 1 1 -eicosenoic acid salt, a sulfonated erucic acid, a sulfonated erucic acid salt, a sulfonated nervonic acid, a sulfonated nervonic acid salt, or any combination thereof.10022] In any one or more sparge compositions of second embodiments, the sparge composition further includes a beneficiating agent. In any one or more sparge compositions of second embodiments, the beneficiating agent comprises, consists essentially of, or consists of one or more hydroxy fatty acids, one or more hydroxy fatty acid salts, or any combination thereof. In any one or more sparge compositions of second embodiments, the beneficiating agent comprises, consists essentially of, or consists of ricitioleic acid, a salt of ricmoleic acid, 12-hydroxystearic acid, a salt of 12-hydroxystearic acid, 9,l()-dihydroxyoctadecanoic acid, a salt of 9,i0-dihydroxyoctadecauoic acid, 9,i0,i8~trihydroxyoctadecanoic acid, a salt of 9,10,18-trihydroxyoctadecanoic acid, lesquerolic acid, a salt of lesquerolic acid, 15- hydroxyhexadecanoic acid, a salt of 15-hydroxyhexadecanoic acid, isorieinoleic acid, a salt of isortcinoleic acid, densipolic acid, a salt of densipolic acid, 14-hydroxy-eieosa-eis-l 1-cis-l 7- dicnoic acid, a salt of 14-hydroxy-eicosa-cis- 11 -cis-17-dienoic acid, 2-hydroxyoleic acid, a salt of 2-hydroxyoleic acid, 2-hydroxylinolcic acid, a salt of 2-hyclroxylmoleic acid, 18- hydroxystearic acid, a salt of 18-hydroxylinoleic acid, 15-hydroxylinoleic acid, a salt of 15- hydroxyhnoleic acid, or any combination thereof.

[0023] In any one or more sparge compositions of second embodiments, the sparge composition furtiter includes one or more emulsifying surfactants, one or more additional collectors, one or more depressants, one or more acti vators, one or more frothing agents, or any comb i nat i on rhe reo f.|0024] Disclosed in third embodiments herein are methods of froth flotation comprising, consisting essentially of, or consisting of combining a medium comprising water, a mineral ore comprising a beneficiary and a gangue, and a collector to form an ore slurry; adding a modifier composition of any of first embodiments to the ore slurry to form a sparge composition of second embodiments, and sparging the sparge composition to yield a sparged slurry comprising an overflow and an underflow. In any one or more methods of third embodiments, the sparging is carried out in a lab scale flotation cell. In any one or more methods of third embodiments, the method further includes collecting the overflow, collecting the underflow, or collecting both the overflow and the underflow.

[0025] In any one or more methods of third embodiments, the mineral ore is a phosphate ore, a lithium ore, or an iron ore. In any one or more methods of third embodiments where the mineral ore is a phosphate ore, the underflow includes a phosphate beneficiary, and the overflow includes a gangue. In any one or more methods of third embodiments, the gangue comprises one or more of a calcite, a dolomite, or a silica. In any one or more methods of third embodiments, the method further includes grinding the mineral ore prior to the combining.

[0026] In any one or more methods of third embodiments, the method further includes combining a pH adjustment agent with the ore slurry, or with the sparge composition prior to the sparging. In any one or more methods of third embodiments, the pH adjustment agent is selected from any one or more of the pH adjustment agents of second embodiments. Accordingly, in some methods of third embodiments, the method further inchides combining a pH adjustment agent with the ore slurry, or with the sparge composition prior to the sparging, in an amount sufficient to obtain a pH of about 2.5 to about 7; while in some other third embodiments, the method further includes combining a pH adjustment agent with the ore slurry, or with the sparge composition prior to the sparging, in an amount sufficient to obtain a pH of about 7 to about 12,

[0027] In any one or more methods of third embodiments, the collector is selected from any one or more of the collectors of second embodiments.

[0028] In any one or more methods of third embodiments, the method further includes adding a beneficiation agent to the mineral ore, to the medium, to the collector, or to the ore slurry, wherein the beneficiation agent is selected from any one or more of the beneficiation agents of second embodiments. In any one or more methods of third embodiments, the beneficiating agent is combined wi th one or more components of the ore slurry, or is combined with the ore slurry, prior to adding the modifier to the ore slurry to form a sparge composition in accordance with second embodiments herein. In any otic or more methods of third embodiments, the collector is mixed with the beneficiation agent, and the collector-beneficiation mixture is then combined with the mineral ore and the medium to form the ore slum.'.

[0029] la any one or more methods of t hird embodiments, adding the modifier composition to the ore slurry comprises, consists essentially of, or consists of admixing the modifier composition with a solvent, and adding the admixed modifier composition to the ore slurry. In some methods of third embodiments, the solvent comprises water and the admixed modifiercomposition includes 0.1 wt% to 99.9 wt% water, in some embodiments 0.1 wt% to 10 wt% water.10030] In any one or more methods of third embodiments, the method further includes adding one or more emulsifying surfactants, one or more additional collectors, one or more depressants, one or more activators, one or more frothing agents, or any combmation thereof to one or more of: the medium, the mineral ore, the collector, the ore slurry', or the sparge composition.(0031 ] Disclosed in fourth embodiments herein is the use of any one or more of the sparge compositions of second embodiments, which include a modifier composition in accordance with any one or more first embodiments herein, to refine a mineral ore using reverse froth flotation to provide a refined mineral ore.|0032] Disclosed in fifth embodiments herein are froth flotation processing kits comprising, consisting essentially of, or consisting of a modifier composition of first embodiments, and a collector composition comprising, consisting essentially of, or consisting of one or more sulfonated fatty acids, one or more sulfonated fatty1acid salts. In any one or more kits of fifth embodiments, the kit includes a modifier composition of first embodiments disposed within a first containment; and a collector composition disposed within a second containment. In any one or more kits of fifth embodiments, the modifier composition, the collector composition, or both the modifier composition and the collector composition further include a solvent. In any' one or more kits of fifth embodiments, the sol vent of the modifier composition is the same or different from the solvent of the collector composition,| 0033] hi any one or more froth flotation processing kits of fifth embodiments, a kit further includes a beneficiation agent. In any one or more such fifth embodiments, the beneficiation agent is present tn the kit as a mixture with the collector composition; or is disposed within a third containment. In embodiments where the beneficiation agent is provided in a third containment, the beneficiation agent optionally further includes a solvent, where the solvent may be the same or different from solvent of the modifier composition and / or the solvent of the collector composition.DETAILED DESCRIPTION10034] Although the present disclosure provides references to preferred embodiments, persons skilled in the art will recognize that changes may' be made in form and detail without departing from the spirit and scope of the in vention. Reference to various embodiments doesnot limit the scope of the claims attached hereto. Additionally, any examples set forth in this specification are not intended to be limiting and merely set forth some of the many possible embodiments for the appended claims.

[0035] Definitions

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In ease of conflict, the present document, inchiding definitions, will control.

[0037] As used herein, rhe terms “comprisc(s),” “include(s),” '‘having,” “has,” “can,” “eonlain(s),” and variants thereof are intended to be open-ended transitional phrases, terms, or words that do not preclude the possibility of additional acts or structures. The singular forms “a,” “and” and "the” include plural references unless the context clearly dictates otherwise. The present disclosure also contemplates other embodiments “comprising,” “consisting of and “consisting essentially of,” the embodiments or elements presented herein, whether explicitly set forth or not.

[0038] .As used herein, the term “optional” or “optionally” means that the subsequently described event or circumstance may but need not occur, and that the description includes instances where the event or circumstance occurs and instances in which it does not.

[0039] As used herein, the term “about” modifying, for example, the quantity of an ingredient in a composition, concentration, volume, process temperature, process time, yield, flow rate, pressure, and like values, and ranges thereof, employed in describing the embodiments of the disclosure, refers to variation in the numerical quantity' that can occur, for example, through typical measuring and handling procedures used for making compounds, compositions, concentrates or use formulations; through inadvertent error in these procedures: through differences in the manufacture, source, or purity of starting materials or ingredients used to carry out the methods, and like proximate considerations. The term “about” also encompasses amounts that differ due to aging of a formulation with a particular initial concentration or mixture, and amounts that differ due to mixing or processing a formulation with a particular initial concentration or mixture. Where modified by the term “about” the claims appended hereto include equivalents to these quantities.Further, where “about” is employed to describe a range of values, for example “about 1 to 5” or “about 1 to aboutthe recitation means “I to 5” and “about I to about 5” and “1 to about 5” and “about 1 to 5” unless specifically limited by context.(0040] As used herein, “ore” or “mineral ore” means a solid material of economic value that is obtained from a subterranean source by excavation, and also the refined or processed products of such solids. Excavation includes but is not limited to quarrying, open -cast mining, or pit mining. Ores include but arc not limited to rocks, minerals, mineral aggregates, metal compounds including both elemental forms of metal and compounds including metal atoms, and any rank of coal (peat, lignite, sub-bituminous, bituminous, or anthracite).(0041 ] As used herein, ‘"beneficiary” refers to the one or more economically valuable products present in a mineral ore as-mined, and also as separated from a mineral ore by refining and / or processing. Accordingly, “beneficiary” herein refers to the mineral(s) present in a mineral ore that are partitioned from a gangue, or are desirably partitioned from a gangue using froth flotation; and are desirably further collected for further purification, thermochemical conversion, or some other process to enable its economic value to be exploited.(0042 ] As used herein, “gangue” refers generally to materials of low or no commercial value that are present in a mineral ore as-mined, for example clay or feldspar; and also as separated from a beneficiary by refining and / or processing of a mineral ore, and also the materials of low or no commercial value desirably partitioned from the beneficiary in order to increase the yield and / or purity of the beneficiary that is collected. Accordingly, “gangue” refers to the one or more materials present in a mineral ore as-mined, that are partitioned from the beneficiary, or are desirably partitioned from the beneficiary using froth flotation.(0043 ] As used herein, “comminute” means to mechanically reduce the size of a solid mass. Non-limiting examples of comminuting include pulverizing, milling, crushing, and grinding.((>044] As used herein, “flotation” or “froth flotation” indicates a process in which a sparge composition is sparged to form a sparged composition, wherein the sparged composition includes an overflow and an underflow.(0045] As used herein, “overflow” refers to the froth portion of a partitioned sparged composition, wherein “froth” refers to a plurality of bubbles present in a sparged composition during sparging, after sparging, or both during and after sparging and collected at or proximal to the liquid-gas interface. The bubbles arc formed by sparging the sparge composition with a gas such as air.

[0046] As used herein, “underflow” refers to the non-froth portion of a partitioned sparged composition; and accordingly an underflow excludes or substantially excludes froth.

[0047] As used herein, a “collector” means a material or mixture of materials that increases adhesion or association of the targeted particles to bubbles of a gas.

[0048] As used herein, “solvent” means a compound or mixture of t’vro or more compounds, wherein the compound or the mixture of compounds is liquid at a temperature between -30 °C and 100 °C at I atm.

[0049] As used herein, “salt” refers to the conjugate base of a carboxylic acid moiety or a sulfonic acid moiety. The term “salt” refers not only to foil salts but also to half-salts and the like, further as specified or determined by context herein. In embodiments, the salts comprise cations selected from Na*, K+, NHfe, and any combination thereof

[0050] Discussion[0051 1 Preferred methods and materials arc described below, although methods and materials similar or equivalent to those described herein can be used in practice or testing of the present invention. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.

[0052] We have found that inclusion of a modifier composition comprising at least one hydroxy fatty acid and / or a salt thereof in a sparge composition comprising a comminuted phosphate ore and a sulfonated fatty acid composition unpredictably improves the purity and / or yield of phosphate beneficiary in reverse froth flotation of the sparge composition.

[0054] Disclosed in first embodiments herein are modifier compositions comprising, consisting essentially of, or consisting of a mixture of one or more fatty acid triglycerides with one or more alkoxylated fatty alcohols. In some first embodiments, the weight proportion of the one or more fatty acid triglycerides to the one or more alkoxylated fatty alcohols in the mixture is between 100:1 and 1:100, for example 90:1 to 1:100, or 80:1 to 1 :100, or 70:1 to 1:100, or 60:1 to 1 :100, or 50:1 to 1:100, or 40:1 to 1: 100, or 30: 1 to 1 :100, or 20:1 to 1:100, or 10:1 to 1: 100, or 1:1 to 1 :100, or 100: 1 to 1:90, or 100: 1 to 1:80, or 100:1 to 1 :70, or 100:1 to 1 :60, or 100:1 to 1:50, or 100:1 to 1:40, or 100:1 to 1:30, or 100:1 to 1 :20, or 100:1 to 1 :10, or 100:1 to 1 :1, or 10: 1 to 1:10, or 2: 1 to 1:1, or 1:1 to 1:2, or 5:1 to 1:1, or 1 :1 to 1 :5, or 10:1to 1:1, or 1 :1 to 1: 10, or 10:1 to 1:10, or 20:1 to 1:1, or 1:1 to 20:1, or 20:1 to 1:20, or 50:1 to 1:1, or 1:1 to 50:1, or 50:1 to 1 :50, or 100:1 to 1 :1, or 1 :1 to 1:100, or about 1:1, or about 1 :2, or about 1 :3, or about 1 :4, or about 1 :5, or about 1 :6, or about 1 :7, or about 1 :8, or about 1 :9, or about 1 : 10, or about 1 : 20, or about 1 : 30, or about 1 :40, or about 1 : 50, or about 1 :60, or about 1:70, or about 1:80, or about 1:90, or about 1:100, or about 2: 1, or about 3:1, or about 4:1, or about 5: 1, or about 6:1, or about 7:1, or about 8:1, or about 9:1, or about 10: 1 , or about 20:1, or about 30: 1 , or about 40: 1 , or about 50: 1 , or about 60: 1 , or about 70: 1 , or about 80: 1 , or about 90: 1 , or about 100: 1 by weight.[00551 In first embodiments, at least one of the one or more alkoxylated fatty alcohols has a structure according to the formula ( 1 ).R’-O-|CHR-’-CHR'-O|t-|CHR'-CHR<-O|„ -R'-(0 wherein R1is a linear, branched, or alicyclic C6-C30 saturated or unsaturated moiety . each R , R’. R*. R and R' is independently selected from H or a C I -C5 linear oi branched alky l moiety, n is 0 or an integer between I and 100. m is 0 or an integer betw een I and 100. and the sum of n - m is at least 2 In any one or more embodiments of the alkoxy latcd fatty alcohol of formula ( I ), R1includes 6-30 carbons, for example X-30 carbons, 10-30 carbons. 10-26 carbons. 10-22 carbons. 6-20 carbons. X-20 carbons, or 10-20 carbons. In any one or more embodiments of the alkoxy lated fatty alcohol of formula ( I ). R1is linear In any one or more embodiments of the alkoxy latcd fatty alcohol of formula ( I ), R!is branched. In any one or more embodiments of the alkoxylated fatty alcohol of formula ( I ). R!includes one oi mote unsaturated moieties In any one or moie embodiments of the alkoxy latcd fatty alcohol of formula ( I ), m and n arc each at least I , each of R R . and R’ is H; and R' is Clh. In any one or more embodiments of the alkoxy latcd fatty alcohol of formula ( I ). m is 0 and R- and R;arc both H In any one or more embodiments of the alkoxylated fatty alcohol of formula ( I ), R ’ and R5are both H; n is a number between 1 and 35, oi between 3 and 30, or between 3 and 20. or between 3 and 15. and m is a numbet between 1 and 35. or between 1 and 20. or between I and 15, or between 3 and 10 In any one or more embodiments of the alkoxylated fatty alcohol of formula ( 1 ). R" is H or CH >.

[0056] hi some first embodiments, the one or more alkoxylated fatty alcohols comprises, consists essentially of. or consists of a first alkoxylated fatty alcohol compusing R' that is a linear or branched C 16-C2O moiety; and a second alkoxylated fatty alcohol comprisingR' that is a linear or branched C6-C 14 moiety. In some such embodiments, the first alkoxylated fatty alcohol comprises R2R*, and R* each of which is H, R5that is CHj, n that is between 1 and 35, and m that is between 1 and 35; and the second alkoxylated fatty alcohol comprises R2R3, and R* each of which i s H , R5that is CHs, n that is between 1 and 35 and m that is between 1 and 35, In any one or more such embodiments, n and m of each of the first and second alkoxylated fatty alcohols are independently between 1 and 5, between 5 and 10, between 10 and 15, between 15 and 20, between 20 and 25, between 25 and 30, or between 30 and 35; or n and m of each of the first and second alkoxylated fatty alcohols are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. II. 12. 13. 14. 15. 16. 17, 18, 19.20.21.22, 23, 24.25.26.27.28, 29.30. 31, 32. 33. 34. or 35. In embodiments, the weight proportion of the first alkoxylated laity alcohol to the second alkoxylated tatty alcohol in the mixture is 100: 1 to 1 : 100. for example for example 90:1 to l:100,or80:l to l:100,or70:l to 1:100, or60:l to 1:100, or50:l to 1:100, or 40:1 to 1:100, or 30:1 to 1:100, or 20:1 to 1:100, or 10:1 to 1:100, or 1:1 to 1:100, or 100:1 to 1:90, or 100: 1 to 1:80, or 100:1 to 1:70, or 100:1 to 1:60, or 100:1 to 1:50, or 100:1 to 1:40, or 100:1 to 1:30, or 100:1 to 1:20, or 100:1 to 1:10, or 100:1 to 1:1, or 10:1 to 1:10, or 2:1 to I: I, or 1:1 to 1:2. or 5: 1 to 1 :1. or 1:1 to 1 :5. or 10:1 to 1 : 1. or 1:1 to 1:10, or 10:1 to 1:10, or 20:1 to 1:1, or 1:1 to 20:1, or 20:1 to 1:20, or 50; I to 1:1, or 1:1 to 50:1. or 50:1 to 1:50, or 100:1 to 1:1, or 1:1 to 1:100, orabout 1:1, orabout l:2,orabout 1:3, orabout 1:4, orabout 1:5, or about 1:6, or about 1:7, or about 1:8, or about 1:9, or about 1:10, or about 1:20, or about 1:30, or about 1:40, or about 1:50, or about 1:60, or about 1:70, or about 1:80, or about 1:90, or about 1 : 100, or about 2: 1 , or about 3 : 1 , or about 4: 1 , or about 5: 1 , or about 6: 1 , or about 7:1, or about 8:1, or about 9:1, or about 10:1, or about 20:1, or about 30:1, or about 40:1, or about 50: 1 , or about 60: 1 , or about 70: 1 , or about 80: 1 , or about 90: 1 , or about 100: 1.10057 ] In first embodiments, each of the one or more fatty acid triglycerides independently has a structure according to formula (2),wherein R . R . and R arc independently selected from saturated or unsaturated C6-C3O linear, branched, or alicyclic moicties. In any one or more embodiments of formula (2). oneor more of R7, R", and R9arc C16-C20 linear moieties. In any one or more embodiments of formula (2), one or more of R’, R*, and R* are unsaturated.

[0058] In some first embodiments, at least one of the one or more fatty acid triglycerides is deri ved from a plant source. Suitable plant sources include whole plants, seeds, stems, flowers, roots, or two or more thereof from cotton, flax, grape, hemp, safflower, olive, palm, peanut, rice, avocado, canola, coconut, corn, sesame, soybean, sunflower, walnut, or any combination thereof. Accordingly, in any one or more first embodiments, the one or more triglycerides are present in a plant oil, are a plant oil, or are part of a plant oil, that is, safflower oil, com oil, and the life, and is extracted from a plant source. Each type of plant oil includes a characteristic blend of triglycerides, as well as one or more free faty acids (that is, saturated or unsaturated C6-C30 linear, branched, or alicyclic carboxylic acids or a salt thereof) and in some cases diglycerides and monoglycerides of one or more forty acids, either as part of the characteristic plant mixture, or as impurities including e.g. impurities arising from refining and or processing thereof

[0059] For example, as reported in "Com oil, industrial and retail, all purpose salad or cooking, fat composition, 100 g” (US National Nutrient Database, Release 28, United States Department of Agriculture; SR Legacy released April 2018) 100g of coni oil includes a characteristic mixture of triglycerides, wherein the fatty acid moieties represented by R7. RL and R'!of formula (2) correspond to about 12.9g saturated fatty acid moieties. about 27.6g monouusaturated fatty acid moieties. and about 54.7g polyunsaturated fatty acid moieties. Additionally, about 99% of the unsaturated fatty acid moieties of com oil are oleic acid moieties.

[0060] In some first embodiments, the modifier composition further includes one or more additional fatty acids or a conjugate base thereof, that is. one or more saturated or unsaturated C6-C30 linear, branched, or alicyclic carboxylic acids or a salt thereof] added to the mixture of forty acid triglyceride and alkoxylated fatty alcohol. In such embodiments, the faty acid is added in an amount of 0.1 wt% to 50 wt% of a modifier composition, such that the fatty acid is no more than 50 wt% of the modifier composition, with the mixture of fatty acid triglyceride and alkoxylated forty alcohol being the remainder of the modifier composition. In some such embodiments, the additional fatty acid or salt thereof is selected from oleic acid, linoleic acid, linolenic acid, tall oil fatty acid, ricinolcic acid, or a combination of two or more thereof.

[0061] In some first embodiments, the modifier composition is provided neat, or added to a composition neat, that is, in the absence of a sol vent (also referred to as “100% actives”). In other first embodiments, the modifier composition farther includes a solvent. In embodiments, the solvent comprises, consists essentially of, or consists of one or more C5-C30 hydrocarbons, one or more C2-CI 2 alcohols, a petroleum distillate such as CAS No. 64741- 44-2, a heavy aromatic solvent such as heavy aromatic naphtha, CAS No. 64742-94-5, toluene, a xylene, a cumene, or any combination thereof. In embodiments, the solvent is water. In embodiments, the modifier composition is present at 0.1 wt% to 99.9 wt% in a solvent, for example 0.1 wt% to 0.5 wt%, or 0.5 wt% to 1 wt%, or I wt% to 1,5 wt%, or 1.5 wt% to 2.0 wt%, or 2.0 wt% to 2.5 wt%, or 2.5 wt% to 3.0 wt%, or 3.0 wt% to 5,0 wt%, or 5.0 wt% to 10.0 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 60 wt%, or 60 wt% to 70 wt%, or 70 wt% to 80 wt%, or 80 wt% to 90 wt%, or 90 wt% to 99 wt%, or 99 wt% to 99.9 wt%, or 90 wt% to 99.9 wt%, or 95 wt% to 99 wt%, or 95 wt% to 99.9 wt% in a solvent. In embodiments, the solvent consists essentially of or consists of water, and the modifier composition or a component thereof is present at 90 wt% to 99,9 wt% in the solvent. In other embodiments, the solvent comprises, consists essentially of, or consists of a petroleum distillate, wherein the modifier composition or a component thereof is present at 50 wt% to 90 wt% in the solvent.

[0062] Second embodiments(00631 Disclosed in second embodiments herein arc sparge compositions comprising, consisting essentially of, or consisting of a medium comprising water; a mineral orc comprising a beneficiary and a gangue; a collector; and a modifier composition of any of first embodiments above.100641 In an\ one or more sparge compositions of second embodiments, the medium comprising water is a liquid medium comprising, consisting essentially of. or consisting of fresh water, sea water, brackish water, tap water, water obtained from a creek, river, or pond, including sedimentation pond; runoff water, industrial waste water, water diverted from or obtained from a water treatment facility, or any combination thereof The medium comprising water is present in a sparge composition of any one or more second embodiments in an amount of 30" o to K0% by volume based on the weight of the orc. for example about 30° <» to 50" <>. or even about 60".. to 80% b> x olumc based on the weight of the ore.

[0065] In any one or more sparge compositions of second embodiments, the mineral ore is a solid material mined from one or more subterranean excavations and comprising, consisting essentially of, or consisting of a beneficiary and a gangue. In any one or more sparge compositions of second embodiments, the mineral ore comprises, consists essentially of or consists of a phosphate ore, a lithium ore, or an iron ore. In any one or more sparge compositions of second embodiments herein, the aniount of a mineral ore in a sparge composition is about 1% to 80%, in embodiments about 10% to 40%, or even about 20% to 30% by weight of the sparge composition.

[0066] As used herein, “phosphate ore” means a mineral ore that comprises a beneficiary comprising a phosphate group and / or phosphate moiety. As used herein, “phosphate” refers to a material comprising a phosphoric acid moiety or a salt thereof comprising PCM3’, HPOr , H2PO4, or any combination thereof as specified or detennined by context herein. Accordingly, a phosphate beneficiary is a beneficiary comprising a phosphate group and or phosphate moiety. In embodiments, a phosphate orc comprises or consists essentially a combination of one or more of C’a' . PO?". F\ OH', CO% silica and or silicate. In embodiments, a phosphate ore comprises a gangue comprising one or more carbonate anions, one or more silicate anions, more or more silicas, or any combination thereof In embodiments, a phosphate ore comprises a gangue comprising calcite, dolomite, a silicate, silica, or any combination thereof. In embodiments, a phosphate beneficiary comprises, consists of, or consists essentially of Ca2+and PO43'. In embodiments, a phosphate ore comprises an apatite, such as fluorapatite, hydroxyapatite, chlorapatite, or any combination thereof. In embodiments, the phosphate orc gangue comprises calcite, dolomite, a silicate, silica, a seashell or seashell portion, or any combination thereof.

[0067] As wed herein, “lithium ore” means a mineral orc comprising, consisting essentially of. or consisting of a pegmatite, a Zinnwaldite, a Jadaritc. or a lithium mica. A lithium ore is a solid material mined from one or more subterranean excavations and containing at least 0.1% by weight of a lithium-bearing compound or mineral, such as spodumene, calculated as \vt% LizO: stated differently, a suitable lithium ore source has a “lithium potential” of at least 0,1% lithium as LizO. In embodiments, the lithium ore source has a lithium potential between 0.1% and 10% lithium as LizO, for example 0.5% to 8%, or 1% to 8%,or 1% to 6%, often between 1% and 4% lithium as LizO. In embodiments the lithium ore source further includes one or more of quartz, clay, feldspar, or another mineral having silicon, aluminum, iron, and / or magnesium content.

[0068] As used herein, “iron ore” refers to an ore including at least 20% by weight of one or more iron compounds, often between 30% and 55% by weight of one or more iron compounds. Typically the iron compounds are in the form of iron oxides such as hematite, magnetite and goethite. In embodiments, an iron ore contains one or more silica, alumina, phosphorous or sulfur compounds. Often, an iron ore includes between 10% and 45% SiCh by weight

[0069] In any one or more sparge compositions of second embodiments, the mineral ore is a comminuted orc. that is. the mineral ore is comminuted after mining, and before addition of the remaining components of the sparge composition. In some such embodiments, a comminuted ore, such as a comminuted phosphate ore, a comminuted lithium ore, or a comminuted iron ore has a particle size as measured by ASTM Cl 36 of 90% less than 4000 microns (#4 US standard mesh), in embodiments about 90% less than 1500 microns, in embodiments 90% less than 1000 microns, in embodiments 90% less than 500 microns, or in embodiments 90" <> less than 250 microns as measured by ASTM C l 36.|0070| In any one or more sparge compositions of second embodiments. 1% to 99% by weight of a comminuted ore has a particle size as measured by ASTM Cl 36 from about 38 microns to about 250 microns, in embodiments 50% to 80% by weight of the comminuted ore has a particle size from about 38 microns to about 250 microns, in embodiments 60% to about 70% has a particle size from about 38 microns to about 250 microns, in embodiments 65% to 70" ,> has a particle size from about 38 microns to about 250 microns, or in embodiments about 68% has a particle size from about 38 microns to about 250 microns as measured by ASTM Cl 36.

[0071] In any one or more sparge compositions of second embodiments, the weight proportion of the mineral ore to the modifier composition of any one of first embodiments in the sparge composition is about I ( MIO: I to 2: 1 . for example 1000: 1 io 500: 1 , or 500: 1 to 400: 1 . or 400: 1 to 300: 1 , or 300: 1 to 200: 1 . or 200: 1 to 100: 1 , or 100: 1 to 90; I . or 90; I to 80: 1 . or 80: 1 to 70: 1 , or 70:1 to 60:1, or 60:1 to 50: 1, or 50:1 to 40:l, or40:l to 30:l, or 30:l to 20:1, or 20:1 to 10:1, or 10:1 to 5:1, or 5:1 to 2:1, or 3:1 to 2:1, or 500:1 to 100:1, or 100:1 to 2:1, or 100:1 to 10:1, or 10:1 to 2: 1 by weight of the mineral ore to the modifier composition in the sparge composition.

[0072] In any one or more sparge compositions of second embodiments, the collector comprises, consists essentially of, or consists of one or more C12-C3O fatty acids, one or more C I 2-C3O fatty acid salts, one or more C I 2-C3O sulfonated fatty acids, one or more C I 2-C3O sulfonated fatty acid sate, or any combination of these. In some such embodiments, thecollector comprises, consists essentially of, or consists of oleic acid, an oleic acid salt, a sulfonated olcic acid, a sulfonated olcic acid salt, linoleic acid, a linoleic acid salt, a sulfonated linoleic acid, a sulfonated linoleic acid salt, linolenic acid, a linolenic acid salt, a sulfonated linolenic acid, a sulfonated linolenic acid salt, ricinoleic acid, a ricinoleic acid salt, a sulfonated ricinoleic acid, a sulfonated ricinoleic acid salt, palmitoleic acid, a palmitoleic acid salt, a sulfonated palmitoleic acid, a sulfonated palmitoleic acid salt, 11-eicosenoic acid, an 1 1- eicosenoic acid salt, a sulfonated 11-eicosenoic acid, a sulfonated 11-eicosenoic acid salt, erucic acid, an erucic acid salt, a sulfonated erucic acid, a sulfonated erucic acid salt, nervonic acid, a nervonic acid salt, a sulfonated nervonic acid, a sulfonated nervonic acid salt, or any combination thereof

[0073] In any one or more sparge compositions of second embodiments, the collector is present in an amount of about 0.001% to 3% by weight or by weight volume in a sparge composition, in embodiments about 0.01 " » to 0.5" <>. about 0.01 " <> to 0.2" '<>. or about 0.010o to 0.1" <> by weight or by weight, volume in a sparge composition.

[0074] In any one or more sparge compositions of second embodiments, the collector comprises, consists of, or consists essentially of a sulfonated fatty acid composition. In embodiments, the sulfonated fatty acid composition comprises, consists of, or consists essentially of one or more sulfonated fatty acids, one or more sulfonated fatty acid salts, or any combination thereof. In some embodiments, the one or more sulfonated fatty acids, one or more sulfonated fatty acid salts, or the combination thereof comprises, consists of, or consists essentially of a sulfonated fatty acid, a sulfonated fatty acid salt, or a combination thereof100751 In any one or more sparge compositions of second embodiments, a sulfonated fatty acid composition comprises, consists of, or consists essentially of a compound or mixture of compounds that is a product of a sulfonation of one or more fatty acids and / or salts thereof] or is the product of neutralizing or partially neutralizing with a base the compound or mixture of compounds that is a product of a sulfonation of the one or more fatty acids; further wherein each compound present in the sulfonated fatty acid composition comprises at least one - COOH group or salt thereof, and at least one -SOsH group or salt thereof. The compound or each compound in the mixture of compounds has a -COOH group or a -CO< group, and at least one -SO<H group or SO< group. Therefore, the sulfonated fatty acid composition comprises one or more fatty acids having sulfonic acid groups and / or salts thereof

[0076] In any one or more sparge compositions of second embodiments, a sulfonated fatty acid composition comprises, consists of, or consists essentially of sulfonated oleic acid, a sulfonated oleic acid salt, sulfonated linoleic acid, a sulfonated linoleic acid salt, sulfonated linolenic acid, a sulfonated linolenic acid salt, sulfonated ricinoleic acid, a sulfonated ricinoleic acid salt, sulfonated palmitoleic acid, a sulfonated palmitic acid salt, sulfonated 11- eicosenoic acid, a sulfonated 11-eicosenoic acid salt, sulfonated erucic acid, a sulfonated erucic acid salt, sulfonated nervonic acid, a sulfonated nervonic acid salt, sulfonated abietic acid, a sulfonated abietic acid salt, or any combination thereof[00771 In any one or more sparge compositions of second embodiments, a sulfonated fatty acid composition comprises one or more sulfonated faty acid sodium salts, one or more sulfonated faty acid potassium salts, one or more sulfonated faty acid ammonium sate, or any combination thereof fa embodiments, the ammonium is selected from inorganic ammonium ( NHj ), primary organic ammonium, secondary organic ammonium, tertiary organic ammonium, quaternary organic ammonium, or any combination thereof. In embodiments, a sulfonated fatty acid composition is a neutralized or partly neutralized product of a sulfonation of a saturated faty acid with a sulfonating agent. In this context, neutralized or partially neutralized means reacted with a base. In embodiments, the sulfonating agent is selected from sulfur trioxide, oleum, chlorosulfonic acid, and sulfuric acid.

[0078] fa any one or more sparge compositions of second embodiments, a sulfonated fatty acid composition comprises, consists of or consists essentially of a sulfonated oleic acid potassium salt. In any one or more sparge compositions of second embodiments, a sulfonated fatty acid composition comprises, consists of or consists essentially of a fatty acid monosulfonate, a faty acid disulfonate, one or more fatty acid sulfonate dimers, one or more fatty acid sulfonate trimers, or any combination thereof In some such embodiments, the sulfonated fatty acid composition comprises a salt of the faty acid nionosulfonatc, a salt of the fatty acid disulfonate, one or more salts of the one or more fatty acid sulfonate dimers, one or more salts of the faty acid sulfonate trimers, or any combination thereof

[0079] A faty acid monosulfonate is a monosulfonated compound that is a product of a sulfonation of a tatty acid, the monosulfonated compound comprising one SOd l or one - SO;' group per molecule of the monosulfonated compound. A fatty acid disulfonate is a disulfonatcd compound that is a product of a sulfonation of a fatly acid, the disulfonatcd compound comprising two -SOaH groups, two -SOf groups, or one -SOsH and one ~SOs’group per molecule of the disulfonated compound. A fatty acid sulfonate dimer is a compound resulting from a chemical combination of a fatty acid sulfonate or its salt with a fatty acid, a fatty acid salt, a fatty acid sulfonate, or a salt of a fatty acid sulfonate.

[0080] A fatty acid sulfonate trimer is a compound resulting from a combination of two molecules of a fatty acid and / or its salt with one molecule of a fatty acid sulfonate or its salt; one molecule of a fatty acid or its salt and two molecutes of a faty acid and / or its salt; and / or three molecules of a fatty acid sulfonate and / or its salt.

[0081] In the way of illustration only, in one non-limiting example, a sulfonated fatty acid employed in any of second embodiments herein is derived from a sulfonation of oleic acid and comprises unsaturated oleic acid monosulfonate ( I), a salt of unsaturated oleic acid monosulfonatc (I ), saturated hydroxy oleic acid nionosulfonate (II ), a salt of saturated hydroxy oleic acid monosulfonatc (11 ), oleic acid 8.10-disulfonatc (111), a salt of oleic acid 8,10-disulfonate (III), oleic acid 9,10-disulfonate (IV), a salt of oleic acid 9,10-disulfonate (IV), dimer (V), a salt of dimer (V), hydroxy sulfonated dimer (VI), a salt of hydroxy sulfonated dimer (VI), sulfonated dimer (VII), a salt of sulfonated dimer (VII), saturated dimer (VIII), a salt of saturated dimer (VIII), trimer (IX), a salt of trimer (IX), saturated trimer (X), a salt of saturated trimer (X), doubly unsaturated dimer (XI), a salt of doubly unsaturated dimer (XI ). C I 4-C I X dimer (XII), a salt of C 14-C 18 dimer (XII), monounsaturated dimer (XIII). a salt of monounsaturated dimer (XIII), C 18-C 14 dimer (XIV), a salt of C18-C 14 dimer (XIV), or any combination thereof. In such embodiments, the faty acid salt composition comprises, consists of, or consists essentially of a salt or salts of any one or more of (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XIII), and (XIV).[0082 j Sulfonation of other fatty' acids other than oleic acid as exemplified above can also produce a mixture of compounds. The mixture of compounds in such embodiments depends on the fatly acid or mixture thereof that is sulfonated.|0083j Saturated and unsaturated fatty acids can be sulfonated by means known in the art to produce sulfonated fatty acids and their salts usefol as collectors in any one or more sparge compositions of second embodiments. The sulfonation of both saturated and unsaturated fattyacids is described for example, in US Patent No. 1,926,442. In any one or more sparge compositions of second embodiments, a sulfonated fatty acid salt composition comprises, consists of, or consists essentially of one or more salts of a sulfonated saturated fatty acid, one or more salts of a sulfonated unsaturated fatty acid, salts of more than one sulfonated saturated fatty acid, salts of more than one unsaturated fatty acid, or any combination thereof

[0084] In any one or more sparge compositions of second embodiments, the sparge composition further includes a pH adjustment agent, such as an acid selected from phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, citric acid, a polymeric acid, or any combination thereof or a base selected from sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, or any combination thereof 'The pH adjustment agent is added to any one or more of the sparge compositions of second embodiments in order to adjust a pH of the sparge composition to a targeted value. Accordingly, in some second embodiments, a sparge composition includes, is present at, or is adjusted to have a pH between 2.5 and 7, for example between 3 and 7, between3.5 and 7, between 4 and 7, between 4.5 and 7, or between 5 and 7. In some sparge compositions of second embodiments, a sparge composition has a targeted pH value between2.5 and 7, which is beneficial for froth flotation of phosphate ore and iron ore, as disclosed in methods of third embodiments below. In some other sparge compositions of second embodiments, a sparge composition has a targeted pH value between 7 and 12, which is beneficial for froth flotation of phosphate ore and lithium ore, as disclosed in methods of t hird embodiments below.

[0085] In any one or more sparge compositions of second embodimen ts, the sparge composition further includes a beneficiating agent. As used herein, “beneficiating agent1means a material or mixture of materials that increases the partitioning of a beneficiary in a froth flotation, or increases the y ield of a beneficiary collected from a froth flotation , and optionally further improves froth characteristics when compared with an otherwise identical sparge composition absent the beneficiating agent.

[0086] In any one or more sparge compositions of second embodiments, the beneficiating agent comprises, consists essentially of, or consists of one or more hydroxy fatty acids, one or more hydroxy faty acid salts, or any combination thereof. As used herein, a “hydroxy fatty acid” is any faty acid having at least one hydroxyl group. Accordingly, a hydroxy faty acid comprises a hydrocarbon chain with at least one hydroxyl group and at least one carboxyl group attached thereto. In embodiments, the hydrocarbon chain has one, two, or three hydroxylgroups attached thereto. In embodiments, the hydrocarbon chain is aliphatic. In embodiments ihe hydrocarbon chain is branched or straight-chain, hi some embodiments the hydrocarbon chain includes at least one -C:::C- double bond, in other embodiments the hydrocarbon chain is saturated. In embodiments, the hydrocarbon chain includes one -C=C- double bond or two “C“C- double bonds, in embodiments, the hydrocarbon chain comprises 5 to 50 carbon atoms, in embodiments 10 to 30 carbon atoms, in embodiments 15 to 25 carbon atoms, in embodiments 15 to 21 carbon atoms, or in embodiments 16 to 20 carbon atoms. In embodiments, the hydroxy fatty acid composition comprises two or more hydroxy fatty acids differing from each other with respect to number of carbon atoms in the hydrocarbon chain.10087] In any one or more sparge compositions of second embodiments, the hydroxy fatty acid comprises, consists of, or consists essentially of a compound having formula (3)GH23u (CHOH)b(CH2)(Cld==CH)c(CH2)dCOOH(3) and / or a salt thereof, wherein a is an integer from 1 to 10; b is an integer from I to 5; c is 0 or 1 ; and d is an integer from 5 to 10. I.n some embodiments where c~l , the CH-CH is cis, in other such embodiments the CH-CH is trans. I.n some embodiments, the GHsan group is a linear u-alkyl group. In other embodiments, the Gf-hs-a group is a branched alkyl group.(00881 In any one or more sparge compositions of second embodiments, the hydroxy fatty acid composition comprises, consists of* or consists essentially of a fatty acid having formula (4),CRioRs tOH (CldiMCHOHXIfr^OOH(4) and / or a salt thereof, wherein R« and Ro are independently selected from C1 -C5 alkyl and hydrogen; e is an integer from 1 to 10; f is 0 or an integer from 1 to 5; and g is an integer from 1 to 20. In some such embodiments, Rso and Rn are both hydrogen.10089] In any one or more sparge compositions of second embodiments, the hydroxy fetiy acid composition comprises, consists of, or consists essentially of a hydroxy fatty acid having formula (5),CsH2.: i(CH=CH)(CH2)b(CHOHXCH3)i(CH==CH)riCH2)pCOOH(5)and / or a salt thereof, wherein a is an integer from I to 10; h is an integer from 1 to 10; i is 0 or an integer from 1 to 10; k is 0 or I , with the proviso that if i-0 then k-0; and p is 0 or an integer from 1 to 10. In some such embodiments, every CH-CH is cis, in some other such embodiments every CH==CH is trans, in still other such embodiments, the hydroxy fatty acid has one cis CH-CH and one trans (CH-CH). In some embodiments, Calhan is a linear n- alkyi group.

[0090] In any one or more sparge compositions of second embodiments, the hydroxy fatty acid composition comprises a fatly acid having formula (6),GH2:<;dCHOHli(CH2)f(CH-CH)(CH2)h(CH-CH)(CH2)i(CHOH)<iCOOH(6) and / or a salt thereof, wherein a is an integer from I to 10; j is 0 or an integer from 1 to 5; r is 0 or an integer from I to 10, with the proviso that if j > 0 then r is at least 1; h is an integer from 1 to 10; q is 0 or I, with the proviso that j + q > 0; and i is 0 or an integer from 1 to 7, with the proviso that if i is 0 then q is also 0. In some such embodiments, both CH-CH moieties are cis, in other such embodiments both CH-CH are trans, in stilt other such embodiments, one CH-CH group is cis and the other CH-CH group is trans.

[0091] In any one or more sparge compositions of second embodiments, the hydroxy fatty acid composition comprises, consists of. or consists essentially of a hydroxy laity acid having formula (7),CJfr^ !-x)(OH)x (CRu-CRL0yCO2H(7) and / or a saitthereof, wherein $ is an integer from 5 to 25, x is an integer from 1 to 5, y is 0 or an integer from 1 to 3, and Rts and Ri.i are independently selected from alkyl or hydrogen. In this context, the empirical formula CiH(?sM.x)(OH)x (CH-CH)>CO2H means that a molecule of the hydroxy fatty acid comprises one -COOH group, from 1 to 5 -OH groups, and at least one alkyl and / or alkylene group; but the empirical formula docs not indicate the arrangement of these groups in the molecule. For example,roXOH)x can be spli t up by one or more intervening CH=CH double bonds into two or more alkylene groups or two or more alkylene groups and an alkyl group. Furthermore, CsHf2sH-x)(OH)x can have any arrangement with respect to (OH) groups. In embodiments, CRn-CRu is efr; in other embodiments, CRn^CRu is / raws.

[0092] In any one or more sparge compositions of second embodiments, the hydroxy fatty acid composition comprises, consists of, or consists essentially of ricinoleic acid, a salt of ricinoleic acid, 12-hydroxystearic acid, a salt of 12-hydroxystearic acid, 9,10* dihydroxyoctadecanoic acid, a salt of 9,10-dihydroxyoctadecanoic acid, 9, 10,18- trihydroxyoctadecanoic acid (phloionolic acid), a salt of phloionolic acid, lesquerolic acid (u- C«HrdCHOH)CH2(CH::::CH)(CH?,)<iCOOH), a salt of lesquerolic acid, 15- hydroxyhexadecanoic acid, a salt of 15-hydroxyhexadccanoic acid, isoricinoleic acid (cis s- C5HU(CH=CH)(CH2)2(CHOH)(CH2)"COOH), a salt of isoricinoleic acid, densipolic acid (cis, cis t?-C’Hi(CM:::CfI)(CH2)2(CHOH)CH2(CH:::CH)(Cfb)?COOI-I), a salt of densipolic acid, 14-hyctoxy-eicosa-cis-l l-cis-17-dienoic acid (auricolic acid, w- QHS(CHK:HXCH2)2(CHOHK?H3(CH===CH)(CH2KOOH)), a salt of auricolic acid, 2- hydroxyoleic acid, a salt of 2-hydroxyoleic acid, 2-hydroxylinoleic acid, a salt of 2- hydroxy linoleic acid, 18-hydroxystearic acid, a salt of I 8-hydroxystearic acid, 15- hydroxylinoleic acid, a salt of 15-hydroxyliaoleic acid, or any combination thereof.

[0093] In any one or more sparge compositions of second embodiments, the hydroxy fatty acid composition comprises, consists of, or consists essentially of sodium ricinoleate, potassium ricinoleate, sodium 12-hydroxystearatc, potassium 12-hydroxystearate, sodium 9, 10-dlhydroxyoctadecanoate, potassium 9,10-dihydroxyoctadecanoate, sodium phloionolate, potassium phloionolate acid, sodium lesquerolate, potassium Icsquerolate, sodium 15- hydroxyhexadecanoate, potassium 15-hydroxyhexadccaaoatessodium isoricinoleate, potassium isoricinoleate, sodium densipolate, potassium densipolate, sodium auricolate, potassium auricolate, sodium 2-hydroxyoIeate, potassium 2-hydroxyoleate, sodium 2- hydroxylinoleate, potassium 2-hydroxyIinoleate, sodium 18-hydroxystearate, potassium 18- hydroxystearate, sodium 1.5-hydmxylinoleate, potassium 15-hydroxylinoleate, or any combination thereof.10094] In any one or more sparge compositions of second embodiments, die beneficiating agent comprises, consists of, or consists essentially of a salt, of ricinoleic acid. In some such embodiments, the salt of the ricinoleic acid is the product of the hydrolysis of castor oil. In embodiments, the hydrolysis of the castor oil is a saponification of the castor oil with an alkali. In embodiments, the alkali is selected from aqueous sodium hydroxide, aqueous potassium hydroxide, or an aqueous ammonium hydroxide. In embodiments, the ammonium of the aqueous ammonium hydroxide is selected from inorganic ammonium, primar y organic ammonium, secondary organic ammonium, tertiary organic ammonium, quaternary organicammonium, or any combination thereof. In embodiments, the salt of the ricinoleic acid comprises, consists of, or consists essentially of sodium ricinoleate or potassium ricinoleate. In some such embodiments, the sodium ricinoleate or potassium ricinoleate is the product of the saponification of castor oil with aqueous sodium hydroxide or aqueous potassium hydroxide respectively.

[0095] In any one or more sparge compositions of second embodiments, the salt of the hydroxy fatty acid is selected from an ammonium salt, a sodium salt, or a potassium salt of the hydroxy fatty acid. In embodiments, the ammonium is inorganic ammonium (NHri), primary organic ammonium, secondary organic ammonium, tertiary organic ammonium, or quaternary organic ammonium.

[0096] In any one or more sparge compositions of second embodiments, a hydroxy fatty acid, a salt of the hydroxy fatty acid, or a combination thereof is a product of hydrolysis of a natural oil. In embodiments, the natural oil is castor oil. In embodiments, the hydrolysis is a saponification with an alkali. In embodiments, the alkali comprises, consists of, or consists essentially of aqueous sodium hydroxide , aqueous potassium hydroxide, an aqueous ammonium hydroxide, or any combination thereof In any one or more sparge compositions of second embodiments, the hydroxy fatty acid, the salt, of the hydroxy fatty acid, or the combination thereof is a product of hydrolysis of a triglyceride that is the ester of at least one hydroxy fatty acid. In embodiments, the hydrolysis is a saponification with an alkali. In embodiments, the alkali comprises, consists of, or consists essentially of aqueous sodium hydroxide, aqueous potassium hydroxide, an aqueous ammonium hydroxide, or any combination thereof

[0097] In. any one or more sparge compositions of second embodiments, the hydroxy faty acid composition comprises two or more hydroxy fatty acids, two or more salts of a single species of hydroxy fatty acid, two or more salts of two or more hydroxy fatty acids, or any combination thereof.

[0098] In any one or more sparge compositions of second embodiments, a beneficiating agent is present in an amount of about 0.001% to 5% by weight or by weight / volume in a sparge composition, in embodiments about 0.01% to 0.5%, about 0.02% to 0.15%, or about 0.03% to 0.12% by weight or by weight / volume in a sparge composition.[00991 In any one or more sparge compositions of second embodiments, the beneficiating agent comprises, consists of, or consists essentially of a hydroxy fatty acid or salt thereof anddie collector comprises, consists of, or consists essentially of a sulfonated fatty acid or salt thereof wherein the weight of the sulfonated fatty acid divided by the weight of the hydroxy fatty acid present in the sparge composition, or the weight of the sulfonated fatty acid salt divided by the weight of the hydroxy fatty acid salt present in the sparge composition is about 0.01 to about 99, for exampie about 0.05 to 1.2, or about 0.05 to 1.1, or about 0.1 to 1.1, or about 0.1 to 1, or its about 0.20 to 1.0, or about 0.30 to 1.0, or about 0.40 to 1.0, or in embodiments about 0,66. In any one or more sparge compositions of second embodiments, the sum of the weight of the sulfonated fatty acid plus the weight of the hydroxy fatty acid is about 0.001% to about 5% of the weight of the mineral ore present in the sparge composition, for example about 0,001 % to I %, or about 0.01 % to about I %, or about 0.05% to about 0.7%, or about 0,1% to about 0.3% of the weight of the mineral ore. In any one or more sparge compositions of second embodiments, the sum of the weight of the sulfonated fatty acid salt plus the weight of the hydroxy fatty acid salt is about 0,001 % to about 7% of die weight of the mineral ore present in the sparge composition, for example about 0.001%) to 5%, or about 0.01% to about 4%, or about 0.05% to about 1.0%, or about 0. 1% to about 0.7% of the weight of the mineral ore.

[0100] In any one or more sparge compositions of second embodiments, a sparge composition further includes one or more additional components selected from one or more emulsifying surfactants, one or more additional collectors, one or more depressants, one or more activators, one or more frothing agents, or any combination thereof, wherein the amount of any one or more additional component present in the sparge composition is about 0.001% to about 5% of the weight of the mineral ore present in the sparge composition

[0101] For example, in any one or more sparge compositions of second embodimen ts, a sparge composition further includes one or more additional fatty acids or conjugate bases thereof that is, one or more saturated or unsaturated C6-C30 linear, branched, or alicyclic carboxylic acids, or a salt thereof In any one or more such embodiments, the fatty acid is added in an amount of 0.001 % to about 5% of the weight of the m ineral ore present in the sparge composition, for example about 0.001% to 4%, or about 0.01%> to 3%, or about 0.05% to 2%, or about 0.01%> to 1%, or about 0.001% to 0.01%j, or about 0.01 % to 0.1%, or about 0.1% to 1% or about 1%> to 2%, or about 2% to 3%, or about 3% to 4%, or about 4% to 5% of the we ight of the mineral ore.10102] Any one or more sparge compositions of second embodiments herein are used for froth flotation employing methods described in third embodiments herein. Any one or moresparge compositions of second embodiments herein are used for reverse froth flotation employing the methods described in third embodiments herein.10104] Disclosed in third embodiments herein are methods of froth flotation comprising, consisting essentially of, or consisting of forming a sparge composition of any of second embodiments above; and sparging the sparge composition to form a sparged shiny, the sparged slurry having an overflow and an underflow. Accordingly, in any one or more methods of third embodiments herein, a method of froth flotation comprises, consists essentially of or consists of combining a mineral ore comprising a beneficiary and a gangue, a medium comprising water, a collector, and a modifier composition of any of first embodiments to form a sparge composition in accordance with second embodiments herein; and sparging the sparge composition to yield a sparged slurry comprising an overflow and an underflow. During and after sparging, bubbles of gas migrate through the sparged composition to form layer of babbles, or froth, at the liquid-air interface. The layer of bubbles is referred to herein as the overflow.(0105] In any one or more methods of third embodiments herein, a method of froth flotation comprises, consists essentially of, or consists of combining the following components a, b, c, d, e to form a sparge composition in accordance with any one or more second embodiments: a. a mineral ore comprising a beneficiary and a gangue, b. a medium comprising water, c. a collector, d. a fatty acid triglyceride, and e. an alJkoxylatcd fatty alcohol; and sparging the sparge composition to yield a sparged slurry comprising an overflow and an underflow.10106] In any one or more methods of third embodiments herein, components a, b, c, d, and e are defined and described in first and second embodiments herein. Accordingly, in any one or more methods of third embodiments, component a is a mineral ore in accordance with any one or more second embodiments herein; component b is a medium in accordance with any one or more second embodiments herein; component c is a collector in accordance with any one or more second embodiments herein; component d is a fatty acid triglyceride in accordance withany one or more first or second embodiments herein; and component e is an aikoxylated alcohol in accordance with any one or more first or second embodiments herein.

[0107] In any one or more methods of third embodiments herein, components a, b, c, d, and e are combined in any order to form a sparge composition. In any one or more methods of third embodiments herein, components c and e are combined, then the c-re combination is farther combined with components a, b, and d in any order. In any one or more methods of third embodiments herein, components d and e are combined, then the d+e combination is further combined with components a, b, and c in any order. In any one or more methods of third embodiments herein, components a and b are combined, then the a* b combination is further combined with components c, d, and e in any order. In any one or more methods of third embodiments herein, components a and b are combined, then the a+b combination is further combined with components c, d, e, in order; or components c, e, d in order. Ln any one or more methods of third embodiments herein, components d and e are combined to form a d+e combination, components a, b, and c are separately combined in any order to form an adb+c combination; and then the d+e combination is combined with the a*b+c combination.

[0108] In any one or more methods of third embodiments herein, a method further comprises combining component f, f. a pH adjustment agent with a sparge composition or with one or more components a, b, c, d, or e listed above. The pH adjustment agents of third embodiments are the same as the pH adjustment agents of second embodiments herein. Accordingly, in any one or more methods of third embodiments herein, components a, b, c, d, e, and fare combined in any order to form a sparge composition. In anyone or more methods of third embodiments herein, the combining comprises combining components a, b, e, d, e to form a sparge composition using any one of the orders of component combination listed above; then measuring a pH of the sparge composi tion, then adjusting pH to a target pH value that is different, from the measured pH value by adding component f to the sparge composition. Ln accordance with the sparge composition targeted pH ranges of second embodiments herein, the targeted pH is 2.5 to 7 where component a (mineral ore) is a phosphate ore or a lithium ore; and the targeted pH is 7 to 12 where component a is a lithium orc or an iron ore,

[0109] In any one or more methods of diird embodiments herein, a method further comprises combining component g,g. a beneficiating agent with the sparge composition or with otic or more components a, b, c, d, e, or f listed above, wherein the beneficiation agent is selected from any one or more of the beneficiation agents of second embodiments above.(OHO] In any one or more methods of third embodiments herein, components a, b, c, d, e, and g are combined in any order to form a sparge composition in accordance with one or more sparge composit ions of second embodiments herein. Accordingly, in any one or more methods of third embodiments herein, componen ts a, b, c, d, e, f, and g are combined in any order to form a sparge composition in accordance with one or more second embodiments herein . In any one or more methods of third embodiments herein, components c, and g are combined, then the erg combination is further combined with components a, b, d, and e in any order to form a sparge composition in accordance with any one or more second embodiments herein. In any one or more methods of third embodi ments herein, components c, e, and g are combined, then the c+e+g combination is further combined with components a, b, and d in any order to form a sparge composition in accordance with any one or more second embodiments herein, in any one or more methods of third embodiments herein, components d and e are combined, then the d+e combination is further combined with components a, b, c, and g in any order in accordance with any one or more second embodiments herein, in any one or more methods of third embodiments herein, components a and b are combined, then the a±b combination is further combined with components c, d, e, and g in any order in accordance with any one or more second embodiments herein. In any one or more methods of third embodiments herein, components a and b are combined, components e and g are combined, then the arb combination is further combined with the c+g combination, and then the a-*b+c*g combination is further combined with component d, then component e, in order; or the a+b+c-i g combination is further combined with component e, then component d, in order, to form a sparge composition in accordance with any one or more second embodiments herein. In any one or more methods of third embodiments herein, components d and e are combined to form a d+e combination, components a, b, c, and g are separately combined in any order to form an a+M-c+g combination; and then the d+e combination is combined with the av-b-t-c+g combination to form a sparge composition in accordance with any one or more second embodiments herein. In any one or more such methods of third embodiments herein, the method further comprises combining component f with any one or more components a, b, c, d, e, g, or with the sparge composition, as described above in order to provide a targeted pH.[01 1 1] In any one or more methods of third embodiments herein, the method further includes adjusting the pH of a sparge composition by combining the mineral ore, meditrm, collector, modifier composition, and optionally beneficiating agent with a pH adjustment agent. In any one or more methods of third embodiments herein, the pH adjustment agent is selected from any one or more of the pH adjustment agents of second embodiments. Accordingly, in some third embodiments, the method further includes combining a pH adjustment agent with the sparge composition prior to the sparging, in an amount sufficient to obtain a pH of about 2,5 to about 7, in accordance with some second embodiments herein; while in other third embodiments, the method further includes combining a pH adjustment agent with the ore slurry, or with the sparge composition prior to the sparging, in an amount sufficient to obtain a pH of about 7 to about 12, in accordance with other second embodiments herein.(0112] In any one or more methods of third embodiments herein, the method further includes adding one or more emulsifying surfactants, one or more additional collectors, one or more depressants, one or more activators, one or more frothing agents, or any combination thereof to one or more of components a, b, c, d, e, f, or g; or to the sparge composition.[01 13 j In any one or more methods of third embodiments herein, there is provided a method of sparging comprising: sparging any of the sparge compositions disclosed hi second embodiments herein, io yield a sparged slurry. The sparged slurry comprises an overflow and an underflow.[01 14| In any one or more methods of third embodiments herein, the sparging is carried out in a lab scale flotation cell. In any one or more methods of third embodiments herein, the method further includes collecting an overflow, collecting an underflow, or collecting both an overflow and an underflow, wherein, the collecting comprises, consists essentially of, or consists of separating at least a portion of an overflow from at least a portion of an underflow arising from sparging a sparge composition of any of second embodiments herein and formed using any of the methods of third embodiments herein. Separating at least a portion of an overflow, from at least a portion of an underflow is accomplished using conventional methods known to those of skill in the art of froth flotation. In any one or more methods of third embodiments herein, such separating comprises, consists of, or consists essentially of: tapping off at least a portion of the overflow, skimming off at least a portion of the overflow, depositing at least a portion of the overflow onto a launder, decanting at least a portion of the overflow, or any combination thereof.

[0115] In any one or more methods of third embodiments herein, the underflow comprises a concentrate and a first portion of the medium; and the overflow comprises tailings and a second portion of the medium. The concentrate comprises, consists of, or consists essentially of the beneficiary. The tailings comprise, consist of, or consist essentially of the gangue. In any one or more methods of third embodiments herein where the mineral ore is a phosphate ore, the underflow includes a phosphate beneficiary, and the overflow includes a gangue comprising a silica.101 I 6] In any one or more methods of third embodiments herein, the method further comprises separating at least a portion of the concentrate from at least a portion of the tailings. In embodiments, the at least the portion of the concentrate is about 90% to 100% by weight of the concentrate in the underflow, in embodiments about 95% to 100%, in embodiments about 98% to 100%, in embodiments about 99% to 100%, or 100% by weight of the concentrate in the underflow. In embodiments the at least the portion of the tailings is about 90% to 100% by weight of the tailings in the froth, in embodiments about 95% to 100%, in embodiments about 98% to 100%, in embodiments about 99% to 100%, or 100% by weight of the tailings in the froth.

[0117] In. any one or more methods of third embodiments herein , the separating the at least the portion of the concentrate from the at least the portion of the tailings comprises, consists of, or consists essentially of separating at least a portion of the overflow from at least a portion of the underflow, wherein the underflow comprises concentrate and the overflow comprises tailings. In some such embodiments , the method comprises separating at least a portion of a froth layer from at least a portion of the underflow.

[0118] Fourth Embodiments

[0119] Disclosed in fourth embodiments herein is the use of any one or more of the sparge compositions of second embodiments, which include a modifier composition in accordance with any one or more first embodiments herein, to refine a mineral ore using reverse froth flotation and provide a refined mineral ore. In any one or more uses of fourth embodiments, the mineral ore is a phosphate ore; and the refined phosphate ore is used to produce phosphoric acid. In the phosphoric acid process, a phosphate orc and an acid such as sulfuric acid are combined and react together to produce phosphoric acid. The greater the proportion of gangue in the phosphate ore, the worse scaling problems and the like that can be encountered in the production of the phosphoric acid. Therefore, froth flotation can be used to produce aconcentrate comprising a higher percentage of the phosphate than in the raw phosphate ore. In such a froth flotation, the higher the grade and the recovery of phosphate, the less problems that can be encountered in subsequent phosphoric acid manufacturing.

[0120] We previously determined that in reverse troth flotation of phosphate ores, increasing the dosage of collector tends to increase the % PsOs in the concentrate (% grade) at the expense of % PsOs recovery of concentrate: that is, improvements in mineral grade conventionally lead to reduced mineral recovery. Similarly, we have found that increasing the dosage of beneficiating agent increases the grade of P3O5 recovered at the expense of % recovery of PsOs,

[0121] Howe ver, in sharp contrast with observations and teachings of this conventional art, we have found that in the uses of fourth embodiments, reverse froth flotation of phosphate ores employing a modifier composition of any one of first embodiments in any one or more sparge compositions of second embodiments, and sparging in accordance with any one or more of the methods of third embodiments herein, obtains an increase of both % grade (wt% in a concentrate) and recovery (total wt% yield from the ore). For example, in any one or more fourth embodiments herein, the use of any one or more of the sparge compositions of second embodiments to refine a phosphate ore using reverse froth flotation in accordance with third embodiments herein obtains a refined phosphate, ore having both improved yield and improved grade of phosphate recovered. This result is unexpected in view of conventional froth flotation art, which teaches that improvements in mineral grade conventionally lead to reduced mineral recovery.

[0122] Additionally, in any one or more fourth embodiments herein, the use of any one or more of the sparge compositions of second embodiments to refine a lithium ore using reverse froth flotation obtains a refined lithium ore having improved grade , improved recovery, or improved grade and recovery of the valuable lithium compound, compared to use of a conventional sparge composition for refining the lithium ore,

[0123] Additionally, in any one or more fourth embodiments herein, the use of any one or more of the sparge compositions of second embodiments to refine an iron ore using reverse froth flotation obtains a refined iron ore having improved grade, improved recovery, or improved grade and recovery of the valuable iron compound, compared to use of a conventional sparge composition for refining the iron ore.(0124] FtfM Embodiments(0125] Disclosed in fifth embodiments herein are froth flotation processing kits comprising, consisting essentially of, or consisting of a first kit composition that is a modifier composition in accordance with first embodiments herein; and a second kit composition that is a collector composition comprising, consisting essentially of, or consisting of one or more sulfonated fatly acids, one or more sulfonated fatty acid salts, or any combination thereof in accordance with second, third, and fourth embodiments herein.(0126] la any one or more kits of fifth embodiments herein, a first kit composition is a modifier composition of any one or more first embodiments, and accordingly comprises, consists essentially of, or consists of one or more alkoxylated fatly alcohols and one or more fatly acid triglycerides; and in some embodiments further includes a solvent, such as any one or more of tire solvents disclosed in first embodiments above.(0127] In any one or more kits of fifth embodiments, a second kit composition comprises, consists essentially of, or consists of a collector in accordance with second embodiments above. In any one or more kits of fifth embodiments, the second kit composition further includes a beneficiating agent in accordance with second embodiments herein, that is, one or more hydroxy faty acids, one or more hydroxy fatty acid salts, or any combination thereof are combined with the collector in the collector composition. In some such second kit compositions, the weight proportion of the collector to the beneficiating agent is between 100: 1 and 1:100, for example 90:1 to 1:100, or 80:1 to 1:100, or 70:1 to 1:100, or 60:1 to 1:100, or 50:1 to 1:100, or 40:1 to 1:100, or 30:1 to 1:100, or 20:1 to 1:100, or 10:1 to 1:100, or 1:1 to 1:100, or 100:1 to 1:90, or 100:1 to 1:80, or 100:1 to 1:70, or 100:1 to 1:60, or 100:1 to 1:50. or 100:1 to 1:40, or 100:1 to 1:30, or 100:1 to 1:20, or 100:1 to 1:10, or 100:1 to 1:1, or 10:1 to 1:10, or 2:1 to 1:1, or 1.1 to 1:2, or 5:1 to 1:1, or 1:1 to I 5. or 10:1 to 1 :1, or 1:1 to 1:10.. or 10:1 to 1:10, or 20:1 to 1:1, or 1:1 to 20:1, or 20:1 to 1 :20, or 50:1 to 1:1 , or 1:1 to 50:1, or 50:1 to 1 :50, or 100:1 to 1 : 1, or 1 : 1 to I : KM), or about 1 : 1, or about 1 :2, or about 1 :3, or about 1 :4, or about 1:5, or about 1 :6, or about 1:7, or about 1 :8, or about 1 :9, or about 1 : 10, or about 1 :20, or about 1 :3(), or about 1 :40, or about 1 :50, or about 1:60, or about 1 :7(), or about 1 :80, or about 1:90, or about 1:100, or about 2:1, or about 3:1, or about 4:1, or about 5:1, or about 6:1, or about ":1, or about 8:1, or about 9:1. or about 10:1. or about 20:1, or about 30:1, or about 40:1, or about 50:1, or about 60:1, or about 70:1, or about 80:1, or about 90:1, or about 100:1 by weight. Accordingly, in any one or more kits of fifth embodiments, the second kit composition comprises, consists essentially of, or consists of a combination of a collector and a beneficia t ingagent in accordance with second embodiments above. Further, in any one or more kits of fifth embodiments, the second kit composition further comprises a solvent, such as any one or more of the solvents disclosed in first embodiments herein. Where both the first and second kit compositions include a solvent, the solvent of the second kit composition is the same as or different from the sol vent of the first ki t composition.|0l 28] In any one or more kits of fifth embodiments herein, a froth flotation processing kit comprises, consists essentially of, or consists of a first kit composition that is a modifier composition in accordance with any one of first embodiments herein; a second kit composition that is a collector composition comprising, consisting essentially of, or consisting of one or more sulfonated fatty acids, one or more sulfonated fatty acid sal ts, or any combination thereof; and a third kit composition that is a beneficiating agent composition comprising, consisting essentially of, or consisting of one or more hydroxy fatly acids, one or more one or more hydroxy fatty acids, one or more hydroxy faty acid salts, or any combination thereof. In some such fifth embodiments, the third kit composition further includes a solvent selected from any of the solvents disclosed in first embodiments herein, wherein the solvent of the third kit composition is the same as or different from the solvent of the fust kit composition and / or the solvent of the second kit composition. That is, any one or more of first, second, or third kit compositions of kits of fifth embodiments herein can include a solvent, further wherein the solvent for each of the kit compositions is individually selected from the solvents o.f first embodiments herein.(0129| In any one or more kits of fifth embodiments herein, a froth flotation processing kit comprises, consists essentially of, or consists of a first kit composition disposed within a first containment; and a second kit composition disposed within a second containment. In any one or more kits of fifth embodiments, a froth flotation processing kit further includes a third kit composition disposed within a third containment. In any one or more kits of fifth embodiments, any one or more of first, second, or third containments are 'formed from glass, metal, or plastic, or any combination of these, in any one or more kits of fifth e mbodiments, a froth flotation processing kit is provided in a package, bag, box, cart, case, or combination of two or more thereof that is suitable for transporting the froth flotation processing kit from a manufacturing location or a storage location to a location proximal to one or more froth flotation cells used for flotation of phosphate ore, lithium ore, or iron ore. In any one or more kit containments of fifth embodiments, a froth flotation processing kit containment is adapted and configured to connect directly to one or more pipes or tubes to establish a sealed fluidconnection for directing a kit composition from within the kit containment into a froth flotation cell. In any one or more kits of fifth embodiments herein, the rate of addition and timing of batch addition of one or more kit compositions to a froth flotation cell is suitably controlled by an operator of the froth flotation cell.|O1 SOI EXPERIMENTAL SI ( TIOX

[0131] Example 1[0132J Collector formulation and modifier formulations were formed by admixing the components of Table 1 in the indicated amounts. The admixed formulations were observed to be stable and homogeneous solutions or emulsions, that is, cadi of the formulations was allowed to sit on a laboratory bench for a period of 24 months, and no phase visible signs of separation, gelling, or other instability was observed.

[0133] Table 1. Components of collector and modifier formulations

[0134] Examples 2 and 3

[0135] The collector formulations and modifier formulation of Example 1 were subjected to reverse froth flotation testing using the following general procedure.

[0136] The reverse froth flotation tests arc conducted in a 1 liter flotation cell using a standard laboratory flotation machine equipped with mechanical stirrer. For each test, a shiny of phosphate ore is made by dispersing a 255g charge of an air-dried, split, and bagged phosphate ore in 750 mL tap water within the flotation cell, while stirring the cell contents at 500 rpm; and then continuously stirring at 500 rpm throughout the following steps: allow the cell contents to be stirred for 1 minute; then add phosphoric acid solution (50-52% PAT) to the cell in an amount sufficient to adjust the pH of the cell contents to a value between 5 and 5.2; then allow the cell contents to be stirred for I minute: then add a collector composition of Table I to the cell in a selected amount; then allow the cell contents to be stirred for I minute; then add a modifier composition of Table 1. if any. to the cell in a selected amount; then, if a modifier composition was added, allow the cell contents to be stirred for 30 seconds.

[0137] Upon completing the foregoing steps, the rate of stirring is increased to 750 rpm, and air is sparged through the contents of the cell at a rate of 5 liters / minute for 3 minutes. Any excess foam appearing in the test cell is noted during the sparging; observations regarding excess foaming are noted following Table 2.

[0138] Then a gangue comprising calcite and or dolomite is floated from the slurry and removed as tailings; and a concentrated phosphate ore comprising apatite remains in the starry as concentrate. Both concentrate and tailings arc filtered, dried, weighed, and the concentrate materials analyzed for P2O5 grade and % recovery. Results of the analysis are shown in Table 2.

[0139] Table 2. Results and observations of reverse froth flotation testing of Formulations 1-4 of Table 1.

[0140] It was father observed during the sparging that a small amount of excess foam was generated in the test of Example 2. w hile no excess foam was generated in the test of Example 3.

[0141] It can be seen from the results in Table 2 that Example 3, employing a modifier formulation in accordance with the modifier compositions of first embodiments herein, and embodying a sparge composition that accords with the sparge compositions of second embodiments herein, and tested using reverse froth flotation in accordance with the methods of third embodiments herein, obtains 1.68% greater grade of P?O in the concentrate, and 0.89% lower grade of P2O in the tailings compared to Example 2. Example 2 employs a modifier formulation that includes an alkoxylated fatty alcohol, but excludes a fatty acid triglyceride. Accordingly, the Modifier 3 formulation is not a modifier composition in accord with first embodiments herein, and the sparge composition of Example 2 is not a sparge composition in accord with any of second embodiments herein.

[0142] It can further be seen from the results in Table 2 that Example 3 obtains 2.26% greater yield (recovery) of P2O5 in the concentrate, and 2.26% less P2O5 in the tailings compared to Example 2. Accordingly, in Example 3, improvements in phosphate grade correlate with improxements m phosphate recovery, which is unexpected and counterintuitive to the understanding of one of skill in the art of froth flotation.

Claims

What is claimed is:

1. A modifier composition comprising a mixture of one or more faty acid triglycerides with one or more alkoxylated faty alcohols.

2. The modifier composition of claim 1 further comprising a solvent, the solvent optionally comprising water, wherein the solvent is 0.1 wt% to 99 wt% of the modifier composition.

3. The modifier composition of claim 1 or claim 2 wherein the weight proportion of the one or more faty acid triglycerides to the one or more alkoxylated fatty alcohols in the mixture is between 100:1 and 1 : 100.

4. The modifier composition of any one of claims 1-3 wherein each of the one or more alkoxylated tatty alcohols independently has a structure according to the formulaR{-O-(CHR2*CHR3-O]n-[CHR4*CHR5-O:|»>“R4whereinR1is a linear, branched, or alicyclic C6-C30 saturated or unsaturated moiety,Ry Ry R4, R’ and Rf' are independently selected from H or a Cl -C5 linear or branched alkyl moiety, n is 0 or an integer between 1 and 100, m is 0 or an integer between I and 100, and the sum of n + m is at. least 2.

5. The modifier composition of claim 4 wherein the one or more alkoxylated laity alcohols comprises a first alkoxylated fatty alcohol comprising R* that is a linear or branched C16-C20 moiety; and a second alkoxylated faty alcohol comprising R5that is a linear or branched C6-C14 moiety.

6. The modifier composition of claim 5 wherein the first alkoxylated fitly alcohol comprises R" Ry and R4each of which is H, R' that is CH?, n that is between I and 35, and m that is between 1 and 35; and the second alkoxylated fatty alcohol comprises R?Rf and R4each of which is H, Rsthat is CH;?, n that is between 1 and 35, and m that is between 1 and 35.

7. The modifier composition of any one of claims 1 -6 wherein each of the one or more fatty acid triglycerides independently has a structure according to the formulawherein R7, R\ and R9are independently selected from saturated or unsaturated C6-C3O linear, branched, or alicyclic moieties.8, The modifier composition of claim 7 wherein one or more of R y R5, and R‘ are C10-C20 moieties, and / or wherein one or more of R7, R8, and R9are unsaturated.

9. The modi fier composition of any one of claims 1-8 wherein each of the one or more faty acid triglycerides are derived from a plant source, optionally wherein the plant source is selected from: coton, flax, grape, hemp, safflower, olive, palm, peanut, rice, avocado, canola, coconut, com, sesame, soybean, sunflower, walnut, or any combination thereof..

10. A sparge composition comprising a mixture of:(i) a medium comprising water;(it) a mineral orc comprising a beneficiary and a gangue;(iii) a collector; and(iv) a modifier composition in accordance with claim 1 .1 1 . The sparge composition of claim 10 wherein the mineral ore is a phosphate ore, a lithium ore, or an iron ore, wherein the phosphate ore comprises an apatite beneficiary and a gangue comprising calcite, dolomite, a silicate, silica, a seashell or seashell portion, or any combination thereof.

12. ’The sparge composition of claim 10 or claim 1 1 further comprising a pH adjustment agent selected from phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, citric acid, a polymeric acid, or any combination thereof; and / or sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, or any combination thereof.

13. The sparge composition of any one of claims 10-12 further comprising a beneficiation agent, wherein the beneficiation agent optionally comprises ricinoleic acid, asalt of ricinoleic acid, 12-hydroxystearic acid, a salt of 12~hydroxystearic acid, 9,10- dihydfoxyoctadecanoic acid, a salt of 9,t0-diliydroxyoctadecanoic acid, 9,10, 18- frihydroxyoctadecanoic acid, a salt of 9,10,i8*trihyd«)xyoctadec.anoic acid, lesquerolic acid, a salt of lesquerolic acid, 15-hydroxyhexadecanoic acid, a salt of 15-hydroxyhexadecanoic acid, isoric-inoleic acid, a salt of isoricinoleic acid, densipolic acid, a salt of densipolic acid, 14-hydroxy-eicosa-cis-l l-cis-17-dienoic acid, a salt of 14-hydroxy-eicosa-cis-i l -cis-17- dienoic acid, 2-hydroxyoleic acid, a salt of 2-hydroxyoleic acid, 2-hydroxylinoleic acid, a salt of 2-hydroxylinoleic acid, 18-hydroxystearic acid, a salt of 18-hydroxylinoleic acid, 15- hydroxylinoleic acid, a salt of 15-hydroxylmoleic acid, or any combination thereof14, The sparge composition of any one of claims 10~ 13 wherein the collector comprises sulfonated oleic acid, a sulfonated oleic acid salt, sulfonated linoleic acid, a sulfonated linoleic acid Salt, sulfonated linolenic acid, a sulfonated linolenic acid salt, sulfonated ricinoleic acid, a sulfonated ricmoleic acid salt, sulfonated palmitoleic acid, a sulfonated palmitoleic acid salt, sulfonated 11-eicosenoic acid, a sulfonated 11-eicosenoic acid salt, sulfonated erucic acid, a sulfonated erucic acid salt, sulfonated nervonic acid, a sulfonated nervonic acid salt, or any combination thereof15, The sparge composition of any one of claims 10-14 further comprising one or more emulsifying surfactants, one or more additional collectors, one or more depressants, one or more activators, one or more frothing agents, or any combination thereof,16, The sparge composition of claim 10 further comprising a beneficiating agent comprising one or more hydroxy fatty acids, one or more hydroxy fatty acid salts, or any combination thereof, wherein the collector comprises one or more sulfonated fatty acids, one or more sulfonated fatty acid salts, or any combination thereof.17 , The sparge composition of any one of claims 10- 16, furt her comprising a pH adjusting agent and having a pH of about 2.5 to about 7.18, The sparge composition of any one of claims 10-16, further comprising a pH adjusting agent and having a pH of about 7 to about 12.19, A method of froth flotation comprising sparging the sparge composition of claim 10 hi a flotation cell to yield a sparged slurry comprising an overflow and an underflow.

20. The method of claim 19 further comprising collecting the overflow, or the underflow, or both the overflow and the underflow.21 , A froth flotation processing kit comprising a modifier composition of claim 1 disposed within a first containment; and a collector composition disposed within a second containment, the collector composition comprising one or more sulfonated fat ty acids, one or more sulfonated fatty acid salts, or any combination thereof.

22. Use of a mixture of one or more fatty acid triglycerides with one or more alkoxylated fatty alcohols io modify the collection of a phosphate ore beneficiary.

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