METHODS AND COMPOSITIONS FOR TREATING IRON ORES

Description

FIELD

The present invention generally relates to treatment of iron ores to reduce the concentration of one or more unwanted mineral species therein.

BACKGROUND

Although iron is one of the most abundant elements in the Earth's crust, the vast majority of this industrially critical element is entrained within silicate or carbonate minerals. The thermodynamic barriers to separating pure iron from these minerals are formidable and energy-intensive; accordingly, the global iron production industry exploits comparatively rarer iron oxide minerals, primarily hematite. Iron oxides are collected from one or more excavation sites as iron ore. The majority of as-mined, or “run of mine” iron ore is processed to make pig iron, which is a principal raw material in steelmaking. Historically, much of the iron ore utilized by industrialized societies has been mined from hematite deposits with grades of around 70% Fe or higher; a grade of at least 62% Fe is required for an iron-bearing ore product to be introduced into a steelmaking process. Increasing demand for steel and therefore iron ore, coupled with the depletion of high-grade hematite ores in the United States, led to the more recent development of lower-grade iron ore sources such as magnetite and taconite. These ores require extensive and/or complicated processing, such as e.g. froth flotation, and notoriously generate large quantities of waste materials in order to achieve sufficient grade for iron ore use in steelmaking.

Due to the complications of remediating lower grade ores for use in making steel, so-called “direct-shipping” iron ore (DSO) deposits, typically hematite deposits, are still being mined on all continents on Earth except Antarctica. DSO grades are generally at least 62% Fe, which is a sufficiently high iron concentration to introduce the ore directly to a steelmaking process, bypassing the extensive processing required for the lower-grade ores. Accordingly, while DSO deposits are rarer than e.g. magnetite-bearing or taconite-bearing banded iron formations, the higher iron content of the DSO and the ability to circumvent complicated ore processing steps such as froth flotation continue to make these deposits commercially viable for excavation.

Despite their high grade of iron, DSO deposits can include significant amounts of unwanted mineral species, which are non-iron based metals, non-iron based metal-containing compounds, and particles containing one or more non-iron based metals and/or one or more non-iron based metal-containing compounds. Principal unwanted mineral species present in DSO are aluminum-, silicon-, and/or phosphorus-containing species, including alumina species such as alumina (Al₂O₃ and other oxides); silica (SiO₂) species such as quartz; aluminosilicate clay mineral species such as kaolinite (Al₂Si₂O₄(OH)₄), smectite, and Illite; and phosphorus minerals such as hydroxyapatite. In some cases, a DSO includes significantly higher concentrations of these unwanted mineral species than even magnetite-bearing or taconite-bearing deposits. For example, a run of mine DSO deposit can include as much as 10 wt %, 12 wt %, or even 15 wt % alumina species, due in significant part to high concentration of aluminosilicate clays such as kaolinite minerals in the rock matrix surrounding the ore product. A DSO may include a similarly significant amount of silica, for example as much as 15 wt % silica in part due to the presence of high clay concentrations. Additionally, DSO may also have high concentrations of phosphates, for example 2 wt % to 3 wt %.

It is desirable to obtain the lowest possible alumina content, and/or the highest possible iron content in an iron ore, in order to provide the highest quality source material possible for introduction to a steelmaking process. Accordingly, there is an ongoing need in the industry for methods and materials useful to reduce the concentration of alumina species in a DSO. Further, there is a need in the industry to reduce the concentration of silicon and/or phosphorus present in a DSO. However, solutions to meet the foregoing needs must account for industry reliance on the simplicity of DSO processing as the principal benefit of these ores. Accordingly, there is a need in the industry to meet the foregoing needs while also avoiding the use of complicated, waste-intensive processes such as froth flotation, since such use would defeat the benefits of a DSO by requiring the same level of processing needed for lower-grade ores.

The iron ore processing industry employs scrubbing methodologies for DSO which in some cases can help to reduce the concentration of alumina species and/or silicon species in the ore. Scrubbing is a continuous process carried out in a scrubber, which is a horizontally disposed screen situated as a continuous web moving in a horizontal direction beneath a series of nozzles or spray heads. In a conventional iron ore process, run-of-mine DSO ore is comminuted and classified, in some cases using wet hydrocyclone. The comminuted, classified DSO particulate is applied to the scrubber's moving web and transported horizontally while water is dispensed onto the classified DSO particulate from the nozzles or spray heads. In a conventional scrubber, water is applied at a rate to obtain about 20% to 80% ore solids on the web during the scrubbing, often 40% to 70% solids on the web during the scrubbing. The screen gauge of the scrubber's moving web is sized to retain the classified ore particulate; and accordingly, the dispensed water, compounds dissolved therein, and particulates able to traverse the screen are continuously separated from the ore by action of gravity while fresh water is dispensed onto the ore as the ore is transported through the scrubber. At the end of the web's path through the scrubber, the scrubbed iron ore is collected from the screen.

In some cases, use of a scrubber to scrub a classified DSO having a particle size between about 0.5 mm and about 50 mm can reduce the alumina content thereof, e.g. reduce the alumina content thereof slightly, e.g. 1% to 3%; however, in most cases scrubbing fails to reduce the content of either clay minerals or alumina from a DSO at all. In still other cases, the alumina content of a DSO is sufficiently high—such as 8 wt %, 10 wt %, 12%, or even 15 wt % or more—that any reduction thereof obtained by conventional scrubbing is insufficient to produce an ore having 5 wt. % alumina or less. Currently, even though they include 62 wt. % Fe or more, such DSO must still be subjected to one or more additional steps, usually froth flotation, in order to reach an acceptable commercial level of unwanted mineral species to enable its use in steel manufacturing.

Accordingly, there remains a need in the industry to provide improved methods for reducing the concentration of alumina in iron ores, without the need to use complicated processing steps such as froth flotation. There is a need in the industry to reduce alumina content in iron ores having an iron content 62 wt % or more and an alumina content of 5 wt % or more without the need to use complicated ore processing steps such as froth flotation. There remains an additional need in the industry to provide improved methods for reducing silicon and/or phosphorus in iron ores, further without the need to use complicated ore processing steps such as froth flotation. And there remains an ongoing need in the industry to provide increased iron content in iron ores, including DSO, without the need to use complicated ore processing steps such as froth flotation.

SUMMARY

Disclosed herein are methods of treating an iron ore to reduce the amount of one or more unwanted mineral species therein, wherein the one or more unwanted mineral species include non-iron metals, non-iron metal-containing compounds, or any particle(s) containing one or more non-iron metals and/or one or more non-iron metal-containing compounds. In any one or more embodiments of the methods herein, the one or more unwanted mineral species comprise, consist essentially of, or consist of one or more alumina species, one or more silicon species, and/or one or more phosphorus species. In any one or more embodiments herein, the methods of treating an iron ore comprise, consist essentially of, or consist of combining water, one or more anionic surfactants, and one or more polymers having a net negative charge (“net negative charge polymers”) to form a treatment composition; contacting an iron ore with the treatment composition to form a treatment slurry; and collecting a treated iron ore and a spent treatment composition from the treatment slurry. Accordingly, in any one or more embodiments herein, the methods herein exclude sparging the treatment composition or the treatment slurry, or addition of a froth to the treatment composition or to the treatment slurry.

In accordance with the foregoing, disclosed herein are treatment compositions comprising, consisting essentially of, or consisting of a mixture of water, one or more anionic surfactants, and one or more net negative charge polymers. In any one or more treatment compositions herein, the one or more anionic surfactants are sulfonate or sulfate surfactants. In any one or more compositions herein, the net negative charge polymer is a water soluble or water dispersible polymer. In any one or more compositions herein, the net negative charge polymer includes a sulfonated monomer.

In any one or more embodiments of the methods herein, the iron ore contacted with the treatment composition is a comminuted, classified iron ore particulate. Accordingly, in any one or more embodiments, the methods herein include comminuting a run of mine iron ore, and classifying the comminuted ore to provide a classified iron ore particulate, which is an iron ore particulate having a selected particle size range. In some embodiments of the methods herein, the classified iron ore particulate comprises, consists essentially of, or consists of particles ranging in size between 0.5 mm and 10 mm, as determined by sieving (screening). In other embodiments of the methods herein, the iron ore contacted with the treatment composition comprises, consists essentially of, or consists of particles ranging in size between 10 mm and 50 mm, as determined by sieving.

Further in any one or more embodiments of the methods herein, the iron ore includes 50 wt % iron or more. In some embodiments of the methods herein, the iron ore includes more than 5 wt % of one or more unwanted mineral species, where an unwanted mineral species is any non-iron based metal, and/or any non-iron based metal-containing compound, and/or any particle(s) containing one or more non-iron based metals and/or one or more non-iron based metal-containing compounds. In some embodiments of the methods herein, the iron ore includes more than 5 wt % of one or more alumina species.

In any one or more embodiments herein, the foregoing methods are carried out using a scrubber. Any one or more such scrubbing methods comprise, consist essentially of, or consist of applying a classified iron ore particulate to a screen that is designed and adapted to retain particles of the selected size (class); directing a treatment composition to be dispensed from a position above the screen in a direction toward the classified iron ore particulate situated on the screen, to obtain contact of the treatment composition with the classified iron ore particulate situated thereon to form a treatment slurry; and collecting a treated iron ore particulate from the screen.

Accordingly, also disclosed herein are treatment slurries comprising, consisting essentially of, or consisting of a mixture of an iron ore, water, one or more anionic surfactants, and one or more net negative charge polymers. In any one or more treatment slurries herein, the iron ore is a comminuted, classified iron ore.

In any one or more scrubbing embodiments herein, the methods herein further include collecting a spent treatment composition from underneath the screen. In such embodiments, one or more unwanted mineral species become dissolved or dispersed in the treatment slurry during the contacting, and subsequently depart, pass through, or drain from the screen along with one or more components of the treatment composition, and the materials draining through the screen are collected therefrom as a spent treatment composition.

Accordingly, also disclosed herein are spent treatment compositions. In any one or more embodiments herein, the spent treatment compositions comprising or consisting essentially of water, one or more components of the treatment composition, and one or more unwanted mineral species, wherein an unwanted mineral species is any non-iron based metal, and/or any non-iron based metal-containing compound, and/or any particle(s) containing one or more non-iron based metals and/or one or more non-iron based metal-containing compounds. In any one or more embodiments herein, an unwanted mineral species is a chemical compound or a particle including one or more of alumina, silica and phosphates.

In any one or more embodiments of the treatment methods herein, a treated iron ore includes 5% to 90% less by weight of one or more unwanted mineral species compared to the amount of the unwanted mineral species present in the iron ore prior to the treatment. In any one or more embodiments of the methods herein, a treated iron ore includes 2% to 90% less by weight of one or more alumina species compared to the amount of the one or more alumina species present in the iron ore prior to the treatment. In any one or more embodiments herein, a treated iron ore includes 2% to 90% less by weight of one or more silicon species compared to the amount of the one or more silicon species present in the iron ore prior to the treatment. In any one or more embodiments herein, a treated iron ore includes 5% to 90% less by weight of one or more phosphorus species compared to the amount of the one or more phosphorus species present in the iron ore prior to the treatment. In any one or more embodiments herein, a treated iron ore includes 2% to 90% less by weight of one or more alumina species, and 2% to 90% less by weight of one or more silicon species compared to the amount of these unwanted mineral species present in the iron ore prior to the treatment. In any one or more embodiments herein, a treated iron ore includes 2% to 90% less by weight of one or more alumina species, and 2% to 90% less by weight of one or more phosphorus species compared to the amount of these unwanted mineral species present in the iron ore prior to the treatment. In any one or more embodiments herein, a treated iron ore includes 2% to 90% less by weight of one or more alumina species, 2% to 90% less by weight of one or more silicon species, and 2% to 90% less by weight of one or more phosphorus species compared to the amount of these unwanted mineral species present in the iron ore prior to the treatment.

Other objects and features will be in part apparent and in part pointed out hereinafter.

DETAILED DESCRIPTION

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 invention. Various embodiments will be described in detail with reference to the drawings, wherein like reference numerals represent like parts and assemblies throughout the several views. Reference to various embodiments does not 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.

Definitions

Unless otherwise indicated, all parts and percentages are by weight and all molecular weights are weight average molecular weights. 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 case of conflict, the present document, including definitions, will control. Preferred methods and materials are 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.

As used herein, the term “monomer” is used in context to mean either an unsaturated compound or a polymerized residue thereof that is a repeat unit (or repeating unit).

As used herein, the term “anionic monomer” refers an unsaturated compound or polymerized residue thereof (that is, “anionic repeat unit”) bearing an acidic group having a pKa of about 5 or less, the conjugate base thereof, or a salt thereof.

As used herein, the term “cationic monomer” means an unsaturated compound or polymerized residue thereof (that is, “cationic repeat unit”) bearing a positive charge, or a salt thereof.

As used herein, the term “net charge” means the theoretical sum of all anionic (negative) charge and all cationic (positive) charge in a polymer. Where the polymer is a synthetic polymer bearing one or more repeat units, each anionic repeat unit in a polymer bears or is capable of bearing a −1 charge and each cationic repeat unit in the polymer bears a +1 charge. Where a repeat unit bears a +2 or −2 charge, such repeat units should be counted as two molar equivalents for the purpose of calculating net charge.

As used herein, a “net negative charge polymer” refers to a polymer having a net charge of −1 or less. Where the net negative charge polymer is a synthetic polymer bearing one or more repeat units, the net negative charge polymer includes at least one anionic repeat unit, further wherein the sum of the one or more anionic repeat units is greater than the sum of the one or more cationic repeat units presents in the net negative charge polymer.

As used herein, the term “solution” indicates one or more materials dissolved or homogeneously dispersed in a liquid comprising water and optionally one or more salts, buffers, acids, bases, water miscible solvents, or surfactants; one or more dissolved, dispersed, or emulsified compounds, materials, or components; or any combination of these.

As used herein, the term “unwanted mineral species” refers to any non-iron based metal, and/or any non-iron based metal-containing compound, and/or any particle(s) containing one or more non-iron based metals and/or one or more non-iron based metal-containing compounds.

The terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, 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.

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.

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” the recitation means “1 to 5” and “about 1 to about 5” and “1 to about 5” and “about 1 to 5” unless specifically limited by context.

As used herein, the term “substantially” means “consisting essentially of”, as that term is construed in U.S. patent law, and includes “consisting of” as that term is construed in U.S. patent law. For example, a solution that is “substantially free” of a specified compound or material may be free of that compound or material, or may have a minor amount of that compound or material present, such as through unintended contamination, side reactions, or incomplete purification. A “minor amount” may be a trace, an unmeasurable amount, an amount that does not interfere with a value or property, or some other amount as provided in context. A composition that has “substantially only” a provided list of components may consist of only those components, or have a trace amount of some other component present, or have one or more additional components that do not materially affect the properties of the composition. Additionally, “substantially” modifying, for example, the type or quantity of an ingredient in a composition, a property, a measurable quantity, a method, a value, or a range, employed in describing the embodiments of the disclosure, refers to a variation that does not affect the overall recited composition, property, quantity, method, value, or range thereof in a manner that negates an intended composition, property, quantity, method, value, or range. Where modified by the term “substantially” the claims appended hereto include equivalents according to this definition.

As used herein, any recited ranges of values contemplate all values within the range and are to be construed as support for claims reciting any sub-ranges having endpoints which are real number values within the recited range. By way of a hypothetical illustrative example, a disclosure in this specification of a range of from 1 to 5 shall be considered to support claims to any of the following ranges: 1-5; 1-4; 1-3; 1-2; 2-5; 2-4; 2-3; 3-5; 3-4; and 4-5.

Discussion

Disclosed herein are methods of treating an iron ore to reduce the amount of unwanted mineral species present therein. In any one or more embodiments herein, the methods comprise, consist essentially of, or consist of combining water, one or more anionic surfactants, and one or more polymers having a net negative charge to form a treatment composition; contacting an iron ore with the treatment composition to form a treatment slurry; and collecting a treated iron ore and a spent treatment composition from the treatment slurry.

Accordingly, described in first embodiments herein are treatment compositions for reducing the amount of one or more unwanted mineral species present in an iron ore. In any one or more first embodiments, a treatment composition comprises, consists essentially of, or consists of water, one or more anionic surfactants, and one or more net negative charge polymers. In any one or more first embodiments herein, a treatment composition comprises, consists essentially of, or consists of an aqueous solution of one or more anionic surfactants and one or more net negative charge polymers.

In any one or more first embodiments herein, one or more of the anionic surfactants is a surfactant having formula I

wherein n is an integer between 1 and 4, R¹ is a linear, branched, cyclic, or alicyclic organic moiety having between 5 and 40 carbons, or between 7 and 30 carbons, or between 10 and 30 carbons, or between 12 and 20 carbons, and optionally one or more nitrogen and/or oxygen atoms; A¹ is SO₃⁻ (sulfonate), OSO₃ (sulfate) or CO₂⁻ (carboxylate); and where n is 1, X is Na, Ka, Li, K, NH₄, primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium; where n is 2, X is Mg, Zn, Zr, Ba, or Ca; where n is 3, X is Al, Mn, or Fe; and where n is 4, X is Ti or Zr. In any one or more embodiments of structure I where n is 1, the primary ammonium is NH₃⁻ CH₂—CH₂—OH. In any one or more embodiments of structure I where n is 1, the secondary ammonium is NH₂(CH₂—CH₂—OH)₂. In any one or more embodiments of structure I where n is 1, the quaternary ammonium is a tetraalkylammonium having four individually selected C1-C5 alkyl groups. In any one or more embodiments of structure I, R¹ is a linear or branched hydrocarbyl moiety. In any one or more embodiments of structure I, R¹ includes one or more ether groups, and/or one or more ester groups. In any one or more embodiments of structure I, R¹ is a dioic acid diester of a C6-C12 alcohol. In some such embodiments, the C6-C12 alcohol is a branched C8-C10 alcohol. In any one or more embodiments of structure I, A¹ is sulfonate. In any one or more embodiments herein, the one or more anionic surfactants includes the sodium salt of butane dioic acid, 2-sulfo-1,4-bis(2-ethylhexyl) ester, also referred to as dioctyl sodium sulfosuccinate, or “DOSS”.

In any one or more embodiments of structure I, A¹ is SO₃⁻ (sulfonate) and R¹ includes one or more ether groups. In any one or more such embodiments, R¹ is CH₃(CH₂)_a—O—(CH₂—CH₂O)_b, -L- that is, an “alketh” moiety, wherein a is 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19; and b is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; and L is a linking group selected from divalent hydrocarbyl moieties optionally including one or more hydroxyl groups. Where R¹ is an alketh moiety and A¹ is SO₃″, structure I is an alketh sulfonate.

In another example of structure I where A¹ is SO₃ (sulfonate) and R¹ includes one or more ether groups, the anionic surfactants is a surfactant having formula IA,

wherein R² is a C₄ to C₂₂ linear or branched alkyl group. In some such embodiments, R² of formula IA is n-hexyl, X is Na, and the anionic surfactant is sodium hexyldiphenyl ether sulfonate.

In another example of structure I where A¹ is SO₃⁻ (sulfonate) and R¹ includes one or more ether groups, the anionic surfactants comprise, consist essentially of, or consist of one or more sulfolipids. Sulfolipids include one or more C12-C30 alkyl or alkenyl groups bonded to a sulfonate group through ether linkages. In embodiments, one or more sulfolipids are naturally occurring compounds. One exemplary sulfolipid is the glycoside sulfoquinovosyl diacylglycerol, sodium salt, which has a structure corresponding to structure IB:

Anionic surfactants having formula I also include alkyl sulfonates such as α-olefin sulfonates (AOS), alkylbenzene sulfonates including C6-C20 linear alkylbenzene sulfonates (LAS); sodium nonanoyloxybenzenesulfonate; and carboxylates such as ammonium stearate, sodium laurate, sodium tallowate, and sodium lauroyl sarcosinate.

Anionic surfactants having formula I also include alkyl sulfates such as sodium lauryl sulfate (SLS), ammonium lauryl sulfate, potassium lauryl sulfate, and sodium tetradecyl sulfate; alketh sulfates such as sodium laureth sulfate, magnesium laureth sulfate and sodium myreth sulfate. In some embodiments of structure I, A¹ is OSO₃⁻ (sulfate) and R¹ includes one or more ether groups. In some embodiments, R¹ is CH₃(CH₂)_a—O—(CH₂—CH₂O)_b—CH₂—CH₂—, that is, an “alketh” moiety, wherein a is 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19; and b is 1, 2, hy3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. Where R¹ is an alketh moiety and A¹ is OSO₃⁻, structure I is an alketh sulfate. In one example of structure I wherein R¹ includes one or more ether groups, n is 1, X is Na, A¹ is OSO₃⁻, R¹ is CH₃(CH₂)₁₁—O—(CH₂—CH₂O)_b—CH₂—CH₂— and b is between 3 and 20; and the compound having structure I is sodium laureth sulfate.

In any one or more first embodiments herein, the one or more anionic surfactants comprise, consist essentially of, or consist of an alkyldiphenyloxide disulfonate surfactant having a structure selected from formulae IIA, IIB, and IIC:

wherein R² is a C₄ to C₂₂ linear or branched alkyl group, and M⁺ is selected from the group consisting of Na⁺, K⁺, NH₄⁺, primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium. In some embodiments, the alkyldiphenyloxide disulfonate is hexyldiphenyl ether disulfonate; in some such embodiments, M⁺ is Na⁺.

In any one or more first embodiments herein, one or more of the anionic surfactants is a phosphate ester surfactant having formula III:

wherein R³, R⁴, and R⁵ are independently selected from: hydrogen; a metal selected from Na, Ka, Li, K, Mg, Zn, Zr, Ba, Ca, Al, Mn, Fe, Ti, or Zr; an ammonium selected from NH₄, NH₃—CH₂—CH₂—OH, or NH₂ (CH₂—CH₂—OH)₂; or Group IIIA:

wherein R⁶ is a C5 to C30 linear or branched alkyl, alkenyl, aryl, alkaryl, or aralkyl group, c is 0 or an integer between 1 and 30, and each R⁷ and R⁸ are independently selected from hydrogen or a C1-C5 linear or branched alkyl moiety, further wherein at least one of R³, R⁴, and R⁵ of formula III is Group IIIA and at least one of R³, R⁴, and R³ of formula III is a metal or an ammonium. In some such embodiments, two of R³, R⁴, and R⁵ are Group IIIA. In some embodiments of Group IIIA, c is 3-5, 5-7, 7-10, 10-13, 13-15, 15-17, 17-20, 20-23, 23-25, 25-27, or 27-30. In some embodiments of Group IIIA, each of the c iterations of R⁷ is hydrogen. In some embodiments of Group IIIA, each of the c iterations of R⁸ is hydrogen. In some embodiments of Group IIIA, all R⁷ and all R⁸ are hydrogen. In some embodiments of Group IIIA, one or more of the c iterations of R⁷ or R⁸ is methyl.

In any one or more first embodiments herein, a net negative charge polymer is a homopolymer or copolymer having a net negative charge, that is, wherein the theoretical sum of all charge in the polymer is-1 or less. Stated differently, a net negative charge polymer includes at least one anionic moiety, such as an anionic moiety bonded to a repeat unit (that is, anionic repeat unit), further wherein the sum of all anionic moieties in the net negative charge polymer is greater than the sum of all cationic moieties in the net negative charge polymer. The copolymers are not particularly limited as to the type of monomers copolymerized therein, and can include 2, 3, 4, 5, 6, 7, or more chemically different monomers copolymerized therein. Further, the monomers incorporated in the copolymers can include both ionic and nonionic monomers, in addition to one or more anionic monomers. The copolymers useful herein can include any number and mixture of monomers incorporated therein, as long as the polymer has a total net ionic charge of at least −1.

In some first embodiments herein, a net negative charge polymer consists of or consists essentially of repeat units derived from unsaturated compounds, and the sum of all anionic repeat units in the net negative charge polymer is greater than the sum of cationic repeat units in the net negative charge polymer.

Accordingly, any one or more first embodiments herein, a net negative charge polymer is a synthetic polymer including one or more anionic repeat units, in some first embodiments two, three, or more chemically different anionic repeat units, wherein anionic repeat unit(s) is/are derived from polymerization of the one or more anionic monomer(s), wherein an anionic monomer includes one or more acidic moieties having a pKa of about 5 or less, a conjugate base thereof bearing a negative charge, or a salt thereof.

In any one or more first embodiments herein, anionic monomers usefully incorporated in a synthetic net negative charge polymer comprise, consist essentially of, or consist of unsaturated compounds having one or more carboxylate, sulfonate, sulfate, phosphate, or phosphonate moieties, or mixtures of two or more thereof. Examples of anionic monomers include acrylic acid, methacrylic acid, itaconic acid, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), vinylphosphonic acid, vinyl phosphoric acid, vinyl sulfonic acid, sulfomethylated acrylamide, styrene sulfonic acid, and conjugate bases or salts of these. Useful salts of anionic monomers include but are not limited to sodium, lithium, potassium, calcium, magnesium, and ammonium salts. In some first embodiments, the anionic monomers comprise, consist essentially of, or consist of acrylic acid (AA) and/or a salt thereof, 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and/or a salt thereof, and/or mixtures of these.

In some first embodiments herein, a net negative charge polymer further includes one or more cationic repeat units, where a cationic repeat unit is derived from polymerization of a cationic monomer, wherein a cationic monomer includes a positive charge or a salt thereof. Examples of cationic monomers include diallyl dimethyl ammonium chloride (DADMAC), 3-chloro-2-hydroxypropyltrimethyl ammonium chloride (CHPTAC) (3-chloro-2-hydroxypropyl)dimethyl[2-[(2-methyl-1-oxoallyl)oxy] ethyl] ammonium chloride (DEAC), [2-(methacryloyloxy) ethyl] trimethylammonium chloride (METAC), trimethyl-(4-vinyl-benzyl)-phosphonium bromide, 1,3-bis(N,N,N-trimethylammonium)-2-propylmethacrylate dichloride, acryloyloxyethyltrimethylammonium chloride, and methacryloxyethyl trimethyl ammonium chloride. In any one or more first embodiments herein, the net negative charge polymer excludes cationic monomers.

In some first embodiments herein, a net negative charge polymer further includes one or more neutral repeat units, where a neutral repeat unit is derived from polymerization of a neutral monomer, wherein neutral monomers comprise, consist essentially of, or consist of nonionic monomers and zwitterionic monomers. Nonionic monomers are unsaturated compounds that bear neither a negative charge nor a positive charge; and zwitterionic monomers are unsaturated compounds bearing both anionic and cationic charge, further wherein the net charge is zero (that is, the monomer bears, or includes, the same total number of positive and negative charges). Suitable nonionic monomers include acrylamide, methacrylamide, N-alkyl acrylamides and other N-functional acrylamides such as N-(2-hydroxyethyl) acrylamide, esters of acrylic acid and methacrylic acid, N-vinyl pyrrolidone, N, N-diallyl amine, and the like. Suitable zwitterionic monomers include phosphobetaine, sulfobetaine, and carboxybetaine esters of acrylic acid and methacrylic acid.

In any one or more first embodiments herein, a net negative charge polymer is synthesized using any one or more methods conventionally employed to form polymers from unsaturated monomers; such methods most often employ homolysis initiated by thermal decomposition, irradiation, redox reaction, persulfate dissociation, sonication, plasma discharge, or even electrolysis. In some such methods, the polymerization is conducted in water or an aqueous solution (that is, a solution including water).

In any one or more first embodiments herein, a net negative charge polymer is a sulfonated natural polymer. In any one or more such embodiments, a sulfonated natural polymer comprises, consists essentially of, or consists of sulfonated lignin, sulfonated starch, sulfonated cellulose, sulfonated guar gum, sulfonated xanthate gum, or any combination thereof. In any one or more sulfonated natural polymers of first embodiments herein, a sulfonated lignin has a weight average molecular weight range of from about 1,000 to about 140,000. In any one or more sulfonated natural polymers of such embodiments, the sulfonated lignin comprises, consists of, or consists essentially of a byproduct of production of wood pulp using sulfite pumping. In some such embodiments, the sulfonated lignin is synthesized as the reaction product of lignin with one or more sulfites, one or more bisulfites, or a combination thereof. In some such embodiments, a sulfonated lignin is synthesized by converting one or more of the —CH₂OH groups present on a lignin to —CH₂SO₃H, —CH₂SO₃, or a combination thereof.

In any one or more sulfonated natural polymers of first embodiments herein, a sulfonated starch comprises a sulfonated amylopectin synthesized by replacing one or more of the —OH groups of an amylose, an amylopectin, or a combination thereof with a sulfonate group (—SO₃H and/or —SO₃⁻). In any one or more sulfonated natural polymers of first embodiments herein, the sulfonated cellulose is synthesized by replacing one or more of the —OH groups in a cellulose molecule with a sulfonate group (—SO₃H and/or —SO₃⁻).

In any one or more first embodiments herein, a net negative charge polymer is water dispersible or water soluble. In any one or more first embodiments herein, a net negative charge polymer consists of or consists essentially of anionic repeat units. In any one or more first embodiments herein, the net negative charge polymer excludes cationic moieties. In any one or more first embodiments herein, the net negative charge polymer excludes cationic repeat units. In any one or more first embodiments herein, the net negative charge polymer excludes nonionic repeat units. In any one or more first embodiments herein, the net negative charge polymer excludes cationic monomers and nonionic monomers.

In any one or more first embodiments herein, the net negative charge polymer comprises, consists essentially of, or consists of a copolymer of acrylic acid and/or a salt thereof (AA). In any one or more first embodiments herein, the net negative charge polymer comprises, consists essentially of, or consists of a copolymer of 2-acrylamido-2-methylpropane sulfonic acid and/or a salt thereof (AMPS). In any one or more first embodiments herein, the net negative charge polymer comprises, consists essentially of, or consists of an AA-AMPS copolymer wherein the molar ratio of AA to AMPS in the copolymer is between 100:1 and 1:100, for example 100:1 to 95:1, 95:1 to 90:1, 90:1 to 85:1, 85:1 to 80:1, 80:1 to 75:1, 75:1 to 70:1, 70:1 to 65:1, 65:1 to 60:1, 60:1 to 55:1, 55:1 to 50:1, 50:1 to 45:1, 45:1 to 40:1, 40:1 to 35:1, 35:1 to 30:1, 30:1 to 25:1, 25:1 to 20:1, 20:1 to 15:1, 15:1 to 10:1, 10:1 to 5:1, 5:1 to 1:1, 1:1 to 1:5, 1:5 to 1:10, 1:10 to 1:15, 1:15 to 1:20, 1:20 to 1:25, 1:25 to 1:30, 1:30 to 1:35, 1:35 to 1:40, 1:40 to 1:45, 1:45 to 1:50, 1:50 to 1:55, 1:55 to 1:60, 1:60 to 1:65, 1:65 to 1:70, 1:70 to 1:75, 1:75 to 1:80, 1:80 to 1:85, 1:85 to 1:90, 1:90 to 1:95, 1:95 to 1:100.

In any one or more first embodiments herein, the weight average molecular weight of the net negative charge polymer, expressed as g/mol or Da is from about 300 to about 5,000,000, in embodiments about 300 to about 1,000,000, in embodiments about 300 to about 500,000, in embodiments about 300 to about 100,000, in embodiments about 300 to about 50,000, in embodiments about 300 to about 35,000, in embodiments about 300 to about 30,000, in embodiments about 300 to about 25,000, in embodiments from about 500 to about 5,000,000, in embodiments about 500 to about 1,000,000, in embodiments about 500 to about 500,000, in embodiments about 500 to about 100,000, in embodiments about 500 to about 50,000, in embodiments about 500 to about 25,000, in embodiments from about 700 to about 5,000,000, in embodiments about 700 to about 1,000,000, in embodiments about 700 to about 500,000, in embodiments about 700 to about 100,000, in embodiments about 700 to about 50,000, in embodiments about 700 to about 25,000, in embodiments from about 1,000 to about 5,000,000, in embodiments about 1,000 to about 1,000,000, in embodiments about 1,000 to about 500,000, in embodiments about 1,000 to about 100,000, in embodiments about 1,000 to about 50,000, in embodiments about 1,000 to about 40,000, in embodiments about 1,000 to about 35,000, in embodiments about 1,000 to about 30,000, in embodiments about 1,000 to about 25,000, in embodiments about 500 to about 20,000, in embodiments about 500 to about 15,000, in embodiments about 500 to about 10,000, in embodiments about 500 to about 7,000, in embodiments about 500 to about 5,000, in embodiments about 500 to about 3,000, in embodiments about 500 to about 1,000, in embodiments about 1,000 to about 25,000, in embodiments about 700 to about 20,000, in embodiments about 700 to about 15,000, in embodiments about 700 to about 10,000, in embodiments about 700 to about 7,000, in embodiments about 700 to about 5,000, in embodiments about 700 to about 3,000, in embodiments about 700 to about 1,000, in embodiments about 1,000 to about 25,000, in embodiments about 1,000 to about 20,000, in embodiments about 1,000 to about 15,000, in embodiments about 1,000 to about 10,000, in embodiments about 1,000 to about 7,000, in embodiments about 1,000 to about 5,000, in embodiments about 1,000 to about 3,000, or in embodiments about 1,000 to about 2,000.

In any one or more first embodiments herein, a treatment composition includes one or more anionic surfactants and one or more net negative charge polymers present therein in a ratio of between 5:1 and 1:5 by weight in the treatment composition, for example 5:1 to 4:1, or 4:1 to 3:1, or 3:1 to 2:1, or 2:1 to 1:1, or 1:1 to 1:2, or 1:2 to 1:3, or 1:3 to 1:4, or 1:4 to 1:5, or 3:2 to 1:1, or 1:1 to 2:3, or 3:2 to 2:3, or 4:3 to 3:2, or 4:3 to 2:3, or 4:3 to 1:1, or 1:1 to 3:4, or 2:3 to 3:4, or 4:3 to 3:4, or 5:3 to 4:3, or 5:3 to 3:2, or 5:3 to 1:1, or 1:1 to 3:5, or 2:3 to 3:5, or 3:4 to 3:5, or about 2:1, or about 3:2, or about 4:3, or about 5:3, or about 5:4, or about 6:5, or about 1:1, or about 5:6, or about 4:5, or about 3:5, or about 3:4, or about 2:3, or about 1:2 by weight in the treatment composition.

In some first embodiments herein, the one or more anionic surfactants and the one or more net negative charge polymers present in a treatment composition include one or more sulfonate moieties. In some first embodiments herein, the one or more anionic surfactants and the one or more net negative charge polymers present in a treatment composition exclude carboxylate moieties. In some first embodiments herein, the one or more anionic surfactants and the one or more net negative charge polymers present in a treatment composition include one or more sulfonate moieties and also exclude carboxylate moieties.

In any one or more first embodiments herein, the one or more anionic surfactants and the one or more net negative charge polymers are collectively referred to as “actives”, that is, treatment composition actives. A treatment composition of any one of first embodiments herein is suitably described as having a “% actives” that refers to the total weight of actives as a weight percent of the composition overall. The weight percent actives in a treatment composition of any one or more embodiments herein is suitably selected to be between 0.1 wt % and 50 wt %. In a first concentration range, a treatment composition concentrate includes 10 wt % to 50 wt % actives, such as 10 wt % to 40 wt %, or 10 wt % to 30 wt %, or 10 wt % to 20 wt %, or 20 wt % to 50 wt %, or 30 wt % to 50 wt %, or 40 wt % to 50 wt %, or 10 wt % to 20 wt %, or 20 wt % to 30 wt %, or 30 wt % to 40 wt %, or 40 wt % to 30 wt % actives. Treatment composition concentrates include a suitable concentration of actives for manufacturing, shipping, and storage within one or more enclosed/sealed containers, without any observable precipitation within the containers for at least 1 year, and in embodiments up to 10 years when stored at a temperature greater than 0° C.

Optionally, any one or more treatment composition concentrates of first embodiments herein further includes an adjuvant for improving the dispersion stability thereof. Where the water dispersibility or solubility of the one or more treatment composition actives in water is relatively low, such as 1 mg per 70 mL water or less at 20° C., a treatment composition concentrate including such active as a component thereof may undergo apparent phase separation over time, and therefore may require mixing after a storage period, further in preparation for use in treating an iron ore as discussed below. Some such treatment composition concentrates can develop visible evidence of bulk phase separation after a storage period of 3 months or less at temperatures ranging between 1° C. and 50° C. (common storage facility temperatures in the field).

Accordingly, in some first embodiments, a stabilized treatment composition concentrate includes an adjuvant comprising, consisting essentially of, or consisting of one or more alkoxylated alkanols, a cationic polysaccharide, or any combination thereof in order to stabilize the concentrate and extend the storage period of time obtained before bulk phase separation is observed. The adjuvant is suitably combined with one or more of the one or more anionic surfactants, or with the net negative charge polymer, or with the treatment composition concentrate (that is, with the mixture of the one or more anionic surfactants with the net negative charge polymer), such that the stabilized treatment composition concentrate comprises, consists essentially of, or consists of a combination of one or more anionic surfactants, a net negative charge polymer, and one or more adjuvants. The stabilized treatment composition concentrate is contacted with an iron ore to obtain all the benefits associated with the treatment compositions concentrates, except that the stabilized treatment composition concentrates obtain a longer period of storage prior to the contact thereof with the iron ore, when compared to the [unstabilized] treatment composition concentrate

Accordingly, in any one or more first embodiments, an adjuvant included in one or more stabilized treatment composition concentrate comprises, consists essentially of, or consists of an alkoxylated alkanols, one or more polysaccharides, one or more cationic polysaccharides, or any combination thereof. In some such embodiments, the alkoxylated alkanol includes one or more C5-C50 alkanols, that is, a “fatty alcohol”, wherein the oxygen atom of the alkanol is appended by 1-50alkoxy repeat units. Thus, in embodiments, an alkoxylated alkanol is a C9, C10, C11, C12, C13, C14, C15, or C16 alkanol alkoxylated with 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 alkoxy repeat units. In some such embodiments, one or more of the alkoxy repeat units comprise, consist essentially of, or consist of ethoxy or propoxy repeat units. In some such embodiments, each of the alkoxy repeat units are ethoxy repeat units.

In any one or more first embodiments, the polysaccharide comprises, consists essentially of, or consists of amylose, amylopectin, pectin, xanthan gum, guar gum, chitin, inulin, dextran, or cellulose; or a derivative thereof hydroxyethyl cellulose, hydroxypropyl cellulose, or carboxymethyl cellulose; or derivatives of these including carboxylated, hydroxylated, or hydroxyalkylated derivatives or a crosslinked derivative thereof.

In any one or more first embodiments, the cationic polysaccharide comprises, consists essentially of, or consists of an ammonium-functionalized polysaccharide, wherein the polysaccharide is derived from one or more plants and chemically modified to add ammonium functionality. In some such embodiments, the polysaccharide modified to form the ammonium-functionalized polysaccharide comprises, consists essentially of, or consists of one or more amyloses, amylopectins, pectins, celluloses, chitins, dextrans, inulins, or any combination thereof or derivatives of these including carboxylated, hydroxylated, or hydroxyalkylated derivatives. In some embodiments, the ammonium functionality of the cationic polysaccharide comprises, consists essentially of, or consists of a trimethylammonioalkyl ether. One example of a useful cationic polysaccharide is an amylopectin having 2-hydroxy-3-(trimethylammonio) propyl ether groups. In any one or more such embodiments, the ammonium-functionalized polysaccharide is further associated with one or more chloride or acetate counterions.

Any one or more stabilized treatment composition concentrate of first embodiments herein further includes one or more adjuvants, wherein the adjuvant is not active in the stabilized treatment composition concentrate. Accordingly, the weight proportion of actives to the adjuvant in the stabilized treatment composition concentrates is about 2:1 to about 1000:1, for example 2:1 to 5:1, 5:1 to 10:1, 10:1 to 20:1, 20:1 to 30:1, 30:1 to 40:1, 40:1 to 50:1, 50:1 to 60:1, 60:1 to 70:1, 70:1 to 80:1, 80:1 to 90:1, 90:1 to 100:1, 100:1 to 110:1, 110:1 to 120:1, 120:1 to 130:1, 130:1 to 140:1, 140:1 to 150:1, 150:1 to 160:1, 160:1 to 170:1, 170:1 to 180:1, 180:1 to 190:1, 190:1 to 200:1, 200:1 to 210:1, 210:1 to 220:1, 220:1 to 230:1, 230:1 to 240:1, 240:1 to 250:1, 250:1 to 260:1, 260:1 to 270:1, 270:1 to 280:1, 280:1 to 290:1, 290:1 to 300:1, 300:1 to 310:1, 310:1 to 320:1, 320:1 to 330:1, 330:1 to 340:1, 340:1 to 350:1, 350:1 to 360:1, 360:1 to 370:1, 370:1 to 380:1, 380:1 to 390:1, 390:1 to 400:1, 400:1 to 410:1, 410:1 to 420:1, 420:1 to 430:1, 430:1 to 440:1, 440:1 to 450:1, 450:1 to 460:1, 460:1 to 470:1, 470:1 to 480:1, 480:1 to 490:1, 490:1 to 500:1, 500:1 to 510:1, 510:1 to 520:1, 520:1 to 530:1, 530:1 to 540:1, 540:1 to 550:1, 550:1 to 560:1, 560:1 to 570:1, 570:1 to 580:1, 580:1 to 590:1, 590:1 to 600:1, 600:1 to 610:1, 610:1 to 620:1, 620:1 to 630:1, 630:1 to 640:1, 640:1 to 650:1, 650:1 to 660:1, 660:1 to 670:1, 670:1 to 680:1, 680:1 to 690:1, 690:1 to 700:1, 700:1 to 710:1, 710:1 to 720:1, 720:1 to 730:1, 730:1 to 740:1, 740:1 to 750:1, 750:1 to 760:1, 760:1 to 770:1, 770:1 to 780:1, 780:1 to 790:1, 790:1 to 800:1, 800:1 to 810:1, 810:1 to 820:1, 820:1 to 830:1, 830:1 to 840:1, 840:1 to 850:1, 850:1 to 860:1, 860:1 to 870:1, 870:1 to 880:1, 880:1 to 890:1, 890:1 to 900:1, 900:1 to 910:1, 910:1 to 920:1, 920:1 to 930:1, 930:1 to 940:1, 940:1 to 950:1, 950:1 to 960:1, 960:1 to 970:1, 970:1 to 980:1, 980:1 to 990:1, or 990:1 to 1000:1. In such embodiments, a stabilized treatment composition concentrate obtain a longer period of storage stability between 1° C. and 50° C. than a corresponding treatment composition concentrate—that is, the stabilized treatment composition concentrate absent the adjuvant. In some such embodiments, the period of stable storage (that is, the period of storage before visible evidence of bulk phase separation develops) of a stabilized treatment composition concentrate is extended by at least 10%, or by 10%-25%, 25% to 50%, 50% to 75%, 75% to 100%, or even more than 100% compared to the corresponding treatment composition concentrate.

In a second concentration range of any of the treatment compositions of first embodiments, including a stabilized treatment composition, a dilute treatment composition includes about 0.1 ppm to 10,000 ppm actives, such as 0.1 ppm to about 10,000 ppm by weight or w/v (where specified) actives, for example 1 ppm to 10,000 ppm, or 10 ppm to 10,000 ppm, or 50 ppm to 10,000 ppm, or 100 ppm to 10,000 ppm, or 200 ppm to 10,000 ppm, or 300 ppm to 10,000 ppm, or 400 ppm to 10,000 ppm, or 500 ppm to 10,000 ppm, or 600 ppm to 10,000 ppm, or 700 ppm to 10,000 ppm, or 800 ppm to 10,000 ppm, or 900 ppm to 10,000 ppm, or 1000 ppm to 10,000 ppm, or 1500 ppm to 10,000 ppm, or 2000 ppm to 10,000 ppm, or 3000 ppm to 10,000 ppm, or 4000 ppm to 10,000 ppm, or 5000 ppm to 10,000 ppm, or 6000 ppm to 10,000 ppm, or 7000 ppm to 10,000 ppm, or 8000 ppm to 10,000 ppm, or 9000 ppm to 10,000 ppm, or 1 ppm to 5000 ppm, or 10 ppm to 5000 ppm, or 50 ppm to 5000 ppm, or 100 ppm to 5000 ppm, or 200 ppm to 5000 ppm, or 300 ppm to 5000 ppm, or 400 ppm to 5000 ppm, or 500 ppm to 5000 ppm, or 600 ppm to 5000 ppm, or 700 ppm to 5000 ppm, or 800 ppm to 5000 ppm, or 900 ppm to 5000 ppm, or 1000 ppm to 5000 ppm, or 1500 ppm to 5000 ppm, or 2000 ppm to 5000 ppm, or 3000 ppm to 5000 ppm, or 4000 ppm to 5000 ppm, or 0.01 to 0.1 ppm, or 0.1 ppm to 1 ppm, or 1 ppm to 10 ppm, or 10 ppm to 50 ppm, or 50 ppm to 100 ppm, or 100 ppm to 200 ppm, or 200 ppm to 300 ppm, or 300 ppm to 400 ppm, or 400 ppm to 500 ppm, or 500 ppm to 600 ppm, or 700 ppm to 800 ppm, or 800 ppm to 900 ppm, or 900 ppm to 1000 ppm, or 0.1 ppm to 1000 ppm, or 1 ppm to 1000 ppm, or 10 ppm to 1000 ppm, or 100 ppm to 1000 ppm, or 0.1 ppm to 500 ppm, or 1 ppm to 500 ppm, or 10 ppm to 500 ppm, or 100 ppm to 500 ppm, or 500 ppm to 700 ppm, or 700 ppm to 1000 ppm, or 1000 ppm to 1500 ppm, or 1500 ppm to 2000 ppm, or 2000 ppm to 2500 ppm, or 2500 ppm to 3000 ppm, or 3000 ppm to 3500 ppm, or 3500 ppm to 4000 ppm, or 4000 ppm to 4500 ppm, or 4500 ppm to 5000 ppm, or 5000 ppm to 5500 ppm, or 5500 ppm to 6000 ppm, or 6000 ppm to 6500 ppm, or 6500 ppm to 7000 ppm, or 7000 ppm to 7500 ppm, or 7500 ppm to 8000 ppm, or 8000 ppm to 8500 ppm, or 8500 ppm to 9000 ppm, or 9000 ppm to 9500 ppm, or 9500 ppm to 10,000 ppm actives by weight or by w/v. The dilute treatment compositions include a suitable range of actives for carrying out one or more methods of second embodiments described below.

In any one more first embodiments herein, the treatment compositions are characterized as providing reduced surface (interfacial) tension in aqueous compositions, that is, a surface tension of 50 mN/m or less, as measured using Wilhelmy plate methodology. In any one more first embodiments herein, the treatment compositions are characterized as providing low surface (interfacial) tension in aqueous compositions, that is, a surface tension of about 50 mN/m to about 1 mN/m, as measured using Wilhelmy plate methodology, for example 1 mN/m to 2 mN/m, 2 mN/m to 3 mN/m, 3 mN/m to 4 mN/m, 4 mN/m to 5 mN/m, 5 mN/m to 6 mN/m, 6 mN/m to 7 mN/m, 7 mN/m to 8 mN/m, 8 mN/m to 9 mN/m, 9 mN/m to 10 mN/m, 10 mN/m to 11 mN/m, 11 mN/m to 12 mN/m, 12 mN/m to 13 mN/m, 13 mN/m to 14 mN/m, 14 mN/m to 15 mN/m, 15 mN/m to 16 mN/m, 16 mN/m to 17 mN/m, 17 mN/m to 18 mN/m, 18 mN/m to 19 mN/m, 19 mN/m to 20 mN/m, 20 mN/m to 21 mN/m, 21 mN/m to 22 mN/m, 22 mN/m to 23 mN/m, 23 mN/m to 24 mN/m, 24 mN/m to 25 mN/m, 25 mN/m to 26 mN/m, 26 mN/m to 27 mN/m, 27 mN/m to 28 mN/m, 28 mN/m to 29 mN/m, 29 mN/m to 30 mN/m, 30 mN/m to 31 mN/m, 31 mN/m to 32 mN/m, 32 mN/m to 33 mN/m, 33 mN/m to 34 mN/m, 34 mN/m to 35 mN/m, 35 mN/m to 36 mN/m, 36 mN/m to 37 mN/m, 37 mN/m to 38 mN/m, 38 mN/m to 39 mN/m, 39 mN/m to 40 mN/m, 40 mN/m to 41 mN/m, 41 mN/m to 42 mN/m, 42 mN/m to 43 mN/m, 43 mN/m to 44 mN/m, 44 mN/m to 45 mN/m, 45 mN/m to 46 mN/m, 46 mN/m to 47 mN/m, 47 mN/m to 48 mN/m, 48 mN/m to 49 mN/m, or 49 mN/m to 50 mN/m using Wilhelmy plate methodology. In any one more first embodiments herein, the treatment compositions are characterized as providing very low surface tension, that is, about 1 mN/m or less, and in some embodiments as low as 0.001 mN/m, as measured using Wilhelmy plate methodology.

In addition to having low surface (interfacial) tension, the treatment compositions of first embodiments are characterized as having a low tendency to foam, meaning that agitating or spraying a treatment composition does not tend to result in bubbles having sufficient longevity to aggregate on or near the point of agitation or the point of spray impact in a manner that results in formation of a foam, that is, a bubble aggregate. Accordingly, the treatment compositions do not form a froth, where a froth is a bubble aggregate capable of supporting (floating) an ore particulate. Accordingly, the treatment compositions of first embodiments are useful in methods that do not require flotation of ore particulates, such as froth flotation, which relies on formation of a froth for operability. The treatment compositions are particularly useful in methods wherein it is beneficial to avoid formation of a foam or a froth.

In accordance with the foregoing, disclosed in second embodiments herein are methods of treating an iron ore to reduce the amount of one or more unwanted mineral species present therein. In any one or more second embodiments herein, the methods comprise, consist essentially of, or consist of contacting an iron ore with a treatment composition of any one of first embodiments to form a treatment slurry; and collecting a treated iron ore and a spent treatment composition from the treatment slurry. Accordingly, in any one or more second embodiments herein, methods of treating an iron ore comprise, consist essentially of, or consist of combining water, one or more anionic surfactants, and one or more polymers having a net negative charge to form a treatment composition; contacting an iron ore with the treatment composition to form a treatment slurry; and collecting a treated iron ore and a spent treatment composition from the treatment slurry.

In any one or more second embodiments herein, an unwanted mineral species is a non-iron metal, a non-iron metal-containing compound, or any particle(s) containing one or more non-iron metals and/or one or more non-iron metal-containing compounds. In any one or more second embodiments herein, the one or more unwanted mineral species comprise, consist essentially of, or consist of one or more aluminum species, one or more silicon species, and/or one or more phosphorus species. In any one or more second embodiments herein, the one or more unwanted mineral species include one or more of: alumina, silica, aluminosilicate, calcium phosphate, hydroxyapatite.

In any one or more second embodiments herein, the iron ore contacted with the treatment composition is a comminuted, classified iron ore particulate (or “classified iron ore particulate” for brevity). In such second embodiments, the iron ore product as collected from a mine, or “run of mine” ore, is comminuted by grinding, crushing, and the like; and the comminuted ore is classified using sieving (screening), cycloning, or any one or more other methods or combinations thereof conventionally employed to classify a mineral ore, such as a comminuted iron ore. Accordingly, any one or more methods of second embodiments herein include comminuting a run of mine iron ore; classifying the comminuted ore to provide a first classified iron ore particulate, which is a classified iron ore particulate having a first particle size range; contacting the first classified iron ore particulate with a treatment composition of any one of first embodiments to form a first treatment slurry; and collecting a first treated iron ore and a first spent treatment composition from the first treatment slurry. In some such second embodiments, the first particle size range is selected by an operator to provide a suitable iron ore particulate for introduction to a first steelmaking process.

In some second embodiments, a second particle size range is further selected by the operator to provide a suitable iron ore particulate for introduction to a second steelmaking process; and third, fourth, etc. particle size ranges may also be selected by an operator for introduction to third, fourth, etc. steelmaking processes. Accordingly, any one or more methods of second embodiments herein include comminuting a run of mine iron ore; classifying the comminuted ore to provide a first classified iron ore particulate and a second classified iron ore particulate; contacting the first classified iron ore particulate with a first treatment composition of any one of first embodiments to form a first treatment slurry; and collecting a first treated iron ore and a first spent treatment composition from the first treatment slurry; and separately contacting the second classified iron ore particulate with a second treatment composition of any one of first embodiments to form a second treatment slurry; and collecting a second treated iron ore and a second spent treatment composition from the second treatment slurry. Similar methods may be carried out using third, fourth, etc. classified iron ore particulates as selected by an operator. The first and second (and optionally third, fourth, etc.) treatment compositions are suitably selected to be the same or different treatment compositions of first embodiments.

In some second embodiments herein, a first classified iron ore particulate consists essentially of or consists of particles ranging in size between 0.5 mm and 10 mm, as determined by sieving (also called screening). In some second embodiments herein, a second classified iron ore particulate consists essentially of or consists of particles ranging in size between 10 mm and 40 mm, as determined by sieving. Third, fourth, or more additional classes of particulates, or different size classes altogether are suitably selected by an operator without limitation. Alternative classes, such as first, second, third, or higher classes may be selected, such as classes consisting essentially of or consisting of particles ranging in size between 1 micron and 0.5 mm, or between 0.5 mm and 1 mm, or between 1 mm and 2 mm, or between 2 mm and 5 mm, or between 5 mm and 8 mm, or between 8 mm and 12 mm, or between 12 mm and 20 mm, or between 20 mm and 25 mm, or between 25 mm and 30 mm, or between 30 mm and 35 mm, or between 35 mm and 40 mm, or between 40 mm and 45 mm, or between 45 mm and 50 mm, or even greater than 50 mm, as determined by sieving. However, we have found that the methods of second embodiments herein obtain the most efficient reduction of one or more unwanted mineral species by contacting the treatment composition with iron ore particles having a particle size of 50 mm or less, as determined by sieving.

Further in some methods of second embodiments herein, the iron ore contacted with a treatment composition of first embodiments includes at least 35 wt % iron (as Fe). In some second embodiments, the iron ore includes more than 5 wt % of one or more unwanted mineral species, where an unwanted mineral species is any non-iron based metal, and/or any non-iron based metal-containing compound, and/or any particle(s) containing one or more non-iron based metals and/or one or more non-iron based metal-containing compounds. In any one or more second embodiments herein, the iron ore includes 5 wt. % or more of an alumina-containing compound. In any one or more second embodiments herein, the iron ore includes 5 wt % or more Al₂O₃. In any one or more second embodiments herein, the iron ore includes at least 35 wt % Fe, and 5 wt. % or more of Al₂O₃ and/or another alumina-containing compound. In any one or more second embodiments herein, the iron ore includes at least 35 wt % Fe, and 5 wt % or more Al₂O₃ and/or another alumina-containing compound. In any one or more second embodiments herein, the iron ore includes 35 wt % to 73 wt % Fe and 5 wt % or more Al₂O₃ and/or another alumina-containing compound. In any one or more second embodiments herein, the iron ore includes 50 wt % to 73 wt % Fe and 5 wt % to 20 wt % Al₂O₃ and/or another alumina-containing compound.

In any one or more second embodiments herein, the iron ore includes more than 5 wt % of one or more phosphorus species, such as calcium phosphate or hydroxyapatite; more than 5 wt % of one or more silicon species, such as silica or an aluminosilicate clay; or more than 5 wt % of one or more phosphorus species and also more than 5 wt % of one or more silicon species.

In any one or more second embodiments herein, the methods are suitably carried out by forming a dilute treatment composition; immersing the iron ore in the dilute treatment composition to form a treatment slurry; agitating the treatment slurry by stirring, rolling, shaking, etc. for a selected period of time, followed by a period of sedimentation (allowing the slurry to sit undisturbed) and then decanting a spent treatment composition as a supernatant from the settled slurry solids; optionally adding additional water or additional dilute treatment composition and repeating the agitating, sedimentation, and decanting to provide a treated iron ore as the settled solids.

In any one or more second embodiments herein, the methods are suitably carried out by using a scrubber, which is a horizontally disposed screen situated as a continuous web moving in a horizontal direction beneath a series of nozzles or spray heads, further wherein the screen gauge of the moving web is sized to retain a selected size class of particles thereon. Accordingly, in any one or more second embodiments herein, a classified iron ore particulate is applied to the moving web and transported horizontally beneath the nozzles or spray heads while water is dispensed onto the classified iron ore particulate from the nozzles or spray heads, further wherein the screen gauge of the moving web is sized to retain the selected class of iron ore particulate. The contact of the treatment composition with the iron ore particulate causes a treatment slurry to form. The treatment slurry consists essentially of or consists of the iron ore contacted with the treatment composition.

The screen gauge of the moving web is sized to retain the selected particle size class of the classified iron ore particulate; and accordingly, as the moving web traverses the scrubber, water dispensed as part of the treatment composition, along with any compounds dissolved therein and particulates small enough to depart through the screen are thereby separated from the treatment slurry by action of gravity, allowing their collection from underneath the screen as a spent treatment composition. In some embodiments, the spent treatment composition further includes some portion or even substantially all, such as more than 80% by weight, of the anionic surfactant and/or the net negative charge polymer applied to the iron ore. The material retained by the screen after departure of the spent treatment composition from the treatment slurry is a treated iron ore. Stated differently, the screen of the scrubber acts to form a treatment slurry, then separate the treatment slurry into a treated iron ore and a spent treatment composition.

Accordingly, in any one or more methods of second embodiments herein, an iron ore is disposed on a screen; the disposed iron ore is combined with a treatment composition to form a treatment slurry; and the treatment slurry is separated by gravitational force to form a treated iron ore and a spent treatment composition. In some such embodiments, the screen is a moving web. In some embodiments that may or may not be further combined with a moving web, the combining of the iron ore with the treatment composition is spraying or pouring the treatment composition onto the iron ore; in some such embodiments the spraying or pouring is obtained by dispensing the treatment composition through one or a plurality of nozzles or spray heads. In some embodiments that may or may not be further combined with a moving web, or spraying or pouring of the treatment composition, the treated ore is collected from the top of the screen. In any one or more of the foregoing embodiments, a spent treatment composition is collected from underneath the screen.

In any one or more second embodiments herein, methods of forming a treatment composition include admixing water with one or more anionic surfactants and one or more polymers having a net negative charge. In any one or more second embodiments herein, the admixing is in any order and is not limited in terms of the method used to accomplish the mixing; any conventional methods employed to mix aqueous polymer solutions is suitably employed to obtain admixing the treatment compositions herein. In any one or more second embodiments herein, the admixed water is an aqueous solution comprising one or more salts, buffers, acids, bases, water miscible solvents, or surfactants; one or more dissolved, dispersed, or emulsified compounds, materials, or components; or any combination of these.

In any one or more second embodiments herein, the methods of forming a treatment composition further include adjusting the pH of the treatment composition to be between about 5 and about 14, such as 5.0 to 5.5, 5.5 to 6.0, 6.0 to 6.5, 6.5 to 7.0, 7.0 to 7.5, 7.5 to 8.0, 8.0 to 8.5, 8.5 to 9.0, 9.0 to 9.5, 9.5 to 10.0, 10.0 to 10.5, 10.5 to 11.0, 11.0 to 11.5, 11.5 to 12.0, 12.0 to 12.5, 12.5 to 13.0, 13.0 to 13.5, 13.5 to 14.0, about 5, about 5.5, about 6, about 6.5, about 7, about 7.5, 8, about 8.5, about 9, about 10, about 11, about 12, about 13, or about 14. In any one or more such second embodiments, pH is suitably adjusted using an inorganic or organic compound conventionally employed to adjust pH of aqueous solutions, including an oxide or hydroxide of an alkaline earth metal or alkali metal, such as sodium hydroxide.

In some second embodiments herein, a dilute treatment composition of first embodiments includes a suitable range of concentration of actives (that is, one or more anionic surfactants and one or more polymers having a net negative charge) for contacting with an iron ore to form a treatment slurry, that is, between 0.1 ppm and 10,000 ppm by weight or weight/volume. Accordingly, in some methods of second embodiments herein, the contacting of the treatment composition with the iron ore is contacting a dilute treatment composition of first embodiments with the iron ore. In any one or more second embodiments herein, a dilute treatment composition is obtained by admixing water or an aqueous solution with a treatment composition concentrate of first embodiments; in other such second embodiments herein, a dilute treatment composition is obtained by admixing water or an aqueous solution with one or more anionic surfactants and one or more polymers having a net negative charge, wherein the admixing is in any order.

In any one or more scrubbing methods of second embodiments herein, the scrubbing is a batch scrubbing process or a continuous scrubbing process. In any one or more continuous scrubbing processes herein, a scrubber includes a moving web, and a plurality of spray heads or nozzles situated above the moving web, from which the treatment composition is dispensed. Accordingly, any one or more continuous scrubbing processes includes continuously applying a classified iron ore particulate to the web, moving the web underneath the spray heads or nozzles while continuously directing the treatment composition to be dispensed from a position above the web in a direction toward the web, to provide contact of the treatment composition with the classified iron ore particulate to form a treatment slurry; and collecting a treated iron ore particulate and a spent treatment composition from the web.

In some continuous scrubbing processes of second embodiments, the contacting of a treatment composition with the classified iron ore particulate is accomplished by dispensing a dilute treatment composition onto the iron ore wherein the dilute treatment composition advantageously includes 0.1 ppm to 1000 ppm actives by weight or weight/volume, for example 0.1 ppm to 500 ppm, or 0.1 ppm to 200 ppm, or 0.1 ppm to 100 ppm, or even 0.1 ppm to 10 ppm or 1 ppm to 10 ppm. Further in such continuous scrubbing processes of second embodiments, the contacting of the dilute treatment composition with the classified iron ore particulate is accomplished by dispensing the dilute treatment composition from one or more spray heads or spray nozzles to contact the iron ore at a rate of between 10 liters and 500 liters per hour per metric ton of iron ore, for example 10 liters to 20 liters per hour per metric ton of iron ore, 20 liters to 30 liters per hour per metric ton of iron ore, 30 liters to 40 liters per hour per metric ton of iron ore, 40 liters to 50 liters per hour per metric ton of iron ore, 50 liters to 60 liters per hour per metric ton of iron ore, 60 liters to 70 liters per hour per metric ton of iron ore, 70 liters to 80 liters per hour per metric ton of iron ore, 80 liters to 90 liters per hour per metric ton of iron ore, 90 liters to 100 liters per hour per metric ton of iron ore, 100 liters to 110 liters per hour per metric ton of iron ore, 110 liters to 120 liters per hour per metric ton of iron ore, 120 liters to 130 liters per hour per metric ton of iron ore, 130 liters to 140 liters per hour per metric ton of iron ore, 140 liters to 150 liters per hour per metric ton of iron ore, 150 liters to 175 liters per hour per metric ton of iron ore, 175 liters to 200 liters per hour per metric ton of iron ore, 200 liters to 250 liters per hour per metric ton of iron ore, 250 liters to 300 liters per hour per metric ton of iron ore, 300 liters to 400 liters per hour per metric ton of iron ore, or 400 liters to 500 liters per hour per metric ton of iron ore. In any one more such embodiments, the continuous scrubbing results in contacting about 10 g to about 500 g of actives with each metric ton of iron ore, for example 10 g to 500 g, or 10 g to 400 g, or 10 g to 300 g, or 10 g to 200 g, or 10 g to 100 g, or 10 g to 50 g, or 50 g to 500 g, or 100 g to 500 g, or 200 g to 500 g, or 300 g to 500 g, or 400 g to 500 g, or 50 g to 100 g, or 100 g to 200 g, or 200 g to 300 g, or 300 g to 400 g of actives contacted with each metric ton of iron ore.

In any one or more second embodiments herein, the methods exclude sparging the treatment composition or the treatment slurry, or adding a froth to the treatment composition or to the treatment slurry. Accordingly, in any one or more embodiments herein, a treatment composition and/or a treatment slurry is suitably characterized as excluding a froth. Further in any one or more embodiments herein, a treatment composition and/or a treatment slurry is suitably characterized as having a low tendency to foam, that is, to form air bubble aggregates therein or thereon, and accordingly in methods of second embodiments herein, the contacting of the treatment composition with the iron ore is characterized as producing no foam or substantially no foam, where “substantially no foam” means that the amount of foam that develops during the contacting does not interfere with separation of the treatment slurry into a treated iron ore and a spent treatment composition, or departure of a spent treatment composition from a treated iron ore, or collection of a treated iron ore or a spent treatment composition. Additionally, since the treatment compositions of first embodiments have a low tendency to foam, agitating or spraying the treatment composition-such as when employing a scrubbing method of second embodiments herein-does not tend to result in bubbles forming and aggregating on or near the point of agitation or the point of spray impact in a manner that results in a foam or a froth. Accordingly, the treatment compositions of first embodiments are particularly useful in conjunction with the scrubbing methods of second embodiments herein, since it is highly beneficial for efficiency and operability of such continuous scrubbing methods to minimize or avoid formation and aggregation of bubbles since formation and aggregation interferes with the gravity-induced separation operable in a continuous scrubbing apparatus.

As a result of employing any one or more methods of second embodiments herein, a treated iron ore, such as a treated classified iron ore particulate, is collected. In any one or more embodiments herein, a treated iron ore includes 5% to 90% less by weight of one or more unwanted mineral species compared to the amount of the unwanted mineral species present in the iron ore prior to the treatment, such as 5% to 10% less by weight, 10% to 20% less by weight, 20% to 30% less by weight, 30% to 40% less by weight, 40% to 50% less by weight, 50% to 60% less by weight, 60% to 70% less by weight, 70% to 80% less by weight, or even 80% to 90% less by weight of the one or more unwanted mineral species. In any one or more embodiments of the methods herein, a treated iron ore includes 5% to 90% less by weight of one or more alumina species compared to the amount of the one or more alumina species present in the iron ore prior to the treatment, such as 5% to 10% less by weight, 10% to 20% less by weight, 20% to 30% less by weight, 30% to 40% less by weight, 40% to 50% less by weight, 50% to 60% less by weight, 60% to 70% less by weight, 70% to 80% less by weight, or even 80% to 90% less by weight of the one or more alumina species. In any one or more embodiments herein, a treated iron ore includes 5% to 90% less by weight of one or more silicon species compared to the amount of the one or more silicon species present in the iron ore prior to the treatment, such as 5% to 10% less by weight, 10% to 20% less by weight, 20% to 30% less by weight, 30% to 40% less by weight, 40% to 50% less by weight, 50% to 60% less by weight, 60% to 70% less by weight, 70% to 80% less by weight, or even 80% to 90% less by weight of the one or more silicon species. In any one or more embodiments herein, a treated iron ore includes 5% to 90% less by weight of one or more phosphorus species compared to the amount of the one or more phosphorus species present in the iron ore prior to the treatment, such as 5% to 10% less by weight, 10% to 20% less by weight, 20% to 30% less by weight, 30% to 40% less by weight, 40% to 50% less by weight, 50% to 60% less by weight, 60% to 70% less by weight, 70% to 80% less by weight, or even 80% to 90% less by weight of the one or more phosphorus species. In any one or more embodiments herein, a treated iron ore includes 5% to 90% less by weight of one or more alumina species, and 5% to 90% less by weight of one or more silicon species compared to the amount of these unwanted mineral species present in the iron ore prior to the treatment. In any one or more embodiments herein, a treated iron ore includes 5% to 90% less by weight of one or more alumina species, and 5% to 90% less by weight of one or more phosphorus species compared to the amount of these unwanted mineral species present in the iron ore prior to the treatment. In any one or more embodiments herein, a treated iron ore includes 5% to 90% less by weight of one or more alumina species, 5% to 10% less by weight of one or more phosphorus species, 5% to 90% less by weight of one or more silicon species, and 5% to 90% less by weight of one or more phosphorus species compared to the amount of these unwanted mineral species present in the iron ore prior to the treatment.

As a result of employing any one or more methods of second embodiments herein, a treated iron ore, such as a treated classified iron ore particulate, is collected. In any one or more embodiments herein, a treated iron ore includes 1% to 30% more by weight of iron or an iron species (e.g. an iron oxide) compared to the amount of the iron or iron species present in the iron ore prior to the treatment, such as 1% to 5% more by weight, 5% to 10% more by weight, 10% to 15% more by weight, 15% to 20% more by weight, 20% to 25% more by weight, 10% to 30% more by weight, 5% to 25% more by weight, 5% to 20% more by weight, 25% to 30% more by weight, 10% to 20% more by weight, or 10% to 25% more by weight of iron or an iron species compared to the amount of the iron or iron species present in the iron ore prior to the treatment. In any one or more embodiments herein, a treated iron ore includes 1% to 30% more total iron by weight (TFe) compared to the TFe of the iron ore prior to the treatment, such as 5% to 10% more by weight, 10% to 15% more by weight, 15% to 20% more by weight, 20% to 25% more by weight, 10% to 30% more by weight, 5% to 25% more by weight, 5% to 20% more by weight, 25% to 30% more by weight, 10% to 20% more by weight, or 10% to 25% more by weight TFe compared to the TFe of the iron ore prior to the treatment.

In any one or more second embodiments herein, one or more unwanted mineral species present in the (untreated) iron ore become dissolved or dispersed in the water present in the treatment slurry, and subsequently depart through the screen as part of the spent treatment composition and are suitably collected along with the remainder of the spent treatment composition for additional purification, treatment, and/or disposal.

Accordingly, disclosed in third embodiments herein are spent treatment compositions that are collected from a treatment slurry using the methods of second embodiments herein. In any one or more third embodiments herein, a spent treatment composition comprises, consists essentially of, or consists of a mixture of water, one or more anionic surfactants, one or more net negative charge polymers, and one or more unwanted mineral species. In any one or more third embodiments herein, a spent treatment composition collected from a treatment slurry in any one or more methods of second embodiments herein includes one or more non-iron based metals, and/or one or more non-iron based metal-containing compound, and/or one or more particles containing one or more non-iron based metals and/or one or more non-iron based metal-containing compounds. In some third embodiments, one or more unwanted mineral species are or include alumina, silica, and/or phosphate. In any one or more embodiments of the methods herein, a spent treatment composition includes water and one or more unwanted mineral species. In any one or more embodiments herein, a spent treatment composition includes water, at least a portion of the components of the treatment composition, and one or more unwanted mineral species dissolved or dispersed therein.

EXPERIMENTAL SECTION

Example 1

DOSS (butane dioic acid, 2-sulfo-, 1,4-bis(2-ethylhexyl) ester, sodium salt, CAS No. 577-11-7; also known as sodium dioctyl sulfosuccinate; or sodium docusate) and a copolymer of AA (acrylic acid) with AMPS (2-methyl-2-[(1-oxo-2-propen-1-yl) amino]-1-propanesulfonic acid, sodium salt), CAS No. 5165-97-9) were mixed with water to form Concentrate 1 having 12.5 wt % DOSS and 8.95 wt % AA/AMPS copolymer (collectively, “actives”); the pH of the mixture was adjusted to pH of about 8. Concentrate 1 was observed to be transparent and homogeneous. For some purposes of use below, the Concentrate 1 was diluted with pH 8 water to a concentration of about 5 wt % actives prior to providing a final dilution as indicated.

An amount of Concentrate 1 was diluted with pH 8 water to provide Composition 1 having 10.7 ppm by weight actives.

A comminuted iron ore having 51.5 wt. % total iron (“T.Fe”), 7.5 wt. % Al₂O₃, and 13.2 wt. % SiO₂ as determined using x-ray fluorescence (XRF) was classified using screens (sieving) to have a particle size of less than 50 mm and 500 g of the comminuted, classified ore (Feed Ore 1) was added to a 5 L container. Composition 1 was added to Feed Ore 1 in the container in an amount sufficient to form a slurry having 25 wt % Feed Ore 1 solids. The slurry was stirred at 500 rpm for about 20 minutes using a paddle; no foaming was observed during the stirring. Then the stirring was stopped, and the slurry was allowed to sit undisturbed for 20 minutes, during which time solids were observed to settle on the bottom of the container. At the end of the undisturbed period, a supernatant (float) was decanted from the container; and the settled solids (sink) were washed once with water by addition and decantation, discarding the decanted wash water before drying the solids.

Chemical analysis of the dried solids was obtained using XRF. Compared to Feed Ore 1, the dried solids of the sink obtained from the foregoing process included 57.2 wt. % TFe, 4.6 wt. % Al₂O₃, and 9.7 wt. % SiO₂. That is, compared the content of Feed Ore 1, alumina was reduced by 2.9%, silica was reduced by 3.5%, and total iron was increased by 5.7%.

The dried solids of the float, which is the spent composition collected as the supernatant in the foregoing process, included 9.4 wt. % Al₂O₃ and 15.5 wt. % SiO₂.

Example 2

The process of Example 1 was repeated, except using Feed Ore 2, which is a scrubber feed ore having 69.8 wt % Fe₂O₃, 13.9 wt % Al₂O₃, and 13.7 wt % SiO₂ as determined using x-ray fluorescence (XRF).

Compared to Feed Ore 2, the dried solids of the sink obtained from the foregoing process included 74.3 wt % Fe₂O₃, 11.8 wt % Al₂O₃, and 11.8 wt % SiO₂. That is, compared the content of Feed Ore 2, alumina was reduced by 2.1%, silica was reduced by 1.9%, and iron oxide was increased by 4.5%.

The dried solids of the float, which is the spent composition collected as the supernatant in the foregoing process, included 14.5 wt % Al₂O₃ and 13.9 wt % SiO₂.

Example 3

The procedure of Example 1 was repeated, except only water was added to Feed Ore 1 (instead of Composition 1). During the stirring of the Control composition combined with Feed Ore 1, foaming was observed on the surface of the slurry. Compared to Feed Ore 1, the dried solids obtained from scrubbing using the Control composition include 51.5 wt. % TFe, 7.5 wt. % Al₂O₃, and 13.1 wt % SiO₂. That is, compared to Feed Ore 1, no effective separation of alumina or silicon species were removed from the ore; and the iron content of the ore was not increased.

Example 4

DOSS and the AA-AMPS copolymer used in Example 1 were mixed with water to form Composition 2 having 12.5 wt % DOSS and 8.95 wt % AA/AMPS copolymer (collectively, “actives”); the pH of the mixture was adjusted to pH of about 8. An aliquot of Composition 2 was stored at 1-2° C., at ambient temperature (about 20° C.), and at 50° C. and was periodically observed during storage over a period of 3 months. Table 1 shows the length of time Composition 2 was stored in the listed storage conditions before visible evidence of phase separation was observed. Evidence of phase separation includes appearance of solid-looking material on bottom, top, or sides of the container in which the Composition is stored. Composition 2 was observed to have a low tendency to foam.

DOSS and the AA-AMPS copolymer of Composition 2 were also mixed with water and the adjuvants listed in Table 1 (below) to form Compositions 2A-2G; the pH of each of these Compositions was adjusted to be about 8. Compositions 2A-2G were all observed to have a low tendency to foam.

Aliquots of the Compositions were stored at 1-2° C., at ambient temperature (about 20° C.), and at 50° C. and were periodically observed during storage over a period of 3 months. Table 1 shows the length of time each Composition was stored in the listed storage conditions before visible evidence of phase separation was observed. Evidence of phase separation includes appearance of solid-looking material on bottom, top, or sides of the container in which a Composition is stored.

TABLE 1
Components and amounts thereof in Compositions 2 and 2A-2G;
and storage stability periods of the Compositions at the
indicated storage temperature, as described in Example 4.

Compo-

Amount,

Storage Stability Period

sition	Component	wt %	1-2° C.	~20° C.	50° C.

2	DOSS	12.5	Not	<1	Not
	AA-AMPS	8.95	stable	hour	stable
	Water	78.6
2A	DOSS	9.50	3	3	6
	AA-AMPS	8.95	months	months	weeks
	Water	78.6
	Alkoxylated alkanol:	3.00
	C16-C18 alkanol
	appended with 30
	ethoxy repeat units
	(CAS No. 68439-46-6)
2B	DOSS	9.50	3	3	5
	AA-AMPS	8.95	months	months	weeks
	Water	78.6
	Alkoxylated alkanol:	3.00
	C16-C18 alkanol
	appended with 25
	ethoxy repeat units
	(CAS No. 68439-46-6)
2C	DOSS	9.50	3	3	9
	AA-AMPS	8.95	months	months	weeks
	Water	79.5
	Alkoxylated alkanol:	2.10
	C12-C14 alkanol
	appended with 30
	ethoxy repeat units
	(CAS No.
	(68439-50-9)
2D	DOSS	12.5	6	6	4
	AA-AMPS	8.95	weeks	weeks	weeks
	Water	77.6
	Amylopectin,	1.00
	2-hydroxy-3-
	(trimethyl-
	ammonio)propyl
	ether, chloride
	(CAS No. 68936-82-3)
2E	DOSS	9.5	No	3	No
	AA-AMPS	8.95	data	months	data
	Water	78.6
	Alkoxylated alkanol:	3
	C12-C14 alkanol
	appended with 30
	ethoxy repeat units
	(CAS No. 68439-50-9)
2F	DOSS	10.00	3	3	3
	AA-AMPS	8.95	months	month	months
	Xanthan gum	0.50
	(CAS No. 11138-66-2)
	water	80.55
2G	DOSS	5.00	3	3	3
	AA-AMPS	8.95	months	months	months
	Xanthan gum	0.50
	(CAS No. 11138-66-2)
	water	85.55

The foregoing results show that adjuvants such as alkoxylated alkanols and cationic polysaccharides obtain improved stability of Compositions including DOSS.

Compositions 2 and 2A-2G were subjected to the following ore cleaning procedure: 500 g of an iron ore having particle size of 40 mm or less is added to 2500 ml process water to form a slurry. The slurry is stirred for 5 minutes at 400-700 rpm, then 500 ppm actives of a selected Composition is added to the slurry. Then the treated slurry is stirred for 4 minutes at 400-700 rpm. Then the stirring is stopped and the treated slurry is allowed to stand undisturbed (settle) for 15 minutes. Finally, the settled slurry is decanted carefully to separate suspended solids from any settled solids present in the settled slurry. Each of the separated fractions are dried and weighed, then subjected to x-ray fluorescence (XRF) analysis to determine the amount of alumina present in the solids derived from each of the separated fractions.

The foregoing test was carried out using Feed Ore 3, an iron ore having 11.59 wt. % Al₂O₃, as determined using XRF. Results are shown in Table 2.

TABLE 2
Percent alumina in concentrates derived from Feed Ore 3, which
has 11.59 wt % alumina, after carrying out the process of Example
4; and % reduction in alumina obtained for Feed Ore 3.

		% Al2O3	% Al2O3 reduction
		compared	compared
Composition	% Al2O3	to Control	to Feed Ore 3

Feed Ore 3 (only)	11.59	—	—
Control (water +	10.79	0.00	0.80
Feed Ore 3)
2	10.38	0.41	1.21
2A	10.38	0.41	1.21
2B	10.70	0.09	0.89
2C	No data	—	—
2D	10.42	0.37	1.17
2E	10.58	0.21	1.01
2F	10.13	0.66	1.46
2G	10.39	0.40	1.20

The results of Table 2 show that the adjuvant combinations with DOSS can obtain comparable reduction in alumina from an iron ore to DOSS alone.

Example 5

Compositions 3-6, the components of which are shown in Table 3, were mixed and stored at 1-2° C., at ambient temperature (about 20° C.), and at 50° C.; and were periodically observed during storage over a period of 3 months. The AA-AMPS copolymer used in each case is the same copolymer used in Example 1. Table 4 shows the length of time each of the Compositions was stored in the listed storage conditions before visible evidence of phase separation was observed. Evidence of phase separation includes appearance of solid-looking material on bottom, top, or sides of the glass container.

TABLE 3
Components and amounts thereof in Compositions 3-6, and storage
stability periods of the Compositions at the indicated storage
temperature, as described in Example 5. The result using Composition
2 of Example 1 is provided for comparison.

Compo-

Amount,

Storage Stability Period

sition	Component	wt %	1-2° C.	~20° C.	50° C.

2	DOSS	12.5	Not	<1	Not
	AA-AMPS	8.95	stable	hour	stable
	Water	78.55
3	Sodium laureth sulfate,	12.5	3	3	3
	3 ethylene oxide repeat		months	months	months
	units (EO) (CAS
	No. 9004-82-4)
	AA-AMPS	8.95
	Water	78.55
4	Sodium hexyldiphenyl	12.5	3	3	3
	ether sulfonate (CAS		months	months	months
	No. 147732-60-3)
	AA-AMPS	8.95
	Water	78.55
5	Sodium laureth sulfate,	8	3	3	3
	3 ethylene oxide repeat		months	months	months
	units (EO) (CAS
	No. 9004-82-4)
	AA-AMPS	8.95
	Water	83.05
6	Sodium laureth sulfate,	4	3	3	3
	3 ethylene oxide repeat		months	months	months
	units (EO) (CAS
	No. 9004-82-4)
	Sorbitan monooleate,	4
	20 ethylene oxide
	repeat units (CAS
	No. 9005-65-6
	AA-AMPS	8.95
	Water	83.05

The ore-cleaning procedure of Example 4 was repeated using Compositions 3-6. Water only as a Control was used to treat Feed Ore 3, an iron ore having 11.59 wt. % Al₂O₃, as determined using XRF.

TABLE 4
Percent alumina in concentrates derived from Feed Ore 3, which has
11.59 wt % alumina, after carrying out the process of Example 5;
and % reduction in alumina obtained for Feed Ore 3. The result
using Composition 2 from Table 1 is provided for comparison.

	%	% Al2O3 reduction	% Al2O3 reduction
Composition	Al2O3	compared to Control	compared to Feed

Feed	11.59	—	0
Control	10.79	0.00	0.80
(water Only)
2	10.38	0.41	1.21
3	10.46	0.33	1.13
4	10.50	0.29	1.09
5	10.46	0.33	1.13
6	10.25	0.54	1.34

Surface tension of Compositions 3-6 were measured using Wilhelmy plate methodology at ambient temperature (about 20° C.); results are shown in Table 5. Viscosity of the Compositions (undiluted) was measured using a Brookfield viscometer at ambient temperature (about 20° C.), with spindle 1 at 30 rpm; results are shown in Table 5. Finally, the Compositions were subjected to a test to determine the relative amount of foam generated when the Compositions are agitated, and the results are also shown in Table 5. Foam generation was measured at ambient temperature (about 20° C.) by diluting the selected Composition to 0.21 wt % actives with water; adding 25 mL of the diluted Composition to a 60 mL test tube; capping the test tube tightly; shaking the capped test tube vigorously by hand for 30 seconds, holding the test tube length horizontally; then setting the test tube upright and determining the volume in mL of any foam present in the test tube, where the measured volume is foam at time=0. The test tube is allowed to stand upright for an additional 2 minutes, and then the volume of any foam present in the test tube is measured and recorded as foam at time=2 min. Water was used as a comparative for assessing surface tension, viscosity, and foaming of the Compositions.

TABLE 5
Surface tension, viscosity, and foam volume generated in the foam
generation test of Example 6 for water and Compositions 2-6.

	Surface
Compo-	tension,	Viscosity,	Foam volume, mL

sition	mN/m	cP	time = 0	time = 2 min

water	72.25	1	0	0
2	29.63	145	57.50	50.00
3	30.64	15.6	57.50	50.00
4	31.63	9.20	37.50	36.38
5	32.6	8.60	Less foaming than	Less foaming than
			Composition 3	Composition 3
6	38.4	6.70	Less foaming than	Less foaming than
			Composition 2	Composition 2

Accordingly, Compositions 2-6 all obtain low surface tension and controllable levels of foaming. Additionally, Compositions 3, 4, 5, and 6 obtain lower viscosity, and improved stability when compared to Composition 2. Additionally, Compositions 4, 5, and 6 obtain lower foaming when compared to Composition 2.