EA046844B1 - MANIFOLDS FOR FLOTATION PROCESS - Google Patents

Description

The present invention relates to the flotation of non-sulfide minerals and ores. In particular, the present invention relates to a collector for the beneficiation of non-sulfide minerals and ores.

Prerequisites for creating the invention

Froth flotation is used for ore beneficiation. In particular, froth flotation can be used to separate valuable minerals contained in an ore from associated gangue or to separate valuable minerals. Froth flotation typically involves mixing an aqueous suspension containing finely ground ore particles with a foaming agent or blowing agent to produce foam. Ideally, ore particles that contain the desired mineral are preferentially extracted or transferred into the foam layer due to the affinity between the foam and the mineral present on the surface of the ore particles. The resulting enriched minerals are then collected by separating them from the foam. The ability of a mineral to float is related to its surface properties. Chemical reagents known as collectors are used to change the surface properties of minerals and can be added to the suspension to increase the selectivity (or selectivity) and efficiency of the separation process.

In reverse flotation, impurities are removed (or floated) from the valuable mineral. In particular, iron ore, calcium carbonate, phosphate and feldspar are often purified in this way. In many cases, silicate minerals are the main component of these impurities that cause the quality of the final product to deteriorate. In addition to quartz, mica and feldspar, they also include muscovite and biotite. For example, high silicate content reduces the quality of iron ore concentrate and so this concentrate is refined by flotation, for example in Brazil, using alkyl ether amines and alkyl ether diamines so that high quality steels can be produced from a low silicate concentrate.

Calcium carbonate is purified from silicate-containing and coloring minerals using quaternary ammonium salts based on fatty acids or fatty alkyl imidazoline compounds in a reverse flotation process. Since calcium carbonate, in addition to kaolin, rutile and talc, is used as a white pigment in the manufacture of paper and plastics, the highest possible degree of whiteness and low concentration of coloring minerals in it are highly desirable. The presence of silicate in calcium carbonate can also lead to increased wear of printing press dies during printing due to the hardness of the silicate. For these reasons, calcium carbonate, in addition to dry refining, is purified using a flotation process.

Typically, reverse flotation attempts to reduce the silicate content, which in the case of calcium carbonate is most often characterized as an acid-insoluble component, to below 1.0% by weight. The silicate content of the raw material may vary and may sometimes range from 10 to 20% SiO ₂ by weight.

A range of amine-based monomer collectors are used in the reverse flotation process for the beneficiation of iron ore, phosphates, calcite and other minerals. Conventional amine-based monomer collectors used in this process lack selectivity for fine particle size ranges. Collectors based on polymer polycondensate exhibit the desired selectivity, but are required in large quantities.

Thus, there is a need to develop new polycondensate-based polymer collectors that exhibit selectivity similar to or even better than that of traditionally used collectors, but can be used in comparatively smaller quantities.

Summary of the invention

Surprisingly, it has been found that the modified polyetheramine of the present invention, when used in a collector composition, exhibits selectivity that is similar to or even better than that of conventional collectors, but can be used in comparatively smaller amounts.

Thus, in a first aspect, the present invention is directed to a modified polyetheramine, wherein the modified polyetheramine contains a repeating unit of formula (I)

- 1 046844

in which R represents a linear or branched aliphatic radical containing from 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds,

R ¹ represents H or linear or branched ^-^-alkyl,

R ² represents H or linear or branched ^-^-alkyl, n, the same or different, is an integer in the range from >1 to <4.

In a second aspect, the present invention is directed to a method for producing a modified polyetheramine containing repeating units of formula (I), which comprises reacting at least one polyetheramine polyol containing at least one hydroxyl group with at least one fatty acid and further modification by quaternization with hydrogen or at least one ^-^-alkyl group.

In a third aspect, the present invention is directed to the use of a modified polyetheramine, as described herein, as a collector for the beneficiation of non-sulfide minerals and ores.

In a fourth aspect, the present invention is directed to a reverse flotation process for beneficiating non-sulfide minerals and non-sulfide ores by collecting (or storing) impurities from the non-sulfide minerals and non-sulfide ores in a froth bed, comprising the steps of:

a) mixing non-sulfide minerals and non-sulfide ores with water to obtain an aqueous mixture;

b) adjusting the pH of the aqueous mixture obtained in step a) to the desired level to obtain an aqueous mixture with a set pH;

c) optionally adding a depressant to the aqueous mixture;

d) adding at least one modified polyetheramine according to any aspect of the present invention to the pH adjusted aqueous mixture;

e) stirring the pH-adjusted aqueous mixture obtained in step d) while blowing air to form foam;

f) collecting impurities in the foam layer;

g) recovery of non-sulfide minerals and non-sulfide ores.

Detailed Description of the Invention

Before describing the compositions and formulations claimed in the present invention, it should be understood that the invention is not limited to the specific compositions and formulations described, since such compositions and formulations may vary in any case. It should also be appreciated that the terminology used herein is not intended for purposes of limitation, as the scope of the present invention will be limited only by the appended claims.

If hereinafter or below a group of inventions is defined to include at least a certain number of embodiments, this means that it also includes a group of inventions that preferably consists only of these embodiments. Also, the terms first, second, third or a, b, c, etc. and so on. in the description and claims are used to distinguish like elements and not necessarily to describe sequential or chronological order. It should be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the present invention described herein may be carried out in sequences other than those described or illustrated herein. In case the terms first, second, third or (A), (B) and (C) or (a), (b), (c), (d), i, ii, etc. relate to steps of a method or application or analysis, there is no consistency in time or time interval between the steps, i.e. stages can be completed

- 2 046844 take place simultaneously or between such stages there may be time intervals of seconds, minutes, hours, days, weeks, months or even years, unless otherwise specified in the specification of the application as set out above or below.

In addition, the ranges defined in the description also include end values, i.e. a range of 1 to 10 implies that both 1 and 10 are included in the range. For the avoidance of doubt, the applicant is entitled to any equivalents subject to applicable law.

The following disclosure defines various aspects of the present invention in more detail. Each aspect so defined may be combined with any other aspect or aspects unless expressly stated otherwise. In particular, any feature indicated as preferred or advantageous may be combined with any other feature or features indicated as preferred or advantageous.

Reference herein to one embodiment or embodiment means that the particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of the present invention. Thus, the presence of phrases in one embodiment or in one of the embodiments at different places in this description does not necessarily refer to the same embodiment, but may be inferred.

Moreover, specific features, structures, or characteristics may be combined in any suitable manner, as will be apparent to one skilled in the art from the disclosure in the specification, in one or more embodiments of the invention. In addition, although some embodiments of the invention described herein include some, but not other, features included in other embodiments, it is understood that combinations of features of various embodiments are within the scope of the present invention and form different embodiments thereof, as would be clear to those skilled in the art of the invention. For example, in the appended claims, any of the embodiments of the invention may be used in any suitable combination.

The term flotation as used here refers to the separation of minerals based on differences in their hydrophobicity and their varying ability to adhere or attach to air bubbles. The purpose of flotation as a mineral processing process is to selectively separate certain materials. Flotation includes froth flotation processes such as, for example, forward flotation or reverse flotation. Direct flotation of non-sulfide minerals or ores refers to processes in which certain non-sulfide minerals or ores are collected or accumulated in a froth layer and impurities remain in suspension. Reverse flotation or inverse flotation of non-sulfide minerals or ores refers to processes in which impurities as unwanted materials are concentrated in a froth layer and the non-sulfide minerals or ores remain in suspension as a cell product.

As used herein, the term cell product has the same meaning as product within the cell or slurry, and means the product remaining in the cell, particularly in reverse flotation processes.

As used herein, the term froth product means the product accumulated in the froth layer, particularly in direct flotation processes.

As used herein, the term concentrate has the meaning of a flotation product and refers to the material obtained as a cell product (value material) in reverse flotation processes, as well as the froth product as a material obtained in a froth bed (value material) in direct flotation processes.

As used herein, the term tailings or flotation tailings is understood from an economic point of view and refers to the unwanted products and impurities that are removed in forward or reverse flotation processes.

As used herein, the term collector refers to substances capable of adsorbing onto a mineral particle and making the ore particle hydrophobic so that the ore particle can attach to air bubbles during flotation. The manifold may include, for example, at least one, two or three different manifolds. The reservoir composition or composition may include reservoir components, which are called, for example, primary, secondary, third reservoir, and may affect the properties of the reservoir composition or composition. Collectors, in particular, may be surface active, may have emulsifying properties, may act as a wetting agent, may be a solubility enhancer and/or a foaming agent or foam regulator.

As used herein, the term grade refers to the content of the desired mineral or valuable or target material in the resulting concentrate after beneficiation by flotation.

As used herein, the term recovery refers to the percentage of valuable material recovered after beneficiation by flotation. The relationship between degree (concentration) and recovery (amount) is a measure of the selectivity of froth flotation. Flotation selectivity increases with increasing degree and/or recovery values. Selectivity can be used to describe

- 3 046844 efficiency/performance of froth flotation.

Modified polyetheramine.

Product.

In an embodiment of the present invention, the modified polyetheramine contains repeating units of formula (I)

formula (I), in which R represents a linear or branched aliphatic radical containing from 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds,

R ¹ represents H or linear or branched Q^-alkyl,

R ² represents H or linear or branched ^-^-alkyl, n, the same or different, is an integer in the range from >1 to <4.

In one embodiment, R is a linear or branched aliphatic radical containing from 6 to 22 carbon atoms and 0, 1,2 or 3 double bonds. Linear or branched aliphatic radicals containing from 6 to 22 carbon atoms include linear or branched C^C^alkyl, linear or branched ^-^^alkenyl and linear or branched ^-^-alkynyl.

In yet another embodiment, linear or branched aliphatic radicals including linear or branched ^-^-alkyl, linear or branched ^-^-alkenyl and linear or branched ^-^-alkynyl are unsubstituted or substituted ^-^-alkyl and Q-Cg-alkyl, preferably linear or branched aliphatic radicals including linear or branched ^-^-alkyl, linear or branched ^-^-alkenyl and linear or branched C^C^alkynyl, are unsubstituted with C ₁ -C ₃ -α-alkyl and ^-^-alkyl.

In one embodiment, R is an unsubstituted linear ^-^-alkyl that is selected from the group consisting of heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl.

In one embodiment, R is an unsubstituted branched ^-^-alkyl, which is selected from the group consisting of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyl decyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl , isododecyl, isotetradecyl, isohexadecyl, isooctadecyl and isoeicosyl.

In one embodiment, R is a straight or branched _C6 - _C22 alkenyl having at least one C=C double bond at any position, preferably 1 to 3 C=C double bonds, more preferably 1 or 2 C double bonds =C, most preferably one C=C double bond, where each carbon atom is included in no more than one double bond.

Typical examples of C ₆ -C ₂₂ -alkenyl include 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl, 1-nonenyl, 2-nonenyl, 1-decenyl, 2-decenyl, 1-undecenyl, 2-undecenyl, 1-dodecenyl, 2-dodecenyl, 1-tridecenyl, 2-tridecenyl, 1-tetradecenyl, 2-tetradecenyl, 1-pentadecenyl, 2-pentadecenyl, 1-hexadecenyl, 2-hexadecenyl, 1- heptadecenyl, 2-heptadecenyl, 1-octadecenyl, 2-octadecenyl, 1-nonadecenyl, 2-nonadecenyl, 1-eicosenyl and 2-eicosenyl.

In one embodiment, n is the same or different and is 1, 2, 3 or 4; preferably n is the same or different and means 1, 2 or 3; more preferably n is the same or different and is 1 or 2; most preferably n is 1.

- 4 046844

In another embodiment of the present invention, the modified polyetheramine contains repeating units of formula (I), in which

R is a linear or branched aliphatic radical containing from 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds;

R ¹ is H;

R ² represents H or linear or branched C1 -Cg alkyl;

n, same or different, means an integer in the range >1 to <4.

In another embodiment of the present invention, the modified polyetheramine contains repeating units of formula (I), in which

R is a linear or branched aliphatic radical containing from 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds;

R ¹ represents H or linear or branched ^-^-alkyl;

R ² represents H or linear or branched C1 -^-alkyl;

n, same or different, means an integer in the range >1 to <3.

In another embodiment of the present invention, the modified polyetheramine contains repeating units of formula (I), in which

R is a linear or branched aliphatic radical containing from 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds;

R ¹ represents H or linear ^-^-alkyl;

R ² represents H or linear C1 -Cg-alkyl;

n, same or different, means 1 or 2.

In a further embodiment of the present invention, the modified polyetheramine contains repeating units of formula (I) in which

R is a linear or branched aliphatic radical containing from 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds;

R ¹ represents linear ^-^-alkyl;

R ² represents H or linear C1 -^-alkyl;

n, same or different, is 1 or 2.

Product characteristics.

In an embodiment of the present invention, the modified polyetheramine has at least one polyetheramine polyol repeating unit that has a weight average molecular weight M _w in the range of >150 to <500,000 g/mol, preferably in the range of >300 to <100,000 g/mol, more preferably in the range from >500 to <50,000 g/mol, even more preferably in the range from >500 to <30,000 g/mol, most preferably in the range from >500 to <10,000 g/mol, determined by gel permeation chromatography using hexafluoroisopropanol/0.05% trifluoroacetic acid potassium salt as mobile phase with polymethyl methacrylate as standard and refractometer as detector.

In another embodiment of the present invention, the modified polyetheramine has a weight average molecular weight Mw in the range of >100 to <500,000 g/mol, preferably in the range of >100 to <300,000 g/mol, more preferably in the range of >100 to <200,000 g/mol mole, even more preferably in the range from >100 to <200,000 g/mol, most preferably in the range from >100 to <100,000 g/mol, especially preferably in the range from >100 to <70,000 g/mol, determined by gel permeation chromatography using hexafluoroisopropanol/0.05% potassium trifluoroacetic acid as the mobile phase with polymethyl methacrylate as the standard and a refractometer as the detector.

In an embodiment of the present invention, the at least one polyetheramine polyol has a polydispersity (M _w /M _n ) in the range of 1.1 to 10, determined by gel permeation chromatography. More preferably, the at least one polyetheramine polyol has a polydispersity (M _w /Mn) in the range of 1.1 to 5, determined by gel permeation chromatography. Most preferably, the at least one polyetheramine polyol has a polydispersity (M _w /M _n ) of 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1. 8, 1.9, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5, determined by gel permeation chromatography.

Synthesis process.

In an embodiment of the present invention, the synthesis of the modified polyetheramine is carried out in accordance with the following process steps:

Synthesis of branched polyetheramine polyol.

1500 g of triethanolamine (TEA) and 20 g of a 50% aqueous solution of H ₃ PO ₂ are loaded into a four-neck flask equipped with a stirrer, a distillation bridge, a gas supply tube and an internal thermometer, and the resulting mixture is heated in a nitrogen atmosphere to 200°C. The reaction mixture is stirred at 200°C for 15.5 hours, during which the condensate formed in the reaction is removed with a moderate flow of N2 as stripping gas through the distillation bridge. By the end of the specified time

- 5 046844 reaction temperature is lowered to 140°C and residual products with low molecular weight are removed under a pressure of 100 mbar. The reaction mixture is then cooled to ambient temperature to produce a branched polyetheramine polyol.

Esterification.

In a glass reactor with a capacity of 1 liter, mix 600 g of oleic acid and 0.9 g of 50% hypophosphorous acid and heat to 60°C. 276 g of branched polyetheramine polyol are then charged, the entire mixture is kept under a vacuum of 50 mbar and gradually heated to 170°C. During heating, the water from the esterification reaction is distilled and the vacuum is slowly increased to 10 mbar. The entire process takes 8 h and the final acid value achieved is 3 mg KOH/g and the nitrogen content is 2.348 μV/g.

Quaternization.

700 g of the ester obtained in the previous reaction are diluted with 100 g of isopropanol in a 1 liter glass reactor and heated to 65°C. At this point, 197 g of dimethyl sulfate are added slowly over 2 hours. Once the quaternization reaction is complete, 284 g of isopropanol are added to thin the product.

Along with this, there are several other methods for the synthesis of branched polyetheramine polyol, which are described in WO 2009/047269, WO 2009/060060, WO 2009/1112379, US 2011/0168064.

In an embodiment of the present invention, the at least one polyetheramine polyol is a polycondensation product of at least one mri-C ₂ -C ₄ alkanolamine.

In one embodiment of the present invention, the tri-C ₂ -C ₄ -alkanolamine is selected from the group consisting of methyldiethanolamine, triisopropylamine, monoethanolamine, diethanolamine and triethanolamine.

In a preferred embodiment of the present invention, the tri-C ₂ -C ₄ -alkanolamine is triethanolamine.

In an embodiment of the present invention, the at least one fatty acid is selected from compounds of general formula (II)

R-C(=O)-OH, in which R is a linear or branched aliphatic radical containing from 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.

In an embodiment of the present invention, the at least one fatty acid is selected from mixtures of fatty acids formed from triglycerides obtained from natural sources such as tall oil, in particular by hydrolysis of triglycerides (fats and oils) of vegetable origin such as soybean oil, coconut oil, palm oil, palm kernel oil, linseed oil, sunflower oil, rice bran oil, grape pomace oil or animal fats such as tallow or tallow, and their fractions.

In an embodiment of the present invention, the at least one fatty acid is selected from mixtures of fatty acids that are present in fully or partially hydrogenated form.

In an embodiment of the present invention, the at least one fatty acid is selected from the group consisting of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid, as well as mixtures of these acids.

In a preferred embodiment of the present invention, the fatty acid is selected from the group consisting of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid.

In a more preferred embodiment of the present invention, the fatty acid is selected from the group consisting of stearic acid, isostearic acid, oleic acid, linoleic acid and linolenic acid.

In a more preferred embodiment of the present invention, the fatty acid is oleic acid.

Tall oil fatty acids (TOFA) are also particularly preferred. Tall oil can be obtained as a by-product from wood pulp. Tall oil includes, for example, a mixture of fatty acids consisting of oleic acid, linoleic acid, conjugated linoleic acid, stearic acid and, for example, other fatty acids and/or other components.

In an embodiment of the present invention, in the case where R ¹ is a linear or branched C ₁ -C3 alkyl, quaternization is carried out by at least one alkyl

- 6 046844 destroying agent, which is selected from the group of alkyl halides, dialkyl sulfates and dialkyl carbonates.

In an embodiment of the present invention, when R ¹ is a linear or branched ^-^-alkyl, the quaternization is carried out by at least one alkylating agent selected from the group consisting of methyl chloride, dimethyl sulfate, diethyl sulfate, dimethyl carbonate and diethyl carbonate.

In a preferred embodiment of the present invention, in the case where R ¹ represents a linear or branched Q^-alkyl, the quaternization is carried out by at least one alkylating agent, which is dimethyl sulfate.

Flotation processes.

Reverse flotation.

In one embodiment, the present invention is directed to a reverse flotation process for beneficiating non-sulfide minerals and non-sulfide ores by collecting impurities from the non-sulfide minerals and non-sulfide ores in a froth bed, comprising the steps of:

a) grinding the non-sulfide ore to the desired particle size distribution using grinding equipment known to those skilled in the art, such as a ball mill or a rod mill;

b) diluting the crushed ore suspension with a large amount of water to obtain an aqueous mixture;

c) adjusting the pH of the aqueous mixture obtained in step b) to the desired level to obtain an aqueous mixture with a set pH;

d) optionally adding a depressant to the aqueous mixture;

e) adding at least one modified polyetheramine of formula (I) to the aqueous mixture with an adjusted pH;

f) stirring the pH-adjusted aqueous mixture obtained in step e) while blowing air to form foam;

g) collecting impurities in the foam layer;

h) recovery of non-sulphide minerals from the chamber product.

In one embodiment, the present invention is directed to a reverse flotation process for beneficiating non-sulfide minerals and non-sulfide ores by collecting impurities from the non-sulfide minerals and non-sulfide ores in a froth bed, comprising the steps of:

a) grinding the non-sulfide ore to the desired particle size distribution using grinding equipment known to those skilled in the art, such as a ball mill or a rod mill;

b) diluting the crushed ore suspension with a large amount of water to obtain an aqueous mixture;

c) adjusting the pH of the aqueous mixture obtained in step b) to the desired level to obtain an aqueous mixture with a set pH;

d) optionally adding a depressant to the aqueous mixture;

e) adding as a collector at least one modified polyetheramine of formula (I)

in which R represents a linear or branched aliphatic radical containing from 10 to 20 carbon atoms and 0, 1, 2 or 3 double bonds;

R ¹ represents H or linear or branched ^-^-alkyl;

- 7 046844

R ² is H and n, the same or different, means an integer in the range from >1 to <2;

to an aqueous mixture with a set pH;

f) stirring the pH-adjusted aqueous mixture obtained in step e) while blowing air to form foam;

g) collecting impurities in the foam layer and

h) recovery of non-sulphide minerals from the chamber product.

Direct flotation.

In another embodiment, the present invention is directed to a direct flotation process for the beneficiation of non-sulfide minerals and non-sulfide ores, comprising the steps of:

a) grinding the non-sulfide ore to the desired particle size distribution using grinding equipment known to those skilled in the art, such as a ball mill or a rod mill;

b) diluting the crushed ore slurry with a large amount of water to obtain an aqueous mixture, adjusting the pH of the aqueous mixture obtained in step a) to the desired level to obtain a pH-adjusted aqueous mixture;

c) optionally adding a depressant to the aqueous mixture;

d) adding at least one modified polyetheramine as a collector to the pH adjusted aqueous mixture;

e) stirring the pH-adjusted aqueous mixture obtained in step d) while blowing air to form foam;

f) collection of non-sulfide minerals in the foam layer.

In another embodiment, the present invention is directed to a direct flotation process for the beneficiation of non-sulfide minerals and non-sulfide ores, comprising the steps of:

a) grinding the non-sulfide ore to the desired particle size distribution using grinding equipment known to those skilled in the art, such as a ball mill or a rod mill,

b) diluting the crushed ore suspension with a large amount of water to obtain an aqueous mixture, adjusting the pH of the aqueous mixture obtained in step a) to the desired level to obtain a pH-adjusted aqueous mixture,

c) optionally adding a depressant to the aqueous mixture,

d) adding as a collector at least one modified polyetheramine of formula (I)

in which R represents a linear or branched aliphatic radical containing from 10 to 20 carbon atoms and 0, 1, 2 or 3 double bonds;

R ¹ represents H or linear or branched C ₁ -C ₃ alkyl;

R ² is H and n, the same or different, means an integer in the range from >1 to <2;

to an aqueous mixture with a set pH;

e) stirring the pH-adjusted aqueous mixture obtained in step d) while blowing air to form foam;

f) collection of non-sulfide minerals in the foam layer.

Minerals.

An embodiment of the present invention relates to a reverse froth flotation process

- 8 046844 non-sulfide ores containing silicates as impurities, especially phosphate ores for the extraction of apatite minerals, in which the above-described compound or composition is used as a collector. In the context of the present invention, the term non-sulfide ore means ores in which the valuable mineral is not in the form of sulfide, and includes any ore that is traditionally classified as non-sulfide, including barite, calamine, calcite, magnesite, cassiterite, coal, feldspar, pyrochlore , fluorite, glass sand, graphite, heavy metal oxides, iron ores, kaolin clay, phosphate, mica, potassium, pyrochlore, quartz, silicates, scheelite and talc.

In an embodiment of the present invention, the non-sulfide ore is selected from the group consisting of iron ores, phosphate ores, calcite, pyrochlore, quartz, kaolin, mica, feldspar and other silicates.

In another preferred embodiment of the present invention, the amount of the collector composition is in the range of 10 g to 10 kg per 1000 kg of non-sulfide minerals and non-sulfide ores; more preferably from 10 g to 8 kg per 1000 kg of non-sulfide minerals and non-sulfide ores; even more preferably from 50 g to 5 kg per 1000 kg of non-sulfide minerals and non-sulfide ores; most preferably from 50 g to 3 kg per 1000 kg of non-sulfide minerals and non-sulfide ores; and particularly preferably from 50 g to 1 kg per 1000 kg of non-sulfide minerals and non-sulfide ores.

Auxiliary agents.

In a preferred embodiment of the present invention, the flotation process, whether direct or reverse, includes the preliminary step of adding one or more modifiers and/or one or more foaming agents and/or one or more depressant(s).

In another preferred embodiment of the present invention, the modifiers are selected from the group consisting of pH modifiers such as sulfuric acid, phosphoric acid, hydrochloric acid, hexafluorosilicic acid, ammonia, sodium hydroxide, sodium carbonate.

In another preferred embodiment of the present invention, the depressants/dispersants are selected from the group consisting of sodium silicate, potassium silicate, sodium polyacrylate, sodium (di)hydrogen phosphate, sodium pyrophosphate, sodium metapolyphosphate, starch (straight or gelatinized with NaOH), other natural polysaccharides, such as guar gum, dextrin, lignin sulfonate, natural tannins such as quebracho extract, sulfonated tannins, poly(ethylene) oxides, etc.

In another preferred embodiment of the present invention, the blowing agents are selected from the group consisting of pine oil, aliphatic alcohols such as MIBC (methyl isobutyl carbinol), polyglycols, polyglycol ethers, polypropylene glycol ethers, polyoxyparaffins, cresylic acid (xylenol), residues of 2-ethylhexanol distillates , 2-ethylhexanol, n-butanol, 2-methyl-2-butanol, isononyl alcohol, isodecyl alcohol, propene hydroformylation products and mixtures thereof. More preferably, the blowing agent is MIBC (methyl isobutyl carbinol), polyglycols, polyglycol ethers, polypropylene glycol ethers, 2-ethylhexanol, 2-ethylhexanol distillate residues.

In another preferred embodiment of the present invention, the depressants are selected from the group consisting of poly(ethylene)oxide, polycarboxylate ethers, sodium polyacrylate, polysaccharides, starch, cellulose derivatives and tannic acid.

The following is a list of embodiments to further illustrate the present disclosure, without intending to limit it to the specific embodiments listed below.

- 9 046844

Embodiments of the Invention

1. Modified polyetheramine containing repeating units of formula (I)

formula (I), in which R represents a linear or branched aliphatic radical containing from 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds;

R ¹ represents H or linear or branched Q^-alkyl;

R ² represents H or linear or branched C ₁ -C ₆ -αalkyl;

n, same or different, means an integer in the range >1 to <4.

2. The modified polyetheramine according to embodiment 1, wherein R is a linear aliphatic radical containing 10 to 20 carbon atoms and 0, 1, 2 or 3 double bonds, R ¹ is H or a linear or branched C ₁ -C ₃ -alkyl, R ² represents H or linear or branched ^-^-alkyl and n, the same or different, means 1 or 2.

3. The modified polyetheramine according to embodiment 1 or 2, wherein R is a linear aliphatic radical containing 10 to 20 carbon atoms and 0, 1 or 2 double bonds, R ¹ is H or a linear C1-C3-alkyl, R ² represents H or linear C1-C3-alkyl and n, the same or different, is 1 or 2.

4. The modified polyetheramine according to any embodiment 1 to 3, wherein R is a linear aliphatic radical containing 10 to 20 carbon atoms and 0, 1 or 2 double bonds and R ¹ is methyl, R ² is H and n is 1.

5. The modified polyetheramine polyol according to any embodiment 1 to 4, wherein the modified polyetheramine polyol has a weight average molecular weight Mw in the range of >1000 to <500,000 g/mol as determined by gel permeation chromatography.

6. The modified polyetheramine according to any embodiment 1 to 5, wherein at least one modified polyetheramine containing repeating units of formula (I) is prepared by reacting at least one polyetheramine polyol containing at least one hydroxyl group, at least with one fatty acid and further modification by quaternization with at least one Q^-alkyl group.

7. The modified polyetheramine of Embodiment 6, wherein the at least one polyetheramine polyol is at least one branched polyetheramine polyol.

8. The modified polyetheramine of embodiment 6 or 7, wherein the repeat unit of the at least one polyetheramine polyol has a weight average molecular weight M _w in the range of >100 to <50,000 g/mol, as determined by gel permeation chromatography.

9. The modified polyetheramine according to any embodiment 6 to 8, wherein the at least one polyetheramine polyol has a polydispersity (Mw/M _n ) in the range of 1.1 to 5, determined by gel permeation chromatography.

10. The modified polyetheramine of any embodiment 6 to 9, wherein the at least one polyetheramine polyol has a hydroxyl number (or number of OH groups) in the range of >100 to <1000 mg KOH/g.

11. The modified polyetheramine according to any embodiment 6 to 10, wherein the at least one polyetheramine polyol is a polycondensation product of at least one tri-^-^-alkanolamine.

- 10 046844

12. The modified polyetheramine of Embodiment 11, wherein the at least one tri-C ₂ -C4 alkanolamine is triethanolamine.

13. The modified polyetheramine according to any embodiment 6 to 12, wherein at least one fatty acid is selected from compounds of general formula (II)

R-C(=O)-OH, in which R is a linear or branched aliphatic radical containing from 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.

14. The modified polyetheramine according to any embodiment 6 to 13, wherein the at least one fatty acid is selected from the group consisting of a mixture of fatty acids derived from natural oils and fats, fully or partially hydrogenated fatty acids, purified fatty acids and synthetic fatty acids.

15. The modified polyetheramine according to any embodiment 6 to 14, wherein the at least one fatty acid is selected from mixtures of fatty acids formed from triglycerides derived from natural sources such as tall oil, in particular from the hydrolysis of plant-derived triglycerides (fats and oils) such as soybean oil, coconut oil, palm oil, palm kernel oil, linseed oil, sunflower oil, rice bran oil, grape pomace oil or fats of animal origin such as tallow or tallow, and their fractions .

16. The modified polyetheramine of embodiment 15, wherein the at least one fatty acid is selected from mixtures of fatty acids that are present in fully or partially hydrogenated form.

17. The modified polyetheramine according to any embodiment 6 to 16, wherein the at least one fatty acid is selected from the group consisting of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid.

18. The modified polyetheramine according to any embodiment 6 to 17, wherein the quaternization is carried out using at least one alkylating agent selected from the group of alkyl halides, dialkyl sulfates and dialkyl carbonates.

19. The modified polyetheramine according to embodiment 18, wherein the at least one alkylating agent is selected from the group consisting of methyl chloride, dimethyl sulfate, diethyl sulfate, dimethyl carbonate and diethyl carbonate.

20. The modified polyetheramine of any embodiment 6 to 19, wherein the molar ratio of hydroxyl groups in the at least one polyetheramine polyol to the carboxyl group of the at least one fatty acid is in the range of >0.7 to <1.0.

21. The modified polyetheramine according to any embodiment 6 to 20, wherein the at least one modified polyetheramine is prepared by:

(a) polycondensing at least one tri-O-alkanolamine to form a branched polyetheramine polyol;

(b) esterifying the branched polyetheramine polyol with at least one fatty acid;

(c) quaternization with at least one alkylating agent.

22. The modified polyetheramine of Embodiment 21, wherein at least one fatty acid is oleic acid.

23. The modified polyetheramine of Embodiment 21, wherein at least one alkylating agent is dimethyl sulfate.

24. Use of at least one modified polyetheramine according to any embodiment 1 to 23 as a collector in the beneficiation process of non-sulfide minerals and non-sulfide ores.

25. Use according to embodiment 24, wherein the non-sulfide minerals and non-sulfide ores are selected from the group consisting of iron ores, phosphate ores, calcite, quartz, kaolin, mica, feldspar and silicates.

26. Use according to embodiment 24, wherein the non-sulfide mineral is calcite.

27. A reverse flotation method for beneficiation of non-sulfide minerals and non-sulfide ores by collecting impurities from non-sulfide minerals and non-sulfide ores in a foam layer, comprising the steps of:

a) grinding the non-sulfide ore to the desired particle size distribution using grinding equipment known to those skilled in the art, such as a ball mill or a rod mill;

b) diluting the ore suspension with additional water to obtain an aqueous mixture;

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c) adjusting the pH of the aqueous mixture obtained in step b) to the desired level to obtain an aqueous mixture with a set pH;

d) optionally adding a depressant to the aqueous mixture;

e) adding at least one modified polyetheramine according to any of paragraphs 1-23 to the aqueous mixture with an established pH;

f) stirring the pH-adjusted aqueous mixture obtained in step e) while blowing air to form foam;

g) collecting impurities in the foam layer;

h) recovery of non-sulphide minerals into the chamber product.

28. The method of embodiment 27, wherein the at least one modified polyetheramine is added in an amount of >50 to <2000 g/1000 kg based on the total weight of non-sulfide minerals or non-sulfide ores.

29. The method of embodiment 27 wherein the non-sulfide mineral is calcite.

Although the present invention has been described in terms of its specific embodiments, certain modifications and equivalents will be apparent to those skilled in the art and are intended to be included within the scope of the present invention.

Examples

The present invention is illustrated in detail by the following non-limiting working examples. In particular, the following test methods are part of the general description of the invention and are not limited to these specific worked examples.

Example 1.

Collector synthesis.

Synthesis of branched polyetheramine polyol.

1500 g of triethanolamine (TEA) and 20 g of a 50% aqueous solution of H ₃ PO ₂ are loaded into a four-neck flask equipped with a stirrer, a distillation bridge, a gas supply tube and an internal thermometer, and the resulting mixture is heated in a nitrogen atmosphere to 200°C. The reaction mixture is stirred at 200°C for 15.5 hours, during which the condensate formed in the reaction is removed with a moderate flow of N2 as stripping gas through the distillation bridge. At the end of the reaction time, the temperature is reduced to 140°C and the residual low molecular weight products are removed under a pressure of 100 mbar.

The reaction mixture is cooled to ambient temperature to obtain a branched polyetheramine polyol.

Mn=4935 g/mol, _Mw =8130 g/mol.

_Mw /Mn=1.6.

Number of OH groups: 620 mg KOH/g.

Amine value: 431 mg KOH/g.

Color number in Hazen units = 363 APHA.

Dynamic viscosity at 60°C: 431 mPa-s.

The number of OH groups is measured in accordance with DIN 53240, part 2.

M _n , M _w and M _w /M _n are determined by gel permeation chromatography using hexafluoroisopropanol/0.05% trifluoroacetic acid potassium salt as the mobile phase with polymethyl methacrylate as the standard and a refractometer as the detector.

Esterification.

In a glass reactor with a capacity of 1 liter, 600 g of oleic acid and 0.9 g of 50% hypophosphorous acid are mixed and heated to 60°C. Then 276 g of Lupasol EO are charged and the entire mixture is kept under a vacuum of 50 mbar and gradually heated to 170°C. During heating, the water from the esterification reaction is distilled and the vacuum is slowly increased to 10 mbar.

The entire process takes 8 h and the final acid value achieved is 3 mg KOH/g and the nitrogen content is 2348 μV/g.

Quaternization.

700 g of the ester obtained in the previous reaction are diluted with 100 g of isopropanol in a 1 liter glass reactor and heated to 65°C. At this point, 197 g of dimethyl sulfate are added slowly over 2 hours. After the quaternization reaction is complete, 284 g of isopropanol are added to thin the product.

Example 2.

Determination of molecular weight.

The molecular weight is determined using gel permeation chromatography.

Solvent: hexafluoroisopropanol (HFIP).

Preparation of samples.

12.4 mg of sample is dissolved in 4 ml of eluent (HFIP + 0.05 wt.% trifluoroammonium acetate) for

- 12 046844 nights. All sample solutions were filtered through a Millipore Millex FG filter (0.2 μm) before injection. Sealed sample vials are placed in an automatic sampler.

Experimental conditions.

An Agilent 1200 HPLC system is used, consisting of an isocratic pump, vacuum degasser, autosampler, and column oven. In addition, the Agilent system contains a differential refractometer or refractive index (DRI) detector and a variable wavelength ultraviolet (UVW) detector. Data acquisition and processing of normal SEC data is performed by Win G. PC Unichrom 8.31, build 8485, PSS (Polymer Standard Services). A combination of four Agilent PL Mixed Bed A (7.5x300 mm, 20 µm) columns are placed in series. The eluent used is hexafluoroisopropanol + 0.05 wt.% trifluoroammonium acetate at a flow rate of 1 ml/min. From each sample, 100 μl of solution is removed and injected. Calibration is carried out using PMMA standards with a narrow molar mass distribution (Polymer Standard Services), having a molar mass range from M=800 to M=2200000 g/mol. Molar masses outside this range are extrapolated.

Molecular weight of quaternized polyetheramine:

Mw=49200 g/mol.

Example 3.

Flotation process.

Materials.

Collector 1: Lupromin® FP 18 AS - polymer cationic collector supplied by BASF and obtained by esterification of triethanolamine, oleic acid and adipic acid in a molar ratio of approximately 1:1:1, using hypophosphoric acid and with the constant removal of water from the distillation process and a subsequent quaternization step using dimethyl sulfate in a molar ratio of 0.97 mol DMS per 1 mol triethanolamine used in step 1.

Collector 2: modified polyetheramine of formula (I) according to example 1.

Foaming agent: not used.

Flotation Cell: Denver Flotation Cell.

Carbonate rock from deposits in Central Europe, containing ~5% SiO ₂ and minor non-ferrous impurities, is crushed by 100% to <80 microns. The 25% solids slurry is transferred to a 2.5 L Denver flotation machine, conditioned with a manifold added as a 10% aqueous solution (see table for dosage) for 1 minute, and floated to completion. Then half the original amount of collector is added again and the flotation is repeated. The combined foam fractions and chamber fractions are dewatered, dried and weighed, after which calcite, acid-insoluble content and whiteness are analyzed (Tappi method). The results are shown in the table.________________________________________________

Collector Dose (g/t) Acid insoluble contents Loss of CaCO ₃ in tailings White Lupromin® FP 18 AS 200+100 2.96 3.2 90.31 300+150 1.55 2.2 92.18 400+200 0.58 8.1 93.70 Modified polyester amine 200+100 L71 3.9 90.59 300+150 1.02 4.4 91.54 400+200 0.24 5.0 93.28

Claims (17)

1. Modified polyetheramine containing repeating units of formula (I) formula (I), in which R represents a linear or branched aliphatic radical containing from 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds; R ¹ represents H or linear or branched ^-^-alkyl; R ² represents H or linear or branched ^-^-alkyl; n is the same or different and means an integer in the range >1 to <4. 2. Modified polyetheramine according to claim 1, in which R represents a linear aliphatic radical containing from 10 to 20 carbon atoms and 0, 1 or 2 double bonds, R ¹ represents H or linear ^-^-alkyl, R ² represents is H or linear ^-^-alkyl and n, the same or different, is 1 or 2. 3. Modified polyetheramine according to any one of claims 1 or 2, in which R is a linear aliphatic radical containing from 10 to 20 carbon atoms and 0, 1 or 2 double bonds, R ¹ is methyl, R ² is H and n is equal to 1. 4. The modified polyetheramine according to any one of claims 1 to 3, wherein the modified polyetheramine has a weight average molecular weight M _w in the range from >100 to <500,000 g/mol, determined using gel permeation chromatography. 5. A modified polyetheramine according to any one of claims 1 to 4, wherein at least one modified polyetheramine containing repeating units of formula (I) is prepared by reacting at least one polyetheramine polyol containing at least one hydroxyl group with at least c one fatty acid and further modification by quaternization with at least one hydrogen or ^-^-alkyl group. 6. The modified polyetheramine of claim 5, wherein the at least one polyetheramine polyol is at least one branched polyetheramine polyol. 7. The modified polyetheramine according to claim 5 or 6, wherein the at least one polyetheramine polyol has a polydispersity (M _w /M _n ) in the range of 1.1 to 5, determined using gel permeation chromatography. 8. The modified polyetheramine according to any one of claims 5 to 7, wherein the at least one polyetheramine polyol is a polycondensation product of at least one tri-C ₂ -C ₄ alkanolamine. 9. Modified polyetheramine according to any one of claims 5 to 8, in which at least one fatty acid is selected from compounds of general formula (II) R-C(O)-OH, in which R is a linear or branched aliphatic radical containing from 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds. 10. Modified polyetheramine according to any one of claims 5 to 9, in which, in the case where R ¹ represents a linear or branched ^-^-alkyl, the quaternization is carried out by at least one alkylating agent selected from the group of alkyl halides, dialkyl sulfates and dialkyl carbonates. 11. The use of a modified polyetheramine according to any one of claims 1-10 as a collector in the process of beneficiation of non-sulfide minerals and non-sulfide ores. 12. Use according to claim 11, wherein the non-sulfide minerals and non-sulfide ores are selected from - 14 046844 group consisting of iron ores, phosphate ores, calcite, quartz, kaolin, mica, feldspar and silicates. 13. Use according to claim 12, wherein the non-sulfide mineral is calcite. 14. A reverse flotation method for beneficiation of non-sulfide minerals and non-sulfide ores by collecting impurities from non-sulfide minerals and non-sulfide ores in a foam layer, comprising the steps of: a) grinding non-sulfide ore to a specified particle size distribution using grinding equipment; b) diluting the ground suspension with additional water to obtain an aqueous mixture; c) adjusting the pH of the aqueous mixture obtained in step b) to a predetermined level to obtain an aqueous mixture with a specified pH; e) adding at least one modified polyetheramine according to any one of claims 1 to 10 to the aqueous mixture with an established pH; f) stirring the pH-adjusted aqueous mixture obtained in step e) while blowing air to form foam; g) collecting impurities in the foam layer; h) recovery of target non-sulfide minerals into the chamber product. 15. The method of claim 14, wherein the at least one modified polyetheramine is added in an amount of >50 to <2000 g/1000 kg based on the total weight of non-sulfide minerals or non-sulfide ores. 16. The method according to claim 14 or 15, wherein the grinding equipment is selected from a ball mill or a rod mill. 17. The method according to any one of claims 14 to 16, further comprising the step of d) adding a depressant to the aqueous mixture.