WO2016161032A1

WO2016161032A1 - Collectors containing oligomeric acids and rosin oils and methods for making and using same

Info

Publication number: WO2016161032A1
Application number: PCT/US2016/025088
Authority: WO
Inventors: David R. Snead
Original assignee: Georgia-Pacific Chemicals Llc
Priority date: 2015-03-31
Filing date: 2016-03-30
Publication date: 2016-10-06
Also published as: WO2016161033A1

Abstract

Collectors for the beneficiation of a crude mineral ore and methods for making and using same. The collector can include a mixture of an oligomeric acid and a rosin oil. The oligomeric acid can include a dimer acid, a trimer acid, or a mixture thereof. The rosin oil can include a decarboxylated rosin acid. The rosin oil can also include less than 25 wt% of rosin acids. The mixture can have an oligomeric acid to rosin oil weight ratio of about 0.5:1 to about 5:1. A method for purifying a crude mineral ore can include combining a crude mineral ore, water, and the collector to produce an aqueous mixture. The crude mineral ore can include a mineral and a gangue material. A purified mineral having a reduced concentration of the gangue material relative to the crude mineral ore can be collected from the aqueous mixture.

Description

COLLECTORS CONTAINING OLIGOMERIC ACIDS AND ROSIN OILS

AND METHODS FOR MAKING AND USING SAME

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No. 62/140,523, filed on March 31, 2015, and to U.S. Provisional Patent Application No. 62/140,518, filed on March 31, 2015, which are both incorporated by reference herein.

BACKGROUND

Field

[0002] Embodiments described generally relate to collectors and methods for making and using same. More particularly, such embodiments relate to collectors containing oligomeric acids and rosin oils and methods for making and using same.

Description of the Related Art

[0003] Froth flotation uses the differences in hydrophobicity values of various particles in an aqueous slurry to selectively separate or purify desirable mineral particles from less desirable gangue particles. Certain heteropolar or nonpolar chemicals called collectors are added to the aqueous slurries to form or enhance water repellencies on the surfaces of the mineral particles. These collectors are designed to selectively attach to one or more of the mineral particles to be separated from the aqueous slurry and form a hydrophobic monolayer on the surfaces of the mineral particles. The formation of the hydrophobic monolayer lowers the surface energy of the mineral particles, which increases the likelihood that the particles will bind with air bubbles passing through in the slurry. The density of the combined air bubble and the mineral particles is less than the displaced mass of the aqueous slurry, which causes the air bubble and the mineral particles to float to the surface of the slurry. A mineral-rich froth is formed by the collection of the floating air bubble and the mineral particles at the surface of the slurry that can be skimmed from the surface of the slurry, while other gangue or remaining materials can be submerged and/or flocculated in the slurry. The gangue or remaining materials can typically contain particles of sand, silica, silicates, feldspar, mica, clays, chrysocola, or potash. [0004] In reverse flotation, impurities are floated out of and away from the mineral particles to be beneficiated or otherwise purified. In particular, phosphate minerals, iron ore, copper ores, and other minerals and/or ores are frequently beneficiated in this manner. In many cases, silicate is the main component of the mineral impurities that cause quality reductions in the purified product. The minerals containing silicates or other silicon oxides include quartz, sand, mica, feldspar, muscovite, and biotite. A high silicate content lowers the quality of the phosphate or other purified material.

[0005] Phosphate ores contain the inorganic compound calcium phosphate that can be represented by the general chemical formula Ca₅(P04)3( ), where X can be either fluoride, chloride, and/or hydroxide. Phosphate ores, therefore, as well as other type of phosphorous containing ores, generally have a polar, hydrophilic surface. Many of the impurities (e.g., silicates) in the slurry, however, also have polar, hydrophilic surfaces and therefore are not easy to selectively separate from the phosphate materials. Conventional collectors for silicate flotation in phosphate beneficiation generally exhibit inadequate results with respect to selectivity and yield of phosphate relative to the impurities. In many cases, phosphate ores that contain high impurity content generally yield lower quality phosphate ore products.

[0006] There is a need, therefore, for improved collectors and methods for making and using same.

SUMMARY

[0007] Collectors for the beneficiation of a crude mineral ore and methods for making and using same are provided. In some examples, the collector can include a mixture of an oligomeric acid and a rosin oil. The oligomeric acid can include a dimer acid, a trimer acid, or a mixture thereof. The rosin oil can include a decarboxylated rosin acid. The rosin oil can also include less than 25 wt% of rosin acids. The mixture can have an oligomeric acid to rosin oil weight ratio of about 0.5 : 1 to about 5 : 1.

[0008] In some examples, a method for making a collector for use in the beneficiation of a crude mineral ore can include mixing an oligomeric acid and a rosin oil to produce a mixture. The oligomeric acid can include a dimer acid, a trimer acid, or a mixture thereof. The rosin oil can include a decarboxylated rosin acid. The rosin oil can also include less than 25 wt% of rosin acids. The mixture can have an oligomeric acid to rosin oil weight ratio of about 0.5 : 1 to about 5 : 1.

[0009] In some examples, a method for purifying a crude mineral ore can include combining a crude mineral ore, water, and a collector to produce an aqueous mixture. The crude mineral ore can include a mineral and a gangue material. The collector can include a mixture of an oligomeric acid and a rosin oil. The oligomeric acid can include a dimer acid, a trimer acid, or a mixture thereof. The rosin oil can include a decarboxylated rosin acid. The rosin oil can also include less than 25 wt% of rosin acids. The mixture can have an oligomeric acid to rosin oil weight ratio of about 0.5 : 1 to about 5 : 1. The method can also include collecting a purified mineral from the aqueous mixture. The purified mineral can have a reduced concentration of the gangue material relative to the crude mineral ore.

DETAILED DESCRIPTION

[0010] It has been surprisingly and unexpectedly discovered that combining one or more oligomeric acids and one or more rosin oils can produce a mixture or "collector" that provides high yields and/or selectivity in the beneficiation of phosphate and/or other minerals. It has also been surprisingly and unexpectedly discovered that mixtures of fatty acids and rosin acids can be processed to convert at least a portion of the fatty acids to oligomeric acids and to convert at least a portion of the rosin acids to rosin oils to produce the mixture or collector that provides high yields and/or selectivity in the beneficiation of phosphate and/or other minerals. Surprisingly, the mixture of oligomeric acids and rosin oils perform better as a collector in flotation (e.g., greater yield and/or selectivity in phosphate beneficiation) than blends of crude tall oils and diesel fuel oil. Without wishing to be bound by theory, it is believed that the mixture of oligomeric acids and rosin oils provide enhanced adhesion to the surfaces of phosphate particles and other minerals, which lowers the surface energy of the particles. This reduced surface energy increases the likelihood for the phosphate particles and/or other minerals to bind or otherwise attract to air bubbles and thus increases the buoyancy of the particles. The purified phosphate and/or other purified minerals can be collected or removed from the aqueous mixture, for example, after floating toward or on a surface of a separation vessel.

[0011] The collector can have an oligomeric acid to rosin oil weight ratio of about 0.5 : 1, about 0.6: 1, about 0.7: 1, about 0.8: 1, about 0.9: 1, about 1 : 1, about 1.1 : 1, about 1.2: 1, about 1.3 : 1, about 1.4:1, about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1, or about 1.9:1 to about 2:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3:1, about 3.2:1, about 3.4:1, about 3.6:1, about 3.8:1, about 4:1, about 4.2:1, about 4.4:1, about 4.6:1, about 4.8:1, about 5:1, about 6:1, about 7:1, about 8:1, about 9:1, about 10:1, or greater. For example, the collector can have an oligomeric acid to rosin oil weight ratio of about 0.5:1 to about 10:1, about 0.5:1 to about 8:1, about 0.5:1 to about 5:1, about 0.5:1 to about 3:1, about 0.5:1 to about 1:1, about 0.7:1 to about 10:1, about 0.7:1 to about 8:1, about 0.7:1 to about 5:1, about 0.7:1 to about 3:1, about 0.7:1 to about 2:1, about 0.9:1 to about 10:1, about 0.9:1 to about 8:1, about 0.9:1 to about 5:1, about 0.9:1 to about 3:1, about 0.9:1 to about 2:1, about 1:1 to about 10:1, about 1:1 to about 8:1, about 1:1 to about 5:1, about 1:1 to about 3:1, about 1:1 to about 2:1, about 1.1:1 to about 10:1, about 1.5:1 to about 10:1, about 1.8:1 to about 10:1, about 2:1 to about 10:1, about 1.1:1 to about 5:1, about 1.2:1 to about 5:1, about 1.3:1 to about 5:1, about 1.4:1 to about 5:1, about 1.5:1 to about 5:1, about 1.6:1 to about 5:1, about 1.7:1 to about 5:1, about 1.8:1 to about 5:1, about 1.9:1 to about 5:1, about 2:1 to about 5:1, about 1.1:1 to about 3:1, about 1.2:1 to about 3:1, about 1.3:1 to about 3:1, about 1.4:1 to about 3:1, about 1.5:1 to about 3:1, about 1.6:1 to about 3:1, about 1.7:1 to about 3:1, about 1.8:1 to about 3:1, about 1.9:1 to about 3:1, about 2:1 to about 3:1, about 1.1:1 to about 2.5:1, about 1.2:1 to about 2.5:1, about 1.3:1 to about 2.5:1, about 1.4:1 to about 2.5:1, about 1.5:1 to about 2.5:1, about 1.6:1 to about 2.5:1, about 1.7:1 to about 2.5:1, about 1.8:1 to about 2.5:1, about 1.9:1 to about 2.5:1, about 2:1 to about 2.5:1, about 1.2:1 to about 2.2:1, about 1.4:1 to about 2.2:1, about 1.6:1 to about 2.2:1, about 1.8:1 to about 2.2:1, or about 1.9:1 to about 2.2:1.

[0012] In some examples, the amount of the oligomeric acid in the collector can be about 20 wt%, about 30 wt%, about 40 wt%, or about 50 wt% to about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, about 91 wt%, about 92 wt%, about 93 wt%, about 94 wt%, about 95 wt%, about 96 wt%, about 97 wt%, about 97.5 wt%, about 98 wt%, about 98.5 wt%, about 99 wt%, about 99.3 wt%, or about 99.5 wt%, based on the total or combined weight of the oligomeric acid and the rosin oil. In some examples, the amount of the oligomeric acid in the collector can be about 20 wt% to about 99 wt%, about 30 wt% to about 98 wt%, about 30 wt% to about 95 wt%, about 30 wt% to about 90 wt%, about 40 wt% to about 99 wt%, about 40 wt% to about 95 wt%, about 50 wt% to about 98 wt%, or about 50 wt% to about 95 wt%, based on the combined weight of the oligomeric acid and the rosin oil.

[0013] The amount of the rosin oil in the collector can be about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, or about 50 wt% to about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, or about 90 wt%, based on the combined weight of the oligomeric acid and the rosin oil. In some examples, the amount of the rosin oil in the collector can be about 5 wt% to about 90 wt%, about 5 wt% to about 80 wt%, about 5 wt% to about 70 wt%, about 5 wt% to about 60 wt%, about 5 wt% to about 50 wt%, about 5 wt% to about 40 wt%, about 5 wt% to about 30 wt%, about 5 wt% to about 20 wt%, about 10 wt% to about 90 wt%, about 10 wt% to about 80 wt%, about 10 wt% to about 70 wt%, about 10 wt% to about 60 wt%, about 10 wt% to about 50 wt%, about 10 wt% to about 40 wt%, about 10 wt% to about 30 wt%, about 10 wt% to about 20 wt%, about 20 wt% to about 90 wt%, about 20 wt% to about 80 wt%, about 20 wt% to about 70 wt%, about 20 wt% to about 60 wt%, about 20 wt% to about 50 wt%, or about 20 wt% to about 40 wt%, based on the combined weight of the oligomeric acid and the rosin oil.

[0014] In one specific example, the collector can include about 50 wt% to about 90 wt% of the oligomeric acid and about 10 wt% to about 50 wt% of the rosin oil, based on the combined weight of the oligomeric acid and the rosin oil. In another specific example, the collector can include about 60 wt% to about 80 wt% of the oligomeric acid and about 20 wt% to about 40 wt% of the rosin oil, based on the combined weight of the oligomeric acid and the rosin oil. In another specific example, the collector can include about 60 wt% to about 70 wt% of the oligomeric acid and about 30 wt% to about 40 wt% of the rosin oil, based on the combined weight of the oligomeric acid and the rosin oil.

[0015] The collector can have an acid value of about 30, about 35, about 40, about 45, about 50, about 55, or about 60 to about 65, about 70, about 75, about 80, about 90, about 100, about 110, about 120, about 130, about 140, about 150, about 160, about 170, or about 180 milligram (mg) of KOH per gram (g) of a combined weight of the oligomeric acid and the rosin oil. The collector can have an acid value of about 30 to about 180, about 40 to about 170, about 50 to about 170, about 50 to about 150, about 50 to about 130, about 70 to about 170, about 70 to about 150, or about 70 to about 130 mg KOH/g of the combined weight of the oligomeric acid and the rosin oil. The acid value (mg KOH/g) of the collector can be measured according to ASTM D465-15.

[0016] The oligomeric acids can include one or more dimer acids, one or more trimer acids, one or more higher acids (e.g., acids containing 4, 5, or more monomer acid units), or any mixture thereof. The oligomeric acid can be or include one or more homomeric acids, where the monomer acid units in the homomeric acids are the same. The oligomeric acids can be or include one or more heteromeric acids, where at least two of the monomer acid units in the heteromeric acids are different.

[0017] The oligomeric acid can be formed, made, produced, or otherwise derived from one or more monomer fatty acids, one or more monomer rosin acids, or a combination of one or more monomer fatty acids and one or more monomer rosin acids. In one example, the monomer fatty acids can include one or more monomer tall oil fatty acids and the monomer rosin acids can include one or more monomer tall oil rosin acids. The monomer fatty acid and the monomer rosin acid can independently include one or more Ci₆-monomer acids, Cn-monomer acids, C₁₈- monomer acids, Ci₉-monomer acids, or C₂o-monomer acids. In some examples, the monomer fatty acid and the monomer rosin acid can independently include one or more compounds having the molecular formula of Ci₆H₂₆0₂, Ci₆H₂₈0₂, Ci₆H₃o0₂, Ci₆H₃₂0₂, Ci₈H₃₀O₂, Ci₈H₃₂0₂, Ci H₃₄0₂, Ci H₃₆0₂, C₂oH₃₄0₂, C₂oH₃₂0₂, C₂oH₃o0₂, or C₂oH₂ 0₂.

[0018] Illustrative monomer fatty acids can include, but are not limited to, oleic acid, palmitic acid, linoleic acid, linolenic acid, eicosatrienoic acid, stearic acid, arachidic acid, behenic acid, isomers thereof, or any mixture thereof. Illustrative monomer rosin acids can be or include, but are not limited to, abietic acid, pimaric acid, dehydroabietic acid, palustric acid, isopimaric acid, neoabietic acid, sandaroco-pimaric acid, levopimaric acid, isomers thereof, or any mixture thereof.

[0019] In some examples, the oligomeric acids can be derived or otherwise produced from one or more fatty acid sources. Illustrative fatty acid sources can be or include, but are not limited to, tall oil fatty acids ("TOFA"), crude tall oils ("CTO"), distilled tall oils ("DTO"), depitched tall oil, tall oil pitches, plant and/or vegetable oils, animal fats or oils, portions thereof, fractions thereof, or any mixture thereof. Other illustrative fatty acid sources can be or include oleic acid, palmitic acid, linoleic acid, linolenic acid, eicosatrienoic acid, stearic acid, arachidic acid, behenic acid, salts thereof, isomers thereof, or any mixture thereof. As used herein, the term crude tall oil ("CTO") refers to the crude by-product, and only the crude by-product, recovered as soap skimmings from the black liquor of a Kraft pulping process. The term crude tall oil ("CTO"), as used herein, purposefully excludes any derivatives and intermediates produced from extraction or distillation.

[0020] Illustrative plant and/or vegetable oils can include, but are not limited to, safflower oil, grapeseed oil, sunflower oil, walnut oil, soybean oil, cottonseed oil, coconut oil, corn oil, olive oil, palm oil, palm olein, peanut oil, rapeseed oil, canola oil, sesame oil, hazelnut oil, almond oil, beech nut oil, cashew oil, macadamia oil, mongongo nut oil, pecan oil, pine nut oil, pistachio oil, grapefruit seed oil, lemon oil, orange oil, watermelon seed oil, bitter gourd oil, buffalo gourd oil, butternut squash seed oil, egusi seed oil, pumpkin seed oil, borage seed oil, blackcurrant seed oil, evening primrose oil, acai oil, black seed oil, flaxseed oil, carob pod oil, amaranth oil, apricot oil, apple seed oil, argan oil, avocado oil, babassu oil, ben oil, borneo tallow nut oil, cape chestnut, algaroba oil, cocoa butter, cocklebur oil, poppyseed oil, cohune oil, coriander seed oil, date seed oil, dika oil, false flax oil, hemp oil, kapok seed oil, kenaf seed oil, lallemantia oil, mafura oil, marula oil, meadowfoam seed oil, mustard oil, okra seed oil, papaya seed oil, perilla seed oil, persimmon seed oil, pequi oil, pili nut oil, pomegranate seed oil, prune kernel oil, quinoa oil, ramtil oil, rice bran oil, royle oil, shea nut oil, sacha inchi oil, sapote oil, seje oil, taramira oil, tea seed oil, thistle oil, tigernut oil, tobacco seed oil, tomato seed oil, wheat germ oil, castor oil, colza oil, flax oil, radish oil, salicornia oil, lung oil, honge oil, jatropha oil, jojoba oil, nahor oil, paradise oil, petroleum nut oil, dammar oil, linseed oil, stillingia oil, vernonia oil, amur cork tree fruit oil, artichoke oil, balanos oil, bladderpod oil, brucea javanica oil, burdock oil, candlenut oil, carrot seed oil, chaulmoogra oil, crambe oil, croton oil, cuphea oil, mango oil, neem oil, rose hip seed oil, rubber seed oil, sea buckthorn oil, sea rocket seed oil, snowball seed oil, tall oil, tamanu oil, tonka bean oil, ucuhuba seed oil, or any mixture thereof. Illustrative animal fats or oils that can be used as the fatty acids can include, but are not limited to, fatty acids from animal sources, such as cows, pigs, lambs, chickens, turkeys, ducks, geese, and other animals, as well as dairy products such as milk, butter, or cheese. Illustrative fatty acids from animal sources can include palmitic acid, stearic acid, myristic acid, oleic acid, palmitoleic acid, linoleic acid, or any mixture thereof. [0021] In some examples, any of the oligomeric acids can be combined, mixed, and/or reacted with one or more reagents to form salts, complexes, adducts, hydrates, or other forms of the oligomeric acids. For example, one or more oligomeric acids can be reacted with one or more fatty acids to form higher order oligomeric acids. The oligomeric acids can be reacted with the one or more reagents, such as compounds with one or more unsaturated bonds, before being combined with other components to form the collector. Alternatively, the oligomeric acids and the one or more reagents can be combined as separate components, at the same time or at different times, to form the collector.

[0022] In some examples, the oligomeric acid can include one or more dimer acids and/or trimer acids and can also include one or more monomer acids. For example, if the oligomeric acids are produced by converting one or more monomer acids, i.e., monomer fatty acids and/or monomer rosin acids, to the dimer acids, trimer acids, and/or higher acids, unreacted monomer acids can remain in the oligomeric acids. In another example, the monomer acids can also be produced or otherwise derived in the production the oligomeric acids and/or the rosin oils. For example, one monomer fatty acid that can be produced or otherwise derived in the production of the oligomeric acid can be or include, but is not limited to, one or more branched-chain fatty acids.

[0023] Branched-chain fatty acids can include, but are not limited to, branched-chain iso-oleic acids and/or branched-chain iso-palmitic acids. Illustrative branched-chain iso-oleic acids can include, but are not limited to, 2-methyl-2- heptadecenoic acid, 3-methyl-2- heptadecenoic acid, 3-methyl-3- heptadecenoic acid, 4-methyl-3- heptadecenoic acid, 4-methyl-4- heptadecenoic acid, 5-methyl-4- heptadecenoic acid, 5-methyl-5- heptadecenoic acid, 6-methyl-5- heptadecenoic acid, 6-methyl-6- heptadecenoic acid, 7-methyl-6- heptadecenoic acid, 7-methyl- 7- heptadecenoic acid, 8-methyl-7- heptadecenoic acid, 8-methyl-8- heptadecenoic acid, 9- methyl-8- heptadecenoic acid, 9-methyl-9-heptadecenoic acid, 10-methyl-9-heptadecenoic acid, 10-methyl-lO- heptadecenoic acid, l l-methyl-10- heptadecenoic acid, 11-methyl-l l- heptadecenoic acid, 12-methyl-l l- heptadecenoic acid, 12-methyl-12- heptadecenoic acid, 13- methyl-12- heptadecenoic acid, 13-methyl-13- heptadecenoic acid, 14-methyl-13- heptadecenoic acid, 14-methyl-14- heptadecenoic acid, 15-methyl-14- heptadecenoic acid, 15-methyl-15- heptadecenoic acid, 16-methyl-15- heptadecenoic acid, 16-m ethyl- 16-heptadecenoic acid. Illustrative branched-chain iso-palmitic acids can include, but are not limited to, 2-methyl-2- pentadecenoic acid, 3 -methyl -2- pentadecenoic acid, 3-methyl-3- pentadecenoic acid, 4-methyl- 3- pentadecenoic acid, 4-methyl-4- pentadecenoic acid, 5-methyl-4- pentadecenoic acid, 5- methyl-5- pentadecenoic acid, 6-methyl-5- pentadecenoic acid, 6-methyl-6- pentadecenoic acid,

7- methyl-6- pentadecenoic acid, 7-methyl-7-pentadecenoic acid, 8-methyl-7- pentadecenoic acid,

8- methyl-8- pentadecenoic acid, 9-methyl-8- pentadecenoic acid, 9-m ethyl -9-pentadecenoic acid, 10-methyl-9-pentadecenoic acid, 10-methyl-lO- pentadecenoic acid, 11 -methyl- 10- pentadecenoic acid, 11 -methyl- 11 -pentadecenoic acid, 12-methyl-l l- pentadecenoic acid, 12- methyl-12- pentadecenoic acid, 13 -methyl- 12-pentadecenoic acid, 13-methyl-13- pentadecenoic acid, 14-methyl- 13 -pentadecenoic acid, 14-methyl-14- pentadecenoic acid, or any mixture thereof. In another example, monomer fatty acids that can be produced or otherwise derived in the production of the oligomeric acid can include elaidic acid, 2-octadecenoic acid, 3- octadecenoic acid, 4-octadecenoic acid, 5-octadecenoic acid, 6-octadecenoic acid, 7- octadecenoic acid, 8-octadecenoic acid, 10-octadecenoic acid, 11-octadecenoic acid, 12- octadecenoic acid, 13-octadecenoic acid, 14-octadecenoic acid, 15-octadecenoic acid, 16- octadecenoic acid, 17-octadecenoic acid, or any mixture thereof.

[0024] The collector can include the one or more monomer fatty acids in an amount of about 0.01 wt%, about 0.1 wt%, about 0.5 wt%, about 0.7 wt%, or about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, about 20 wt%, or about 25 wt% to about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, or about 95 wt%, based on the total or combined weight of the monomer acid, the dimer acid, and the trimer acid, i.e., the combined weight of the monomer acid and any dimer acid and any trimer acid. In some examples, the oligomeric acid can include one or more monomer acids in an amount of less than 15 wt%, less than 12 wt%, less than 10 wt%, less than 9 wt%, less than 8 wt%, less than 7 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, or less than 0.5 wt%, based on the combined weight of monomer acid, the dimer acid, and the trimer acid. In other examples, the oligomeric acid can include one or more monomer acids in an amount of about 0.01 wt% to less than 40 wt%, about 0.01 wt% to less than 30 wt%, about 0.01 wt% to less than 25 wt%, about 0.01 wt% to less than 20 wt%, about 0.01 wt% to less than 15 wt%, about 0.01 wt% to less than 10 wt%, about 0.01 wt% to less than 8 wt%, about 0.01 wt% to less than 6 wt%, about 0.01 wt% to less than 5 wt%, about 0.01 wt% to less than 4 wt%, about 0.01 wt% to less than 3 wt%, about 0.01 wt% to less than 2 wt%, about 0.01 wt% to less than 1 wt%, about 0.01 wt% to less than 0.5 wt%, about 0.1 wt% to less than 10 wt%, about 0.1 wt% to less than 8 wt%, about 0.1 wt% to less than 6 wt%, about 0.1 wt% to less than 5 wt%, about 0.1 wt% to less than 4 wt%, about 0.1 wt% to less than 3 wt%, about 0.1 wt% to less than 2 wt%, about 0.1 wt% to less than 1 wt%, about 0.1 wt% to less than 0.5 wt%, about 1 wt% to less than 12 wt%, about 1 wt% to less than 10 wt%, about 1 wt% to less than 8 wt%, about 1 wt% to less than 6 wt%, about 1 wt% to less than 5 wt%, about 1 wt% to less than 4 wt%, about 1 wt% to less than 3 wt%, or about 1 wt% to less than 2 wt%, based on the combined weight of the monomer acid, the dimer acid, and the trimer acid. In some specific examples, the oligomeric acid can include one or more monomer acids in an amount of about 0.01 wt% to less than 70 wt%, about 0.1 wt% to less than 60 wt%, about 0.01 wt% to less than 50 wt%, about 0.01 wt% to less than 40 wt%, about 0.01 wt% to less than 30 wt%, about 0.01 wt% to less than 20 wt%, about 0.01 wt% to less than 10 wt%, about 0.01 wt% to less than 5 wt%, or about 0.1 wt% to less than 5 wt%, based on the combined weight of the monomer acid, the dimer acid, and the trimer acid.

[0025] The dimer acid can include one or more C₃₀-dimer acids, one or more C₃₂-dimer acids, one or more C₃4-dimer acids, one or more C₃₆-dimer acids, one or more C₃₈-dimer acids, one or more C4o-dimer acids, one or more C4₂-dimer acids, or one or more C44-dimer acids. In some examples, the dimer acid can include one or more compounds having the molecular formula of C₃₆H₆₂0₄, C₃₆H₆₄0₄, C₃6H₆₆0₄, C₃₆H₆₈0₄, C₃₆Hvo0₄, C₃₈H₆₂0₄, C₃₈H₆₄0₄, C₃₈H6₆0₄, C₃₈H₆₈0₄, or C40H00O4. In some examples, the oligomeric acid can be or include one or more homomeric acids that are dimer acids, where the monomer acid units in the dimer acid are the same. In some examples, the oligomeric acid can be or include one or more heteromeric acids that are dimer acids, where the monomer acid units in the dimer acid are different. In other examples, the oligomeric acid can be or include one or more heteromeric acids that are dimer acids formed from two different monomer rosin acids. In other examples, the oligomeric acid can be or include one or more heteromeric acids that are dimer acids formed from a monomer fatty acid and a monomer rosin acid. For example, the heteromeric dimer having the molecular formula of C₃₈H₆₄0₄, can be formed from a monomer fatty acid having the molecular formula of Ci₈H₃₄0₂ and a monomer rosin acid having the molecular formula of C₂oH₃₀0₂. In other examples, the oligomeric acid can include one or more heteromeric compounds that can be formed from a monomer acids and a monomer rosin oil. For example, the heteromeric compound having the molecular formula of C₃₇H₆₄0₂, can be formed from a monomer fatty acid having the molecular formula of Ci₈H₃₄0₂ and a monomer rosin oil having the molecular formula of Ci₉H₃₀.

[0026] In some examples, the oligomeric acid can include the dimer acid in an amount of about 40 wt%, about 50 wt%, or about 60 wt% to about 70 wt%, about 80 wt%, about 85 wt%, about 87 wt%, about 90 wt%, about 91 wt%, about 92 wt%, about 93 wt%, about 94 wt%, about 95 wt%, about 96 wt%, about 97 wt%, about 98 wt%, about 99 wt%, or about 100 wt%, based on the combined weight of the dimer acid and the trimer acid. In other examples, the oligomeric acid can include the dimer acid in an amount of greater than 40 wt%, greater than 50 wt%, or greater than 60 wt% to greater than 70 wt%, greater than 80 wt%, greater than 85 wt%, greater than 87 wt%, greater than 90 wt%, greater than 91 wt%, greater than 92 wt%, greater than 93 wt%, greater than 94 wt%, greater than 95 wt%, greater than 96 wt%, greater than 97 wt%, greater than 98 wt%, greater than 99 wt%, or about 100 wt%, based on the combined weight of the dimer acid and the trimer acid. For example, the oligomeric acid can include the dimer acid in an amount of about 40 wt% to about 100 wt%, about 40 wt% to about 99 wt%, about 40 wt% to about 98 wt%, about 40 wt% to about 95 wt%, about 40 wt% to about 92 wt%, about 40 wt% to about 90 wt%, about 40 wt% to about 85 wt%, about 40 wt% to about 80 wt%, about 40 wt% to about 75 wt%, about 40 wt% to about 70 wt%, about 40 wt% to about 65 wt%, about 40 wt% to about 60 wt%, about 40 wt% to about 55 wt%, about 40 wt% to about 50 wt%, about 50 wt% to about 100 wt%, about 50 wt% to about 99 wt%, about 50 wt% to about 98 wt%, about 50 wt% to about 95 wt%, about 50 wt% to about 92 wt%, about 50 wt% to about 90 wt%, about 50 wt% to about 85 wt%, about 50 wt% to about 80 wt%, about 50 wt% to about 75 wt%, about 50 wt% to about 70 wt%, about 50 wt% to about 65 wt%, about 50 wt% to about 60 wt%, about 50 wt% to about 55 wt%, about 60 wt% to about 100 wt%, about 60 wt% to about 99 wt%, about 60 wt% to about 98 wt%, about 60 wt% to about 95 wt%, about 60 wt% to about 92 wt%, about 60 wt% to about 90 wt%, about 60 wt% to about 85 wt%, about 60 wt% to about 80 wt%, about 60 wt% to about 75 wt%, or about 60 wt% to about 70 wt%, based on the combined weight of the dimer acid and the trimer acid. In some specific examples, the oligomeric acid can include the dimer acid in an amount of about 40 wt% to about 100 wt%, about 50 wt% to about 100 wt%, about 60 wt% to about 100 wt%, about 40 wt% to about 90 wt%, about 50 wt% to about 90 wt%, about 60 wt% to about 90 wt%, about 40 wt% to about 85 wt%, about 50 wt% to about 85 wt%, or about 60 wt% to about 85 wt%, based on the combined weight of the dimer acid and the trimer acid.

[0027] The trimer acid can include one or more C₄5-trimer acids to C₇o-trimer acids, for example, that can include, but are not limited to, C₄₈-trimer acids, C₅₄-trimer acids, or C₆₀-trimer acids. In some examples, the trimer acid can include one or more compounds having the molecular formula of C54H92O6, C54H94O6, C54H%06, C5₄H₉₈06, or C6oH₉₀06. The oligomeric acid can be or include one or more homomeric acids that are trimer acids, where the monomer acid units are the same. For example, the homomeric acids can be trimer acids, where the monomer acid units are derived from the same fatty acid, e.g., oleic acid. In other examples, the oligomeric acid can be or include one or more homomeric acids that are trimer acids, wherein the monomer acid units are derived from the same rosin acid. In other examples, the oligomeric acid can be or include one or more heteromeric acids that are trimer acids, where at least two of the monomer units are derived from different fatty acids or rosin acids. For example, the heteromeric acids can be trimer acids, where at least one monomer unit is derived from a rosin acid and at least one monomer unit is derived from a fatty acid. In another example, the heteromeric acids can be trimer acids, where at least one monomer unit is derived from a first fatty acid, e.g., oleic acid, and at least one monomer unit is derived from a second fatty acid, e.g., palmitic acid.

[0028] In some examples, the oligomeric acid can include the one or more trimer acids and/or the one or more higher acids (e.g., acids containing 4, 5, or more monomer acid units) in an amount of about 0.01 wt%, about 0.1 wt%, about 0.5 wt%, or about 1 wt% to about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, about 18 wt%, about 20 wt%, about 22 wt%, about 25 wt%, about 28 wt%, about 30 wt%, about 35 wt%, or about 40 wt%, based on the combined weight of the dimer acid and the trimer acid. In some examples, the oligomeric acid can include the one or more trimer acids and/or the one or more higher acids in an amount of less than 40 wt%, less than 30 wt%, less than 25 wt%, less than 20 wt%, less than 18 wt%, less than 15 wt%, less than 12 wt%, less than 10 wt%, less than 9 wt%, less than 8 wt%, less than 7 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, or less than 0.5 wt%, based on the combined weight of the dimer acid and the trimer acid. For example, the oligomeric acid can include the one or more trimer acids and/or the one or more higher acids in an amount of about 0.01 wt% to about 40 wt%, about 0.01 wt% to about 30 wt%, about 0.01 wt% to about 25 wt%, about 0.01 wt% to about 20 wt%, about 0.01 wt% to about 18 wt%, about 0.01 wt% to about 15 wt%, about 0.01 wt% to about 10 wt%, about 0.01 wt% to about 8 wt%, about 0.01 wt% to about 6 wt%, about 0.01 wt% to about 5 wt%, about 0.01 wt% to about 4 wt%, about 0.01 wt% to about 3 wt%, about 0.01 wt% to about 2 wt%, about 0.01 wt% to about 1 wt%, about 0.01 wt% to about 0.5 wt%, about 0.1 wt% to about 40 wt%, about 0.1 wt% to about 30 wt%, about 0.1 wt% to about 25 wt%, about 0.1 wt% to about 20 wt%, about 0.1 wt% to about 18 wt%, about 0.1 wt% to about 15 wt%, about 0.1 wt% to about 12 wt%, about 0.1 wt% to about 10 wt%, about 0.1 wt% to about 8 wt%, about 0.1 wt% to about 6 wt%, about 0.1 wt% to about 5 wt%, about 0.1 wt% to about 4 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 2 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt% to about 0.5 wt%, about 1 wt% to about 40 wt%, about 1 wt% to about 30 wt%, about 1 wt% to about 25 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 18 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 12 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 8 wt%, about 1 wt% to about 6 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 4 wt%, about 1 wt% to about 3 wt%, about 1 wt% to about 2 wt%, about 5 wt% to about 40 wt%, about 5 wt% to about 35 wt%, about 5 wt% to about 30 wt%, about 5 wt% to about 25 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 18 wt%, about 5 wt% to about 15 wt%, about 5 wt% to about 12 wt%, about 5 wt% to about 10 wt%, about 5 wt% to about 8 wt%, or about 5 wt% to about 6 wt%, based on the combined weight of the dimer acid and the trimer acid. In some specific examples, the oligomeric acid can include the one or more trimer acids and/or the one or more higher acids in an amount of about 0.1 wt% to about 30 wt%, about 1 wt% to about 30 wt%, about 1 wt% to about 20 wt%, about 5 wt% to about 30 wt%, about 5 wt% to about 20 wt%, about 10 wt% to about 30 wt%, or about 10 wt% to about 20 wt%, based on the combined weight of the dimer acid and the trimer acid.

[0029] In some examples, the oligomeric acid can include about 60 wt% to about 95 wt% or about 70 wt% to about 95 wt% of the dimer acid and about 5 wt% to about 40 wt% or about 5 wt% to about 30 wt% of the trimer acid, based on the combined weight of the dimer acid and the trimer acid. In other examples, the oligomeric acid can include about 70 wt% to about 90 wt% or about 75 wt% to about 90 wt% of the dimer acid and about 10 wt% to about 30 wt% or about 10 wt% to about 25 wt% of the trimer acid, based on the combined weight of the dimer acid and the trimer acid. In other examples, the oligomeric acid can include about 0.1 wt% to about 5 wt% of the monomer acid, about 60 wt% to about 95 wt% of the dimer acid and about 5 wt% to about 25 wt% of the trimer acid, based on the total or combined weight of the monomer acid, the dimer acid, and the trimer acid. In other examples, the oligomeric acid can include about 70 wt% to about 90 wt% of the dimer acid and about 10 wt% to about 20 wt% of the trimer acid, on the combined weight of the monomer acid, the dimer acid, and the trimer acid.

[0030] In some examples, the oligomeric acid can have an acid value of about 100, about 120, about 140, about 150, or about 160 to about 170, about 180, about 190, about 200, about 210, about 220, about 230, about 240, about 250, about 260, about 270, about 280, about 290, or about 300 mg KOH/g of oligomeric acid. In other examples, the oligomeric acid can have an acid value of at least 100, at least 120, at least 140, at least 150, at least 160, at least 170, or at least 180 to about 190, about 200, about 210, about 220, about 230, about 240, about 250, about 260, about 270, about 280, about 290, or about 300 mg KOH/g of oligomeric acid. In other examples, the oligomeric acid can have an acid value of about 170 to about 180, about 182, about 184, about 186, about 188, about 190, about 192, about 194, about 196, about 198, about 200, about 202, about 204, about 206, about 208, about 210, or about 220 mg KOH/g of oligomeric acid. In some examples, the oligomeric acid can have an acid value of about 150 to about 400, about 150 to about 300, about 160 to about 250, about 160 to about 230, about 170 to about 220, about 170 to about 200, about 180 to about 200, or about 180 to about 195 mg KOH/g of oligomeric acid. The acid value (mg KOH/g) of the oligomeric acid can be measured according to ASTM D465-15.

[0031] The rosin oil can be formed, made, produced, or otherwise derived from one or more rosin acids and/or one or more rosin acid sources. Illustrative rosin acids can be or include, but are not limited to, abietic acid, pimaric acid, dehydroabietic acid, palustric acid, isopimaric acid, neoabietic acid, sandaroco-pimaric acid, levopimaric acid, isomers thereof, or any mixture thereof. In some examples, suitable rosin acids or rosin acid sources can be or include, but are not limited to, tall oil rosin acids and crude tall oil. The tall oil rosin acids can also be referred to as monomer tall oil rosin acids. In addition to or in lieu of the CTO and/or fractions thereof, other suitable rosin acid sources can be or include wood rosin, gum rosin, or a mixture thereof.

[0032] In some examples, the rosin oil can include rosin acids in an amount of less than 50 wt%, less than 40 wt%, less than 30 wt%, less than 20 wt%, less than 15 wt%, less than 10 wt%, less than 9 wt%, less than 8 wt%, less than 7 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, or less than 1 wt%. For example, the rosin oil can include rosin acids in an amount of about 0.01 wt% to less than 15 wt%, about 0.01 wt% to less than 10 wt%, about 0.01 wt% to less than 8 wt%, about 0.01 wt% to less than 6 wt%, about 0.01 wt% to less than 5 wt%, about 0.01 wt% to less than 4 wt%, about 0.1 wt% to less than 15 wt%, about 0.1 wt% to less than 10 wt%, about 0.1 wt% to less than 8 wt%, about 0.1 wt% to less than 6 wt%, about 0.1 wt% to less than 5 wt%, about 0.1 wt% to less than 4 wt%, about 1 wt% to less than 15 wt%, about 1 wt% to less than 10 wt%, about 1 wt% to less than 8 wt%, about 1 wt% to less than 6 wt%, about 1 wt% to less than 5 wt%, or about 1 wt% to less than 4 wt%. In some specific examples, the rosin oil can include rosin acids in an amount of about 0.01 wt% to less than 15 wt%, about 0.01 wt% to less than 10 wt%, or about 0.01 wt% to less than 5 wt%. The amount of rosin acid in the rosin oil and/or the collector can be measured using any desired method. For example, the amount of any rosin acids in the rosin oil and/or the collector can be measured via gas chromatography mass spectrometry (GC-MS) and/or liquid chromatography mass spectrometry (LC-MS).

[0033] In some examples, the rosin oil can have an acid value of about 1, about 10, about 20, about 30, or about 50 mg to about 60, about 80, about 100, about 110, about 120, about 130, about 140, or about 150 mg KOH/g of rosin oil. In other examples, the rosin oil can have an acid value of less than 150, less than 140, less than 130, less than 120, less than 110, less than 100, less than 90, less than 80, less than 70, less than 60, less than 50, less than 40, less than 30, less than 20, less than 10, less than 5, less than 3, or about 1 mg KOH/g of rosin oil. In other examples, the rosin oil can have an acid value of about 1 to about 150, about 1 mg to about 130, about 1 mg to about 110, about 50 to about 150, about 50 to about 130, or about 50 to about 110 mg KOH/g of rosin oil. The acid value (mg KOH/g) of the oligomeric acid can be measured according to ASTM D465-15.

[0034] In some examples, the collector can include the oligomeric acid having about 50 wt% to about 100 wt% of a dimer acid and the rosin oil containing less than 25 wt% of rosin acids. The rosin oil can have an acid value of less than 150 mg KOH/g of rosin oil and the collector can have an oligomeric acid to rosin oil weight ratio of about 1.2: 1 to about 3 : 1. In other examples, the collector can include the oligomeric acid having about 70 wt% to about 95 wt% of a dimer acid and the rosin oil containing less than 25 wt% of rosin acids. The rosin oil can have an acid value of less than 142 mg KOH/g of rosin oil and the collector can have an oligomeric acid to rosin oil weight ratio of about 1.5 : 1 to about 2.5 : 1.

[0035] In some examples, the collector can be produced by heating a mixture that can include one or more monomer fatty acids and one or more rosin acids to a temperature of about 150°C to about 500°C. In one example, the collector can include one or more oligomeric acids and one or more rosin oils, where the collector can have an oligomeric acid to rosin oil weight ratio of about 0.5 : 1 to about 5 : 1 or about 1.1 : 1 to about 5 : 1. The oligomeric acids can be derived from the monomer fatty acids, where the oligomeric acids can include one or more dimer acids, one or more trimer acids, or mixtures thereof. The rosin acids can be derived from the rosin acids, where the rosin oils can include less than 50 wt%, less than 25 wt%, or less than 10 wt% of rosin acids.

[0036] The one or more fatty acids or fatty acid sources can be reacted with each other to produce or otherwise form the one or more oligomeric acids. Illustrative fatty acids or fatty acid sources can be or include one or more fatty acids, TOFA, CTO, DTO, depitched tall oil, tall oil pitches, plant or vegetable oils, animal fats or oils, portions thereof, fractions thereof, or any mixture thereof. One or more catalysts can be used to accelerate the oligomerization (e.g., dimerization or trimerization) reactions of the fatty acids.

[0037] The fatty acids can be reacted to form the oligomeric acids at a temperature of about 50°C, about 60°C, about 70°C, about 80°C, about 90°C, about 100°C, about 1 10°C, about 120°C, about 130°C, about 140°C, about 150°C, about 160°C, about 170°C, about 180°C, about 190°C, about 200°C, or about 250°C to about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, about 400°C, about 410°C, about 420°C, about 430°C, about 440°C, about 450°C, about 460°C, about 470°C, about 480°C, about 490°C, or about 500°C. For example, the fatty acids can be reacted at a temperature of about 0°C to about 300°C, about 10°C to about 250°C, about 20°C to about 225°C, about 20°C to about 200°C, about 20°C to about 190°C, about 20°C to about 180°C, about 20°C to about 175°C, about 20°C to about 165°C, about 20°C to about 150°C, about 50°C to about 225°C, about 50°C to about 500°C, about 50°C to about 190°C, about 50°C to about 180°C, about 50°C to about 175°C, about 50°C to about 165°C, about 50°C to about 150°C, about 100°C to about 225°C, about 100°C to about 1,000°C, about 100°C to about 190°C, about 100°C to about 180°C, about 100°C to about 175°C, about 100°C to about 165°C, about 100°C to about 150°C, about 120°C to about 225°C, about 120°C to about 1,200°C, about 120°C to about 190°C, about 120°C to about 180°C, about 120°C to about 175°C, about 120°C to about 165°C, or about 120°C to about 150°C to form the oligomeric acids. The fatty acids can be reacted for about 0.5 hr to about 24 hr, about 1 hr to about 24 hr, about 1 hr to about 12 hr, about 2 hr to about 12 hr, about 2 hr to about 6 hr, about 2 hr to about 5 hr, or about 2 hr to about 4 hr to form the oligomeric acids.

[0038] In some examples, the collector can include one or more rosin oils that are derived, formed, or otherwise produced, in part, from one or more rosin acids or rosin acid sources. The one or more rosin acids or rosin acid sources can be decarboxylated with heat and/or catalyst exposure to produce or otherwise form the one or more rosin oils. One or more catalysts can be used to improve the rate of decarboxylation of the rosin acids, such as to accelerate the loss of rosin carboxylic acid groups, and/or to decrease reaction temperatures. One or more decarboxylation catalysts can be contacted with the rosin acids to produce the rosin oils. Illustrative decarboxylation catalysts can be or include, but are not limited to, sulfuric acid, phosphoric acid, diphenyl sulfide, benzyl phenyl sulfide, ditolyl sulfide, dinaphthyl sulfide, diheptyl sulfide, sodium sulfide, potassium sulfide, lithium sulfide, magnesium sulfide, calcium sulfide, iron sulfide, or any mixture thereof. Processes that can be used to produce the rosin oils from rosin acids can include those discussed and described in U.S. Patent No. 4,515,713.

[0039] The rosin acids can be reacted to form the rosin oils at a temperature of about 50°C, about 60°C, about 70°C, about 80°C, about 90°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, about 150°C, about 160°C, about 170°C, about 180°C, about 190°C, about 200°C, or about 250°C to about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, about 400°C, about 410°C, about 420°C, about 430°C, about 440°C, about 450°C, about 460°C, about 470°C, about 480°C, about 490°C, or about 500°C. For example, the rosin acids can be reacted at a temperature of about 0°C to about 300°C, about 10°C to about 250°C, about 20°C to about 225°C, about 20°C to about 200°C, about 20°C to about 190°C, about 20°C to about 180°C, about 20°C to about 175°C, about 20°C to about 165°C, about 20°C to about 150°C, about 50°C to about 225°C, about 50°C to about 500°C, about 50°C to about 190°C, about 50°C to about 180°C, about 50°C to about 175°C, about 50°C to about 165°C, about 50°C to about 150°C, about 100°C to about 225°C, about 100°C to about 1,000°C, about 100°C to about 190°C, about 100°C to about 180°C, about 100°C to about 175°C, about 100°C to about 165°C, about 100°C to about 150°C, about 120°C to about 225°C, about 120°C to about 1,200°C, about 120°C to about 190°C, about 120°C to about 180°C, about 120°C to about 175°C, about 120°C to about 165°C, or about 120°C to about 150°C to form the rosin oils. The rosin acids can be reacted for about 0.5 hr to about 24 hr, about 1 hr to about 24 hr, about 1 hr to about 12 hr, about 2 hr to about 12 hr, about 2 hr to about 6 hr, about 2 hr to about 5 hr, or about 2 hr to about 4 hr to form the rosin oils.

[0040] In some examples, a mixture that includes one or more monomer fatty acids and one or more rosin acids can be heated at a temperature of about 250°C to about 400°C for at least 2 hr to produce the collector. In other examples, the mixture that includes one or more monomer fatty acids and one or more rosin acids can be heated at a temperature of about 275°C to about 380°C for about 3 hr to about 24 hr to produce the collector.

[0041] In at least one example, the oligomeric acid can be derived from the fatty acids and/or the rosin acids in a crude tall oil and the rosin oil can be derived from the rosin acids in the crude tall oil. For example, the oligomeric acid and the rosin oil can both be derived from a crude tall oil that includes monomer fatty acids and rosin fatty acids. The crude tall oil can be heated under conditions sufficient to convert at least a portion of the monomer fatty acids and/or the rosin acids to the oligomeric acid and to decarboxylate at least a portion of the rosin acids to the rosin oil to produce the collector.

[0042] In one example, CTO can be made or produced as an acidified byproduct in the kraft or sulfate processing of wood. Crude tall oil, prior to refining, can include a mixture of rosin acids, fatty acids, sterols, high-molecular weight alcohols, and other alkyl chain materials. The components of CTO can depend on a variety of factors, such as the particular species of the wood being processed (wood type), the geographical location of the wood source, the age of the wood, the particular season that the wood is harvested, and others. Thus, depending on the particular source, CTO can contain about 20 wt% to about 75 wt% of fatty acids (e.g., about 30 wt% to about 60 wt% of fatty acids), about 20 wt% to about 65 wt% of rosin acids (e.g., about 30 wt% to about 60 wt% of rosin acids), and the balance being neutral and non-saponifiable components. In some examples, the CTO can include at least 3 wt%, at least 5 wt%, at least 8 wt%, or at least 10 wt% of neutral materials or non-saponifiable components. [0043] Distillation of CTO can be used to recover a mixture of fatty acids, referred to as distilled tall oil, "DTO fraction", or "DTO", where the fatty acids can have about 16 carbon atoms to about 20 carbon atoms. In some examples, these fatty acids can be used to produce or otherwise form the oligomeric acids. Fatty acids found in tall oils can include, but are not limited to, oleic acid, linoleic acid, linolenic acid, eicosatrienoic acid, stearic acid, and palmitic acid. Rosin acids found in tall oils can include, but are not limited to, abietic acid, dehydroabietic acid, isopimaric acid, and pimaric acid.

[0044] Distilled tall oil can have a fatty acids and/or esters of fatty acids concentration of about 55 wt%, about 60 wt%, or about 65 wt% to about 85 wt%, about 90 wt%, or about 95 wt%. Distilled tall oil can have a rosin acids or rosins concentration of about 5 wt%, about 10 wt%, or about 15 wt% to about 30 wt%, about 35 wt%, or about 40 wt%. Distilled tall oil can have a neutrals concentration of about 0.1 wt%, about 1 wt%, or about 1.5 wt% to about 2 wt%, about 3.5 wt%, or about 5 wt%. Distilled tall oil can have an acid value of about 20, about 25, or about 30 to about 40, about 45, or about 50. Distilled tall oil can have a viscosity (centipoise at 85°C) of about 10 cP, about 20 cP, about 30 cP, or about 40 cP to about 100 cP, about 120 cP, about 135 cP, or about 150 cP. The distilled tall oil can have a density of about 840 g/L, about 860 g/L, or about 880 g/L to about 900 g/L, about 920 g/L, or about 935 g/L. Distilled tall oil can have a saponification number of about 180, about 185, or about 190 to about 200, about 205, or about 210. Distilled tall oil can have an iodine value of about 115, about 117, or about 120 to about 130, about 135, or about 140.

[0045] In some examples, the rosin acids derived from CTO can also be in an intermediate fraction produced from the distillation of CTO, referred to as tall oil rosin acids. The tall oil rosin acids can have a concentration of rosin acids of about 80 wt%, about 85 wt%, or about 90 wt% to about 93 wt%, about 95 wt%, or about 99 wt%. The tall oil rosin acids can have a concentration of abietic acid of about 35 wt%, about 40 wt%, or about 43 wt% to about 50 wt%, about 55 wt%, or about 60 wt%. The tall oil rosin acids can have a concentration of dehydroabietic acid of about 10 wt%, about 13 wt%, or about 15 wt% to about 20 wt%, about 23 wt%, or about 25 wt%. The tall oil rosin acids can have a concentration of isopimaric acid of about 10 wt% or less, about 8 wt% or less, about 5 wt% or less, or about 3 wt% or less. The tall oil rosin acids can have a concentration of pimaric acid of about 10 wt% or less, about 8 wt% or less, about 5 wt% or less, or about 3 wt% or less. The tall oil rosin acids can have a fatty acids concentration of about 0.5 wt%, about 1 wt%, or about 2 wt% to about 3 wt%, about 5 wt%, or about 10 wt%. The tall oil rosin acids can have a concentration of neutral materials of about 0.5 wt%, about 1 wt%, or about 2 wt% to about 3 wt%, about 5 wt%, or about 10 wt%. The tall oil rosin acids can have a density of about 960 g/L, about 970 g/L, or about 980 g/L to about 1,000 g/L, about 1,010 g/L, or about 1,020 g/L. The tall oil rosin acids can have an acid value of about 150, about 160, or about 165 to about 170, about 175, or about 180.

[0046] Representative tall oil products, which can be fatty acid sources used to form the oligomeric acids, can be or include, but are not limited to, saturated and unsaturated fatty acids in the Ci₆-Ci₈ range, as well as various amounts of rosin acids, and can include XTOL^® 100, XTOL^® 300, XTOL^® 304, XTOL^® 520, and XTOL^® 3030, all of which are commercially available from Georgia-Pacific Chemicals LLC, Atlanta, GA. XTOL^® 100 can include about 1.6 wt% of palmitic acid, about 2.5 wt% of stearic acid, about 37.9 wt% of oleic acid, about 26.3 wt% of linoleic acid, about 0.3 wt% of linolenic acid, about 2.9 wt% of linoleic isomers, about 0.2 wt% of arachidic acid, about 3.6 wt% eicosatrienoic acid, about 1.4 wt% of pimaric acid, less than 0.16 wt% of sandarocopimaric, less than 0.16 wt% of isopimaric acid, less than 0.16 wt% of dehydroabietic acid, about 0.2 wt% of abietic acid, with the balance being neutrals and high molecular weight species. XTOL^® 520 DTO includes about 0.2 wt% of palmitic acid, about 3.3 wt% of stearic acid, about 37.9 wt% of oleic acid, about 26.3 wt% of linoleic acid, about 0.3 wt% of linolenic acid, about 2.9 wt% of linoleic isomers, about 0.2 wt% of arachidic acid, about 3.6 wt% eicosatrienoic acid, about 1.4 wt% of pimaric acid, less than 0.16 wt% wt% of sandarocopimaric, less than 0.16 wt% of isopimaric acid, less than 0.16 wt% of dehydroabietic acid, about 0.2 wt% of abietic acid, with the balance being neutrals and high molecular weight species. Such tall oil products can be used in the reaction with the fatty acid or a mixture of fatty acids. Other fatty acids and mixtures of fatty acids, including oxidized tall oil can also be used.

[0047] Representative tall oil products, which can be rosin acid sources used to form the oligomeric acids and/or the rosin oil, can be or include, but are not limited to, LYTOR^® 100, LYTOR^® 105, LYTOR^® 105K, LYTOR^® 110, and LYTOR^® 307, which are are commercially available from Georgia-Pacific Chemicals LLC, Atlanta, GA. LYTOR^® 100, for example, can include less than 0.16 wt% of palmitic acid, less than 0.16 wt% of stearic acid, about 0.2 wt% of oleic acid, about 0.2 wt% of arachidic acid, about 0.2 wt% eicosatrienoic acid, about 2.2 wt% of pimaric acid, about 0.6 wt% of sandarocopimaric, about 8.5 wt% of palustric acid, about 1.6 wt% of levopimaric acid, about 2.8 wt% of isopimaric acid, about 15.3 wt% of dehydroabietic acid, about 51.4 wt% of abietic acid, about 2.4 wt% of neoabietic acid, with the balance being neutrals and high molecular weight species.

[0048] In some examples, additional fatty acid sources can be or include a fatty acid, a mixture of fatty acids, a fatty acid ester, a mixture of fatty acid esters, or a mixture of one or more fatty acids and one or more fatty acid esters. The additional fatty acid sources or fatty acids can be combined with one or more crude tall oils or fractions thereof to produce a mixture and the mixture can be reacted to produce or otherwise form the one or more oligomeric acids. In other examples, the additional fatty acid sources or fatty acids can be used instead of crude tall oil or fractions thereof. Also, one or more vegetable oils can be used alone or in combination with crude tall oil, fractions thereof, and/or the additional fatty acids sources from which the oligomeric acids can be produced.

[0049] In some examples, oligomeric acids and rosin oils can be made, formed, or otherwise produced by one or more catalytic processes. A first catalyst and a mixture that includes fatty acids and rosin acids can be combined and heated to a first temperature to produce a first reaction mixture. In some examples, a second catalyst and the first reaction mixture can be mixed or otherwise combined and heated to a second temperature to produce a second reaction mixture. In other examples, the second catalyst can be omitted and the first reaction mixture, without the second catalyst, can be heated to the second temperature to produce the second reaction mixture. The second temperature can be greater than the first temperature. The second temperature can be greater than 250°C, such as about 260°C, about 275°C, or about 300°C to about 350°C, about 425°C, or about 500°C. The second reaction mixture can include oligomeric acids that can be produced from the fatty acids and/or rosin acids and rosin oils that can be produced from the rosin acids. The second reaction mixture can have a rosin oil yield of greater than 25%, such as about 30% to about 95%. The first reaction mixture can have an enriched dehydroabietic acid concentration compared to the mixture that includes fatty acids and rosin acids.

[0050] In another example, one or more iron sources, one or more iodine sources, and optionally, one or more nitrogen sources can be added in succession to a mixture that includes one or more fatty acids and one or more rosin acids to produce a first mixture. The first mixture can be heated at a temperature of about 150°C to about 260°C to produce the first reaction mixture. A catalyst and the first reaction mixture can be mixed and heated at a temperature of greater than 250°C to produce a second reaction mixture. The second catalyst can be or include one or more Bransted or Lewis acids, such as methanesulfonic acid.

[0051] The first catalyst and the mixture that includes the fatty acids and the rosin acids can be mixed, blend, or otherwise combined to produce a first mixture. In some examples, when the first catalyst and the mixture that includes the fatty acids and the rosin acids are mixed, the iron source, the nitrogen source, and the iodine source can be added in succession to the mixture that includes fatty acids and rosin acids. The first catalyst can be or include one or more iron sources, one or more nitrogen sources, one or more iodine sources, or any mixture thereof. The iron source can be or include metallic iron, ferric compounds, and ferrous compounds, including, but not limited to iron halides, iron oxides, iron hydroxides, iron sulfides, organic-iron compounds, or any mixture thereof. Illustrative iron sources can be or include, but are not limited to, one or more of metallic iron, ferrous chloride, ferric chloride, ferrous iodide, ferric iodide, ferrous bromide, ferric bromide, ferrous oxide, ferric oxide, ferrous hydroxide, ferric hydroxide, ferrous sulfide, ferric sulfide, ferrous selenide, ferric selenide, hydrates thereof, or any mixture thereof. Nitrogen sources can be or include, but are not limited to, one or more ammonium compounds, one or more amine compounds, one or more urea compounds, or any mixture thereof. Illustrative nitrogen sources can be or include, but are not limited to, ammonium carbonate, a mixture of carbonate and carbamate, urea carbonate, urea, dimethylurea, tetramethylurea, ammonium chloride, ammonium bromide, ammonium iodide, ammonium hydroxide, alkanolamines, ethylenediamine, diethylenetriamine, or any mixture thereof. Illustrative iodine sources can be or include, but are not limited to, elemental iodine (I₂), iodide salts of alkaline metals (e.g., lithium iodide, sodium iodide, potassium iodide, cesium iodide), iodide salts of rare earth metals (e.g., magnesium iodide or calcium iodide), transition metal iodides (e.g., ferrous or ferric iodide), or any mixture thereof. In some examples, the iron source can be or include one or more iron halides, the nitrogen source can be or include ammonium carbonate or ethylenediamine, and the iodine source can be or include elemental iodine. If the iron source is an iron chloride, then the iron source can be or include ferric chloride, ferrous chloride, hydrates thereof, or any mixture thereof. In some examples, the iron source and the iodine source can both be or include ferrous iodide or ferric iodide. [0052] The first mixture can include the first catalyst in an amount of about 0.01 wt%, about 0.02 wt%, about 0.03 wt%, about 0.05 wt%, about 0.07 wt%, about 0.1 wt%, about 0.15 wt%, or about 0.2 wt% to about 0.25 wt%, about 0.3 wt%, about 0.35 wt%, about 0.4 wt%, about 0.45 wt%, about 0.5 wt%, about 0.55 wt%, about 0.6 wt%, about 0.65 wt%, about 0.7 wt%, about 0.75 wt%, about 0.8 wt%, about 0.85 wt%, about 0.9 wt%, about 1 wt%, about 1.2 wt%, about 1.4 wt%, about 1.6 wt%, about 1.8 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, or about 5 wt%, based on the total or combined weight of the fatty acids and the rosin acids. For example, the first mixture can include the first catalyst in an amount of about 0.01 wt% to about 2 wt%, about 0.03 wt% to about 2 wt%, about 0.05 wt% to about 2 wt%, about 0.1 wt% to about 1.5 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt% to about 0.8 wt%, about 0.1 wt% to about 0.6 wt%, about 0.1 wt% to about 0.5 wt%, about 0.2 wt% to about 1.5 wt%, about 0.2 wt% to about 1 wt%, about 0.2 wt% to about 0.6 wt%, about 0.2 wt% to about 0.5 wt%, about 0.4 wt% to about 1.5 wt%, about 0.4 wt% to about 1 wt%, about 0.4 wt% to about 0.8 wt%, about 0.4 wt% to about 0.6 wt%, about 0.5 wt% to about 1.5 wt%, about 0.5 wt% to about 1 wt%, or about 0.5 wt% to about 0.8 wt%, about 0.01 wt% to about 1 wt%, about 0.03 wt% to about 1 wt%, about 0.05 wt% to about 1 wt%, about 0.01 wt% to about 0.5 wt%, about 0.03 wt% to about 0.5 wt%, about 0.05 wt% to about 0.5 wt%, about 0.01 wt% to about 0.1 wt%, about 0.03 wt% to about 0.1 wt%, about 0.05 wt% to about 0.1 wt%, based on the combined weight of the fatty acids and the rosin acids.

[0053] The first mixture can be heated to a first temperature. The first temperature can be about 50°C, about 80°C, about 100°C, about 120°C, about 150°C, or about 180°C to about 190°C, about 200°C, about 210°C, about 220°C, about 225°C, about 230°C, about 235°C, about 240°C, about 245°C, about 250°C, about 255°C, about 260°C, about 265°C, or about 270°C, to produce the first reaction mixture. For example, the first mixture can be heated to about 50°C to about 270°C, about 50°C to about 260°C, about 50°C to about 250°C, about 100°C to about 250°C, about 150°C to about 250°C, about 180°C to about 250°C, about 200°C to about 250°C, about 220°C to about 250°C, about 230°C to about 250°C, about 100°C to about 230°C, about 150°C to about 230°C, about 180°C to about 230°C, about 200°C to about 230°C, or about 220°C to about 230°C. In other examples, the mixture that includes the first catalyst, the fatty acids, and the rosin acids can be heated to about 50°C to less than 270°C, about 50°C to less than 260°C, about 100°C to less than 260°C, about 150°C to less than 260°C, about 180°C to less than 260°C, about 200°C to less than 260°C, about 220°C to less than 260°C, about 50°C to less than 250°C, about 100°C to less than 250°C, about 150°C to less than 250°C, about 180°C to less than 250°C, about 200°C to less than 250°C, or about 220°C to less than 250°C. The first mixture can be heated to the first temperature for about 1 min, about 5 min, about 10 min, or about 15 min to about 20 min, about 30 min, about 1 hr, about 2 hr, about 3 hr, about 4 hr, about 6 hr, or longer to produce the first reaction mixture. For example, the first mixture can be heated for about 1 min to about 6 hr, about 1 min to about 4 hr, about 1 min to about 2 hr, about 1 min to about 1 hr, about 1 min to about 30 min, about 1 min to about 20 min, about 1 min to about 8 min, about 10 min to about 4 hr, about 10 min to about 5 hr, or about 10 min to about 1 hr. The first mixture can be heated to about 150°C or about 180°C to 250°C or less than 250°C for about 1 min to about 30 min or about 5 min to about 20 min to produce the first reaction mixture. In some examples, one or more acids, such as oxalic acid, can be added to first reaction mixture to quench the first catalyst, ceasing the disproportionation reaction, and bleaching the first reaction mixture.

[0054] In some examples, the mixture that includes fatty acids and rosin acids can have a first dehydroabietic acid concentration. The first reaction mixture can have a second dehydroabietic acid concentration. The second dehydroabietic acid concentration can be greater than the first dehydroabietic acid concentration. The first reaction mixture, therefore, can have an enriched dehydroabietic acid concentration relative to the mixture that includes fatty acids and rosin acids, in part, due to the disproportionation reaction that produces the first reaction mixture. The first dehydroabietic acid concentration can be about 0.5 wt%, about 1 wt%, about 2 wt%, or about 3 wt% to about 4 wt% about 5 wt%, about 7 wt%, about 9 wt%, about 10 wt%, or about 12 wt%, based on the combined weight of the fatty acids and the rosin acids. For example, the first dehydroabietic acid concentration can be about 1 wt% to about 10 wt%, about 2 wt% to about 8 wt%, about 2 wt% to about 5 wt%, about 3 wt% to about 5 wt%, about 3 wt% to about 10 wt%, about 3 wt% to about 8 wt%, or about 5 wt% to about 8 wt%, based on the combined weight of the fatty acids and the rosin acids.

[0055] The first reaction mixture can have a second dehydroabietic acid concentration of about 1 wt%, about 2 wt%, about 3 wt%, or about 5 wt% to about 7 wt%, about 9 wt%, about 10 wt%, about 12 wt%, about 10 wt%, about 12 wt%, about 15 wt%, about 18 wt%, about 20 wt%, about 22 wt%, about 25 wt%, or about 30 wt%, based on the combined weight of the fatty acids and the rosin acids. For example, the second dehydroabietic acid concentration can be about 1 wt% to about 30 wt%, about 2 wt% to about 25 wt%, about 2 wt% to about 20 wt%, about 5 wt% to about 25 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 15 wt%, or about 5 wt% to about 12 wt%, based on the combined weight of the fatty acids and the rosin acids. The enriched dehydroabietic acid ratio, such as the second dehydroabietic acid concentration to the first dehydroabietic acid concentration, of the first reaction mixture can be greater than 1, about 1.5, about 2, about 2.5, about 3, about 3.5, about 4, about 4.5, about 5, about 6, about 7, about 8, about 9, about 10, about 12, about 15, or about 20.

[0056] In some examples, the second catalyst and the first reaction mixture can be mixed, blend, or otherwise combined to produce the second mixture. In other examples, the second catalyst can be omitted and the first reaction mixture can be further heated to produce the second reaction mixture. The second catalyst can be or include one or more acids, such as, for example, one or more Bransted acids and/or one or more Lewis acids. Illustrative Bransted acids can be or include methanesulfonic acid, p-toluenesulfonic acid (4-methylbenzenesulfonic acid), phosphoric acids, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, sulfuric acid, isomers thereof, salts thereof, esters thereof, or any mixture thereof. Illustrative Lewis acids can be or include one or more clays, such as, for example, montmorillonite. The second catalyst can also be or include one or more metal-containing compounds, such as zinc compounds, aluminum compounds, iron compounds, tin compounds, or any mixture thereof. In some examples, metal- containing compounds can be or include one or more metal halides, such as, but not limited to, zinc chloride, aluminum chloride, iron chlorides, tin chlorides, or any mixture thereof.

[0057] The second mixture can include the second catalyst in an amount of about 0.05 wt%, about 0.07 wt%, about 0.1 wt%, about 0.15 wt%, or about 0.2 wt% to about 0.25 wt%, about 0.3 wt%, about 0.35 wt%, about 0.4 wt%, about 0.45 wt%, about 0.5 wt%, about 0.55 wt%, about 0.6 wt%, about 0.65 wt%, about 0.7 wt%, about 0.75 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, about 1.2 wt%, about 1.4 wt%, about 1.6 wt%, about 1.8 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, or about 5 wt%, based on the combined weight of the fatty acids and the rosin acids in the first reaction mixture. For example, the second mixture can include the second catalyst in an amount of about 0.05 wt% to about 3 wt%, about 0.05 wt% to about 2.5 wt%, about 0.05 wt% to about 2 wt%, about 0.1 wt% to about 1.5 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt% to about 0.8 wt%, about 0.1 wt% to about 0.6 wt%, about 0.1 wt% to about 0.5 wt%, about 0.2 wt% to about 1.5 wt%, about 0.2 wt% to about 1 wt%, about 0.2 wt% to about 0.8 wt%, about 0.2 wt% to about 0.6 wt%, about 0.2 wt% to about 0.5 wt%, about 0.4 wt% to about 1.5 wt%, about 0.4 wt% to about 1 wt%, about 0.4 wt% to about 0.8 wt%, about 0.4 wt% to about 0.6 wt%, about 0.5 wt% to about 1.5 wt%, about 0.5 wt% to about 1 wt%, about 0.5 wt% to about 0.8 wt%, or about 0.5 wt% to about 0.7 wt%, based on the combined weight of the fatty acids and the rosin acids in the first reaction mixture.

[0058] One or more chelating agents can be combined with the second reaction mixture and can be used to chelate and deactivate iron in the second reaction mixture. The chelating agent can be or include one or more amines. Illustrative amines can be or include, but are not limited to, one or more monoamines, one or more polyamines (e.g., diamine or triamine), one or more alkanolamines, or any mixture thereof. The amine can be or include one or more C₂-C₂₀- monoamines, one or more C₂-C₂o-diamines, one or more C3-C₂o-triamines, salts thereof, or any mixture thereof. In some examples, the amine can be or include one or more polyamines, such as one or more C₂-C₅-diamines. Illustrative amines or other basic or alkaline compounds useful as the second catalyst can be or include, but are not limited to, ethylamine, ethylenediamine, diethylenetriamine, propylamine, propylenediamine, laurylamine, octadecylamine, isomers thereof, salts thereof, or any mixture thereof. In some examples, the second catalyst and the chelator can be included into the mixture separately or together and can be or include methanesulfonic acid, ethylenediamine, or a mixture thereof.

[0059] The second reaction mixture can include the chelating agent in an amount of about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, or about 0.5 wt% to about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, about 1.2 wt%, about 1.4 wt%, about 1.6 wt%, about 1.8 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt%, based on the combined weight of the fatty acids and the rosin acids in the first reaction mixture. For example, the second reaction mixture can include the chelating agent in an amount of about 0.1 wt% to about 10 wt%, about 0.1 wt% to about 8 wt%, about 0.1 wt% to about 5 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 1 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 5 wt%, or about 1 wt% to about 3 wt%, based on the combined weight of the fatty acids and the rosin acids in the first reaction mixture. [0060] The first mixture or the second mixture with or without the second catalyst can be heated to a second temperature. The second temperature can be greater than 250°C, about 252°C, about 255°C, or about 260°C to about 265°C, about 270°C, about 275°C, about 280°C, about 285°C, about 290°C, about 295°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 400°C, about 450°C, or about 500°C to produce the second reaction mixture. For example, the second mixture can be heated to greater than 250°C to about 500°C, greater than 250°C to about 400°C, greater than 250°C to about 350°C, greater than 250°C to about 330°C, greater than 250°C to about 320°C, greater than 250°C to about 310°C, greater than 250°C to about 300°C, or greater than 250°C to about 280°C. In other examples, the second mixture can be heated to about 280°C to about 350°C, about 280°C to about 330°C, about 280°C to about 320°C, or about 280°C to about 300°C.

[0061] The second mixture can be heated for about 0.5 hr, about 0.75 hr, about 1 hr, or about 1.25 hr to about 1.5 hr, about 2 hr, about 3 hr, about 4 hr, about 5 hr, about 6 hr, about 7 hr, about 8 hr, about 10 hr, about 12 hr, about 15 hr, about 18 hr, about 20 hr, about 24 hr, about 30 hr, about 40 hr, about 48 hr, or longer to produce the second reaction mixture. For example, the second mixture can be heated for about 0.5 hr to about 48 hr, about 1 hr to about 24 hr, about 2 hr to about 12 hr, about 2 hr to about 10 hr, about 2 hr to about 8 hr, about 2 hr to about 6 hr, about 2 hr to about 4 hr, about 3 hr to about 12 hr, about 3 hr to about 10 hr, about 3 hr to about 8 hr, about 3 hr to about 6 hr, about 3 hr to about 4 hr, about 4 hr to about 12 hr, about 4 hr to about 10 hr, about 4 hr to about 8 hr, or about 4 hr to about 6 hr. In one specific example, the second mixture can be heated to greater than 250°C to about 350°C or about 280°C to about 320°C for about 1 hr to about 24 hr or about 2 hr to about 12 hr to produce the second reaction mixture.

[0062] The rosin oils in the second reaction mixture can be produced from the rosin acids in the starting mixture that includes fatty acids and rosin acids. A rosin oil yield can be calculated by taking the weight percent of rosin oil produced in the second reaction mixture over the weight percent of rosin acid in the starting mixture that includes fatty acids and rosin acids (e.g., CTO or DTO). The second reaction mixture can have a rosin oil yield of greater than 25%, about 26%, about 28%, about 30%, or about 35% to about 36%, about 38%, about 40%, about 42%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 97%, about 98%, or about 99%. The second reaction mixture can have a rosin oil yield of greater than 25% to about 95%, about 30% to about 95%, about 30% to about 85%, about 35% to about 80%, about 40% to about 95%, or about 40% to about 85%). In some examples, the second reaction mixture can have a rosin oil yield of about 30% to about 95% or about 35% to about 80%.

[0063] The second reaction mixture can be cooled to ambient temperature (about 23°C). The second reaction mixture can include oligomeric acids and rosin acids. The oligomeric acids can include one or more dimer acids, one or more trimer acids, one or more higher acids (e.g., acids containing 4, 5, or more monomer acid units), or any mixture thereof. The oligomeric acid can be or include one or more homomeric acids and/or one or more heteromeric acids. The oligomeric acid can be produced from one or more monomer fatty acids that can include, but are not limited to, oleic acid, palmitic acid, linoleic acid, stearic acid, arachidic acid, behenic acid, isomers thereof, or any mixture thereof. The oligomeric acid can include one or more dimer acids and/or trimer acids. The oligomeric acid can have an acid value of about 100, about 150, or about 160 to about 170, about 200, about 250, or about 300 mg KOH/g of oligomeric acid. The oligomeric acid can have an acid value of about 150 to about 400, about 150 to about 300, about 160 to about 250, or about 170 to about 200 mg KOH/g of oligomeric acid.

[0064] The rosin oil can include rosin acids in an amount of less than 60 wt%, less than 50 wt%, less than 40 wt%, less than 30 wt%, less than 20 wt%, less than 15 wt%, less than 10 wt%, less than 5 wt%, or less than 1 wt%. For example, the rosin oil can include rosin acids in an amount of about 0.01 wt% to less than 15 wt%, about 0.01 wt% to less than 10 wt%, about 0.01 wt% to less than 5 wt%, or about 1 wt% to less than 15 wt%. The rosin oil can have an acid value of about 1, about 20, about 30, or about 50 to about 60, about 80, about 100, about 120, about 140, or about 150 mg KOH/g of rosin oil. The rosin oil can have an acid value of less than 150, less than 130, less than 1 10, less than 100, less than 80, less than 60, less than 50, less than 40, less than 20, less than 10, less than 5, or about 1 mg KOH/g of rosin oil. The rosin oil can have an acid value of about 1 to about 150, about 1 to about 130, or about 50 to about 130 mg KOH/g of rosin oil.

[0065] In another example, one or more rosin oils can be mixed, blended, or otherwise combined with one or more oligomeric acids to make, form, or otherwise produce the collector, the aqueous mixture, and/or other mixtures or compositions. In some examples, the one or more rosin oils can be combined with the oligomeric acid and subsequently added with other components to make, form, or otherwise produce the collector, the aqueous mixture, and/or other compositions. In other examples, the one or more rosin oils and the oligomeric acid can independently be combined with one or more components to make, form, or otherwise produce the collector, the aqueous mixture, and/or other compositions. When the one or more rosin oils and the oligomeric acid are independently combined with one or more components, the rosin oil and the oligomeric acid can be combined at the same time, the rosin oil can be added before the oligomeric acid, or the oligomeric acid can be added before the rosin oil.

[0066] In some examples, a method for purifying one or more minerals or ores, such as phosphorous containing materials, or other materials, can include agitating, blending, mixing, or otherwise combining one or more crude mineral ores that can include a silicate material, a collector that can include one or more oligomeric acids and one or more rosin oils, and water to produce an aqueous mixture. The oligomeric acid can include a dimer acid, a trimer acid, or a mixture thereof, and the rosin oil can include less than 50 wt%, less than 25 wt%, or less than 10 wt% of rosin acids, where the collector can have an oligomeric acid to rosin oil weight ratio of about 0.5: 1 to about 5: 1 or about 1.1 : 1 to about 5: 1. The method can include collecting or separating a purified mineral or ore from the aqueous mixture having a reduced weight concentration of the silicate relative to the crude mineral ore and collecting or separating a gangue or impurity material, e.g., one or more silicate materials, from the aqueous mixture. In some examples the purified mineral or ore can be recovered from the surface of the aqueous mixture and the gangue or impurity material can be recovered as a bottoms fraction from the aqueous mixture.

[0067] In some examples, any or all of the one or more minerals or ores, one or more oligomeric acids, one or more rosin oils, and water can be combined with one another, in any order, to produce the aqueous mixture. For example, one or more oligomeric acids and one or more rosin oils can be combined with one another to produce a collector, water and one or more minerals or ores can be combined to produce an aqueous slurry, and the collector can be added to the aqueous slurry. In another example, a collector that includes the oligomeric acids and the rosin oil can be produced by converting a mixture that includes one or more fatty acids and one or more rosin acids to the oligomeric acid and the one or more rosin oils. In such an example, the oligomeric acids and rosin oil can be produced in the presence of one another. [0068] In some examples, the method for purifying one or more minerals or ores (e.g., phosphorous containing materials) can include combining one or more minerals or ores, one or more oligomeric acids, one or more rosin oils, and water to produce an aqueous mixture and collecting a purified or beneficiated mineral or ore from the aqueous mixture. Generally, in some examples, the minerals or ores can be floated toward or to a surface of the aqueous mixture or slurry where the minerals or ores can be removed therefrom, e.g., by skimming off the surface of the aqueous mixture, and the silicates, silicon oxides, and/or other gangue materials can be submerged or otherwise left in the aqueous mixture. In other examples, the silicates, silicon oxides, and/or other gangue materials can be floated away from the aqueous mixture or slurry and the minerals or ores can be submerged or otherwise left in the aqueous mixture.

[0069] The method for purifying the phosphorous or other mineral containing material can also include contacting the aqueous mixture with a gas, e.g., air. For example, the method can include agitating the aqueous mixture by passing gas bubbles, e.g., air bubbles, through the aqueous mixture, mechanically stirring (e.g., impeller, paddle, stirrer), shaking, directing sound waves (e.g., ultrasonic sound waves) into the aqueous mixture, or otherwise moving the aqueous mixture, or any combination thereof. The aqueous mixture can be an aqueous solution, slurry, suspension, dispersion, or the like.

[0070] The collectors containing one or more oligomeric acids and one or more rosin oils and the purification or beneficiation methods that use the collectors can be used to recover, collect, or otherwise purify one or more materials from less pure mixtures, such as, ores and/or minerals. The collectors can be used in froth flotation processes for the beneficiation of a wide variety of materials. Illustrative materials to be purified can be or include, but are not limited to, minerals, elements, or metals such as, but are not limited to, phosphorous (e.g., phosphate or other phosphorous oxides), iron, copper, aluminum, nickel, gold, silver, platinum, palladium, titanium, chromium, molybdenum, tungsten, manganese, magnesium, lead, zinc, potassium (e.g., potash), sodium, calcium, graphite, uranium, cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, scandium, terbium, thulium, ytterbium, yttrium, potash, feldspar, bauxite, other precious metals thereof, oxides thereof, ores thereof, or any mixture thereof. The crude mineral ore can be beneficiated to produce a purified mineral ore or material that has less gangue, e.g., silicates. In one or more examples, the mineral ore, such as the crude mineral ore to be beneficiated can be or include a phosphorous ore, an iron ore, an aluminum ore, an alkaline metal ore (e.g., a potassium ore, a sodium ore, or a cesium ore), a rare earth metal ores (e.g., a calcium ore, a magnesium ore, or strontium ore), potash, feldspar, bauxite, kaolin, coal ore or any mixtures thereof. The raw materials to be purified and recovered generally can contain or include gangue. The gangue can be or include one or more silicates, sand, silica, quartz, clay, rocks, and other materials.

[0071] In some examples, the collector containing one or more oligomeric acids and one or more rosin oils can be used in froth flotation processes for the beneficiation of phosphorous containing materials, such as phosphate. The phosphorous or phosphate containing ores, rocks, minerals, or other materials, as well as the recovered or collected phosphate materials can include one or more tribasic phosphate salts. The tribasic phosphate salts can include alkaline earth metals, alkali metals, adducts thereof, complexed salts thereof, hydrates thereof, or any mixture thereof. For example, the phosphorous ore or the phosphate material can include calcium phosphate.

[0072] In some examples, the amount of the collector in the aqueous mixture that includes the collector and the mineral or ore to be beneficiated can be about 0.0005 wt%, about 0.001 wt%, about 0.005 wt%, about 0.01 wt%, about 0.02 wt%, about 0.03 wt%, about 0.04 wt%, about 0.05 wt%, about 0.06 wt%, about 0.07 wt%, about 0.08 wt%, about 0.09 wt%, about 0.1 wt%, about 0.1 1 wt%, about 0.12 wt%, about 0.13 wt%, about 0.14 wt%, about 0.15 wt%, about 0.16 wt%, about 0.17 wt%, about 0.18 wt%, about 0.19 wt%, about 0.2 wt%, about 0.25 wt%, about 0.3 wt%, about 0.35 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt%, based on the weight of the ore or mineral (e.g., phosphorous ore) to be beneficiated. In some examples, the amount of the collector in the aqueous mixture can be about 0.001 wt% to about 10 wt%, about 0.005 wt% to about 5 wt%, about 0.005 wt% to about 2 wt%, about 0.005 wt% to about 1 wt%, about 0.005 wt% to about 0.5 wt%, about 0.005 wt% to about 0.1 wt%, about 0.005 wt% to about 0.09 wt%, or about 0.005 wt% to about 0.05 wt%, based on the weight of the ore or mineral to be beneficiated. In other examples, the amount of the collector in the aqueous mixture can be greater than 0.001 wt% to about 10 wt%, greater than 0.005 wt% to about 5 wt%, greater than 0.005 wt% to about 2 wt%, greater than 0.005 wt% to about 1 wt%, greater than 0.005 wt% to about 0.5 wt%, greater than 0.005 wt% to about 0.1 wt%, greater than 0.005 wt% to about 0.09 wt%, or greater than 0.005 wt% to about 0.05 wt%, based on the weight of the ore or mineral to be beneficiated. In other examples, the amount of the collector in the aqueous mixture can be about 0.001 wt% to less than 10 wt%, about 0.005 wt% to less than 5 wt%, about 0.005 wt% to less than 2 wt%, about 0.005 wt% to less than 1 wt%, about 0.005 wt% to less than 0.5 wt%, about 0.005 wt% to less than 0.1 wt%, about 0.005 wt% to less than 0.09 wt%, or about 0.005 wt% to less than 0.05 wt%, based on the weight of the ore or mineral to be beneficiated.

[0073] In some examples, the amount of the oligomeric acid in the aqueous mixture that includes the collector and the ore or mineral to be beneficiated can be about 0.0001 wt%, about 0.0005 wt%, about 0.001 wt%, about 0.005 wt%, about 0.01 wt%, about 0.02 wt%, about 0.03 wt%, about 0.04 wt%, about 0.05 wt%, about 0.06 wt%, about 0.07 wt%, about 0.08 wt%, about 0.09 wt%, about 0.1 wt%, about 0.11 wt%, about 0.12 wt%, about 0.13 wt%, about 0.14 wt%, about 0.15 wt%, about 0.16 wt%, about 0.17 wt%, about 0.18 wt%, about 0.19 wt%, about 0.2 wt%, about 0.25 wt%, about 0.3 wt%, about 0.35 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, about 5 wt%, based on the weight of the ore or mineral to be beneficiated. In some examples, the amount of the oligomeric acid in the aqueous mixture can be about 0.0001 wt% to about 2 wt%, about 0.0005 wt% to about 1 wt%, about 0.001 wt% to about 1 wt%, about 0.005 wt% to about 1 wt%, about 0.005 wt% to about 0.5 wt%, about 0.005 wt% to about 0.1 wt%, about 0.005 wt% to about 0.09 wt%, or about 0.005 wt% to about 0.05 wt%, based on the weight of the ore or mineral to be beneficiated. In other examples, the amount of the oligomeric acid in the aqueous mixture can be greater than 0.0001 wt% to about 2 wt%, greater than 0.0005 wt% to about 1 wt%, greater than 0.001 wt% to about 1 wt%, greater than 0.005 wt% to about 1 wt%, greater than 0.005 wt% to about 0.5 wt%, greater than 0.005 wt% to about 0.1 wt%, greater than 0.005 wt% to about 0.09 wt%, or greater than 0.005 wt% to about 0.05 wt%, based on the weight of the ore or mineral to be beneficiated. In other examples, the amount of the oligomeric acid in the aqueous mixture can be about 0.0001 wt% to less than 2 wt%, about 0.0005 wt% to less than 1 wt%, about 0.001 wt% to less than 1 wt%, about 0.005 wt% to less than 1 wt%, about 0.005 wt% to less than 0.5 wt%, about 0.005 wt% to less than 0.1 wt%, about 0.005 wt% to less than 0.09 wt%, or about 0.005 wt% to less than 0.05 wt%, based on the weight of the ore or mineral to be beneficiated. [0074] In some examples, the amount of the rosin oil in the aqueous mixture that includes the collector and the ore or mineral to be beneficiated can be about 0.0001 wt%, about 0.0005 wt%, about 0.001 wt%, about 0.005 wt%, about 0.01 wt%, about 0.02 wt%, about 0.03 wt%, about 0.04 wt%, about 0.05 wt%, about 0.06 wt%, about 0.07 wt%, about 0.08 wt%, about 0.09 wt%, about 0.1 wt%, about 0.1 1 wt%, about 0.12 wt%, about 0.13 wt%, about 0.14 wt%, about 0.15 wt%, about 0.16 wt%, about 0.17 wt%, about 0.18 wt%, about 0.19 wt%, about 0.2 wt%, about 0.25 wt%, about 0.3 wt%, about 0.35 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, about 5 wt%, based on the weight of the ore or mineral to be beneficiated. In some examples, the amount of the rosin oil in the aqueous mixture can be about 0.0001 wt% to about 2 wt%, about 0.0005 wt% to about 1 wt%, about 0.001 wt% to about 1 wt%, about 0.005 wt% to about 1 wt%, about 0.005 wt% to about 0.5 wt%, about 0.005 wt% to about 0.1 wt%, about 0.005 wt% to about 0.09 wt%, or about 0.005 wt% to about 0.05 wt%, based on the weight of the ore or mineral to be beneficiated. In some examples, the amount of the rosin oil in the aqueous mixture can be greater than 0.0001 wt% to about 2 wt%, greater than 0.0005 wt% to about 1 wt%, greater than 0.001 wt% to about 1 wt%, greater than 0.005 wt% to about 1 wt%, greater than 0.005 wt% to about 0.5 wt%, greater than 0.005 wt% to about 0.1 wt%, greater than 0.005 wt% to about 0.09 wt%, or greater than 0.005 wt% to about 0.05 wt%, based on the weight of the ore or mineral to be beneficiated. In some examples, the amount of the rosin oil in the aqueous mixture can be about 0.0001 wt% to less than 2 wt%, about 0.0005 wt% to less than 1 wt%, about 0.001 wt% to less than 1 wt%, about 0.005 wt% to less than 1 wt%, about 0.005 wt% to less than 0.5 wt%, about 0.005 wt% to less than 0.1 wt%, about 0.005 wt% to less than 0.09 wt%, or about 0.005 wt% to less than 0.05 wt%, based on the weight of the ore or mineral to be beneficiated.

[0075] The aqueous mixture can include water, one or more crude mineral ores (e.g., phosphorous ores containing gangue), one or more oligomeric acids, and one or more rosin oils. The aqueous mixture can be or include aqueous suspensions, dispersions, slurries, solutions, or mixtures and can be conditioned for a given time period during and between steps of combining components. Conditioning the aqueous mixture can facilitate contact between the water, the crude mineral or ore, the oligomeric acids, and the rosin oils. Conditioning can include, but is not limited to, agitating the aqueous mixture for a given time period prior to subjecting the aqueous mixture to separation or collection techniques. For example, the aqueous mixtures can be stirred, blended, mixed, air or gas bubbled, or otherwise agitated for a time of about 30 sec, about 1 min, about 2 min, about 3 min, about 4 min, about 5 min, about 6 min, about 7 min, about 8 min, about 9 min, about 10 min, about 12 min, about 15 min, about 20 min, about 30 min, about 1 hr, or about 24 hr. Conditioning the aqueous mixture can also include heating (or cooling) mixture at a temperature of about 15°C, about 20°C, about 25°C, about 30°C, about 35°C, about 60°C, about 80°C, or about 95°C.

[0076] Conditioning the aqueous mixture can also include adjusting the pH value of the aqueous mixture or any portions thereof. The aqueous mixture containing the crude mineral ores, the oligomeric acid, the rosin oil, and water can be maintained at or adjusted to have a pH value of greater than 7, such as about 7.5, about 8, about 8.5, about 9, about 9.5, about 10, about 10.5, about 1 1, about 1 1.5, about 12, about 12.5, or about 13. In one or more examples, the pH value of the aqueous mixture can be or can be adjusted to about 8.5 to about 10.5, about 9 to about 10, about 9.2 to about 9.8, or about 9.5. In other examples, the pH value of the aqueous mixture can be or can be adjusted to about 8.5 to about 10.5, about 9 to about 10, about 9.2 to about 9.8, or about 9.5. Any one or combination of acid and/or base compounds can be combined with the mixtures to adjust the pH values thereof.

[0077] Illustrative acid compounds that can be used to maintain or adjust the pH value of the aqueous mixture can include, but are not limited to, one or more mineral acids, one or more organic acids, one or more acid salts, or any mixture thereof. Illustrative mineral acids can include, but are not limited to, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, or any mixture thereof. Illustrative organic acids can include, but are not limited to, acetic acid, formic acid, citric acid, oxalic acid, uric acid, lactic acid, or any mixture thereof. Illustrative acid salts can include, but are not limited to, ammonium sulfate, sodium bi sulfate, sodium metabi sulfite, or any mixture thereof.

[0078] Illustrative base compounds that can be used to maintain or adjust the pH value of any of the aqueous mixtures can include, but are not limited to, hydroxides, carbonates, ammonia, amines, or any mixture thereof. Illustrative hydroxides can include, but are not limited to, sodium hydroxide, potassium hydroxide, ammonium hydroxide (e.g., aqueous ammonia), lithium hydroxide, and cesium hydroxide. Illustrative carbonates can include, but are not limited to, sodium carbonate, sodium bicarbonate, potassium carbonate, and ammonium carbonate. Illustrative amines can include, but are not limited to, trimethylamine, triethylamine, triethanolamine, diisopropylethylamine (Hunig's base), pyridine, 4-dimethylaminopyridine ("DMAP"), and l,4-diazabicyclo[2.2.2]octane ("DABCO").

[0079] In some examples, the aqueous mixture or slurry can be aerated in a conventional flotation machine or bank of rougher cells to float the mineral or ore, e.g., phosphates or other phosphorous containing materials. Any conventional flotation unit can be employed. The collector can be used to separate a wide variety of contaminants from the mineral or ore. For example, the collector can be used to separate siliceous contaminants such as sand, clay, and/or ash from aqueous liquid suspensions or slurries containing one or more of these siliceous contaminants.

[0080] An effective amount of the collector can be added to the aqueous mixture to interact with the mineral or ore. An effective amount can be determined depending, at least in part, on a number of variables (e.g., the type and concentration of contaminant). In other examples, the treatment can involve contacting the aqueous mixture or slurry continuously with a fixed bed of the collector, in solid form. Separation of the mineral or ore can be effected by flotation (with or without the use of rising air bubbles, such as in froth flotation. Filtration or straining can also be an effective means for removing the agglomerated floes of solid particulates on the surface of the aqueous mixture or slurry.

[0081] As used herein, the term "purifying" refers to any process for beneficiation, upgrading, and/or recovering, a mineral or an ore discussed and described herein, such as phosphates or other phosphorous or mineral containing materials. In some examples, the aqueous mixture or slurry can include the clay-containing aqueous suspensions or brines, which accompany ore refinement processes. The production of purified phosphate from mined calcium phosphate rock, for example, generally relies on one or more separations of solid particulates from aqueous media, whereby such separations can be improved using the collector. In the overall process, calcium phosphate can be mined from deposits and the phosphate rock can be initially recovered in a matrix containing sand and clay impurities. The matrix can be mixed with water to form a slurry, which after mechanical agitation, can be screened to retain phosphate pebbles and to allow fine clay particles to pass through as a clay slurry effluent with large amounts of water. [0082] In addition to the phosphate pebbles that can be retained by screening and the clay slurry effluent described above, a mixture of sand and finer particles of phosphate can also obtained in the initial processing of mined phosphate matrix. The sand and phosphate in this stream can be separated by froth flotation which, as described above, can be improved using the collector as a depressant for the sand.

[0083] In some examples, the mineral or ore, e.g., phosphate, which can be collected, recovered or otherwise purified from the aqueous mixture due to the collector can be compared to the initial or total amount of the phosphate material contained in the phosphorous ore. For example, the collected or recovered phosphate material can be about 90 wt%, about 91 wt%, about 92 wt%, about 93 wt%, about 94 wt%, about 95 wt%, about 96 wt%, about 97 wt%, about 97.1 wt%, about 97.2 wt%, about 97.3 wt%, about 97.4 wt%, about 97.5 wt%, about 97.6 wt%, about 97.7 wt%, about 97.8 wt%, or about 97.9 wt%, about 98 wt%, about 98.1 wt%, about 98.2 wt%, about 98.3 wt%, about 98.4 wt%, about 98.5 wt%, about 98.6 wt%, about 98.7 wt%, about 98.8 wt%, about 98.9 wt%, about 99 wt%, about 99.1 wt%, about 99.2 wt%, about 99.3 wt%, about 99.4 wt%, about 99.5 wt%, about 99.6 wt%, about 99.7 wt%, about 99.8 wt%, or about 99.9 wt% of the total phosphate material contained in the phosphorous ore. In other examples, the collected or recovered phosphate material can be about 90 wt% to about 99.9 wt%, about 91 wt% to about 99.9 wt%, about 92 wt% to about 99.9 wt%, about 93 wt% to about 99.9 wt%, about 94 wt% to about 99.9 wt%, about 95 wt% to about 99.9 wt%, about 96 wt% to about 99.9 wt%, about 97 wt% to about 99.9 wt%, about 98 wt% to about 99.9 wt%, about 99 wt% to about 99.9 wt%, about 99.1 wt% to about 99.9 wt%, about 99.2 wt% to about 99.9 wt%, about 99.3 wt% to about 99.9 wt%, about 99.4 wt% to about 99.9 wt%, about 99.5 wt% to about 99.9 wt%, about 99.6 wt% to about 99.9 wt%, about 99.7 wt% to about 99.9 wt%, about 95 wt% to about 99.7 wt%, about 96 wt% to about 99.7 wt%, about 97 wt% to about 99.7 wt%, about 98 wt% to about 99.7 wt%, about 99 wt% to about 99.7 wt%, about 95 wt% to about 99.5 wt%, about 96 wt% to about 99.5 wt%, about 97 wt% to about 99.5 wt%, about 98 wt% to about 99.5 wt%, or about 99 wt% to about 99.5 wt% of the total phosphate material contained in the phosphorous ore. In one specific example, the collected phosphate material can be about 98 wt% to about 99.9 wt% of the total phosphate material contained in the phosphorous ore.

[0084] In other examples, the mineral or ore, e.g., phosphate, which can be collected, recovered or otherwise purified from the aqueous mixture due, at least in part, to the collector can include some acid insoluble materials, gangue, and/or other impurities contained in the crude mineral or ore. The collectors having one or more oligomeric acids and one or more rosin oils can provide a relatively high degree of selectivity for phosphate over such impurities within the aqueous mixture or slurry. The collected or recovered phosphate material can have an amount of acid insoluble material (also known as acid insoluble recovery) of less than 20 wt%, less than 15 wt%, less than 10 wt%, less than 9 wt%, less than 8 wt%, less than 7 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.9 wt%, less than 0.8 wt%, less than 0.7 wt%, less than 0.6 wt%, less than 0.5 wt%, less than 0.4 wt%, less than 0.3 wt%, less than 0.2 wt%, or less than 0.1 wt%, based on the total or combined weight of the recovered phosphate material and the acid insoluble material. In other examples, the collected or recovered phosphate material can have an amount of acid insoluble material of about 0.05 wt%, about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, or about 0.5 wt% to about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 12 wt%, about 15 wt%, or about 20 wt%, based on the combined weight of the recovered phosphate material and the acid insoluble material. For example, the collected or recovered phosphate material can have an amount of acid insoluble material of about 0.05 wt% to about 20 wt%, about 0.1 wt% to about 15 wt%, about 0.1 wt% to about 12 wt%, about 0.1 wt% to about 10 wt%, about 0.1 wt% to about 5 wt%, about 0.1 wt% to about 4 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 2 wt%, about 0.1 wt% to about 1 wt%, about 0.5 wt% to about 15 wt%, about 0.5 wt% to about 12 wt%, about 0.5 wt% to about 10 wt%, about 0.5 wt% to about 5 wt%, about 0.5 wt% to about 4 wt%, about 0.5 wt% to about 3 wt%, about 0.5 wt% to about 2 wt%, about 0.5 wt% to about 1 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 12 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 4 wt%, about 1 wt% to about 3 wt%, or about 1 wt% to about 2 wt%, based on the combined weight of the recovered phosphate material and the acid insoluble material.

[0085] In another example, the collectors having one or more oligomeric acids and one or more rosin oils can provide a greater mineral or ore grade, e.g., phosphate grade, over traditional collectors. The grade of phosphate rock is expressed as its percentage of phosphorous pentoxide (P₂O5) content. As such, a purified phosphate product that has a grade of 28%, for example, means the purified phosphate produce includes 28% of phosphorous pentoxide. The collected or recovered phosphate material can have a phosphate grade of about 20 wt%, about 22 wt%, about 24 wt%, or about 25 wt% to about 25.5 wt%, about 26 wt%, about 26.5 wt%, about 27 wt%, about 27.5 wt%, about 28 wt%, about 28.5 wt%, about 29 wt%, about 29.5 wt%, or about 30 wt%, based on the weight of the recovered phosphate material. In some examples, the collected or recovered mineral or ore can have a grade of greater than 20 wt%, greater than 21 wt%, greater than 22 wt%, greater than 23 wt%, greater than 24 wt%, greater than 25 wt%, greater than 25.5 wt%, greater than 26 wt%, greater than 26.5 wt%, greater than 27 wt%, greater than 27.5 wt%, greater than 28 wt%, greater than 28.5 wt%, greater than 29 wt%, greater than 29.5 wt%, or greater than 30 wt%, based on the weight of the recovered mineral or ore, e.g., phosphate material. For example, the collected or recovered mineral or ore can have a phosphate grade of about 20 wt% to about 30 wt%, about 24 wt% to about 30 wt%, about 25 wt% to about 30 wt%, about 26 wt% to about 30 wt%, about 27 wt% to about 30 wt%, about 28 wt% to about 30 wt%, or about 29 wt% to about 30 wt%, based on the weight of the recovered mineral or ore, e.g., phosphate material.

[0086] In some examples, a tail material can be submerged, flocculated, sunk, suspended, or otherwise rejected or not floated at or toward the surface or top of the aqueous mixture or slurry. The tail material can be or include acid insoluble materials, gangue, and/or other impurities formerly contained in the mineral or ore, e.g., phosphorous or phosphate containing ores, rocks, minerals, or other materials. The tail material can be or include, but not limited to, silicates, silica, sand, quartz, and other silicon oxide materials. The tail material flocculated in the aqueous mixture can be collected or otherwise recovered, separately from the recovered phosphate material. The tail material can generally be less than 99 wt% of the total acid insolubles (AI) contained in the phosphorous ore. For example, the tail material can be less than 97 wt%, less than 95 wt%, less than 90 wt%, less than 85 wt%, less than 80 wt%, less than 75 wt%, less than 70 wt%, less than 65 wt%, less than 60 wt%, less than 65 wt%, less than 50 wt% to about 40 wt%, about 30 wt%, about 20 wt%, about 10 wt%, about 5 wt%, or less, based on the total acid insolubles contained in the phosphorous ore. In some examples, the acid insolubles can be about 10 wt% to less than 97 wt%, about 25 wt% to less than 95 wt%, about 40 wt% to less than 95 wt%, about 50 wt% to less than 95 wt%, about 60 wt% to less than 95 wt%, about 70 wt% to less than 95 wt%, about 80 wt% to less than 95 wt%, about 90 wt% to less than 95 wt%, about 50 wt% to about 90 wt%, about 60 wt% to about 90 wt%, about 70 wt% to about 90 wt%, or about 80 wt% to about 90 wt%, based on the total acid insolubles contained in the phosphorous ore. In one specific example, a tail material can be collected or recovered that can be flocculated on the bottom of the aqueous mixture, where the tail material can include acid insolubles, and the acid insolubles can be about 70 wt% to about 90 wt% of the total acid insolubles contained in the phosphorous ore.

[0087] The separation efficiency is defined as E_s = R_Po - RA_I, where Rpo is the ratio of the weight of the recovered phosphate material over the weight of the phosphate material contained in the phosphorous ore and RA_I is the ratio of the weight of the recovered acid insolubles over the weight of the phosphorous ore. The collector can provide a separation efficiency for purified minerals or ores, e.g., phosphate, of about 50 wt% of greater, such as about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 81 wt%, about 82 wt%, about 83 wt%, about 84 wt%, about 85 wt%, about 86 wt%, about 87 wt%, about 88 wt%, about 89 wt%, about 90 wt%, about 91 wt%, about 92 wt%, about 93 wt%, about 94 wt%, about 95 wt%, about 96 wt%, about 97 wt%, about 98 wt%, or about 99 wt%.

Examples

[0088] In order to provide a better understanding of the foregoing discussion, the following non- limiting examples are offered. Although the examples can be directed to specific embodiments, they are not to be viewed as limiting the invention in any specific respect.

[0089] Selective phosphate flotations were conducted with a CTO-diesel fuel oil collector (Comparative Examples 1A-1K) and with collectors containing oligomeric acids and rosin oils (Examples 2A-2G, 3A-3G, 4A-4C, and 5A-5G).

Preparation of Collectors:

[0090] Examples 1A-1K: CTO (about 66.6 g) and diesel fuel oil (about 33.3 g) were blended at room temperature (e.g., about 25°C) to produce the CTO-diesel fuel oil collector used in Examples 4A-4K.

[0091] Examples 2A-2G: A rosin acid (about 500 g), commercially available as LYTOR^®100 tall oil rosin acid from Georgia-Pacific Chemicals LLC, was stirred in a flask and heated at a temperature of about 320°C for about 24 hr under a nitrogen atmosphere to produce a rosin oil that had an acid value of about 6.6 mg KOH/g. About 33.3 g of this rosin oil was mechanically stirred with about 66.6 g of a dimer-trimer mixture for about 0.5 hr to produce the oligomeric acid that included and rosin oil collector used in Examples 2A-2G. The dimer-trimer mixture was UNIDYME^® 35 dimer acid, acquired from Arizona Chemical Company, which included up to 4 wt% monomer acids, about 71 wt% to about 85 wt% dimer acids, and about 15 wt% to about 25 wt% trimer and higher acids.

[0092] Examples 3A-3G: A rosin acid (about 500 g), commercially available as LYTOR^®100 tall oil rosin acid from Georgia-Pacific Chemicals LLC, was stirred in a flask and heated at a temperature of about 320°C for about 24 hr under a nitrogen atmosphere to produce a rosin oil that had an acid value of about 6.6 mg KOH/g. About 500 g of a TOFA, commercially available as XTOL^® 100 from Georgia-Pacific Chemicals LLC, was stirred in a flask and heated at a temperature of about 300°C for about 2.5 hr under a nitrogen atmosphere to produce an oligomeric acid mixture that contained monomer, dimer, and trimer acids. About 33.3 g of the rosin oil was mechanically stirred with about 66.6 g of the oligomeric acid mixture for about 0.5 hr to produce the oligomeric acid and rosin oil collector used in Examples 3 A-3G.

[0093] Examples 4A-4C: A fatty acids mixture (about 20g), commercially available as XTOL®100 tall oil fatty acids from Georgia-Pacific Chemicals LLC, and a rosin acids mixture (about 10 g), commercially available as LYTOR®100 tall oil rosin acid from Georgia-Pacific Chemicals LLC, were added to a 50 mL 3-neck round-bottom flask equipped with a thermocouple, condenser, nitrogen gas-inlet, and magnetic stir bar. The combined mixture of the fatty acids mixture and the rosin acids mixture added to the flask contained about 33.8 wt% oleic acid, about 25.0 wt% linoleic acid, about 0.2 wt% linolenic acid, about 0.8 wt% eicosatrienoic acid, about 0.4 wt% palmitic acid, about 13.3 wt% abietic acid, about 7.8 wt% dehydroabietic acid, about 3.4 wt% palustric acid, and about 1.3 wt% pimaric acid. The reactor was purged for about 10 min with nitrogen. The mixture of fatty acids and rosin acids was heated to a temperature of about 200°C. Iron(III) chloride (FeCl₃) (about 10 mg), ammonium carbonate (( H4)₂C0₃) (about 36 mg), and iodine (I₂) (about 90 mg) were added to the flask in succession while the flask was maintained under positive nitrogen pressure. The mixture was heated to a temperature of about 230°C and held for about 15 min. Ethylenediamine (about 30 mg) and methanesulfonic acid (70 wt%, about 0.214 g) were added to the flask and the reaction mixture was rapidly cooled to a temperature of about 23 °C with an external ice-bath under nitrogen. The temperature of the mixture was increased to about 300°C. Heating continued for about 4 hr at which point a reaction product was cooled to a temperature of about 23 °C under nitrogen to produce a collector that included oligomeric acid and rosin oil that was used in Examples 4A-4C. The collector included about 15.6 wt% oleic acid, about 0.2 wt% linoleic acid, about 0.1 wt% linolenic acid, about 0.2 wt% palmitic acid, and about 1 wt% dehydroabietic acid. The collector included about 13.9 wt% rosin oils.

[0094] Examples 5-5G: CTO (about 30 g) was added to a 50 mL 3-neck round-bottom flask equipped with a thermocouple, condenser, nitrogen gas-inlet, and magnetic stir bar. The CTO included about 19.3 wt% oleic acid, about 21.8 wt% linoleic acid, about 0.2 wt% linolenic acid, about 1.7 wt% eicosatrienoic acid, about 3.5 wt% palmitic acid, about 11.5 wt% abietic acid, about 3.6 wt% dehydroabietic acid, about 5.8 wt% palustric acid, and about 3.2 wt% pimaric acid. The reactor was purged for about 10 min with nitrogen, and the reactor was heated to a temperature of about 200°C. Iron(III) chloride (FeCl₃) ( about 12 mg), ammonium carbonate (( H4)₂C0₃)) (about 36 mg), and iodine (I₂) (about 90 mg) were added in succession to the flask while the flask was maintained under positive nitrogen pressure. The temperature was increased to about 230°C and held for about 15 min. Ethylenediamine (about 30 mg) and methanesulfonic acid (about 0.214 g, 70 wt%) were added and the reaction mixture was rapidly cooled to a temperature of about 23°C with an external ice-bath under nitrogen. The temp was increased to about 300°C. Heating continued for about 4 hr at which point the reaction mixture was cooled to about 23 °C under nitrogen to produce the collector that included oligomeric acid and rosin oil collector used in Examples 5A-5G. The collector included about 18.5 wt% oleic acid, about 0.2 wt% linoleic acid, about 3.1 wt% of palmitic acid, and about 3 wt% or dehydroabietic acid, and about 14 wt% rosin oils.

Beneficiation Procedures and Results:

[0095] The following phosphate beneficiation procedure was used for the collectors produced in Examples 1A-1D, 2A-2C, and 3A-3C. About 500 g of first Florida phosphate feed and about 214 g of water were added to a 2 L capacity stainless steel beaker equipped with a cruciform impeller. The mixture was stirred for about 0.5 min and maintained at a pH value of about 7 (if needed, 1 N NaOH solution was added to adjust the pH value) to produce a mixture of about 70 wt% solids. In each Example, the listed collector at the respective dosage was added to the mixture and stirred at about 400 rpm for about 5 min. The mixture was transferred to in a stainless steel flotation cell. About 1,300 g of water was added to the mixture that was stirred for about 0.5 min to produce a mixture of about 25 wt% solids. An air injection valve on the flotation cell was opened and frothing was ensued as air was introduced into the mixture. After about 2 min, the froth was collected from the flotation cell. The froth concentrate and the tailings remaining in the flotation cell were separately filtered, dewatered, and weighed. The dried froth concentrate and the tailings were separately analyzed for phosphate (Bone Phosphate of Lime, BPL) content using inductively coupled plasma (ICP) and for acid insoluble content using an acid digestion. The results of the beneficiation of the first Florida phosphate feed are shown in Table 1.

[0096] Surprisingly and unexpectedly, as demonstrated by Examples 2A-2C, a rosin acid can be converted to a rosin oil and blended with a dimer-trimer mixture in a simple and economical process to give a collector that produces a significantly greater P₂0₅ grade, as compared to the grade obtained with the CTO-diesel mixture. Also surprisingly and unexpectedly, as demonstrated by Examples 3A-3C, a rosin acid and a TOFA can be converted to a rosin oil and an oligomeric acid, respectively, which can be blended with one another in a simple and economical process to give a collector that produces a significantly greater P₂0₅ grade, as compared to the grade obtained with the CTO-diesel mixture. Additionally, there was no need for petroleum based co-reagents. [0097] The following phosphate beneficiation procedure was used for the collectors produced in Examples 1E-1H, 2D-2G, 3D-3G, and 5A-5D. About 500 g of second Florida phosphate feed and about 214 g of water were added to a 2 L capacity stainless steel beaker equipped with a cruciform impeller. The mixture was stirred for about 0.5 min and maintained at a pH value of about 7 (if needed, 1 N NaOH solution was added to adjust the pH value) to produce a mixture of about 70 wt% solids. In each Example, the listed collector at the respective dosage was added to the mixture and stirred at about 400 rpm for about 5 min. The mixture was transferred to in a stainless steel flotation cell. About 1,300 g of water was added to the mixture that was stirred for about 0.5 min to produce a mixture of about 25 wt% solids. An air injection valve on the flotation cell was opened and frothing was ensued as air was introduced into the mixture. After about 2 min, the froth was collected from the flotation cell. The froth concentrate and the tailings remaining in the flotation cell were separately filtered, dewatered, and weighed. The dried froth concentrate and the tailings were separately analyzed for phosphate (Bone Phosphate of Lime, BPL) content using inductively coupled plasma (ICP) and for acid insoluble content using an acid digestion. The results of the beneficiation of the second Florida phosphate feed are shown in Table 2.

and rosin oil

oligomeric acid

5B and rosin oil 1 79.68 28.8 1.61 11.88 oligomeric acid

5C and rosin oil 2 93.78 25.36 3.89 21.61 oligomeric acid

5D and rosin oil 3 93.21 23.75 5.11 26.19

[0098] Surprisingly and unexpectedly, as demonstrated by experiments 2D-2G a rosin acid can be converted to a rosin oil and blended with a dimer-trimer mixture in a simple and economical to give a collector that produces a significantly greater P₂0₅ grade, as compared to the grade obtained with the CTO-diesel mixture. Also, surprisingly and unexpectedly, as demonstrated by Examples 3D-3G, a rosin acid and a TOFA can be converted to a rosin oil and an oligomeric acid, respectively, which can be blended with one another in a simple and economical process to give a collector that produces a significantly greater P₂0₅ grade, as compared to the grade obtained with the CTO-diesel mixture. Also, surprisingly and unexpectedly, as demonstrated by experiments 5A-5D, CTO can be upgraded in a simple and economical reaction procedure to give a collector offering higher P₂0₅ grade at comparable recovery, as compared to the grade and recovery obtained in use of CTO itself. Additionally, there is no need for petroleum based co- reagents.

[0099] The following phosphate beneficiation procedure was used for the collectors produced in Examples 1I-1K, 4A-4C, and 5E-5G. About 500 g of third Florida phosphate feed and about 214 g of water were added to a 2 L capacity stainless steel beaker equipped with a cruciform impeller. The mixture was stirred for about 0.5 min and maintained at a pH value of about 7 (if needed, 1 N NaOH solution was added to adjust the pH value) to produce a mixture of about 70 wt% solids. In each Example, the listed collector at the respective dosages were added to the mixture and stirred at about 400 rpm for about 5 min. The mixture was transferred to in a stainless steel flotation cell. About 1,300 g of water was added to the mixture that was stirred for about 0.5 min to produce a mixture of about 25 wt% solids. An air injection valve on the flotation cell was opened and frothing was ensued as air was introduced into the mixture. After about 2 min, the froth was collected from the flotation cell. The froth concentrate and the tailings remaining in the flotation cell were separately filtered, dewatered, and weighed. The dried froth concentrate and the tailings were separately analyzed for phosphate (Bone Phosphate of Lime, BPL) content using inductively coupled plasma (ICP) and for acid insoluble content using an acid digestion. The results of the beneficiation of the third Florida phosphate feed are shown in Table 3.

[00100] Surprisingly and unexpectedly, as demonstrated by Examples 4A-4C, a rosin acid and a TOFA can be converted to a rosin oil and an oligomeric acid, respectively, which can be blended with one another in a simple and economical process to give a collector that produces a significantly greater P₂0₅ grade, as compared to the grade obtained with the CTO-diesel mixture. Also, surprisingly and unexpectedly, as demonstrated by Examples 5E-5G, CTO can be upgraded in a simple and economical reaction procedure to give a collector offering higher P₂0₅ grade at comparable recovery, as compared to the grade and recovery obtained in use of CTO itself. Additionally, there is no need for petroleum based co-reagents.

[00101] Embodiments of the present disclosure further relate to any one or more of the following paragraphs:

[00102] 1. A collector, comprising: an oligomeric acid comprising a dimer acid, a trimer acid, or a mixture thereof; and a rosin oil having an acid value of less than 150 mg KOH/g; wherein the collector has an oligomeric acid to rosin oil weight ratio of about 0.5: 1 to about 5: 1.

[00103] 2. A method for purifying a mineral, comprising: combining crude mineral ore, water, and a collector to produce an aqueous mixture, wherein the crude mineral ore comprises a silicate material, and wherein the collector comprises: an oligomeric acid comprising a dimer acid, a trimer acid, or a mixture thereof, and a rosin oil comprising less than 25 wt% of rosin acids, wherein the collector has an oligomeric acid to rosin oil weight ratio of about 0.5: 1 to about 5: 1; collecting a purified mineral ore from the aqueous mixture having a reduced weight concentration of the silicate relative to the crude mineral ore; and collecting a flocculated material comprising the silicate material from the aqueous mixture.

[00104] 3. The method of paragraph 2, wherein the purified mineral ore comprises a phosphorous ore, an iron ore, an aluminum ore, a potassium ore, a sodium ore, a calcium ore, a magnesium ore, potash, feldspar, bauxite, kaolin, coal, or any mixture thereof.

[00105] 4. The method of paragraph 2, wherein the oligomeric acid to rosin oil weight ratio is about 1.2: 1 to about 3 : 1.

[00106] 5. The method of paragraph 2, wherein the oligomeric acid comprises about 50 wt% to about 100 wt% of the dimer acid, based on the total weight of the dimer acid and the trimer acid, and wherein the rosin oil has an acid value of about 1 mg KOH/g to about 130 mg KOH/g.

[00107] 6. The method of paragraph 2, wherein the oligomeric acid comprises about 60 wt% to about 95 wt% of the dimer acid and about 5 wt% to about 30 wt% of the trimer acid, based on the total weight of the dimer acid and the trimer acid.

[00108] 7. A method for making a collector, comprising: heating a mixture comprising a monomer fatty acid and a rosin acid at a temperature of about 250°C to about 400°C for at least 2 hours to produce a collector, wherein the collector comprises: an oligomeric acid derived from the monomer fatty acid, the rosin acid, or the monomer fatty acid and the rosin acid, wherein the oligomeric acid comprises a dimer acid, a trimer acid, or a mixture thereof; and wherein the rosin oil has an acid value of less than 150 mg KOH/g and comprises less than 25 wt% of rosin acids; wherein the collector has an oligomeric acid to rosin oil weight ratio of about 0.5 : 1 to about 5: 1.

[00109] 8. The method of paragraph 7, wherein the mixture is heated at a temperature of about 275°C to about 380°C for about 3 hours to about 24 hours to produce the collector, wherein the monomer fatty acid comprises tall oil fatty acids, and wherein the rosin acid comprises tall oil rosin acids.

[00110] 9. The method of paragraph 7, wherein the monomer fatty acid comprises oleic acid, palmitic acid, linoleic acid, linolenic acid, eicosatrienoic acid, stearic acid, arachidic acid, behenic acid, isomers thereof, or any mixture thereof, and wherein the rosin acid comprises abietic acid, pimaric acid, dehydroabietic acid, palustric acid, isopimaric acid, neoabietic acid, sandaroco-pimaric acid, levopimaric acid, isomers thereof, or any mixture thereof.

[00111] 10. A method for making a collector, comprising: combining a first catalyst and a mixture comprising fatty acids and rosin acids to produce a first mixture, wherein the mixture comprising fatty acids and rosin acids has a first dehydroabietic acid concentration; heating the first mixture at a first temperature to produce a first reaction mixture, wherein the first reaction mixture has a second dehydroabietic acid concentration greater than the first dehydroabietic acid concentration; and heating the first reaction mixture at a second temperature to produce a second reaction mixture, wherein: the second temperature is greater than the first temperature, the second temperature is greater than 250°C, the second reaction mixture comprises oligomeric acids and rosin oils, the rosin oils are produced from the rosin acids, and the second reaction mixture has a rosin oil yield of greater than 25%.

[00112] 11. A method for making a collector, comprising: combining a first catalyst and a mixture comprising fatty acids and rosin acids to produce a first mixture; heating the first mixture at a first temperature to produce a first reaction mixture; combining a second catalyst and the first reaction mixture to produce a second mixture; and heating the second mixture at a second temperature to produce a second reaction mixture, wherein: the second temperature is greater than the first temperature, the second temperature is greater than 250°C, the second reaction mixture comprises oligomeric acids and rosin oils, the rosin oils are produced from the rosin acids, and the second reaction mixture has a rosin oil yield of greater than 25%.

[00113] 12. The method of paragraph 10 or 11, wherein the second reaction mixture has a rosin oil yield of about 30% to about 95%.

[00114] 13. The method of paragraph 10 or 11, wherein the first catalyst comprises an iron source and an iodine source, or a mixture thereof.

[00115] 14. The method of paragraph 10 or 11, wherein the fatty acids and the rosin acids are mixed with one another prior to mixing the first catalyst therewith, wherein an iron source and an iodine source are added in succession to the mixture comprising fatty acids and rosin acids. [00116] 15. The method of paragraph 14, wherein the iron source comprises an iron halide and the iodine source comprises elemental iodine (I₂).

[00117] 16. The method of paragraph 10, wherein the first catalyst comprises an iron source, a nitrogen source, an iodine source, or any mixture thereof.

[00118] 17. The method of paragraph 10 or 11, wherein the fatty acids and the rosin acids are mixed with one another prior to mixing the first catalyst therewith, wherein an iron source, a nitrogen source, and an iodine source are added in succession to the mixture comprising fatty acids and rosin acids.

[00119] 18. The method of paragraph 17, wherein the iron source comprises an iron halide, the nitrogen source comprises an ammonium compound, an amine compound, an urea compound, or any mixture thereof, and the iodine source comprises elemental iodine (I₂).

[00120] 19. The method of paragraph 10 or 11, wherein the first catalyst is combined with the mixture comprising fatty acids and rosin acids in an amount of about 0.01 wt% to about 2 wt%, based on the total weight of the fatty acids and the rosin acids.

[00121] 20. The method of paragraph 10 or 11, wherein the mixture comprising the first catalyst, the fatty acids, and the rosin acids is heated to about 180°C to 250°C for about 1 min to about 30 min to produce the first reaction mixture.

[00122] 21. The method of paragraph 20, wherein a second catalyst is combined with the first reaction mixture, and wherein the first reaction mixture comprising the second catalyst is heated to the second temperature to produce the second reaction mixture.

[00123] 22. The method of paragraph 11 or 21, wherein the second catalyst comprises a Bransted acid or a Lewis acid, and wherein the second catalyst is added to the first reaction mixture.

[00124] 23. The method of paragraph 11 or 21, wherein the second catalyst comprises methanesulfonic acid, p-toluenesulfonic acid, phosphoric acids, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, sulfuric acid, isomers thereof, salts thereof, esters thereof, or any mixture thereof.

[00125] 24. The method of paragraph 11 or 21, wherein the second catalyst is combined with the first reaction mixture in an amount of about 0.05 wt% to about 3 wt%, based on the total weight of the fatty acids and the rosin acids. [00126] 25. The method of paragraph 11 or 21, wherein the mixture comprising the second catalyst and the first reaction mixture is heated to about 280°C to about 320°C for about 2 hr to about 12 hr to produce the second reaction mixture.

[00127] 26. The method of paragraph 11, wherein the mixture comprising fatty acids and rosin acids has a first dehydroabietic acid concentration, wherein the first reaction mixture has a second dehydroabietic acid concentration, and wherein the second dehydroabietic acid concentration is greater than the first dehydroabietic acid concentration.

[00128] 27. A method for making a collector, comprising: combining a first catalyst and a mixture comprising fatty acids and rosin acids to produce a first mixture, wherein the mixture comprising fatty acids and rosin acids has a first dehydroabietic acid concentration; heating the first mixture at a first temperature to produce a first reaction mixture, wherein the first reaction mixture has a second dehydroabietic acid concentration greater than the first dehydroabietic acid concentration; and heating the first reaction mixture at a second temperature to produce a collector, wherein: the second temperature is greater than the first temperature, the second temperature is greater than 250°C, the collector comprises oligomeric acids and rosin oils, the rosin oils are produced from the rosin acids, the collector has a rosin oil yield of greater than 25%, and the collector has an oligomeric acid to rosin oil weight ratio of about 0.5: 1 to about 5: 1.

[00129] 28. The collector or method according to any one of the paragraphs 1-27, wherein the oligomeric acid to rosin oil weight ratio is about 1.2: 1 to about 3 : 1.

[00130] 29. The collector or method according to any one of the paragraphs 1-28, wherein the oligomeric acid comprises about 50 wt% to about 100 wt% of the dimer acid, based on the total weight of the dimer acid and the trimer acid.

[00131] 30. The collector or method according to any one of the paragraphs 1-29, wherein the oligomeric acid comprises about 60 wt% to about 95 wt% of the dimer acid and about 5 wt% to about 30 wt% of the trimer acid, based on the total weight of the dimer acid and the trimer acid.

[00132] 31. The collector or method according to any one of the paragraphs 1-30, wherein the dimer acid comprises one or more C₃₂-dimer acids, one or more C₃₄-dimer acids, one or more C36-dimer acids, one or more C₃₈-dimer acids, one or more C4o-dimer acids, or any mixture thereof.

[00133] 32. The collector or method according to any one of the paragraphs 1-31, wherein the dimer acid comprises one or more compounds having the molecular formulas of C₃₆H₆₂0₄, C₃₆H₆₄0₄, C₃₆H₆60₄, C₃₆H₆80₄, C₃₆H7o0₄, C₃₈H₆₂0₄, C₃₈H₆₄0₄, C₃₈H₆₆0₄, or C₃₈H₆₈0₄.

[00134] 33. The collector or method according to any one of the paragraphs 1-32, wherein the oligomeric acid is derived from monomer tall oil fatty acids, monomer tall oil rosin acids, or a mixture thereof, and wherein the rosin oil is derived from monomer tall oil rosin acids.

[00135] 34. The collector or method of paragraph 33, wherein the monomer tall oil fatty acids comprise oleic acid, palmitic acid, linoleic acid, linolenic acid, eicosatrienoic acid, stearic acid, arachidic acid, behenic acid, isomers thereof, or any mixture thereof, and wherein the monomer tall oil rosin acids comprise abietic acid, pimaric acid, dehydroabietic acid, palustric acid, isopimaric acid, neoabietic acid, sandaroco-pimaric acid, levopimaric acid, isomers thereof, or any mixture thereof.

[00136] 35. The collector or method according to any one of the paragraphs 1-34, wherein the oligomeric acid comprises about 0.01 wt% to less than 5 wt% of a monomer acid.

[00137] 36. The collector or method according to any one of the paragraphs 1-35, wherein the oligomeric acid has an acid value of about 160 mg KOH/g to about 230 mg KOH/g, and wherein the rosin oil comprises less than 25 wt% of rosin acids and has an acid value of about 1 mg KOH/g to about 130 mg KOH/g.

[00138] 37. The collector or method according to any one of the paragraphs 1-36, wherein the rosin oil comprises about 0.01 wt% to less than 5 wt% of a monomer acid.

[00139] 38. A collector for the beneficiation of a crude mineral ore, comprising: a mixture of an oligomeric acid and a rosin oil, wherein: the oligomeric acid comprises a dimer acid, a trimer acid, or a mixture thereof, the rosin oil comprises a decarboxylated rosin acid, and the mixture has an oligomeric acid to rosin oil weight ratio of about 0.5: 1 to about 5: 1.

[00140] 39. A collector for the beneficiation of a crude mineral ore, comprising: a mixture of an oligomeric acid and a rosin oil, wherein: the oligomeric acid comprises a dimer acid, a trimer acid, or a mixture thereof, the rosin oil comprises a decarboxylated rosin acid and less than 25 wt% of rosin acids, and the mixture has an oligomeric acid to rosin oil weight ratio of about 0.5: 1 to about 5: 1.

[00141] 40. A method for making a collector for use in the beneficiation of a crude mineral ore, comprising: mixing an oligomeric acid and a rosin oil to produce a mixture, wherein: the oligomeric acid comprises a dimer acid, a trimer acid, or a mixture thereof, the rosin oil comprises a decarboxylated rosin acid, and the mixture has an oligomeric acid to rosin oil weight ratio of about 0.5: 1 to about 5: 1.

[00142] 41. A method for purifying a crude mineral ore, comprising: combining a crude mineral ore, water, and a collector to produce an aqueous mixture, wherein the crude mineral ore comprises a mineral and a gangue material, and wherein the collector comprises: a mixture of an oligomeric acid and a rosin oil, wherein: the oligomeric acid comprises a dimer acid, a trimer acid, or a mixture thereof, the rosin oil comprises a decarboxylated rosin acid, and the mixture has an oligomeric acid to rosin oil weight ratio of about 0.5: 1 to about 5: 1 ; collecting a purified mineral from the aqueous mixture, wherein the purified mineral has a reduced concentration of the gangue material relative to the crude mineral ore.

[00143] 42. An aqueous slurry composition comprising: water, a crude mineral ore, and a collector, wherein the crude mineral ore comprises a mineral and a gangue material, and wherein the collector comprises a mixture of an oligomeric acid and a rosin oil, wherein: the oligomeric acid comprises a dimer acid, a trimer acid, or a mixture thereof, the rosin oil comprises a decarboxylated rosin acid, and the mixture has an oligomeric acid to rosin oil weight ratio of about 0.5: 1 to about 5: 1.

[00144] 43. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 or 40 to 42, wherein the rosin oil comprises less than 25 wt% of rosin acids.

[00145] 44. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 or 40 to 43, wherein the rosin oil comprises less than 23 wt% of rosin acids.

[00146] 45. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 44, wherein the rosin oil comprises less than 20 wt% of rosin acids.

[00147] 46. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 45, wherein the rosin oil comprises less than 15 wt% of rosin acids. [00148] 47. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 46, wherein the rosin oil comprises less than 10 wt% of rosin acids.

[00149] 48. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 47, wherein the rosin oil comprises less than 5 wt% of rosin acids.

[00150] 49. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 48, wherein the rosin oil comprises less than 3 wt% of rosin acids.

[00151] 50. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 49, wherein the rosin oil comprises less than 1 wt% of rosin acids.

[00152] 51. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 50, wherein the mixture has an oligomeric acid to rosin oil weight ratio of about 0.7: 1 to about 4.6: 1.

[00153] 52. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 51, wherein the mixture has an oligomeric acid to rosin oil weight ratio of about 1 : 1 to about 3.5: 1.

[00154] 53. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 52, wherein the mixture has an oligomeric acid to rosin oil weight ratio of about 1.2: 1 to about 3 : 1.

[00155] 54. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 53, wherein the mixture has an oligomeric acid to rosin oil weight ratio of about 1.3 to about 2.8.

[00156] 55. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 54, wherein the mixture has an oligomeric acid to rosin oil weight ratio of about 1.5 to about 3 : 1.

[00157] 56. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 55, wherein the oligomeric acid comprises about 50 wt% to about 100 wt% of the dimer acid, based on a combined weight of the dimer acid and any trimer acid. [00158] 57. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 56, wherein the oligomeric acid comprises about 40 wt% to about 80 wt% of the dimer acid, based on a combined weight of the dimer acid and any trimer acid.

[00159] 58. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 57, wherein the oligomeric acid comprises about 70 wt% to about 90 wt% of the dimer acid, based on a combined weight of the dimer acid and any trimer acid.

[00160] 59. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 58, wherein: the mixture further comprises a monomer acid, the monomer acid comprises one or more monomer fatty acids, one or more monomer rosin acids, or a mixture of one or more monomer fatty acids and one or more monomer rosin acids, and the mixture comprises about 5 wt% to about 75 wt% of the monomer acid, based on a combined weight of the monomer fatty acid, any dimer acid, and any trimer acid.

[00161] 60. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 59, wherein the mixture further comprises one or more branched-chain fatty acids.

[00162] 61. The collector, the method, or the aqueous slurry composition according to paragraph 60, wherein one or more branched-chain fatty acids comprise one or more branched-chain iso- oleic acids, one or more branched-chain iso-palmitic acids, or any mixture thereof.

[00163] 62. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 61, wherein the rosin oil has an acid value of less than 150 mg KOH/g of rosin oil.

[00164] 63. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 62, wherein the rosin oil has an acid value of about 1 mg KOH/g of rosin oil to about to less than 130 mg KOH/g of rosin oil.

[00165] 64. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 63, wherein the rosin oil has an acid value of about 10 mg KOH/g of rosin oil to less than 100 mg KOH/g of rosin oil. [00166] 65. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 64, wherein the rosin oil has an acid value of about 20 mg KOH/g of rosin oil to less than 80 mg KOH/g of rosin oil.

[00167] 66. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 65, wherein the mixture further comprises about 0.01 wt% to less than 5 wt% of a monomer acid, based on a combined weight of the monomer acid, any dimer acid, and any trimer acid.

[00168] 67. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 66, wherein the oligomeric acid comprises about 60 wt% to about 95 wt% of the dimer acid and about 5 wt% to about 30 wt% of the trimer acid, based on a combined weight of the dimer acid and the trimer acid.

[00169] 68. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 67, wherein the dimer acid comprises one or more C₃2-dimer acids, one or more C₃4-dimer acids, one or more C₃₆-dimer acids, one or more C₃₈-dimer acids, one or more C₄o- dimer acids, or any mixture thereof.

[00170] 69. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 68, wherein the oligomeric acid is derived from monomer tall oil fatty acids, monomer tall oil rosin acids, or a mixture thereof, and wherein the rosin oil is derived from monomer tall oil rosin acids.

[00171] 70. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 69, wherein the oligomeric acid and the rosin oil are both derived from a crude tall oil comprising monomer fatty acids and rosin fatty acids, wherein the crude tall oil is heated under conditions sufficient to convert at least a portion of the monomer fatty acids to the oligomeric acid and to decarboxylate at least a portion of the rosin acids to the rosin oil.

[00172] 71. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 70, wherein the oligomeric acid has an acid value of about 160 mg KOH/g of the oligomeric acid to about 230 mg KOH/g of the oligomeric acid, and wherein the rosin oil comprises less than 20 wt% of rosin acids and has an acid value of about 1 mg KOH/g to about 120 mg KOH/g of the rosin oil. [00173] 72. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 71, wherein: the mixture further comprises about 0.01 wt% to less than 5 wt% of a monomer acid, based on a combined weight of any dimer acid and any trimer acid, the mixture has an oligomeric acid to rosin oil weight ratio of about 1.2: 1 to about 3 : 1, the oligomeric acid comprises about 50 wt% to about 100 wt% of the dimer acid, based on a combined weight of the dimer acid and any trimer acid, and the rosin oil has an acid value of less than 150 mg KOH/g of rosin oil.

[00174] 73. The collector, the method, or the aqueous slurry composition according to any one of paragraphs 38 to 71, wherein: the mixture further comprises a about 5 wt% to about 75 wt% of a monomer acid, based on a combined weight of any dimer acid and any trimer acid, the monomer acid comprises one or more monomer fatty acids, one or more monomer rosin acids, or a mixture of one or more monomer fatty acids and one or more monomer rosin acids, and the mixture has an acid value of about 30 mg KOH/g of the mixture to about 180 mg KOH/g of the mixture.

[00175] 74. The method according to any one of paragraphs 40 or 44 to 73, wherein the oligomeric acid and the rosin oil are mixed by reacting two or more fatty acids with one another to produce the dimer acid, the trimer acid, or the mixture thereof and by decarboxylating one or more rosin acids to the rosin oil in the presence of one another.

[00176] 75. The method or the aqueous slurry composition according to any one of paragraphs of 41, 42, or 44-73, wherein the purified mineral comprises a phosphorous ore, an iron ore, an aluminum ore, a potassium ore, a sodium ore, a calcium ore, a magnesium ore, potash, feldspar, bauxite, kaolin, coal, or any mixture thereof.

[00177] 76. The method or the aqueous slurry composition according to any one of paragraphs of 41, 42, 44-73, or 75, wherein purified mineral ore is a phosphorous ore, and wherein the gangue material comprises a silicate material.

[00178] 77. The method or the aqueous slurry composition according to any one of paragraphs of 41, 42, 42-73, 75, or 76, further comprising passing air through the aqueous mixture to cause the mineral ore to float to a surface of the aqueous mixture; and separating the purified mineral from the surface of the aqueous mixture. [00179] 78. A method for making a collector for use in the beneficiation of a crude mineral ore, comprising: combining a first catalyst and a mixture comprising fatty acids and rosin acids to produce a first mixture, wherein the mixture comprising fatty acids and rosin acids has a first dehydroabietic acid concentration; heating the first mixture to a first temperature that is less than 250°C to produce a first reaction mixture having a second dehydroabietic acid concentration greater than the first dehydroabietic acid concentration; and heating the first reaction mixture to a second temperature that is greater than 250°C to produce a second reaction mixture, wherein the second reaction mixture comprises rosin oil, oligomeric acids, and monomer acids, and has a rosin oil yield of greater than 25%, and wherein and the collector has an oligomeric acid to rosin oil weight ratio of about 0.5: 1 to about 5: 1.

[00180] 79. The method according to paragraph 78, further comprising adding the collector ton an aqueous slurry comprising a crude mineral ores to produce an aqueous slurry composition comprising: water, the crude mineral ore, and the collector.

[00181] 80. The method according to paragraph 79, further comprising, recovering a purified mineral from the aqueous slurry composition.

[00182] 81. The method according to paragraph 80, wherein purified mineral ore is a phosphorous ore, and wherein the gangue material comprises a silicate material.

[00183] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges including the combination of any two values, e.g., the combination of any lower value with any upper value, the combination of any two lower values, and/or the combination of any two upper values are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below. All numerical values are "about" or "approximately" the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

[00184] Various terms have been defined above. To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[00185] While the foregoing is directed to embodiments, other and further embodiments of the invention can be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

Claims: What is claimed is:

1. A collector for the beneficiation of a crude mineral ore, comprising:

a mixture of an oligomeric acid and a rosin oil, wherein:

the oligomeric acid comprises a dimer acid, a trimer acid, or a mixture thereof, the rosin oil comprises a decarboxylated rosin acid and less than 25 wt% of rosin acids, and

the mixture has an oligomeric acid to rosin oil weight ratio of about 0.5 : 1 to about

5: 1.

2. The collector of claim 1, wherein the mixture has an oligomeric acid to rosin oil weight ratio of about 1.2: 1 to about 3 : 1.

3. The collector of claim 1, wherein the oligomeric acid comprises about 50 wt% to about 100 wt% of the dimer acid, based on a combined weight of the dimer acid and any trimer acid.

4. The collector of claim 1, wherein:

the mixture further comprises a monomer acid,

the monomer acid comprises one or more monomer fatty acids, one or more monomer rosin acids, or a mixture of one or more monomer fatty acids and one or more monomer rosin acids, and

the mixture comprises about 5 wt% to about 75 wt% of the monomer acid, based on a combined weight of the monomer fatty acid, any dimer acid, and any trimer acid.

5. The collector of claim 1, wherein the mixture further comprises one or more branched- chain fatty acids.

6. The collector of claim 1, wherein the rosin oil has an acid value of less than 150 mg KOH/g of rosin oil.

7. The collector of claim 1, wherein the mixture further comprises about 0.01 wt% to less than 5 wt% of a monomer acid, based on a combined weight of the monomer acid, any dimer acid and any trimer acid.

8. The collector of claim 1, wherein the oligomeric acid comprises about 60 wt% to about 95 wt% of the dimer acid and about 5 wt% to about 30 wt% of the trimer acid, based on a combined weight of the dimer acid and the trimer acid.

9. The collector of claim 1, wherein the dimer acid comprises one or more C₃2-dimer acids, one or more C₃4-dimer acids, one or more C₃₆-dimer acids, one or more C₃₈-dimer acids, one or more C₄₀-dimer acids, or any mixture thereof.

10. The collector of claim 1, wherein the oligomeric acid is derived from monomer tall oil fatty acids, monomer tall oil rosin acids, or a mixture thereof, and wherein the rosin oil is derived from monomer tall oil rosin acids.

11. The collector of claim 1, wherein the oligomeric acid and the rosin oil are both derived from a crude tall oil comprising monomer fatty acids and rosin fatty acids, wherein the crude tall oil is heated under conditions sufficient to convert at least a portion of the monomer fatty acids to the oligomeric acid and to decarboxylate at least a portion of the rosin acids to the rosin oil.

12. The collector of claim 1, wherein the oligomeric acid has an acid value of about 160 mg KOH/g of the oligomeric acid to about 230 mg KOH/g of the oligomeric acid, and wherein the rosin oil comprises less than 25 wt% of rosin acids and has an acid value of about 1 mg KOH/g to about 130 mg KOH/g of the rosin oil.

13. The collector of claim 1, wherein:

the mixture further comprises about 0.01 wt% to less than 5 wt% of a monomer acid, based on a combined weight of any dimer acid and any trimer acid,

the mixture has an oligomeric acid to rosin oil weight ratio of about 1.2: 1 to about 3 : 1, the oligomeric acid comprises about 50 wt% to about 100 wt% of the dimer acid, based on a combined weight of the dimer acid and any trimer acid, and

the rosin oil has an acid value of less than 150 mg KOH/g of rosin oil.

14. The collector of claim 1, wherein:

the mixture further comprises a about 5 wt% to about 75 wt% of a monomer acid, based on a combined weight of any dimer acid and any trimer acid,

the mixture has an acid value of about 30 mg KOH/g of the mixture to about 180 mg KOH/g of the mixture.

15. A method for making a collector for use in the beneficiation of a crude mineral ore, comprising:

mixing an oligomeric acid and a rosin oil to produce a mixture, wherein:

the mixture has an oligomeric acid to rosin oil weight ratio of about 0.5: 1 to about 5: 1.

16. The method of claim 15, wherein the oligomeric acid and the rosin oil are mixed by reacting two or more fatty acids with one another to produce the dimer acid, the trimer acid, or the mixture thereof and by decarboxylating one or more rosin acids to the rosin oil in the presence of one another.

17. A method for purifying a crude mineral ore, comprising:

combining a crude mineral ore, water, and a collector to produce an aqueous mixture, wherein the crude mineral ore comprises a mineral and a gangue material, and wherein the collector comprises:

a mixture of an oligomeric acid and a rosin oil, wherein: the oligomeric acid comprises a dimer acid, a trimer acid, or a mixture thereof,

the rosin oil comprises a decarboxylated rosin acid and less than 25 wt% of rosin acids, and

the mixture has an oligomeric acid to rosin oil weight ratio of about 0.5: 1 to about 5: 1;

collecting a purified mineral from the aqueous mixture, wherein the purified mineral has a reduced concentration of the gangue material relative to the crude mineral ore.

18. The method of claim 17, wherein the purified mineral comprises a phosphorous ore, an iron ore, an aluminum ore, a potassium ore, a sodium ore, a calcium ore, a magnesium ore, potash, feldspar, bauxite, kaolin, coal, or any mixture thereof.

19. The method of claim 17, wherein purified mineral ore is a phosphorous ore, and wherein the gangue material comprises a silicate material.

20. The method of claim 17, further comprising passing air through the aqueous mixture to cause the mineral ore to float to a surface of the aqueous mixture; and separating the purified mineral from the surface of the aqueous mixture.