US 2016.0114338A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2016/0114338 A1 Snead (43) Pub. Date: Apr. 28, 2016

(54) CATIONIC COLLECTORS WITH MIXED (52) U.S. Cl. POLYAMDOAMINES AND METHODS FOR CPC ...... B03D3/06 (2013.01); C07C233/37 MAKING AND USING SAME (2013.01); C07C233/36 (2013.01); C07C (71) Applicant: Georgia-Pacific Chemicals LLC, 2101/08 (2013.01) Atlanta, GA (US) (72) Inventor: David R. Snead, Atlanta, GA (US) (57) ABSTRACT (73) Assignee: GEORGIA-PACIFIC CHEMICALS LLC, Atlanta, GA (US) Compositions that include a polyamidoamine, aqueous mix tures that include the polamidoamine and an ore, and methods (21) Appl. No.: 14/920,844 for making and using same. The composition can include a (22) Filed: Oct. 22, 2015 polyamidoamine having the chemical formula (A). In the chemical formula (A), R and R can be different and can be Related U.S. Application Data selected from a saturated or unsaturated, Substituted or unsub (60) Provisional application No. 62/067,672, filed on Oct. stituted, linear or branched, cyclic, heterocyclic, or aromatic 23, 2014. hydrocarbyl group, RandR' can independently behydrogen Publication Classification or a saturated or unsaturated, Substituted or unsubstituted, linear or branched, cyclic, heterocyclic, or aromatic hydro (51) Int. C. carbyl group, each m can be an integer of 1 to 5, and n can be BO3D 3/06 (2006.01) CD7C233/36 (2006.01) an integer of 2 to 8. The aqueous mixture can include an ore, C07C 233/37 (2006.01) water, and the composition. US 2016/0114338 A1 Apr. 28, 2016

CATIONC COLLECTORS WITH MIXED flotation in phosphate beneficiation generally exhibit inad POLYAMDOAMINES AND METHODS FOR equate results with respect to selectivity and yield of phos MAKING AND USING SAME phate relative to the impurities. 0008 Monoamidoamines have been used in phosphate CROSS-REFERENCE TO RELATED beneficiation, but are difficult to handle and use as a collector APPLICATION due to generally being highly viscous liquids or waxy Solids 0001. This application claims priority to U.S. Provisional at room temperature, e.g., about 25° C. Monoamidoamines Patent Application No. 62/067,672, filed on Oct. 23, 2014, also exhibit inadequate selectivity of silicate over phosphate which is incorporated by reference herein. and, therefore, provide a phosphate product with a higher impurity content than other conventional collectors. In addi BACKGROUND tion to lower purity, phosphate products recovered with monoamidoamines generally are recovered in lower yields 0002 1. Field relative to other conventional collectors. 0003 Embodiments described generally relate to compo 0009. There is a need, therefore, for improved collectors sitions that can include a polyamidoamine and methods for and methods for making and using same. making and using same. More particularly, such embodi ments relate to compositions that include a polyamidoamine, aqueous mixtures that include the polyamidoamine and an SUMMARY ore, and methods for making and using same. 0010 Compositions that include a polyamidoamine, 0004 2. Description of the Related Art aqueous mixtures that include the polamidoamine and an ore, 0005 Froth flotation is a method that uses the differences and methods for making and using same are provided. In one in the hydrophobicity of the mineral particles to be separated or more embodiments, the composition can include a polya or purified from aqueous slurries containing the mineral par midoamine having the chemical formula: ticles and one or more impurities. Certain heteropolar or nonpolar chemicals called collectors are typically added to the aqueous slurries to enhance or form water repellencies on (A) the surfaces of these mineral particles. These collectors are O O designed to selectively attach to one or more of the mineral particles to be separated and form a hydrophobic monolayer on the surfaces of the mineral particles. The formation of the ------, hydrophobic monolayer lowers the Surface energy of the min R3 R4 eral particles, which increases the chance that the particles will bind with air bubbles passing through in the slurry. The density of the combined air bubble and mineral particles is 0011 where R' and Rican be different and can be selected less than the displaced mass of the aqueous slurry, which from a saturated or unsaturated, Substituted or unsubstituted, causes the air bubble and mineral particles to float to the linear or branched, cyclic, heterocyclic, or aromatic hydro surface of the slurry. A mineral-rich froth is formed by the carbyl group, R and R' can independently be hydrogen or a collection of the floating air bubble and mineral particles at saturated or unsaturated, Substituted or unsubstituted, linear the surface of the slurry that can be skimmed off from the or branched, cyclic, heterocyclic, or aromatic hydrocarbyl Surface, while other minerals or material, e.g., impurities, group, each m can be an integer of 1 to 5, and n can be an remain submerged and/or flocculated in the slurry. The flota integer of 2 to 8. tion of minerals with a negative Surface charge, Such as silica, 0012. In one or more embodiments, the aqueous mixture silicates, feldspar, mica, clays, chrysocolla, potash and oth can include an ore; water, and a polyamidoamine having the ers, from an aqueous slurry can be achieved using cationic chemical formula (A), where R' and R can be different and collectors. can be selected from a saturated or unsaturated, Substituted or 0006. In reverse flotation, impurities are floated out of and unsubstituted, linear or branched, cyclic, heterocyclic, or aro away from the unpurified or crude materials to be beneficiated matic hydrocarbyl group, R and R' can independently be or otherwise purified. In particular, phosphate minerals, iron hydrogen or a saturated or unsaturated. Substituted or unsub ore, copper ores, and other minerals and/or ores are fre stituted, linear or branched, cyclic, heterocyclic, or aromatic quently beneficiated in this manner. In many cases, silicate is hydrocarbyl group, each m can be an integer of 1 to 5, and in the main component of the mineral impurities that cause can be an integer of 2 to 8. quality reductions in the purified product. The minerals con 0013. In one or more embodiments, a method for purifying taining silicates or other silicon oxides include quartz, sand, an ore can include combining an ore, water, and a polyami mica, feldspar, muscovite, and biotite. A high silicate content doamine to produce an aqueous mixture. The ore can include lowers the quality of the phosphate or other purified material. an impurity. The polyamidoamine can have the chemical 0007 Phosphorous ores generally contain impurities and formula (A), where R' and R can be different and can be phosphate materials, e.g., calcium phosphate that can be rep selected from a saturated or unsaturated, Substituted or unsub resented by the general chemical formula Cas(PO) (X). stituted, linear or branched, cyclic, heterocyclic, or aromatic where X can be fluoride, chloride, and/or hydroxide. Phos hydrocarbyl group, RandR' can independently behydrogen phate materials, such as calcium phosphate, generally have a or a saturated or unsaturated, Substituted or unsubstituted, polar, hydrophilic Surface. Many of the impurities, e.g., sili linear or branched, cyclic, heterocyclic, or aromatic hydro cates, in the phosphorus ore also have polar, hydrophilic carbyl group, each m can be an integer of 1 to 5, and n can be Surfaces and are not easy to selectively separate from the an integer of 2 to 8. A flocculated material that can include the phosphate material. Conventional collectors used for silicate impurity and the polyamidoamine from the aqueous mixture US 2016/0114338 A1 Apr. 28, 2016 can be collected. A purified ore that contains less of the 0018. In one or more examples, R. R. R. and R' can impurity than the ore can also be collected from the aqueous independently be derived from one or more sources. mixture. Illustrative fatty acid sources can be or include, but are not limited to, one or more fatty acids, tall oil fatty acids (TOFA), DETAILED DESCRIPTION rosin acids, crude tall oils (CTO), distilled tall oils (DTO), tall 0014. It has been surprisingly and unexpectedly discov oil pitches, portions thereof, fractions thereof, or any mixture ered that compositions containing one or more polyamidoam thereof. Other illustrative fatty acid sources can be or include ines that have two or more amido groups with different hydro , , isostearic acid, naphthenic acid, oleic carbyl groups provide high yields and/or selectivity by acid, , linolenic acid, , salts thereof, impurity, e.g., silicate, flotation in an aqueous mixture for the isomers thereof, or any mixture thereof. In some examples, purification or beneficiation of one or more ores. For Rand R' can both be hydrogen and R' and R can indepen example, the compositions containing the polyamidoamines dently be derived from lauric acid, Stearic acid, isostearic Surprisingly and unexpectedly perform better, e.g., greater acid, naphthenic acid, , linoleic acid, linolenic acid, yield and/or selectivity, in phosphate beneficiation than palmitic acid, other fatty acids, isomers thereof, or any mix monoamidoamines. Without wishing to be bound by theory, it ture thereof. is believed that the compositions containing one or more (0019. In some examples of polyamidoamines, R', R. R. polyamidoamines that have two or more amido groups with and R' can independently have all saturated bonds, such as different hydrocarbyl groups provide enhanced adhesion to saturated fatty acid groups, and therefore no unsaturated the Surfaces of impurities, e.g., silicate particles and other bonds. In other examples of polyamidoamines, R', R. R. gangue material, which lowers the Surface energy of the and Reach can independently have one or more unsaturated impurities. This reduced surface energy increases the likeli bonds, such as unsaturated fatty acid groups. For example, hood for the impurities to bind or otherwise attract to air bubbles and thus increases the buoyancy of the impurities. R", R. R. and R' can independently have 0, 1,2,3,4, 5, 6, The purified ores can be collected or removed from the aque 7, 8, 9, 10, 11, 12, 15, 20, or more unsaturated bonds. In some ous mixture, for example, after settling toward or on a bottom examples, R', R. R. and R' can independently have less of a separation vessel. Accordingly, the compositions can be than 10 unsaturated bonds, less than 8 unsaturated bonds, less used as cationic collectors. than 6 unsaturated bonds, or less than 5 unsaturated bonds, 0015 The polyamidoamine can be or include one or more Such as, for example, 0, 1, 2, 3, or 4 unsaturated bonds. amidoamines having the chemical formula (A): (0020. In some examples, R' and R' can be different and can be a C6 to C24 chain having 0, 1, 2, 3, 4, 5, or more (A) unsaturated bonds. For example, RandR can be a C8 to C24 O O chain having 0 to 5.0 to 4, 0 to 3, or 0 to 2 unsaturated bonds. In other examples, R' and R can be a C10 to C18 chain having 0 to 3 unsaturated bonds. In other examples, RandR ------. can be CoHo. CoH17, CoH is. CoH is: CH2s. CH2, R3 R4 Cls Hss, Cls H31, C1s H29, C17Hss, C17Hss, C17H31, C17H29. C19H7, C19Hss, C19Hss, C19H1, C19H29, isomers thereof, combinations thereof, or any mixture thereof In some 0016 where R' and R can be different and can be selected examples, R' and R can be the CH-CH (CHs)CHCH from a saturated or unsaturated. Substituted or unsubstituted, hydrocarbyl, such as derived from naphthenic acid. RandR linear or branched, cyclic, heterocyclic, or aromatic hydro can independently be hydrogen or a C6 to C24 chain having carbyl group, Rand R' can independently be hydrogen or a 0, 1, 2, 3, 4, 5, or more unsaturated bonds. For example, R saturated or unsaturated, Substituted or unsubstituted, linear and R' can independently behydrogen. In other examples, R or branched, cyclic, heterocyclic, or aromatic hydrocarbyl and R' can independently be a C8 to C24 chain having 0 to 3 group, each m can be an integer of 1, 2, 3, 4, 5, 6, 7, 8, or unsaturated bonds. In other examples, R and R' can inde greater, and n can be an integer of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. pendently be hydrogen, an amino, an amido, or a C10 to C18 11, 12, or greater. I0017. In some examples, R. R. R. and R' can indepen chain having 0 to 3 unsaturated bonds. dently be an alkyl, an alkenyl, an alkynyl, an aryl, an alkoxyl, 0021. The value of m defines number of carbonatoms, i.e., a carboxylic acid, an amino, an amido, a saturated and/or the carbon chain length, of the organic diyl group having the unsaturated fatty acid group, and/or isomers thereof. R. R. N(R)(CH), portion of the chemical formula (A). In one or R, and R' can independently be a hydrocarbyl group with 1, more examples, each m can be 1, 2, 3, 4, 5, 6, 7, 8, or greater. 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, In some examples, eachm can be 1 to 8, 1 to 7, 1 to 6, 1 to 5, 21,22, 25.30, or more carbonatoms. For example, R',R,R, 1 to 4, 1 to 3, or 1 to 2. For example, eachm can be 1, 2, 3, 4, and R' can independently be a C4 to C30 chain, a C8 to C24 5, 6, 7, or 8, and the organic diyl group having the N(R) chain, a C9 to C30 chain, a C9 to C24 chain, a C9 to C21 (CH), portion of the chemical formula (A) can be or include chain, a C9 to C20 chain, a C9 to C19 chain, a C9 to C18 methanediyl (—CH2—), ethanediyl (—CHCH ), pro chain, a C9 to C17 chain, a C9 to C15 chain, a C10 to C24 chain, a C10 to C20 chain, a C10 to C18 chain, a C11 to C21 panediyl ( CHCHCH ), butanediyl ( CH (CH) chain, a C11 to C19 chain, a C11 to C17 chain, a C12 to C20 2CH2—), pentanediyl (—CH2(CH2)CH2—), hexanediyl chain, a C14 to C20 chain, a C14 to C19 chain, a C14 to C18 (—CH2(CH2)CH2—), heptanediyl (-CH3(CH2)CH2—), chain, a C14 to C17 chain, a C14 to C16 chain, a C14 to C15 octanediyl (-CH(CH2)CH ), or isomers thereof, chain, a C15 to C20 chain, a C15 to C19 chain, a C15 to C18 respectively. In some specific examples, eachm can be 1,2,3, chain, a C15 to C17 chain, or a C15 to C16 chain. or 4, and the organic diyl group having the N(R)(CH2), US 2016/0114338 A1 Apr. 28, 2016 portion of the chemical formula (A) can include methylene, ethylene, propylene, or butylene, respectively. (B) O 0022. The value of n defines number of organic diyl groups having the N(R)(CH), portion of the chemical for N R2, mula (A). In one or more examples, in can be 1, 2, 3, 4, 5, 6, 7, art YY 8, 9, 10, 11, 12, or greater. In some examples, in can be 1 to 12, R3 O 1 to 10, 1 to 8, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 12, 2 to 10, 2 to 8, 2 to 6, 2 to 5, 2 to 4, or 2 to 3. For example, n can 0027 where R', R. R. R', and n are defined as above for be 2, 3, 4, or 5 and the polyamidoamines can be or include the chemical formula (A). diamidomonoamines, diamidodiamines, diamidotriamines, 0028 Polyethylene polyamidoamines can include poly or diamidotetraamines, respectively. In other examples, the ethylene diamidoamines, polyethylene triamidoamines, and polyamidoamines can be or include triamidomonoamines, polyethylene polyamidoamines with four or more amido triamidodiamines, triamidotriamines, or triamidotet groups. In some examples of polyamidoamines having the raamines. chemical formula (B), R and R can be different and can be I0023. In one example, R in each of the organic diyl selected from a C8 to C24 chain having 0 to 5 or 0 to 3 unsaturated bonds or a C10 to C18 chain having 0 to 5 or 0 to groups having the N(R)(CH), portion of the chemical for 3 unsaturated bonds. In other examples of polyamidoamines mula (A) contained in a single polyamidoamine molecule can having the chemical formula (B), R and R can be different be the same group or can independently be different groups and can be selected from CoHo, CoH7, CoHs, CH, with respected to one another. Therefore, each of the R CH23. CH2, C1s Hss, Cishs 1, C15H29, C17Hss, C17H3s. groups can independently be hydrogenora Saturated or unsat C17H31, C17H29, C19H7, C19Hss, C19Hss, C19H1, or urated, substituted or unsubstituted, linear or branched, CoHo. In some examples of polyamidoamines having the cyclic, heterocyclic, or aromatic hydrocarbyl group. Simi chemical formula (B), RandR' can independently behydro larly, each m can independently be selected for each organic gen, an amino, an amido, or a C10 to C18 chain having 0 to 3 diyl group. For example, if n is 2, then the organic diyl groups unsaturated bonds. In some examples of polyamidoamines having the N(R)(CH), portionis N(R)(CH)N(R)(CH) having the chemical formula (B), n can be 1, 2, 3, 4, 5, 6, 7, or and the polyamidoamine can include N(H)(CH)N(H) 8. For example, n can be 2 to 8, 2 to 5, 2 to 4, or 2 to 3. (CH), (if both Rs are hydrogen), N(CH)(CH)N(CH) 0029. In some specific examples, the polyamidoamines (CH), (if both Rs are methyl), N(H)(CH)N(CH) can have the chemical formula (B), where R' and R can be (CH), (if one R is hydrogen and one R is methyl), or any different and can be selected from a C8 to C24 chain, Rand other permutation. R" can be hydrogen, and n can be 2,3,4, or 5. In other specific examples, the polyamidoamines can have the chemical for I0024. In another example, R', R. R. and R' can indepen mula (B), where R' and R can be different and can be dently be or include one or more amino groups, one or more selected from a C10 to C18 chain, RandR can be hydrogen, amido groups, or one or more amidoamino groups. For and n can be 2, 3, or 4. example, R', R. R. and R' can independently be or include 10030. In other illustrative polyamidoamines, R and R' one or more amido groups and the polyamidoamines can can be hydrogen in the chemical formula (A). The polyami include triamidoamines, tetraamidoamines, pentamidoam doamines, therefore, can be or include one or more amidoam ines, or higher polyamidoamines. ines having the chemical formula (C): 0025. In some examples, the polyamidoamines can be or include one or more amidoamines, where R' and R can be different and can be selected from a C8 to C24 chain having (C) 0 to 3 unsaturated bonds, Rand R' can be hydrogen, each m O O can be an integer of 2 to 4, and n can be an integer of 2 to 5. For example, RandR can be different and can be selected from ------. CoH 19. CoH 17, CoH is, CoH13. CH23. CH21, C1s Has. C15H1, C15H29, C17Hss, C17Hss, C17H31, C17H29, C19H7. CoHss, CoHss, C19H1, or CoHo. In other examples, the polyamidoamines can be or include one or more amidoam 10031) where R', R, m, and n are defined as above for the ines where R' and R can be different and can be selected chemical formula (A). from a C10 to C18 chain having 0 to 3 unsaturated bonds, R 0032. In some specific examples, the polyamidoamines and R' can be hydrogen, each m can be an integer of 2 or 3, can have the chemical formula (C), where R' and R can be and n can be an integer of 2, 3, or 4. For example, R' and R' different and can be selected from a C8 to C24 chain, each m can be 2, 3, or 4, and n can be 2, 3, 4, or 5. In other specific can be CH2s. CH2, C1s Hss, Cls Hs 1, C1s H29, C17Hss, examples, the polyamidoamines can have the chemical for C17Hss, C17H31, or C17H29, and n can be 2. mula (C), where R' and R can be a C10 to C18 chain, eachm 0026. In some illustrative polyamidoamines, m can be 2, can be 2 or 3, and n can be 2, 3, or 4. where the organic diyl group having the N(R)(CH2), portion I0033. In other illustrative polyamidoamines, R and R' of the chemical formula (A) can include an ethanediyl or can be hydrogen and m can be 2, where the organic diyl group ethylene group. These polyamidoamines can be referred to as having the N(R)(CH), portion of the chemical formula (A) polyethylenepolyamidoamines and can have the chemical can include an ethanediyl or ethylene group. These polyeth formula (B): ylenepolyamidoamines can have the chemical formula (D): US 2016/0114338 A1 Apr. 28, 2016

C15H29. C17Hss, C17Hss, C17H31. C17H29. C19H7. C19Hss, (D) CoHss, CoH, or CoHo. In other examples of polyami doamines having the chemical formulas (E)-(G), R' and R' can be a CoHis CoHLs. CH2s. CH2, C1s Has CSH 1, C15H29, C17Hss, C17Hss, C17H31, or C17H29. 0038. In one or more examples, m can be 2 in the chemical formula (A), and the polyamidoamines can be or include one or more polyethylenepolyamidoamines having the chemical 0034) where R', R, and n are defined as above for the formula (H): chemical formula (A). 0035. In some specific examples, the polyamidoamines can have the chemical formula (D), where R' and R can be (H) different and can be selected from a C8 to C24 chain and n can O i O be 2, 3, 4, or 5. In other specific examples, the polyamidoam ines can have the chemical formula (D), where R' and R can R1 l 1N- N-npi N l R2, be CoHo. CoH 7. CoHis CoH is: CH2s. CH2, Cls Hss, C15H1, C15H29, C17Hss, C17Hss, C17H31, C17H29, C19H7. R3 R C19Hss, C19Hss, C19H1, or C19H29 and n can be 2, 3, or 4. In other specific examples, the polyamidoamines can have the 0039 where R', R. R. R., and n are defined as above for chemical formula (D), where R' and R can be CHs, C.H., the chemical formula (A), and where R can behydrogen or a CH23. CH2, C1s Hss, Cushi, Cish 29, C17Hss, C17H3s. saturated or unsaturated, Substituted or unsubstituted, linear CH, Or CH and n can be 2, 3, or 4. or branched, cyclic, heterocyclic, or aromatic hydrocarbyl 0036. In other examples, the polyamidoamines can have group. In some examples, Rican be or include hydrogen or the chemical formula (A), where RandR' can be hydrogen, any hydrocarbyl group disclosed for R. R. R. or R. For m can be 2, and n can be 2, 3, or 4, thereby providing poly example, R. R. and each Rican independently be hydrogen ethylenepolyamidoamines having the chemical formulas (E), or a saturated or unsaturated, Substituted or unsubstituted, (F), and (G), respectively: linear or branched, cyclic, heterocyclic, or aromatic hydro carbyl group. In some examples, R. R. and each Rican all be hydrogen. In other examples, R. R. R. R. and each R (E) can independently be a hydrocarbyl group that can be or O O include one or more alkyl, alkenyl, alkynyl, aryl, alkoxyl, carboxylic acid, amino, amido, Saturated and/or unsaturated ------. fatty acid group, isomers thereof, combinations thereof, or mixtures thereof. h h 10040. In some examples, R. R', and each R can be (F) hydrogen in the chemical formula (H), and the polyamidoam O H H ines can be or include one or more polyethylenepolyami doamines having the chemical formula (I): RI - 1N1- - N-1SN1)n- R. s h h O (I) (G) O O R1)=0 R1 l th- N N-n l R2, H-N H h I0041 where R', R, and n are defined as above for the chemical formula (H). 0042. In some examples of the polyethylenepolyami doamines having the chemical formula (I), n can be 1, 2, 3, 4, 5, 6, 7, 8, or greater. For example, the polyamidoamines can have the chemical formula (I), where n can be 1, 2, or 3, thereby providing the above chemical formulas (E), (F), and (G), respectively. 0043. In one or more examples, any of the polyamidoam 0037 where R' and Rare defined as above for the chemi ines having the chemical formulas (A)-(I) can be combined, cal formula (A). In some examples of polyamidoamines hav mixed, and/or reacted with one or more reagents to form salts, ing the chemical formulas (E)-(G), R' and R can be different complexes, adducts, hydrates, or other forms of the polyami and can be selected from a C8 to C24 chain having 0 to 3 doamines. For example, one or more polyamidoamines can unsaturated bonds or a C10 to C18 chain having 0 to 3 unsat be reacted with one or more acids to form one or more polya urated bonds. In other examples of polyamidoamines having midoaminates. The polyamidoamines can be reacted with the the chemical formulas (E)-(G), R and R can be a CoHo. one or more reagents, such as acid, before being combined CoH17, CoH1s. CoH13. CH23. CH2, C1s Hss, Cls Hs 1. with other components to form the composition. Alterna US 2016/0114338 A1 Apr. 28, 2016

tively, the polyamidoamines and the one or more reagents can jugate bases, or a mixture thereof. The X can be, for example, be combined as separate components, at the same time or at but not limited to, one or more organic conjugate bases of different times, to form the composition. monocarboxylic acids, dicarboxylic acids, tricarboxylic or 0044. In one example, one or more organic acids can be higher acids, amino acids, Sugars, isomers thereof, hydrates mixed, blended, or otherwise combined with one or more thereof, salts thereof, complexes thereof, adducts thereof, or polyamidoamines. Combining the organic acid with the any mixture thereof. Illustrative conjugate bases can be or polyamidoamine can make, form, or otherwise produce one include, but are not limited to, acetate, glycolate, lactate, or more salts of the polyamidoamines, e.g., polyamidoami pyruvate, formate, propionate, butyrate, Valerate (pen nates. Illustrative organic acid sources or organic acids can tanoate), oxalate, malonate, malonate, caproate, enanthate, include, but are not limited to, acetic acid, glycolic acid, lactic caprylate, pelargonate, caprate, undecylate, laurate, malonic acid, pyruvic acid, formic acid, propionic acid, butyric acid, acid, caproic acid, enanthic acid, , pelargonic Valeric acid (pentanoic acid), oxalic acid, malonic acid, cap acid, , undecylic acid, lauric acid, alkyl derivatives roic acid, enanthic acid, caprylic acid, pelargonic acid, capric thereof, isomers thereof, or salts thereof. acid, undecylic acid, lauric acid, isomers thereof, hydrates 0049. The A and X groups in the polyamidoamines or thereof, salts thereof, complexes thereof, adducts thereof, or polyamidoaminates can vary depending on the one or more any mixture thereof. In some examples, the one or more reagents used to complex the polyamidoamines. Therefore, organic acids can be or include acetic acid. In other example, the values of y and Z can also vary relative to the particular the one or more organic acids can be or include glacial acetic reagent combined with the polyamidoamine. For example, acid. acetic acid is a monoprotic acid that provides one proton, e.g., 0045. It has been surprisingly and unexpectedly discov H", and one conjugate base, e.g., AcO, while oxalic acid is a ered that combining the polyamidoamine, e.g., diamidoam diprotic acid that provides two protons, e.g., 2H, and one ines and/or triamidoamines, and the organic acid, e.g., acetic conjugate base, e.g., CO. In various compositions of the acid, produces a free flowing, homogeneous Solution at room polyamidoamines or polyamidoaminates, y and Z can be temperature, e.g., about 25°C. For example, a mixture of the equal or Substantially to each other, y can be greater than Z, or polyamidoamine and organic acid, e.g., acetic acid, Surpris Z can be greater thany. ingly and unexpectedly produces a composition that has a 0050. In some examples of the polyamidoamines or polya lower viscosity and is freer flowing at a temperature of about midoaminates, y and/or Z can be integers, such as 1, 2, 3, 4, 5, 25°C. than monoamidoamines or polyamidoamines free of 6, 7, 8, 9, or 10. Alternatively, in other examples of the the organic acid, which are often solids, waxy solids, or polyamidoamines or polyamidoaminates, y and/or Z can be highly viscous liquids at a temperature of about 25°C. non-integers or fractions which can indicate a mixture of 0046. In some examples, the polyamidoamines can be or molecules which are partially cationic and/or anionic func include one or more polyamidoaminates and/or complexes of tionalized. Each y and Z can independently be about 0.1, the amidoamines having the chemical formula (J): about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, (J) about 2, about 2.5, about 3, about 3.5, about 4, about 4.5, O about 5, about 5.5, about 6, about 6.5, about 7, about 7.5, O about 8, about 8.5, about 9, about 9.5, about 10, or greater. In |Aly R1 N 1)\ m l X, Some examples, eachy and Z can independently be about 0.1 in N R2 to about 8, about 0.5 to about 8, about 1 to about 8, about 1 to R3 about 4. In other examples, eachy and Z can independently be 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2. 0051. In one or more examples, illustrative polyami 0047 where R', R. R. R., each m, and n are defined as doaminates can be or include one or more polyethylene above for the chemical formula (A), and where 'A' can be polyamidoaminates having the chemical formula (K): hydrogen, one or more alkali metals, one or more alkaline earth metals, ammonium, alkylammonium compounds, one or more hydrocarbyl groups, or one or more cationic species, (K) 'X' can be one or more conjugate bases, halides, e.g., F. Cl, O R A Br, or I anions, hydroxide, or other anionic species, and each ! --> O y” and “Z” can independently be about 0.1 to about 8, such R1 N N l as, for example, about 1 to about 8 or about 1 to about 4. X N R2, 0048. The Acan be hydrogen, lithium, sodium, potassium, R3 cesium, magnesium, calcium, ammonium, monoalkylammo nium, dialkylammonium, trialkylammonium, tetraalkylam monium, adducts thereof, complexed salts thereof, hydrates 0052 where R', R. R. R., each R, and n are defined as thereof, or mixtures thereof. In some examples, the A can be above for the chemical formula (H), and where A and X are bonded to the nitrogen atom of the N(R)(CH), portion to defined as above for the chemical formula (J). In some produce a cationic N(A)(R)(CH)," portion of the polya examples. A can be a hydrogen or a Saturated or unsaturated, midoamine. Such as a quaternary ammonium cation. The X substituted or unsubstituted, linear or branched, cyclic, het can be one or more one or more anionic species coordinated erocyclic, or aromatic hydrocarbyl group. with the cationic N(A)(R)(CH)," portion of the polyami 0053. In some illustrative polyethylene polyamidoami doamine. In some examples, the X can be one or more con nates having chemical formula (K), R and R can indepen jugate bases, such as organic conjugate bases, inorganic con dently be a saturated or unsaturated, Substituted or unsubsti US 2016/0114338 A1 Apr. 28, 2016 tuted, linear or branched, cyclic, heterocyclic, or aromatic polyamidoamine acetate (n=2), tetraethylene polyamidoam hydrocarbyl group, R. R. and each Rican independently be ine acetate (n-3), or pentaethylene polyamidoamine acetate hydrogen or a saturated or unsaturated. Substituted or unsub (n=4). stituted, linear or branched, cyclic, heterocyclic, or aromatic 0060. In one or more examples, the polyamidoamines can hydrocarbyl group, in can be an integer of 1 to 8. A can be be made, formed, synthesized, or otherwise produced by hydrogen, one or more alkali metals, one or more alkaline reacting one or more polyamines and one or more fatty acids earth metals, ammonium, alkylammonium compounds, or or other carboxylic acids. The polyamidoamines can be pro one or more other cationic species, and X can be one or more duced by combining and reacting greater than one molar conjugate bases, halides, e.g., F. Cl, Br, or I anions, hydrox equivalent of the fatty acids with one molar equivalent of the ide, or other anionic species. polyamines. In some examples, the polyamidoamines can be I0054) In some examples, R' and R can be an alkyl, an produced by combining and reacting greater than 1, about 1.1, alkenyl, an alkynyl, an aryl, an alkoxyl, a carboxylic acid, an about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, amino, an amido, a saturated and/or unsaturated fatty acid about 1.8, about 1.9, about 2, about 2.1, about 2.2, about 2.3, group, isomers thereof, combinations thereof, or mixtures about 2.4, about 2.5, about 2.6, about 2.7, about 2.8, about 2.9, thereof, R. R. and each Rican be hydrogen, in can be 1,2,3, about 3, about 3.1, about 3.2, about 3.3, about 3.4, about 3.5, 4, or 5. A can be hydrogen, and X can be or include one or about 3.6, about 3.7, about 3.8, about 3.9, about 4, about 4.5, more conjugate bases which include acetate, glycolate, lac or about 5 molar equivalents of the fatty acid with one molar tate, pyruvate, formate, propionate, butyrate, Valerate, equivalent of the polyamine. Processes that can be used to oxalate, alkyl derivatives thereof, isomers thereof, or mix produce the polyamidoamines from polyamine and fatty acid tures thereof. are discussed and described in, for example, U.S. Pat. Nos. 0055 For example, R. R', and each R can all be hydro 2,857,331; 2,927,692; and 3,166,548. gen in the chemical formula (K), and the polyamidoaminates 0061 The one or more polyamines and one or more fatty can be or include one or more polyethylene polyamidoami acids or other carboxylic acids can be reacted to form the nates having the chemical formula (L): polyamidoamines at a temperature of about 0°C., about 10° C., about 20° C., about 25°C., about 30° C., about 40° C., about 50° C., about 60° C., about 70° C., about 80°C., about (L) 90° C., about 100° C., about 110° C., about 120° C., about O H. A 130° C., about 140°C., about 150° C., about 160° C., about ls V+/ O 170° C., about 180° C., about 190° C., about 200° C., about R N N l 250° C., or about 300° C. For example, the one or more X N R2, polyamines and one or more fatty acids or other carboxylic H H acids can be reacted to form the polyamidoamines at a tem perature 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 0056 where R', R, n, A, and X are defined as above for 200°C., about 20° C. to about 190° C., about 20° C. to about the chemical formula (K). 180°C., about 20° C. to about 175°C., about 20° C. to about 0057. In one or more examples. A can be hydrogen and X 165° C., about 20° C. to about 150° C., about 50° C. to about can be acetate in the chemical formula (L), and the polyeth 225°C., about 50° C. to about 500° C., about 50° C. to about ylene polyamidoaminates can be or include one or more 190° C., about 50° C. to about 180°C., about 50° C. to about polyethylene polyamidoamine acetates having the chemical 175° C., about 50° C. to about 165° C., about 50° C. to about formulas (M) and (N): 150° C., about 100° C. to about 225° C., about 100° C. to about 1000°C., about 100° C. to about 190° C., about 100° C. to about 180°C., about 100° C. to about 175°C., about 100° (M) C. to about 165° C., about 100° C. to about 150° C., about O H. H. O 120° C. to about 225°C., about 120° C. to about 1200° C., N about 120° C. to about 190° C., about 120° C. to about 180° RI ls. -->"OAc), N l R2, C., about 120° C. to about 175° C., about 120° C. to about 165° C., or about 120° C. to about 150° C. The one or more H h polyamines and one or more fatty acids or other carboxylic (N) acids can be reacted to form the polyamidoamines for about O H. H. O 10 minto about 24 hr, about 0.5 hr to about 12 hr., about 0.75 ls \ l hr to about 10 hr, about 1 hr to about 5 hr, about 2 hr to about RI ~,S-r R2, 4 hr, or about 3 hr. H H 0062. In one or more examples, the composition can include one or more polyamidoamines that can be derived, formed, or otherwise produced from one or more polyamines 0058 where R', R, and n are defined as above for the or polyamine sources. The one or more polyamines or chemical formula (K). polyamine sources can be reacted with one or more fatty acids 0059. In some examples, in can be 1 for the polyethylene to produce or otherwise form the one or more polyamidoam polyamidoamine acetates having the chemical formula (M) to ines. Illustrative polyamines can include, but are not limited provide illustrative diethylene polyamidoamine acetates that to, dimethylenetriamine, trimethylenetetramine, tetramethyl have the chemical formula (N). In other illustrative polyeth enepentamine, pentamethylenehexamine, diethylenetri ylene polyamidoamine acetates having the chemical formula amine (DETA), triethylenetetramine (TETA), tetraethylene (M), n can be 2, 3, 4, 5, or greater, for example, triethylene pentamine (TEPA), pentaethylenehexamine (PEHA), US 2016/0114338 A1 Apr. 28, 2016

dipropylenetriamine, tripropylenetetramine, tetrapropylene % of stearic acid, about 0.01 wt % to about 5 wt % of pentamine, pentapropylenehexamine, dibutylenetriamine, palmitoleic acid, about 0.01 wt % to about 3 wt % of linoleic tributylenetetramine, tetrabutylenepentamine, pentabutyle acid, about 0.01 wt % to about 2.5 wt % of caproic acid, about nehexamine, aminoethylpiperazine, dipropylenetriamine, 0.01 wt % to about 2.5 wt % of arachidic acid, isomers spermine, spermidine, heavy polyamine X (HPAX), tallow thereof, or any mixture thereof. In other examples, the coco amines, isomers thereof, salts thereof, complexes thereof, nut oil fatty acids can include about 44 wt % to about 52 wt % adducts thereof, or any mixture thereof. In some examples, of lauric acid, about 13 wt % to about 19 wt % of myristic the polyamine can be or include a mixture of linear, branched, acid, about 8 wt % to about 11 wt % of palmitic acid, about 6 and/or cyclic ethyleneamines and/or other alkyleneamines, wt % to about 10 wt % of capric acid, about 5 wt % to about polyethylene polyamines, pentaethylenehexamine mixtures, 9 wt % of caprylic acid, about 5 wt % to about 8 wt % of oleic tetraethylenepentamine mixtures, triethylenetetramine mix acid, about 1 wt % to about 3 wt % of stearic acid, about 0.01 tures, isomers thereof, salts thereof, or any mixture thereof. wt % to about 2.5 wt % of palmitoleic acid, about 0.01 wt % For example, Such polyamine can be or include heavy to about 1 wt % of linoleic acid, about 0.01 wt % to about 0.8 polyamine X (HPAX), commercially available from Dow wt % of caproic acid, about 0.01 wt % to about 0.5 wt % of Chemical Company, and can have components that contain arachidic acid, isomers thereof, or any mixture thereof. six or more nitrogen atoms per molecule. Polyamine sources 0065. In one example, CTO can be made or produced as an can be or include Salts, adducts, complexes, or other forms of acidified byproduct in the kraft or sulfate processing of wood. polyamines or other compounds which provide a source of Crude tall oil, prior to refining, can include a mixture of rosin polyamines which can be used to make polyamidoamines. acids, fatty acids, sterols, high-molecular weight alcohols, Polyamine sources can produce polyamines, for example, but and other alkyl chain materials. The components of CTO can not limited to, upon heating, adjusting the pH or concentra depend on a variety of factors, such as the particular species of tion, or reacting with other reagents or compounds. the wood being processed (wood type), the geographical 0063. In one or more examples, the composition can location of the wood source, the age of the wood, the particu include one or more polyamidoamines that can be derived, lar season that the wood is harvested, and others. Thus, formed, or otherwise produced, in part, from one or more depending on the particular source, CTO can contain about 20 fatty acids or fatty acid sources. The one or more fatty acids or wt % to about 75 wt % of fatty acids, e.g., about 30 wt % to fatty acid sources can be reacted with one or more polyamines about 60 wt % of fatty acids, about 20 wt % to about 65 wt % to produce or otherwise form the one or more polyamidoam of rosin acids, e.g., about 30 wt % to about 60 wt % of rosin ines. Illustrative fatty acids or fatty acid sources can be or acids, and the balance being neutral and non-Saponifiable include one or more fatty acids, TOFA, rosin acids, CTO. components. In some examples, the CTO can include at least DTO, tall oil pitches, portions thereof, fractions thereof, or 8 wt % or about 10 wt % of neutral materials or non-saponi any mixture thereof. In some specific examples, the fatty fiable components. acids or fatty acid sources can be or include TOFA, lauric 0.066 Distillation of CTO can be used to recover a mixture acid, Stearic acid, isostearic acid, naphthenic acid, oleic acid, offatty acids, referred to as DTO or DTO fraction, which can linoleic acid, linolenic acid, palmitic acid, coconut oil fatty have about 16 carbon atoms to about 20 carbon atoms. In acid, isomers thereof, or any mixture thereof. Some examples, these fatty acids can be included with the 0064. In one or more examples, the fatty acids or fatty acid polyamines to produce or otherwise form the polyamidoam Sources can be or include coconut oil fatty acids. Illustrative ines. Fatty acids found in tall oils can include, but are not coconut oil fatty acids can include lauric acid, , limited to, oleic acid, linoleic acid, Stearic acid, and palmitic palmitic acid, capric acid, caprylic acid, oleic acid, Stearic acid. Rosinacids found in tall oils, include, but are not limited acid, palmitoleic acid, linoleic acid, caproic acid, arachidic to, abietic acid, dehydroabietic acid, isopimaric acid, and acid, one or more other fatty acids, isomers thereof, or any pimaric acid. mixture thereof. The composition can include one or more 0067. The DTO fraction can have a fatty acids and/or polyamidoamines that can be derived, formed, or otherwise esters of fatty acids concentration of about 55 wt %, about 60 produced from at least 6, at least 7, at least 8, at least 9, at least wt %, or about 65 wt % to about 85 wt %, about 90 wt %, or 10, or at least 11 fatty acids selected from lauric acid, myristic about 95 wt %. The DTO fraction can have a rosin acids or acid, palmitic acid, capric acid, caprylic acid, oleic acid, rosins concentration of about 5 wt %, about 10 wt %, or about Stearic acid, palmitoleic acid, linoleic acid, caproic acid, 15 wt % to about 30 wt %, about 35 wt %, or about 40 wt %. arachidic acid, one or more other fatty acids, isomers thereof, The DTO fraction can have a neutrals concentration of about or any mixture thereof. For example, the one or more polya 0.1 wt %, about 1 wt %, or about 1.5 wt % to about 2 wt %, midoamines can be derived, formed, or otherwise produced about 3.5 wt %, or about 5 wt %. The DTO fraction can have from about 6 to about 10, about 7 to about 10, about 8 to about an acid value of about 20, about 25, or about 30 to about 40, 10, about 6 to about 11, about 7 to about 11, about 8 to about about 45, or about 50. The DTO fraction can have a viscosity 11, about 9 to about 11, or about 10 to about 11 fatty acids (centipoise at 85°C.) of about 10cP. about 20 cB. about 30cP. selected from lauric acid, myristic acid, palmitic acid, capric or about 40 cF to about 100 cP, about 120 cP. about 135 cP or acid, caprylic acid, oleic acid, Stearic acid, palmitoleic acid, about 150 cp. The distilled tall oil can have a density of about linoleic acid, caproic acid, arachidic acid, one or more other 840 g/L, about 860 g/L, or about 880 g/L to about 900 g/L, fatty acids, isomers thereof, or any mixture thereof. In some about 920 g/L, or about 935 g/L. The DTO fraction can have examples, the coconut oil fatty acids can include about 40 wit a saponification number of about 180, about 185, or about 190 % to about 55 wt % of lauric acid, about 10 wt % to about 25 to about 200, about 205, or about 210. The DTO fraction can wt % of myristic acid, about 5 wt % to about 15 wt % of have an iodine value of about 115, about 117, or about 120 to palmitic acid, about 4 wt % to about 15 wt % of capric acid, about 130, about 135, or about 140. about 3 wt % to about 12 wt % of caprylic acid, about 3 wt % 0068. The rosin acids derived from CTO are also an inter to about 12 wt % of oleic acid, about 0.5 wt % to about 5 wt mediate fraction that can be produced from the distillation of US 2016/0114338 A1 Apr. 28, 2016

CTO. The tall oil rosin can have a concentration of rosinacids one or more fatty acids and one or more fatty acid esters. The of about 80 wt %, about 85 wt %, or about 90 wt % to about fatty acid sources or fatty acids can be combined with the tall 93 wt %, about 95 wt %, or about 99 wt %. The tall oil rosin oils and one or more polyamines, and Subsequently reacted to can have a concentration of abietic acid of about 35 wt %, produce or otherwise form the one or more polyamidoamines. about 40 wt %, or about 43 wt % to about 50 wt %, about 55 In other examples, the fatty acid sources or fatty acids can be wt %, or about 60 wt %. The tall oil rosin can have a concen used instead of the tall oils, therefore, the fatty acids can be tration of dehydroabietic acid of about 10 wt %, about 13 wit reacted with one or more polyamines to produce or otherwise %, or about 15 wt % to about 20 wt %, about 23 wt %, or about form the one or more polyamidoamines. Illustrative fatty acid 25 wt %. The tall oil rosin can have a concentration of isopi Sources or fatty acids can be or include, but are not limited to, maric acid of about 10 wt % or less, about 8 wt % or less, oleic acid, lauric acid, linoleic acid, linolenic acid, palmitic about 5 wt % or less, or about 3 wt % or less. The tall oil rosin acid, Stearic acid, isostearic acid, ricinoleic acid, myristic can have a concentration of pimaric acid of about 10 wt % or acid, arachidic acid, behenic acid, capric acid, caprylic acid, less, about 8 wt % or less, about 5 wt % or less, or about 3 wit caproic acid, palmitoleic acid, isomers thereof, or any mix % or less. The tall oil rosin can have a fatty acids concentra ture thereof. tion of about 0.5 wt %, about 1 wt %, or about 2 wt % to about 0071. In some examples, fatty acid sources or fatty acids 3 wt %, about 5 wt %, or about 10 wt %. The tall oil rosin can which can be reacted with one or more polyamines to produce have a concentration of neutral materials of about 0.5 wt %, or otherwise form the one or more polyamidoamines can about 1 wt %, or about 2 wt % to about 3 wt %, about 5 wt %, include fatty acids from various plant and/or or about 10 wt %. The tall oil rosin can have a density of about Sources. Illustrative plant or vegetable oils that can be used as 960 g/L, about 970 g/L, or about 980 g/L to about 1,000 g/L, the fatty acids can include, but are not limited to, safflower oil, about 1,010 g/L, or about 1,020 g/L. The tall oil rosin can have grapeseed oil, , walnut oil, soybean oil, cotton an acid value of about 150, about 160, or about 165 to about seed oil, coconut oil, corn oil, olive oil, palm oil, palm olein, 170, about 175, or about 180. peanut oil, rapeseed oil, canola oil, sesame oil, hazelnut oil, 0069. Representative tall oil products, which can be fatty almond oil, beech nut oil, cashew oil, macadamia oil, mon acid sources used to form the polyamidoamines, can be or gongo nut oil, pecan oil, pine nut oil, pistachio oil, grapefruit include, but are not limited to, Saturated and unsaturated fatty seed oil, lemon oil, orange oil, watermelon seed oil, bitter acids in the C-Cls range, as well as minor amounts of rosin gourd oil, buffalo gourd oil, butternut Squash seed oil, egusi acids, and can include XTOL(R) 100, XTOLR 300, and seed oil, pumpkin seed oil, borage seed oil, blackcurrant seed XTOLR 304, XTOL(R) 520, and LYTOR(R) 100, all of which oil, evening primrose oil, acai oil, black seed oil, flaxseed oil, are commercially available from Georgia-Pacific Chemicals carob pod oil, amaranth oil, apricot oil, apple seed oil, argan LLC, Atlanta, Ga. XTOL(R) 100 includes about 1.6 wt % of oil, avocado oil, babassu oil, ben oil, borneo tallow nut oil, palmitic acid, about 2.5 wt % of stearic acid, about 37.9 wt % cape chestnut, algaroba oil, cocoa butter, cocklebur oil, pop of oleic acid, about 26.3 wt % of linoleic acid, about 0.3 wt % pyseed oil, cohune oil, coriander seed oil, date seed oil, dika oflinolenic acid, about 2.9 wt % of linoleic isomers, about 0.2 oil, false flax oil, hemp oil, kapok seed oil, kenaf seed oil, wt % of arachidic acid, about 3.6 wt % eicosatrienoic acid, lallemantia oil, mafura oil, manila oil, meadowfoam seed oil, about 1.4 wt % of pimaric acid, <0.16 wt % of sandarocopi mustard oil, okra seed oil, papaya seed oil, perilla seed oil, maric, <0.16 wt % of isopimaric acid, <0.16 wt % of dehy persimmon seed oil, pequi oil, pili nut oil, pomegranate seed droabietic acid, about 0.2 wt % of abietic acid, with the oil, prune kernel oil, quinoa oil, queefoil, ramtiloil, rice bran balance being neutrals and high molecular weight species. oil, royle oil, shea nut oil, Sacha inchi oil, sapote oil, see oil, LYTOR(R) 100 includes <0.16 wt % of palmitic acid, <0.16wt taramira oil, tea seed oil, thistle oil, tigernut oil, tobacco seed % of stearic acid, about 0.2 wt % of oleic acid, about 0.2 wt % oil, tomato seed oil, wheat germ oil, castor oil, colza oil, flax of arachidic acid, about 0.2 wt % eicosatrienoic acid, about oil, radish oil, salicornia oil, tung oil, honge oil, jatropha oil, 2.2 wt % of pimaric acid, about 0.6 wt % of sandarocopima jojoba oil, nahor oil, paradise oil, petroleum nut oil, dammar ric, about 8.5 wt % of palustric acid, about 1.6 wt % of oil, linseed oil, stillingia oil, Vernonia oil, amur cork tree fruit levopimaric acid, about 2.8 wt % of isopimaric acid, about oil, artichoke oil, balanos oil, bladderpod oil, brucea javanica 15.3 wt % of dehydroabietic acid, about 51.4 wt % of abietic oil, burdock oil, candlenut oil, carrot seed oil, chaulmoogra acid, about 2.4 wt % of neoabietic acid, with the balance being oil, crambe oil, croton oil, cuphea oil, honesty oil, mango oil, neutrals and high molecular weight species. XTOL(R) 520 neem oil, oojon oil, rose hip seed oil, rubber seed oil, sea DTO includes about 0.2 wt % of palmitic acid, about 3.3 wt % buckthorn oil, sea rocket seed oil, Snowball seed oil, tall oil, of stearic acid, about 37.9 wt % of oleic acid, about 26.3 wt % tamanu oil, tonka bean oil, ucuhuba seed oil, or any mixture oflinoleic acid, about 0.3 wt % of linolenic acid, about 2.9 wt thereof. Illustrative animal fats or oils that can be used as the % of linoleic isomers, about 0.2 wt % of arachidic acid, about fatty acids can include, but are not limited to, fatty acids from 3.6 wt % eicosatrienoic acid, about 1.4 wt % of pimaric acid, animal sources, such as cows, pigs, lambs, chickens, turkeys, <0.16 wt % wt % of sandarocopimaric, <0.16 wt % of isopi ducks, geese, and other animals, as well as dairy products maric acid, <0.16 wt % of dehydroabietic acid, about 0.2 wt % such as milk, butter, or cheese. Illustrative fatty acids from of abietic acid, with the balance being neutrals and high animal sources can include palmitic acid, Stearic acid, myris molecular weight species. Such tall oil products can be used tic acid, oleic acid, palmitoleic acid, linoleic acid, or any in the reaction with the polyamine or a mixture of mixture thereof. polyamines. Other fatty acids and mixtures of fatty acids, 0072. If the fatty acid source includes two or more fatty including oxidized and/or dimerized tall oil, such those dis acids, each fatty acid can be present in the same amount or cussed below can also be employed. different amounts with respect to one another. For example, a 0070. In one or more examples, illustrative fatty acid first fatty acid can be present with respect to another or “sec Sources can be or include a fatty acid, a mixture offatty acids, ond' fatty acid contained therein in a weight ratio of about a fatty acid ester, a mixture offatty acid esters, or a mixture of 10,000:1, about 9,000:1, about 8,000:1, about 7,000:1, about US 2016/0114338 A1 Apr. 28, 2016

6,000:1, about 5,000:1, about 4,000:1, about 3,000:1, about mineral particles in the aqueous solutions or slurries. In other 2,000:1, about 1,000:1, about 900:1, about 800:1, about 700: aspects, the irregularities in structure can also provide lower 1, about 600:1, about 500:1, about 400:1, about 300:1, about melting points for the polyamidoamine and/or the composi 200:1, about 150:1, about 100:1, about 99:1, about 90:10, tion, which in turn can be increase the utility of the polyami about 80:20, about 70:30, about 60:40, about 50:50, about doamine or the composition in cold-weather applications. 40:60, about 30:70, about 20:80, about 10:90, about 1:99, 0077. In other examples, the composition can include a about 1:100, about 1:150, about 1:200, about 1:300, about polyamidoamine that can have varying carbon chain lengths 1:400, about 1:500, about 1:600, about 1:700, about 1:800, in the R' and Rhydrocarbyl groups can be prepared to have about 1:900, about 1,000, about 2,000, about 1:3,000, about a desired collecting power based on mineral particle size in 1:4,000, about 1:5,000, about 1:6,000, about 1:7,000, about the aqueous solutions or slurries. In some examples, if the R' 1:8,000, about 1:9,000, or about 1:10,000. Similarly, if three and Rhydrocarbyl groups include long carbon chains, such or more fatty acids are mixed, the three or more fatty acids can as a C18 to C24 chain, then the polyamidoamine can favor be present in any ratio. Therefore, the two or more fatty acids collecting particles having a particle size of greater than 150 can be reacted with one or more polyamines to produce or um, Such as greater than 150 um to about 750 um. Alterna otherwise form polyamidoamines with different R' and R' tively, in other examples, if the R' and Rhydrocarbyl groups groups in any of the chemical formulas (A)-(M). include short carbon chains, such as a C6 to C12 chain, then 0073. In some examples, one or more organic acid sources the polyamidoamine can favor collecting particles having a or organic acids can be combined with one or more fatty acid particle size of less than 75 um, such as less than 75 um to Sources or fatty acids and one or more polyamines, and Sub about 5um. In some examples, diamidoamines, triamidoam sequently reacted to produce or otherwise form the one or ines, and other polyamidoamines having intermediate sized more polyamidoamines. In other examples, organic acid carbon chain lengths, such as a C6 to C24 chain, can be Sources or organic acids can be used instead of the fatty acid produced or otherwise formed from mixed fatty acids with Sources or fatty acids, therefore, the organic acid sources or varying carbon chain lengths, then the polyamidoamine can organic acids can be reacted with one or more polyamines to favor collecting particles having a particle size of about 75um produce or otherwise form the one or more polyamidoamines. to about 150 lum. Illustrative organic acid sources or organic acids can include, 0078. In one or more examples, a hydrophilic-lipophilic but are not limited to, glycolic acid, lactic acid, pyruvic acid, balance (HLB) value of the polyamidoamine can be tuned or formic acid, acetic acid, propionic acid, butyric acid, Valeric otherwise selected, at least in part, by varying the carbon acid, oxalic acid, malonic acid, caproic acid, enanthic acid, chain lengths of the RandR hydrocarbyl groups. Polyami caprylic acid, pelargonic acid, capric acid, undecylic acid, doamines having an intermediate HLB value can be produced lauric acid, isomers thereof, hydrates thereof, salts thereof, which would not be obtained from synthesis with a single complexes thereof, adducts thereof, or any mixture thereof. fatty acid. The HLB value of the polyamidoamine can be 0074. In some specific examples, the polyamines that can determined by the Davies’ Method that assigns a value to be reacted with the fatty acids to produce the polyamidoam different functional groups based on polarity and also uses the ines can be or include diethylenetriamine, triethylenetetra following equation: mine, tetraethylenepentamine, or a mixture thereof, and the fatty acids that can be reacted with the polyamines to produce the polyamidoamines can be or include tall oil fatty acids, 0079 where “H” is the value assigned to each specific lauric acid, Stearic acid, isostearic acid, naphthenic acid, iso hydrophilic functional group, "m is the numerical amount of mers thereof, or any mixture thereof. the specified hydrophilic functional groups, “H” is the value 0075. The polyamidoamine can have a total amine value assigned to each specific lipophilic group, and “n” is the (TAV) of about 50, about 60, about 70, about 80, about 90, numerical amount of the specified lipophilic groups. For about 100, about 110, about 120, about 130, about 140, about example, H., can have an amine value of 10 and an amide 150, about 160, about 170, about 180, about 190, about 200, value of 4, and H can have a CH, value of -0.475. The HLB about 210, about 220, about 230, about 240, about 250, about value and the equation for determining the HLB value by the 260, about 270, about 280, about 290, or about 300, based on Davies’ Method are discussed and described in, for example, mg of KOH perg of polyamidoamine. In some examples, the Davies, J. T., "A Quantitative Kinetic Theory of Emulsion polyamidoamine can have a TAV of about 50 to about 300, Type, I. Physical Chemistry of the Emulsifying Agent. Gas/ about 50 to about 200, about 50 to about 100, about 80 to Liquid and Liquid/Liquid Interfaces, Proceedings of the 2" about 120, about 180 to about 300, about 200 to about 300, International Congress Surface Activity, Butterworths, Lon about 220 to about 280, about 230 to about 270, about 240 to don, pgs. 426-438, 1957. about 260, or about 245 to about 255, based on mg of KOH 0080. In one or more examples, the polyamidoamines can per g of polyamidoamine. generally have an HLB of about 2, about 5, about 8, about 10, 0076. In one or more examples, a critical micelle concen about 12, about 15, about 18, about 20, about 25, about 30, tration (CMG) of a polyamidoamine (having any one of the about 35, about 40, about 45, or about 50, based on the chemical formulas (A)-(M)) can be increased where R' and Davies’ Method for hydrophilic-lipophilic balance. For Rare or include different hydrocarbyl groups, relative to a example, the polyamidoamines can generally have an HLB of polyamidoamine, having the same chemical formula except about 2 to about 50, about 5 to about 50, about 5 to about 20, where R' and Rare or include the same hydrocarbyl group. about 5 to about 15, about 10 to about 25, about 10 to about Disorder in chemical structure, such as branching or irregu 20, about 20 to about 35, about 20 to about 30, about 25 to larities in the R' and Rhydrocarbyl groups, can inhibit for about 35, about 25 to about 30, or about 30 to about 35, based mation of micelles in the aqueous solutions or slurries. In on the Davies Method for hydrophilic-lipophilic balance. Some examples, preventing or minimizing micelle formation I0081. In some examples, the polyamidoamines can be or can provide more available polyamidoamine for adhering to include one or more amidoamines having chemical formula US 2016/0114338 A1 Apr. 28, 2016

(A), where n can be 2 and the polyamidoamine can have an doamine having any one of the chemical formulas (A)-(D) HLB of about 7.5 to about 12, n can be 3 and the polyami where n is 2 and a second polyamidoamine having any one of doamine can have an HLB of about 16.5 to about 21, or n can the chemical formulas (A)-(D) where n is 3, 4, or 5. In another be 4 and the polyamidoamine can have an HLB of about 25.5 example, the mixture of polyamidoamines can include a first to about 30, based on the Davies’ Method for hydrophilic polyamidoamine having any one of the chemical formulas lipophilic balance. In other examples, the polyamidoamines (A)-(D) where n is 2, a second polyamidoamine having any can be or include one or more amidoamines having chemical one of the chemical formulas (A)-(D) where n is 3, and a third formula (A), where n can be 2 and the polyamidoamine can polyamidoamine having any one of the chemical formulas have an HLB of about 8.5 to about 11, in can be 3 and the (A)-(D) where n is 4 or 5. In some examples, the mixture of polyamidoamine can have an HLB of about 17.5 to about 20, polyamidoamines can be or include a mixture of polyethyl or n can be 4 and the polyamidoamine can have an HLB of enepolyamidoamines, such as, but is not limited to, the poly about 26 to about 29, based on the Davies Method for hydro ethylenepolyamidoamines having the chemical formulas (E), philic-lipophilic balance. In other examples, the polyami (F), and (G). For example, the mixture of polyethylenepolya doamines can be or include one or more amidoamines having midoamines can include a first polyethylenepolyamidoamine chemical formula (A), where n can be 2 and the polyami having the chemical formula (E) and a second polyethylene doamine can have an HLB of about 9 to about 10.5, in can be polyamidoamine having the chemical formula (F) or (G). In 3 and the polyamidoamine can have an HLB of about 18 to another example, the mixture of polyethylenepolyamidoam about 19.5, or n can be 4 and the polyamidoamine can have an ines can include a first polyethylenepolyamidoamine having HLB of about 26.5 to about 28.5 or about 27 to about 28, the chemical formula (E), a second polyethylenepolyami based on the Davies Method for hydrophilic-lipophilic bal doamine having the chemical formula (F), and a third poly aCC. ethylenepolyamidoamine having the chemical formula (G). 0082 In some examples, a mixture of two, three, or more I0085. In one or more examples, an aqueous mixture can polyamidoamines having any one of the chemical formulas include one or more ores, one or more polyamidoamines, (A)-(D) can have an HLB of about 7.5 to about 30 and can optionally acetic acid and/or other organic acid, and water, include one or more polyamidoamines having any one of the where the polyamidoamines can be or include one or more chemical formulas (A)-(D) where n is 2, one or more polya amidoamines having any one of the chemical formulas (A)- midoamines having any one of the chemical formulas (A)-(D) (M). In some examples, an aqueous mixture of an ore can where n is 3, one or more polyamidoamines having any one of include one or more phosphorous ores, one or more polyami the chemical formulas (A)-(D) where n is 4 or 5, or any doamines, optionally acetic acid and/or other organic acid, mixture thereof. In other examples, a mixture of two, three, or and water, where the polyamidoamines can be or include one more polyethylenepolyamidoamines can have an HLB of or more amidoamines having any one of the chemical formu about 7.5 to about 30 and can include one or more polyeth las (A)-(M). In some examples, an aqueous mixture of an ore ylenepolyamidoamines having the chemical formula (E), one can include one or more phosphorous ores, one or more or more polyethylenepolyamidoamines having the chemical polyamidoamines, optionally acetic acid and/or other organic formula (F), one or more polyethylenepolyamidoamines hav acid, and water, where the polyamidoamines can be or ing the chemical formula (G), or any mixture thereof. include one or more amidoamines having any one of the 0083. In one or more examples, the polyamidoamines can chemical formulas (A)-(M). be or include a mixture of three or more polyamidoamines I0086. In some examples, the polyamidoamines can be or having any one of the chemical formulas (A)-(M), where the include one or more amidoamines having chemical formula mixture can include at least a first diamidoamine, a second (A), where R' and R can be different and can be selected diamidoamine, and a third diamidoamine. The first diami from a saturated or unsaturated, Substituted or unsubstituted, doamine can have R' and R as the same hydrocarbyl group, linear or branched, cyclic, heterocyclic, or aromatic hydro a second diamidoamine can have R' and R as the same carbyl group, R and R' can independently be hydrogen or a hydrocarbyl group, but different hydrocarbyl groups as the saturated or unsaturated, Substituted or unsubstituted, linear first diamidoamine, and the third diamidoamine can have R' or branched, cyclic, heterocyclic, or aromatic hydrocarbyl and R as different hydrocarbyl groups, such that the R' group, each m can be an integer of 1 to 5, and n can be an hydrocarbyl group in the third diamidoamine is the same as integer of 2 to 8. In other examples, the polyamidoamines can the R' and Rhydrocarbyl groups in the first diamidoamine be or include one or more amidoamines having the chemical and the Rhydrocarbyl group in the third diamidoamine is the formula (B), where R' and R can be different and can be same as the R' and Rhydrocarbyl groups in the second Selected from CoHo. CoH 17, CoH is, CoH is, CH2CH2. diamidoamine. For example, the R' and R hydrocarbyl Cls Hss, Cls H31, C1s H29, C17Hss, C17Hss, C17H31, C17H29. groups in the first diamidoamine and the R' hydrocarbyl C19H7, C19Hss, C19Hss, C19H1, or C19H29, and n can be an group in the third diamidoamine can be same hydrocarbyl integer of 2, 3, or 4. group, and the R' and Rhydrocarbyl groups in the second I0087. In one example, the polyamidoamine can be or diamidoamine and the Rhydrocarbyl group in the third dia include one or more products formed by reacting a polyamine midoamine can be same hydrocarbyl group, but different than and a fatty acid, where the polyamine can be or include the R' and Rhydrocarbyl groups in the first diamidoamine diethylenetriamine, triethylenetetramine, tetraethylenepen and the R' hydrocarbyl group in the third diamidoamine. tamine, pentaethylenehexamine, or any mixture thereof, and 0084. In one or more examples, the polyamidoamines can the fatty acid can be or include tall oil fatty acids, coconut oil be or include a mixture of two, three, or more polyamidoam fatty acids, lauric acid, Stearic acid, isostearic acid, naph ines having any one of the chemical formulas (A)-(M), where thenic acid, oleic acid, linoleic acid, linolenic acid, palmitic the mixture can include polyamidoamines of different acid, isomers thereof, or any mixture thereof. In some specific amounts of amido groups and/or amine groups. For example, examples, the polyamine can be or include one or more dieth the mixture of polyamidoamines can include a first polyami ylenetriamine, triethylenetetramine, tetraethylenepentamine, US 2016/0114338 A1 Apr. 28, 2016

or any mixture thereof, and the fatty acid can be or include one phate material from the aqueous mixture. Generally, in some or more tall oil fatty acids, lauric acid, Stearic acid, isostearic examples, silicates, silicon oxides, and/or other gangue mate acid, naphthenic acid, isomers thereof, or any mixture rials can be floated away from the aqueous mixture or slurry thereof. In other examples, a mixture of fatty acids can be providing the beneficiation or purification of the phosphate used to make or form the polyamidoamines. The mixture of material. The polyamidoamines can be or include one or more fatty acids can be or include at least 2, 3, 4, 5, 6, 7, 8, 9, or 10 amidoamines having any one of the chemical formulas (A)- fatty acids selected from lauric acid, myristic acid, palmitic (M). In some examples, the method can include the use of the acid, capric acid, caprylic acid, oleic acid, Stearic acid, palmi amidoamines having any one of the chemical formulas (A)- toleic acid, linoleic acid, caproic acid, arachidic acid, isomers (M), where R' and R can be different and can be selected thereof, or any mixture thereof. from a saturated or unsaturated, Substituted or unsubstituted, 0088. In another example, one or more organic acids can linear or branched, cyclic, heterocyclic, or aromatic hydro be combined with one or more polyamidoamines to make, carbyl group. The organic acid can be or include acetic acid, form, or otherwise produce the composition and/or the aque e.g., glacial acetic acid. ous mixture. In some examples, the one or more organic acids 0091. In some examples, the purification or beneficiation can be combined with the polyamidoamine and Subsequently of the ore such as a phosphorous ore or other phosphorous added with other components to make, form, or otherwise containing material can include the use of the amidoamines produce the composition and/or the aqueous mixture. In other having the chemical formula (A), where R' and R can be examples, the one or more organic acids and the polyami different and can be selected from a saturated or unsaturated, doamine can independently be combined with one or more substituted or unsubstituted, linear or branched, cyclic, het components to make, form, or otherwise produce the compo erocyclic, or aromatic hydrocarbyl group, RandR' can inde sition and/or the aqueous mixture. When the one or more pendently be hydrogen or a saturated or unsaturated, Substi organic acids and the polyamidoamine are independently tuted or unsubstituted, linear or branched, cyclic, combined with one or more components, the organic acid and heterocyclic, or aromatic hydrocarbyl group, each m can be the polyamidoamine can be combined at the same time, the an integer of 1 to 5, and n can be an integer of 2 to 8. In some organic acid can be added before the polyamidoamine, or the examples, the method can include the use of the amidoamines polyamidoamine can be added before the organic acid. Illus having the chemical formula (A), where R' and R can be a trative organic acid sources or organic acids can include gly C10 to C18 chain having 0 to 3 unsaturated bonds, Rand R' colic acid, lactic acid, pyruvic acid, formic acid, acetic acid, can be hydrogen, each m can be an integer of 2 or 3, and n can propionic acid, butyric acid, Valeric acid, oxalic acid, malonic be an integer of 2, 3, or 4. acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, isomers thereof, 0092. In some examples, the purification or beneficiation hydrates thereof, salts thereof, complexes thereof, adducts of the ore such as a phosphorous containing material can include the use of the amidoamines having the chemical thereof, or any mixture thereof. formula (B), where R' and R can be different and can be 0089. In some examples, one or more ores such as phos selected from a saturated or unsaturated, Substituted or unsub phorous containing materials can be purified by agitating, stituted, linear or branched, cyclic, heterocyclic, or aromatic blending, mixing, or otherwise combining the ore, one or hydrocarbyl group, RandR' can independently behydrogen more polyamidoamines, and water to produce an aqueous or a saturated or unsaturated, Substituted or unsubstituted, mixture and recovering a purified product therefrom. In some linear or branched, cyclic, heterocyclic, or aromatic hydro example, one or more organic acids, e.g., acetic acid, can also carbyl group, and n can be an integer of 2 to 8. be combined with the ore, the polyamidoamine, and water to produce the aqueous mixture. In some examples, any or all of 0093. The polyamidoamines can be produced by reacting the ore, the polyamidoamine, organic acid, and water can be one or more polyamines and one or more fatty acids, where combined with one another, in any order, to produce the the polyamines can be or include diethylenetriamine, trieth aqueous mixture. In other examples, the ore, the polyami ylenetetramine, tetraethylenepentamine, pentaethylenehex doamines, the organic acid, and water can be separately com amine, or any mixture thereof, and the fatty acids can be or bined with one another, in any order, to produce the aqueous include tall oil fatty acids, lauric acid, Stearic acid, isostearic mixture. In other examples, the polyamidoamine and the acid, naphthenic acid, oleic acid, linoleic acid, linolenic acid, organic acid can be combined with one another to produce a palmitic acid, isomers thereof, or any mixture thereof. first mixture and the ore and water can be combined to pro 0094. In some examples, the purification or beneficiation duce a second mixture and the first and second mixtures can of a phosphorous containing material can include combining be combined to produce the aqueous mixture. In some the organic acid, e.g., acetic acid, and the polyamidoamine to examples, the one or more polyamidoamines and organic acid produce a cationic collector and combining the cationic col can be combined with one another to produce the composi lector and the phosphorous ore to produce the aqueous mix tion, and Subsequently, the composition can be combined ture. The acetic acid can be glacial acetic acid. The cationic with the ore and water to produce the aqueous mixture. In collector can include about 10 wt % to about 60 wt % of the other examples, the one or more polyamidoamines, organic acetic acid and about 40 wt % to about 95 wt % of the acid, and water can be combined with one another to produce polyamidoamine, based on the combined weight of the polya the composition, and Subsequently, the composition can be midoamine and the acetic acid. The cationic collector can also added or combined with the ore material and if desired addi include about 2 wt % to about 50 wt % of water, based on the tional water to produce the aqueous mixture. combined weight of the polyamidoamine, the acetic acid, and 0090. In some examples, a phosphorous containing mate the water. The composition can include about 10 wt % to rial can be purified by combining one or more phosphorous about 60 wt % of acetic acid and about 40 wt % to about 95 wt ores, the polyamidoamine, an organic acid, and water to pro % of the polyamidoamine, based on a combined weight of the duce an aqueous mixture and collecting or recovering a phos polyamidoamine and the acetic acid. The composition can US 2016/0114338 A1 Apr. 28, 2016

also include about 2 wt % to about 50 wt % of water, based on %, about 98 wt %, about 98.5 wt %, about 99 wt %, about 99.3 the combined weight of the polyamidoamine, the acetic acid, wt %, or about 99.5 wt %, based on the combined weight of and the water. the polyamidoamine and the organic acid, e.g., acetic acid. In 0095. The aqueous mixture can also be contacted with a Some examples, the amount of the polyamidoamine in the gas, e.g., air. For example, the aqueous mixture can be by composition or the cationic collector can be about 20 wt % to passing air bubbles or other gas bubbles through the aqueous about 99 wt %, about 30 wt % to about 98 wt %, about 30 wit mixture, mechanically stirring, e.g., impeller, paddle, and/or % to about 95 wt %, about 30 wt % to about 90 wt %, about stirrer, shaking; directing sound waves, e.g., ultrasonic Sound 40 wt % to about 99 wt %, about 40 wt % to about 95 wt %, waves, into the aqueous mixture, or otherwise moving the about 50 wt % to about 98 wt %, or about 50 wt % to about 95 aqueous mixture, or any combination thereof. The aqueous wt %, based on the combined weight of the polyamidoamine mixture can be an aqueous solution, slurry, Suspension, dis and the organic acid. In one or more examples, the organic persion, or the like. acid can be or include acetic acid in the cationic collector. 0096. The cationic collectors containing the polyami 0099. The amount of the organic acid, e.g., acetic acid in doamines and the purification or beneficiation methods that the composition or the cationic collector can be about 5 wt %, use the cationic collectors can be used to recover, collect, or about 10 wt %, about 15 wt %, about 20 wt %, about 25 wt %, otherwise purify one or more materials from less pure mix about 30 wt %, about 35 wt %, about 40 wt %, about 45 wt %, tures, such as an ores. The cationic collectors can be used in about 50 wt %, about 55 wt %, about 60 wt %, about 65 wt %, froth flotation processes for the beneficiation of a wide variety about 70 wt %, about 75 wt %, about 80 wt %, about 85 wt %, of ores. The ore can generally be or include an aggregate of or about 90 wt %, based on the combined weight of the minerals and gangue from which one or more metals and/or polyamidoamine and the organic acid. In some examples, the oxides thereof can be separated or extracted. Illustrative ores amount of the organic acid in the composition or the cationic that can be purified can be or include, but are not limited to, collector can be about 5 wt % to about 90 wt %, about 5 wt % minerals, elements, and/or metals. Illustrative metals can be to about 80 wt %, about 5 wt % to about 70 wt %, about 5 wt or include, but are not limited to, phosphorous, e.g., phos % to about 60 wt %, about 5 wt % to about 50 wt %, about 5 phate or other phosphorous oxides, iron, copper, aluminum, wt % to about 40 wt %, about 5 wt % to about 30 wt %, about nickel, gold, silver, platinum, palladium, titanium, chro 5 wt % to about 20 wt %, about 10 wt % to about 90 wt %, mium, molybdenum, tungsten, manganese, magnesium, lead, about 10 wt % to about 80 wt %, about 10 wt % to about 70 wit Zinc, potassium, e.g., potash, Sodium, calcium, graphite, ura %, about 10 wt % to about 60 wt %, about 10 wt % to about nium, cerium, dysprosium, erbium, europium, gadolinium, 50 wt %, about 10 wt % to about 40 wt %, about 10 wt % to holmium, lanthanum, lutetium, neodymium, praseodymium, about 30 wt %, about 10 wt % to about 20 wt %, about 20 wit promethium, Samarium, Scandium, terbium, thulium, ytter % to about 90 wt %, about 20 wt % to about 80 wt %, about bium, yttrium, potash, feldspar, bauxite, other precious met 20 wt % to about 70 wt %, about 20 wt % to about 60 wt %, als thereof, oxides thereof, ores thereof, or any mixture about 20 wt % to about 50 wt %, or about 20 wt % to about 40 thereof. In one or more examples, the ore, such as a crude wt %, based on the combined weight of the polyamidoamine mineral ore to be beneficiated and produce a purified ore or and the organic acid. material, can be or include, but is not limited to, a phospho 0100. In one specific example, the composition or the cat rous ore, an iron ore, an aluminum ore, a potassium ore, a ionic collector can include about 10 wt % to about 60 wt % of Sodium ore, a calcium ore, potash, feldspar, bauxite, any the organic acid, e.g., acetic acid, and about 40 wt % to about mixture thereof. The raw materials to be purified and recov 90 wt % of the polyamidoamine, based on the combined ered generally contains or includes gangue. The gangue can weight of the polyamidoamine and the organic acid. In be or include one or more silicates, sand, quartz, clay, rocks, another specific example, the composition or the cationic other materials, or any mixture thereof. The cationic collec collector can include about 20 wt % to about 50 wt % of the tors can be selective toward the gangue, and especially selec organic acid and about 50 wt % to about 80 wt % of the tive toward silicates, sand, quartz, and other silicon oxide polyamidoamine, based on the combined weight of the polya materials. midoamine and the organic acid. In another specific example, 0097. In one or more examples, the cationic collector con the composition or the cationic collector can include about 40 taining one or more polyamidoamines and organic acid, e.g., wt % to about 60 wt % of the organic acid and about 60 wt % acetic acid, can be used in froth flotation processes for the to about 40 wt % of the polyamidoamine, based on the com beneficiation of phosphorous containing materials, such as bined weight of the polyamidoamine and the organic acid. In phosphate. The phosphorous or phosphate containing ores, another specific example, the composition or the cationic e.g., rocks, minerals, or other materials, as well as the recov collector can include about 10 wt % to about 45 wt % of the ered or collected purified ore can include one or more tribasic organic acid and about 55 wt % to about 90 wt % of the phosphate salts. The tribasic phosphate salts can include alka polyamidoamine, based on the combined weight of the polya line earth metals, alkali metals, adducts thereof, complexed midoamine and the organic acid. salts thereof, hydrates thereof, or mixtures thereof. For 0101. In another example, the amount of the polyami example, the phosphorous ore or the phosphate material can doamine in the composition or the cationic collector can be include calcium phosphate. about 5 wt %, about 10 wt %, about 20 wt %, about 30 wt %, 0098. In one or more examples, the amount of the polya about 40 wt %, about 50 wt %, about 55 wt %, about 60 wt %, midoamine in the composition or the cationic collector can be about 65 wt %, about 70 wt %, about 75 wt %, about 80 wt %, about 20 wt %, about 30 wt %, about 40 wt %, about 50 wt %, about 85 wt %, about 90 wt %, about 91 wt %, about 92 wt %, about 55 wt %, about 60 wt %, about 65 wt %, about 70 wt %, about 93 wt %, about 94 wt %, about 95 wt %, about 96 wt %, about 75 wt %, about 80 wt %, about 85 wt %, about 90 wt %, about 97 wt %, about 97.5 wt %, about 98 wt %, about 98.5 wt about 91 wt %, about 92 wt %, about 93 wt %, about 94 wt %, %, about 99 wt %, about 99.3 wt %, or about 99.5 wt %, based about 95 wt %, about 96 wt %, about 97 wt %, about 97.5 wt on the combined weight of the polyamidoamine, the organic US 2016/0114338 A1 Apr. 28, 2016

acid, e.g., acetic acid, and the water. In some examples, the or about 20 wt % to about 40 wt %, based on the combined amount of the polyamidoamine in the composition or the weight of the polyamidoamine, the organic acid, and the cationic collector can be about 5 wt % to about 99 wt %, about Water. 10 wt % to about 98 wt %, about 20 wt % to about 99 wt %, 0104. In one specific example, the composition or the cat about 30 wt % to about 98 wt %, about 30 wt % to about 95 wt ionic collector can include about 2 wt % to about 50 wt % of %, about 30 wt % to about 90 wt %, about 40 wt % to about the organic acid, e.g., acetic acid, about 2 wt % to about 50 wit 99 wt %, about 40 wt % to about 95 wt %, about 50 wt % to % of water, and about 30 wt % to about 95 wt % of the about 98 wt %, or about 50 wt % to about 95 wt %, based on polyamidoamine, based on the combined weight of the polya the combined weight of the polyamidoamine, the organic midoamine, the organic acid, and the water. In another spe acid, and the water. In one or more examples, the organic acid cific example, the composition or the cationic collector can can be or include acetic acid in the cationic collector. include about 5 wt % to about 45 wt % of the organic acid, 0102 The amount of the organic acid, e.g., acetic acid, in about 5 wt % to about 45 wt % of water, and about 40 wt % to the composition or the cationic collector can be about 1 wt %, about 90 wt % of the polyamidoamine, based on the com about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %, about bined weight of the polyamidoamine, the organic acid, and 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %, about 10 the water. In another specific example, the composition or the wt %, about 12 wt %, about 15 wt %, about 20 wt %, about 25 cationic collector can include about 10 wt % to about 40 wt % wt %, about 30 wt %, about 35 wt %, about 40 wt %, about 45 of the organic acid, about 10 wt % to about 40 wt % of water, wt %, about 50 wt %, about 55 wt %, about 60 wt %, about 65 and about 40 wt % to about 90 wt % of the polyamidoamine, wt %, about 70 wt %, about 75 wt %, about 80 wt %, about 85 based on the combined weight of the polyamidoamine, the wt %, or about 90 wt %, based on the combined weight of the organic acid, and the water. In another specific example, the polyamidoamine, the organic acid, and the water. In some composition or the cationic collector can include about 20 wt examples, the amount of the organic acid in the composition % to about 60 wt % of the organic acid, about 20 wt % to about or the cationic collector can be about 1 wt % to about 90 wt %, 60 wt % of water, and about 30 wt % to about 80 wt % of the about 2 wt % to about 80 wt %, about 3 wt % to about 70 wit polyamidoamine, based on the combined weight of the polya %, about 4 wt % to about 70 wt %, about 5 wt % to about 70 midoamine, the organic acid, and the water. wt %, about 5 wt % to about 90 wt %, about 5 wt % to about 0105. In one or more examples, the composition or the 80 wt %, about 5 wt % to about 70 wt %, about 5 wt.% to about cationic collector can include one or more polyamidoamines 60 wt %, about 5 wt % to about 50 wt %, about 5 wt.% to about which can be or include one or more polyalkylene polyami 40 wt %, about 5 wt % to about 30 wt %, about 5 wt % to about doamines. Illustrative polyalkylene polyamidoamines can 20 wt %, about 10 wt % to about 90 wt %, about 10 wt % to include, but are not limited to, polyethylene polyamidoam about 80 wt %, about 10 wt % to about 70 wt %, about 10 wit ines, polypropylene polyamidoamines, polybutylene polya % to about 60 wt %, about 10 wt % to about 50 wt %, about midoamines, or any combination thereof. In some examples, 10 wt % to about 40 wt %, about 10 wt % to about 30 wt %, the composition or the cationic collector can include one or about 10 wt % to about 20 wt %, about 20 wt % to about 90 wit more polyamidoamines which can be or include one or more %, about 20 wt % to about 80 wt %, about 20 wt % to about polyethylene polyamidoamines. Illustrative polyethylene 70 wt %, about 20 wt % to about 60 wt %, about 20 wt % to polyamidoamines can include, but are not limited to, poly about 50 wt %, or about 20 wt % to about 40 wt %, based on ethylene diamidoamines, polyethylene triamidoamines, the combined weight of the polyamidoamine, the organic polyethylene polyamidoamines with four or more amido acid, and the water. groups, or any mixture thereof. In some examples, the com 0103) The amount of the water in the composition or the position or the cationic collector can include one or more cationic collector can be about 1 wt %, about 2 wt %, about 3 polyamidoamines which can be or include one or more mix wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 7 wt tures of polyethylene diamidoamines and polyethylene tria %, about 8 wt %, about 9 wt %, about 10 wt %, about 12 wt %, midoamines. about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt %, 0106 The mixture of polyethylene diamidoamines and about 35 wt %, about 40 wt %, about 45 wt %, about 50 wt %, polyethylene triamidoamines can include about 0.5 mol %, about 55 wt %, about 60 wt %, about 65 wt %, about 70 wt %, about 1 mol%, about 2 mol%, about 3 mol%, about 4 mol%, about 75 wt %, about 80 wt %, about 85 wt %, or about 90 wit about 5 mol%, about 6 mol%, about 7 mol%, about 8 mol%, %, based on the combined weight of the polyamidoamine, the about 9 mol%, about 10 mol%, about 11 mol%, about 12 mol organic acid, e.g., acetic acid, and the water. In some %, about 13 mol %, about 14 mol %, about 15 mol %, about examples, the amount of the water in the composition or the 16 mol%, about 17 mol%, about 18 mol%, about 19 mol%, cationic collector can be about 1 wt % to about 90 wt %, about about 20 mol %, about 25 mol %, about 30 mol %, about 35 2 wt % to about 80 wt %, about 3 wt % to about 70 wt %, about mol %, about 40 mol %, about 45 mol %, about 50 mol %, 4 wt % to about 70 wt %, about 5 wt % to about 70 wt %, about about 55 mol %, about 60 mol %, about 65 mol %, about 70 5 wt % to about 90 wt %, about 5 wt % to about 80 wt %, about mol %, about 75 mol %, about 80 mol %, about 81 mol %, 5 wt % to about 70 wt %, about 5 wt % to about 60 wt %, about about 82 mol %, about 83 mol %, about 84 mol %, about 85 5 wt % to about 50 wt %, about 5 wt % to about 40 wt %, about mol %, about 86 mol %, about 87 mol %, about 88 mol %, 5 wt % to about 30 wt %, about 5 wt % to about 20 wt %, about about 89 mol %, about 91 mol %, about 92 mol %, about 93 10 wt % to about 90 wt %, about 10 wt % to about 80 wt %, mol %, about 94 mol %, about 95 mol %, about 96 mol %, about 10 wt % to about 70 wt %, about 10 wt % to about 60 wit about 97 mol %, about 98 mol%, about 99 mol %, about 99.1 %, about 10 wt % to about 50 wt %, about 10 wt % to about mol %, about 99.2 mol %, about 99.3 mol %, about 99.4 mol 40 wt %, about 10 wt % to about 30 wt %, about 10 wt % to %, about 99.5 mol %, about 99.6 mol %, about 99.7 mol %, about 20 wt %, about 20 wt % to about 90 wt %, about 20 wit about 99.8 mol %, or about 99.9 mol % of the polyethylene % to about 80 wt %, about 20 wt % to about 70 wt %, about diamidoamines, based on the combined moles of the polyeth 20 wt % to about 60 wt %, about 20 wt % to about 50 wt %, ylene diamidoamines and the polyethylene triamidoamines. US 2016/0114338 A1 Apr. 28, 2016

For example, the mixture of polyethylene diamidoamines and % of the polyethylene triamidoamines, based on the com polyethylene triamidoamines can include about 5 mol % to bined moles of the polyethylene diamidoamines and the poly about 99.5 mol %, about 10 mol % to about 99 mol %, about ethylene triamidoamines. 20 mol% to about 95 mol %, about 30 mol% to about 95 mol 0108. In some examples, the mixtures of polyethylene %, about 40 mol % to about 95 mol %, about 50 mol % to diamidoamines and polyethylene triamidoamines can about 95 mol%, about 60 mol% to about 95 mol%, about 70 include about 70 mol % to about 99.5 mol % of the polyeth mol % to about 95 mol%, about 80 mol% to about 95 mol%, ylene triamidoamines and about 0.5 mol% to about 30 mol% about 90 mol % to about 95 mol %, about 60 mol % to about of the polyethylene triamidoamines, based on the combined 90 mol %, about 70 mol % to about 90 mol %, about 80 mol weight of the polyethylene diamidoamines and the polyeth % to about 90 mol %, about 85 mol % to about 99.5 mol %, ylene triamidoamines. In other examples, the mixtures of about 86 mol% to about 99.5 mol%, about 87 mol% to about polyethylene diamidoamines and polyethylene triamidoam 99.5 mol %, about 88 mol % to about 99.5 mol %, about 89 ines can include about 80 mol % to about 99.5 mol % of the mol% to about 99.5 mol%, about 90 mol% to about 99.5 mol polyethylene triamidoamines and about 0.5 mol % to about 20 mol % of the polyethylene triamidoamines, based on the %, about 91 mol % to about 99.5 mol %, about 92 mol % to combined weight of the polyethylene diamidoamines and the about 99.5 mol%, about 93 mol% to about 99.5 mol%, about polyethylene triamidoamines. In other examples, the mix 94 mol% to about 99.5 mol %, about 95 mol% to about 99.5 tures of polyethylene diamidoamines and polyethylene tria mol %, about 96 mol% to about 99.5 mol%, about 97 mol% midoamines can include about 90 mol% to about 99.5 mol% to about 99.5 mol %, about 98 mol% to about 99.5 mol %, or of the polyethylene triamidoamines and about 0.5 mol % to about 99 mol % to about 99.5 mol % of the polyethylene about 10 mol% of the polyethylene triamidoamines, based on diamidoamines, based on the combined moles of the polyeth the combined weight of the polyethylene diamidoamines and ylene diamidoamines and the polyethylene triamidoamines. the polyethylene triamidoamines. 0107 The mixture of polyethylene diamidoamines and 0109. In one or more examples, the composition or the polyethylene triamidoamines can include about 0.1 mol %, cationic collector can include one, two, three, or more polya about 0.2 mol%, about 0.3 mol%, about 0.4 mol%, about 0.5 midoaminates and have a free flowing Viscosity. The compo mol %, about 0.6 mol %, about 0.7 mol %, about 0.8 mol %, sition or the cationic collector can have a viscosity of about 10 about 0.9 mol%, about 1 mol%, about 2 mol%, about 3 mol cP, about 20 cP, about 30 cP, about 40 cP, about 50 cP. about %, about 4 mol%, about 5 mol%, about 6 mol%, about 7 mol 60 cP, about 70 cP, about 80 cP, about 90 cP, about 100 cP. %, about 8 mol %, about 9 mol %, about 10 mol %, about 11 about 110 cP, about 120 cP, about 130 cP. about 140 cP. about mol %, about 12 mol %, about 13 mol %, about 14 mol %, 150 cP, about 160 cP. about 170 cP, about 180 cP. about 190 about 15 mol %, about 16 mol %, about 17 mol %, about 18 cP, about 200 cP, about 210 cP, about 220 cP, about 230 cP. mol %, about 19 mol %, about 20 mol %, about 25 mol %, about 240 cB, about 250 cP, about 260 cP. about 270 cP, about about 30 mol %, about 35 mol %, about 40 mol %, about 45 280 cP. about 290 cP, about 300 cP to about 350cP. about 400 mol %, about 50 mol %, about 55 mol %, about 60 mol %, cP, about 450 cP, about 500 cP, about 600 cP, about 700 cP, or about 65 mol %, about 70 mol %, about 75 mol %, about 80 about 800 cp at a temperature of about 25°C. For example, mol %, about 85 mol %, about 90 mol %, or about 95 mol % the composition or the cationic collector can have a viscosity of the polyethylene triamidoamines, based on the combined of about 10 cP to about 500 cP, about 10 cP to about 450 cP. moles of the polyethylene diamidoamines and the polyethyl about 10 cP to about 400 cP. about 10 cP to about 350 cP. ene triamidoamines. For example, the mixture of polyethyl about 10 cP to about 300 cP. about 10 cP to about 250 cP. ene diamidoamines and polyethylene triamidoamines can about 10 cP to about 200 cP. about 10 cP to about 150 cP. include about 0.5 mol% to about 95 mol%, about 1 mol% to about 10 cP to about 125 cP. about 10 cP to about 100 cP. about 90 mol %, about 1 mol % to about 80 mol %, about 1 about 10 cp to about 80 cP, about 30 cP to about 500cP, about mol % to about 70 mol %, about 1 mol% to about 60 mol %, 30 cP to about 450 cP, about 30 cP to about 400 cP, about 30 about 1 mol % to about 50 mol%, about 1 mol% to about 40 cP to about 350 cP, about 30 cP to about 300 cP. about 30 cP mol %, about 1 mol % to about 30 mol %, about 1 mol % to to about 250 cP, about 30 cP to about 200 cP, about 30 cp to about 20 mol %, about 1 mol % to about 10 mol %, about 5 about 150 cP, about 30 cp to about 125 cP, about 30 cP to mol % to about 90 mol %, about 5 mol% to about 80 mol %, about 100 cP, about 30 cP to about 80 cP, about 50 cP to about about 5 mol % to about 70 mol %, about 5 mol% to about 60 500 cP, about 50 cP to about 450 cP, about 50 cP to about 400 mol %, about 5 mol % to about 50 mol %, about 5 mol % to cP. about 50 cP to about 350 cP, about 50 cP to about 300 cP. about 40 mol %, about 5 mol % to about 30 mol %, about 5 about 50 cP to about 250 cP. about 50 cP to about 200 cP. mol % to about 20 mol %, about 5 mol% to about 10 mol %, about 50 cP to about 150 cP. about 50 cP to about 125 cP. about 0.5 mol% to about 30 mol%, about 0.5 mol% to about about 50 cP to about 100 cP, or about 50 cP to about 80 cPat 25 mol %, about 0.5 mol% to about 20 mol %, about 0.5 mol a temperature of about 25°C. In some examples, the compo % to about 19 mol %, about 0.5 mol % to about 18 mol %, sition or the cationic collector can have a viscosity of about 10 about 0.5 mol% to about 17 mol%, about 0.5 mol% to about cP to less than 500 cP, about 10 cP to less than 400 cP, about 16 mol%, about 0.5 mol% to about 15 mol %, about 0.5 mol 10 cp to less than 300 cP, about 10cP to less than 250cP, about % to about 14 mol %, about 0.5 mol % to about 13 mol %, 10 cp to less than 200 cP, about 10cP to less than 150 cP, about about 0.5 mol% to about 12 mol%, about 0.5 mol% to about 10 cp to less than 125 cP, about 10cP to less than 100 cP, about 11 mol%, about 0.5 mol% to about 10 mol %, about 0.5 mol 10 cP to less than 80 cP, about 50 cP to less than 500cP, about % to about 9 mol%, about 0.5 mol% to about 8 mol%, about 50cP to less than 400 cP, about 50cP to less than 300 cP, about 0.5 mol % to about 7 mol %, about 0.5 mol % to about 6 mol 50cP to less than 250cP, about 50cP to less than 200 cP, about %, about 0.5 mol % to about 5 mol %, about 0.5 mol % to 50cP to less than 150 cP, about 50cP to less than 125cP, about about 4 mol %, about 0.5 mol % to about 3 mol %, about 0.5 50 cP to less than 100 cp, or about 50 cP to about 80 cp at a mol % to about 2 mol %, or about 0.5 mol % to about 1 mol temperature of about 25°C. In other examples, the composi US 2016/0114338 A1 Apr. 28, 2016

tion or the cationic collector can have a viscosity of about 400 combined weight of the polyamidoamine, the organic acid, cP to about 5,000 cP, about 400 cP to about 4,500 cP. about and the water. In other examples, the when the composition or 400 cP to about 4,000 cP, about 400 cP to about 3,500 cP. the cationic collector includes the organic acid the composi about 400 cP to about 3,000 cP, about 400 cP to about 2,500 tion or the cationic collector can have a viscosity of about 10 cP, about 400 cP to about 2,000 cP, about 400 cP to about cP, about 20 cP, about 30 cP, about 40 cP, about 50 cP. about 1,500 cP, about 400 cP to about 1,250 cP, about 400 cP to 60 cP, about 70 cP, about 80 cP, about 90 cP, about 100 cP. about 1,000 cP. about 400 cP to about 800 cB, about 500 cP to about 110 cP, about 120 cP, about 130 cP. about 140 cP, about about 5,000 cP, about 500 cP to about 4,500 cP. about 500 cP 150 cP, about 160 cP. about 170 cP, about 180 cP. about 190 to about 4,000 cP, about 500 cp to about 3,500 cP, about 500 cP, about 200 cP, about 210 cP, about 220 cP, about 230 cP. cP to about 3,000 cP, about 500 cP to about 2,500 cP. about about 240 cB, about 250 cP, about 260 cP. about 270 cP, about 500 cP to about 2,000 cP, about 500 cP to about 1,500 cB. 280 cP. about 290 cP, about 300 cP to about 350cP. about 400 about 500 cP to about 1,250 cP, about 500 cP to about 1,000 cP, about 450 cP, about 500 cP, about 600 cP, about 700 cP, or cP. about 500 cp to about 800 cP, about 700 cP to about 5,000 about 800 cp at a temperature of about 25° C. when the cP, about 700 cP to about 4,500 cP, about 700 cP to about composition or the cationic collector includes about 20 wt % 4,000 cP, about 700 cP to about 3,500 cP, about 700 cP to to about 60 wt % of the organic acid, about 20 wt % to about about 3,000 cP, about 700 cP to about 2,500 cP. about 700 cP 60 wt % of water, and about 30 wt % to about 80 wt % of the to about 2,000 cP, about 700 cp to about 1,500 cP, about 700 polyamidoamine, based on the combined weight of the polya cP to about 1,250 cP. about 700 cP to about 1,000 cP, or about midoamine, the organic acid, and the water. 700 cF to about 800 cF at a temperature of about 25° C. 0112 The viscosity of the various compositions discussed 0110. The composition or the cationic collector can have a and described herein can be determined using a viscometer at viscosity of about 10 cp about 20 cp, or about 30 cp to about a specified temperature, such as about 25°C. or about 80°C. 40cP, about 50cP. about 60 cP, about 70 cP, about 80 cP, about For example, a viscometer, Model DV-II+, commercially 90 cP, about 100 cP, about 110 cP, about 120 cP, about 130 cP. available from the Brookfield Company, with a small sample about 140 cP. about 150 cP, about 160 cP, about 170 cP, about adapter with, for example, a number 3 spindle, can be used. 180 cP, about 190 cP, about 200 cP, about 210 cP. about 220 The Small sample adapter can allow the sample to be cooled cP, about 230 cP, about 240 cB, about 250 cP, about 260 cP. or heated by the chamberjacket to maintain the temperature about 270 cP, about 280 cP, about 290 cP, or about 300 cPat of the sample surrounding the spindle at a temperature of a temperature of about 80° C. For example, the composition about 25°C. (unless otherwise noted). or the cationic collector can have a viscosity of about 10 cF to 0113. In one or more examples, the amount of the compo about 300 cP, about 10 cp to about 250 cP, about 10 cP to sition or the cationic collector in the aqueous mixture can be about 200 cP, about 10 cp to about 150 cP, about 10 cP to about 0.0005 wt %, about 0.001 wt %, about 0.005 wt %, about 125 cP, about 10 cp to about 100 cP, about 10 cP to about 0.01 wt %, about 0.02 wt %, about 0.03 wt %, about about 80 cP, about 10 cP to about 60 cP, about 10 cP to about 0.04 wt %, about 0.05 wt %, about 0.06 wt %, about 0.07 wt 50 cP, about 20 cP to about 300 cP, about 20 cP to about 250 %, about 0.08 wt %, about 0.09 wt %, about 0.1 wt %, about cP, about 20 cp to about 200 cP, about 20 cP to about 150 cP. 0.11 wt %, about 0.12 wt %, about 0.13 wt %, about 0.14 wit about 20 cP to about 125 cP, about 20 cP to about 100 cP. %, about 0.15 wt %, about 0.16 wt %, about 0.17 wt %, about about 20 cP to about 80 cP, about 20 cP to about 60 cP, about 0.18wt %, about 0.19 wt %, about 0.2 wt %, about 0.25 wt %, 20 cP to about 50 cP, about 30 cP to about 300 cP, about 30 cP about 0.3 wt %, about 0.35 wt %, about 0.4 wt %, about 0.5 wt to about 250 cP, about 30 cP to about 200 cP, about 30 cp to %, about 0.6 wt %, about 0.7 wt %, about 0.8 wt %, about 0.9 about 150 cP, about 30 cp to about 125 cP, about 30 cP to wt %, about 1 wt %, about 1.5 wt %, about 2 wt %, about 2.5 about 100 cP, about 30 cP to about 80 cP, about 30 cP to about wt %, about 3 wt %, about 3.5 wt %, about 4 wt %, about 4.5 60 cB, or about 30 cF to about 50 cB at a temperature of about wt %, about 5 wt %, about 6 wt %, about 7 wt %, about 8 wit 80° C. In some examples, the composition or the cationic %, about 9 wt %, or about 10 wt %, based on the weight of the collector can have a viscosity of about 10 cp to less than 300 ore, e.g., a phosphorous ore. In some examples, the amount of cP, about 10cP to less than 250cP. about 10cP to less than 200 the composition or the cationic collector in the aqueous mix cP, about 10cP to less than 150cP. about 10cP to less than 125 ture can be about 0.001 wt % to about 10 wt %, about 0.005 wt cP, about 10 cP to less than 100 cP, about 10 cP to less than 80 % to about 5 wt %, about 0.005 wt % to about 2 wt %, about cP, about 10 cP to less than 60 cP, or about 10 cP to less than 0.005 wt % to about 1 wt %, about 0.005 wt % to about 0.5 wt 50 cF at a temperature of about 80° C. %, about 0.005 wt % to about 0.1 wt %, about 0.005 wt % to 0111. In other examples, when the composition or the about 0.09 wt %, or about 0.005 wt % to about 0.05 wt %%, cationic collector includes the organic acid the cationic col based on the weight of the ore. In other examples, the amount lector can have a viscosity of about 10 cp about 20 cp about of the composition or the cationic collector in the aqueous 30cP, about 40 cP. about 50 cP, about 60 cP, about 70 cP, about mixture can be greater than 0.001 wt % to about 10 wt %, 80 cP, about 90 cP, about 100 cP, about 110 cB, about 120 cP. greater than 0.005 wt % to about 5 wt %, greater than 0.005 wt about 130 cP. about 140 cB, about 150 cP, about 160 cP, about % to about 2 wt %, greater than 0.005 wt % to about 1 wt %, 170 cP, about 180 cP, about 190 cP, about 200 cP. about 210 greater than 0.005 wt % to about 0.5 wt %, greater than 0.005 cP, about 220 cP, about 230 cP, about 240 cB, about 250 cP. wt % to about 0.1 wt %, greater than 0.005 wt % to about 0.09 about 260 cP. about 270 cP, about 280 cP, about 290 cP, about wt %, or greater than 0.005 wt % to about 0.05 wt %%, based 300 cP to about 350 cP, about 400 cP, about 450 cP, about 500 on the weight of the ore. In other examples, the amount of the cP. about 600 cB. about 700 cB, or about 800 cF at a tempera composition or the cationic collector in the aqueous mixture ture of about 25° C. when the cationic collector includes can be about 0.001 wt % to less than 10 wt %, about 0.005 wt about 2 wt % to about 50 wt % of the organic acid, e.g., acetic % to less than 5 wt %, about 0.005 wt % to less than 2 wt %, acid, about 2 wt % to about 50 wt % of water, and about 30 wt about 0.005 wt % to less than 1 wt %, about 0.005 wt.% to less % to about 95 wt % of the polyamidoamine, based on the than 0.5 wt %, about 0.005 wt % to less than 0.1 wt %, about US 2016/0114338 A1 Apr. 28, 2016

0.005 wt % to less than 0.09 wt %, or about 0.005 wt % to less greater than 0.005 wt % to about 0.1 wt %, greater than 0.005 than 0.05 wt %%, based on the weight of the ore. wt % to about 0.09 wt %, or greater than 0.005 wt % to about 0114. In one or more examples, the amount of the polya 0.05 wt %%, based on the weight of the ore. In some midoamine in the aqueous mixture can be about 0.0001 wt %, examples, the amount of the organic acid in the aqueous about 0.0005 wt %, about 0.001 wt %, about 0.005 wt %, mixture can be about 0.0001 wt % to less than 2 wt %, about about 0.01 wt %, about 0.02 wt %, about 0.03 wt %, about 0.0005 wt % to less than 1 wt %, about 0.001 wt % to less than 0.04 wt %, about 0.05 wt %, about 0.06 wt %, about 0.07 wt 1 wt %, about 0.005 wt % to less than 1 wt %, about 0.005 wt %, about 0.08 wt %, about 0.09 wt %, about 0.1 wt %, about % to less than 0.5 wt %, about 0.005 wt % to less than 0.1 wit 0.11 wt %, about 0.12 wt %, about 0.13 wt %, about 0.14 wit %, about 0.005 wt % to less than 0.09 wt %, or about 0.005 wt %, about 0.15 wt %, about 0.16 wt %, about 0.17 wt %, about % to less than 0.05 wt %%, based on the weight of the ore. In 0.18wt %, about 0.19 wt %, about 0.2 wt %, about 0.25 wt %, one or more examples, the organic acid can be or include about 0.3 wt %, about 0.35 wt %, about 0.4 wt %, about 0.5 wt acetic acid, e.g., glacial acetic acid. %, about 0.6 wt %, about 0.7 wt %, about 0.8 wt %, about 0.9 0116. The aqueous mixtures which can include water, one wt %, about 1 wt %, about 1.5 wt %, about 2 wt %, about 2.5 or more ores such as a phosphorous ore, one or more polya wt %, about 3 wt %, about 3.5 wt %, about 4 wt %, about 4.5 midoamines, and one or more organic acids, e.g., acetic acid, wt %, about 5 wt %%, based on the weight of the ore, e.g., a including aqueous Suspensions, dispersions, slurries, solu phosphorous ore. In some examples, the amount of the polya tions, or mixtures, can be conditioned for a given time period midoamine in the aqueous mixture can be about 0.0001 wt % during and between steps of combining components. Condi to about 2 wt %, about 0.0005 wt % to about 1 wt %, about tioning the aqueous mixture upon the addition of water, one or 0.001 wt % to about 1 wt %, about 0.005 wt % to about 1 wit more ores, one or more polyamidoamines, and one or more %, about 0.005 wt % to about 0.5 wt %, about 0.005 wt % to organic acids, e.g., acetic acid, can facilitate contact between about 0.1 wt %, about 0.005 wt % to about 0.09 wt %, or about the components. Conditioning can include, but is not limited 0.005 wt % to about 0.05 wt %%, based on the weight of the to, agitating the aqueous mixture for a given time period prior ore. In other examples, the amount of the polyamidoamine in to Subjecting the aqueous mixture to separation or collection the aqueous mixture can be greater than 0.0001 wt % to about techniques. For example, the aqueous mixtures can be stirred, 2 wt %, greater than 0.0005 wt % to about 1 wt %, greater than blended, mixed, air or gas bubbled, or otherwise agitated for 0.001 wt % to about 1 wt %, greater than 0.005 wt % to about a time of about 30 seconds, about 1 minute, about 2 minutes, 1 wt %, greater than 0.005 wt % to about 0.5 wt %, greater about 3 minutes, about 4 minutes, about 5 minutes, about 6 than 0.005 wt % to about 0.1 wt %, greater than 0.005 wt % to minutes, about 7 minutes, about 8 minutes, about 9 minutes, about 0.09 wt %, or greater than 0.005 wt % to about 0.05 wt about 10 minutes, about 12 minutes, about 15 minutes, about %%, based on the weight of the ore. In other examples, the 20 minutes, about 30 minutes, about 1 hour, or about 24 hours. amount of the polyamidoamine in the aqueous mixture can be Conditioning the aqueous mixture can also include heating about 0.0001 wt % to less than 2 wt %, about 0.0005 wt % to (or cooling) mixture to a temperature of about 15° C., about less than 1 wt %, about 0.001 wt % to less than 1 wt %, about 20°C., about 25°C., about 30°C., about 35°C., about 60°C., 0.005 wt % to less than 1 wt %, about 0.005 wt % to less than about 80°C., or about 95°C. 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 0117 Conditioning the aqueous mixture can also include 0.05 wt %%, based on the weight of the ore. adjusting the pH values of any of portions of and including the 0115. In one or more examples, the amount of the organic aqueous mixtures. The aqueous mixture containing the ore, acid, e.g., acetic acid, in the aqueous mixture can be about e.g., phosphorous ore, the polyamidoamine, the organic acid, 0.0001 wt %, about 0.0005 wt %, about 0.001 wt %, about e.g., acetic acid, and water can be maintained at or adjusted to 0.005 wt %, about 0.01 wt %, about 0.02 wt %, about 0.03 wit have a pH value of greater than 7, such as about 7.5, about 8, %, about 0.04 wt %, about 0.05 wt %, about 0.06 wt %, about about 8.5, about 9, about 9.5, about 10, about 10.5, about 11, 0.07 wt %, about 0.08 wt %, about 0.09 wt %, about 0.1 wt %, about 11.5, about 12, about 12.5, or about 13. In one or more about 0.11 wt %, about 0.12 wt %, about 0.13 wt %, about examples, the pH value of the aqueous mixture can be or can 0.14 wt %, about 0.15 wt %, about 0.16 wt %, about 0.17 wt be adjusted to about 8.5 to about 10.5, about 9 to about 10, %, about 0.18 wt %, about 0.19 wt %, about 0.2 wt %, about about 9.2 to about 9.8, or about 9.5. In other examples, the pH 0.25 wt %, about 0.3 wt %, about 0.35 wt %, about 0.4 wt %, value of the aqueous mixture can be or can be adjusted to about 0.5 wt %, about 0.6 wt %, about 0.7 wt %, about 0.8wt about 8.5 to about 10.5, about 9 to about 10, about 9.2 to about %, about 0.9 wt %, about 1 wt %, about 1.5 wt %, about 2 wit 9.8, or about 9.5. Any one or combination of acid and/or base %, about 2.5 wt %, about 3 wt %, about 3.5 wt %, about 4 wit compounds can be combined with the mixtures to adjust the %, about 4.5 wt %, about 5 wt %%, based on the weight of the pH values thereof. ore, e.g., a phosphorous ore. In some examples, the amount of 0118 Illustrative acid compounds that can be used to the organic acid in the aqueous mixture can be about 0.0001 maintain or adjust the pH value of any of the aqueous mix wt % to about 2 wt %, about 0.0005 wt % to about 1 wt %, tures can include, but are not limited to, one or more mineral about 0.001 wt % to about 1 wt %, about 0.005 wt % to about acids, one or more organic acids, one or more acid salts, or any 1 wt %, about 0.005 wt % to about 0.5 wt %, about 0.005 wt mixture thereof. Illustrative mineral acids can include, but are % to about 0.1 wt %, about 0.005 wt % to about 0.09 wt %, or not limited to, hydrochloric acid, nitric acid, phosphoric acid, about 0.005 wt % to about 0.05 wt %%, based on the weight Sulfuric acid, or any mixture thereof. Illustrative organic acids of the ore. In some examples, the amount of the organic acid can include, but are not limited to, acetic acid, formic acid, in the aqueous mixture can be greater than 0.0001 wt % to citric acid, oxalic acid, uric acid, lactic acid, or any mixture about 2 wt %, greater than 0.0005 wt % to about 1 wt %, thereof. Illustrative acid salts can include, but are not limited greater than 0.001 wt % to about 1 wt %, greater than 0.005 wt to, ammonium sulfate, sodium bisulfate, Sodium met % to about 1 wt %, greater than 0.005 wt % to about 0.5 wt %, abisulfite, or any mixture thereof. US 2016/0114338 A1 Apr. 28, 2016

0119 Illustrative base compounds that can be used to concentrate. A degree of separation is thereby provided. In maintain or adjust the pH value of any of the aqueous mix “reverse' froth flotation, it is the contaminant that can pref tures can include, but are not limited to, hydroxides, carbon erentially float and concentrated at the surface, with the ore ates, ammonia, amines, or any mixture thereof. Illustrative and/or other value material concentrated in the bottoms. The hydroxides can include, but are not limited to, sodium relatively hydrophobic fraction of the material can have a hydroxide, potassium hydroxide, ammoniumhydroxide, e.g., selective affinity for the rising bubbles and can float to the aqueous ammonia, lithium hydroxide, and cesium hydroxide. surface, where it can be skimmed off and recovered. The Illustrative carbonates can include, but are not limited to, relatively hydrophilic fraction of the material can flow or Sodium carbonate, Sodium bicarbonate, potassium carbonate, otherwise move toward the bottom of the aqueous mixture and ammonium carbonate. Illustrative amines can include, and can be recovered as a bottoms fraction. Froth flotation is but are not limited to, trimethylamine, triethylamine, trietha a separation process well known to those skilled in the art. nolamine, diisopropylethylamine (Hunig's base), pyridine, 0.124. As used herein, the term “purifying broadly refers 4-dimethylaminopyridine (DMAP), and 1,4-diazabicyclo[2. to any process for beneficiation, upgrading, and/or recover 2.2]octane (DABCO). ing, a value material as described herein, Such as phosphates 0120 In one or more examples, the aqueous mixture or or other phosphorous containing materials. In some slurry can be aerated in a conventional flotation machine or examples, the aqueous mixture or slurry can include the clay bank of rougher cells to float phosphates or other phospho containing aqueous Suspensions or brines, which accompany rous containing materials. Any conventional flotation unit can ore refinement processes, including those described above. be employed. The composition or the cationic collector can The production of purified phosphate from mined calcium be used to separate a wide variety of contaminants from a phosphate rock, for example, generally relies on multiple liquid, e.g., water. For example, the composition or the cat separations of Solid particulates from aqueous media, ionic collector can be used to separate siliceous contaminants whereby such separations can be improved using the cationic Such as sand, clay, and/or ash from aqueous liquid Suspen collector. In the overall process, calcium phosphate can be sions or slurries containing one or more of these siliceous mined from deposits and the phosphate rock can be initially contaminants. Aqueous Suspensions or slurries can therefore recovered in a matrix containing sand and clay impurities. be treated with the cationic collector allowing for the effective The matrix can be mixed with water to form a slurry, which separation of at least a portion of the contaminants, in a after mechanical agitation, can be screened to retain phos contaminant-rich fraction, to provide a purified liquid. The phate pebbles and to allow fine clay particles to pass through contaminant-rich fraction contains a higher percentage of as a clay slurry effluent with large amounts of water. Solid contaminants than originally present in the aqueous 0.125. These clay-containing effluents can have high flow mixture or slurry. Conversely, the purified liquid has a lower rates and generally carry less than 10 wt % of Solids, e.g., percentage of Solid contaminants than originally present in about 1 wt % to about 5 wt % of solids. The dewatering, e.g., the aqueous mixture or slurry. by settling or filtration, of this waste clay, which allows for 0121 The treatment can involve adding an effective recycle of the water, poses a significant challenge for recla amount of the composition or the cationic collector to interact mation. The time required to dewater the clay, however, can with and either coagulate or flocculate one or more solid be decreased through treatment of the clay slurry effluent, contaminants into larger agglomerates. An effective amount obtained in the production of phosphate, with the cationic can be readily determined depending, at least in part, on a collector. Reduction in the clay settling time allows for effi number of variables, e.g., the type and concentration of con cient re-use of the purified water, obtained from clay dewa taminant. In other examples, the treatment can involve con tering, in the phosphate production operation. In one example tacting the aqueous mixture or slurry continuously with a of the purification method, where the aqueous mixture or fixed bed of the composition or the cationic collector, in solid slurry is a clay-containing effluent slurry from a phosphate form. production facility, the purified liquid can contain less than 1 0122. During or after the treatment of the aqueous mixture wt % solids after a settling or dewatering time of less than 1 or slurry with the composition or the cationic collector, the month. coagulated or flocculated Solid contaminant (which can now I0126. In addition to the phosphate pebbles and clay slurry be, for example, in the form of larger, agglomerated particles effluent that can be produced by screening the slurry of the or flocs) can be removed. Removal can be effected by flota matrix that can contain sand and clay impurities described tion (with or without the use of rising air bubbles, such as in above, a mixture of sand and finer particles of phosphate can afroth flotation. Filtration or straining can also be an effective also obtained in the initial processing of mined phosphate means for removing the agglomerated flocs of Solid particu matrix. The sand and phosphate can be separated by froth lates on the Surface of the aqueous mixture or slurry. flotation which, as described above, can be improved using 0123 Considering froth flotation in more detail, froth flo the cationic collector as a depressant for the sand. tation is a separation process based on differences in the I0127. In one or more examples, the phosphate material tendency of various materials to associate with rising air that can be collected, recovered or otherwise purified from the bubbles. The composition or cationic collector and optionally aqueous mixture due to the cationic collector can be com a dispersant, a depressant, and/or other additives can be com pared to the initial or total amount of the phosphate material bined with water and an ore that includes one or more con contained in the phosphorous ore. For example, the collected taminants to produce an aqueous slurry or other mixture. A or recovered phosphate material can be about 90 wt %, about gas, e.g., air, can be flowed, forced, or otherwise passed 91 wt %, about 92 wt %, about 93 wt %, about 94 wt %, about through the mixture. Some materials (e.g., value minerals) 95 wt %, about 96 wt %, about 97 wt %, about 97.1 wt %, will, relative to others (e.g., contaminants), exhibit preferen about 97.2 wt %, about 97.3 wt %, about 97.4 wt %, about tial affinity for air bubbles, causing them to rise to the surface 97.5 wt %, about 97.6 wt %, about 97.7 wt %, about 97.8wt of the aqueous slurry, where they can be collected in a froth %, or about 97.9 wt %, about 98 wt %, about 98.1 wt %, about US 2016/0114338 A1 Apr. 28, 2016

98.2 wt %, about 98.3 wt %, about 98.4 wt %, about 98.5 wt can provide a separation efficiency for purified materials, %, about 98.6 wt %, about 98.7 wt %, about 98.8 wt %, about including phosphate, of about 50 wt % of greater, Such as 98.9 wt %, about 99 wt %, about 99.1 wt %, about 99.2 wt %, about 55 wt %, about 60 wt %, about 65 wt %, about 70 wt %, about 99.3 wt %, about 99.4 wt %, about 99.5 wt %, about about 75 wt %, about 80 wt %, about 81 wt %, about 82 wt %, 99.6 wt %, about 99.7 wt %, about 99.8wt %, or about 99.9 wit about 83 wt %, about 84 wt %, about 85 wt %, about 86 wt %, % of the total phosphate material contained in the phospho about 87 wt %, about 88 wt %, about 89 wt %, about 90 wt %, rous ore. In other examples, the collected or recovered phos about 91 wt %, about 92 wt %, about 93 wt %, about 94 wt %, phate material can be about 90 wt % to about 99.9 wt %, about about 95 wt %, about 96 wt %, about 97 wt %, about 98 wt %, 91 wt % to about 99.9 wt %, about 92 wt % to about 99.9 wit or about 99 wt %. %, about 93 wt % to about 99.9 wt %, about 94 wt % to about 0.130. In one or more examples, the compositions or the 99.9 wt %, about 95 wt % to about 99.9 wt %, about 96 wt % cationic collectors having one or more polyamidoamines to about 99.9 wt %, about 97 wt.% to about 99.9 wt %, about which incorporate at least one naphthenate group can be used 98 wt % to about 99.9 wt %, about 99 wt % to about 99.9 wit to increase the flotation of silicate materials, such as sand. The %, about 99.1 wt % to about 99.9 wt %, about 99.2 wt % to polyamidoamine can be formed by reacting one or more about 99.9 wt %, about 99.3 wt % to about 99.9 wt %, about polyamines with naphthenic acid and optionally one or more 99.4 wt % to about 99.9 wt %, about 99.5 wt % to about 99.9 other fatty acids or other carboxylic acids. For example, the wt %, about 99.6 wt % to about 99.9 wt %, about 99.7 wt % polyamidoamine can be formed by reacting DETA, TETA, to about 99.9 wt %, about 95 wt % to about 99.7 wt %, about TEPA, and/or PEHA with naphthenic acid and one or more of 96 wt % to about 99.7 wt %, about 97 wt % to about 99.7 wt lauric acid, isostearic acid, oleic acid, linoleic acid, TOFA, %, about 98 wt % to about 99.7 wt %, about 99 wt % to about and/or other fatty acids. 99.7 wt %, about 95 wt % to about 99.5 wt %, about 96 wt % I0131. In one example, the polyamidoamines having the to about 99.5 wt %, about 97 wt.% to about 99.5 wt %, about chemical formula (D) where R is anaphthenate group, can be 98 wt % to about 99.5 wt %, or about 99 wt % to about 99.5 or include one or more amidoamines having the chemical wt % of the total phosphate material contained in the phos formula (0): phorous 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. (O) 0128. In some examples, a tail material can be submerged, flocculated, sunk, Suspended, or otherwise rejected or not O H CH3, floated at the top of the aqueous mixture or slurry. The tail material can include acid insoluble materials and/or other impurities formerly contained in the phosphorous or phos --~! -O phate containing ores, rocks, minerals, or other materials. The h O tail material flocculated in the aqueous mixture can be col lected or otherwise recovered, separately from the recovered (0132) where R' and naredefined as above for the chemical phosphate material. The tail material can generally be less formula (D). Naphthenic acid can generally include mixtures than 99 wt % of the total acid insolubles (AI) contained in the of carboxylic acid compounds having cyclopentyl, cyclo phosphorous ore. For example, the tail material can be less hexyl cyclic, and/or other cyclic motifs with C6 to C24 than 97 wt %, less than 95 wt %, less than 90 wt %, less than chains, e.g., backbone chains or carboxylic acid chains. Such 85 wt %, less than 80 wt %, less than 75 wt %, less than 70 wit as C9 to C20 chains, C9 to C19 chains, and/or C10 to C16 %, less than 65 wt %, less than 60 wt %, less than 65 wt %, less chains. Naphthenic acids and naphthenate groups can include than 50 wt % to about 40 wt %, about 30 wt %, about 20 wt %, one or more cyclopentyl carboxylic acids or one or more about 10 wt %, about 5 wt %, or less, based on the total acid cyclohexylcarboxylic acids that have one or more C9 to C20 insolubles contained in the phosphorous ore. In some chains, C9 to C19 chains, and/or C10 to C16 chains as back examples, the acid insolubles can be about 10 wt % to less bone chains or carboxylic acid chains. than 97 wt %, about 25 wt % to less than 95 wt %, about 40 wit I0133. In some specific examples, the polyamidoamines % to less than 95 wt %, about 50 wt % to less than 95 wt %, can have the chemical formula (O), where R' can be a C6 to about 60 wt % to less than 95 wt %, about 70 wt % to less than C24 chain or a C8 to C24 chain and n can be 2, 3, 4, or 5. In 95 wt %, about 80 wt % to less than 95 wt %, about 90 wt % other examples, the polyamidoamines can have the chemical to less than 95 wt %, about 50 wt % to about 90 wt %, about formula (O), where R' can be a C10 to C24 chain having 0 to 60 wt % to about 90 wt %, about 70 wt % to about 90 wt %, 2 unsaturated bonds and n can be 2, 3, or 4. In other examples, or about 80 wt % to about 90 wt %, based on the total acid the polyamidoamines can have the chemical formula (O), insolubles contained in the phosphorous ore. In one specific where R' can be CoHo, CH 7, CoH is, CH, CHs. example, a tail material can be collected or recovered that can CH21, C1s Has. Cls Hs 1, C15H29, C17Hss, C17Hss, C17H31. be flocculated on the bottom of the aqueous mixture, where C17H29C9H7, C19Hss, C19Hss, C19H1, or C19H29 and in the tail material can include acid insolubles, and the acid can be 2, 3, or 4. In other examples, the polyamidoamines can insolubles can be about 70 wt % to about 90 wt % of the total have the chemical formula (O), where R' can be a laurate acid insolubles contained in the phosphorous ore. group, a stearate group, an isostearate group, an oleate group. 0129. The separation efficiency is defined as E-R-R, a linoleate group, isomers thereof, or any mixture thereof and where R is the ratio of the total weight of the recovered n can be 2, 3, or 4. phosphate material over the total weight of the phosphate material contained in the phosphorous ore and R is the ratio EXAMPLES of the total weight of the recovered acid insolubles over the I0134. In order to provide a better understanding of the total weight of the phosphorous ore. The cationic collector foregoing discussion, the following non-limiting examples US 2016/0114338 A1 Apr. 28, 2016 are offered. Although the examples can be directed to specific Examples 2A-2B embodiments, they are not to be viewed as limiting the inven tion in any specific respect. 0140. The lauric acid-TOFA-DETA polyamidoamine was 0135 The cationic collectors contained polyamidoamines made by the following: To a 40 mL scintillation vial equipped with varying types of hydrocarbyl groups on the amido with a magnetic stir bar, about 10 g of tall oil fatty acid and groups and varying amounts and types of amine groups about 6.95 g of lauric acid were added under an air atmo between the amido groups. The synergetic effects for selec sphere. The mixture was stirred and warmed to about 80°C., tive phosphate flotation were due, at least in part, to these and about 3.7 g of DETA was added over about 4 min. The novel polyamidoamines to form the cationic collectors as mixture exothermed to a temperature of about 105° C. to highlighted by the results of Examples 1A-10B, summarized about 110°C., and then the mixture was heated for about 15 below in Table 1. minto reach a temperature of about 165° C. As the reaction 0136. The synergetic effects for viscosity and homogene mixture neared 165° C., bubbling commenced, indicating ity of the cationic collectors were due, at least in part, to the reaction progress. The mixture was maintained at about 165° combination of the polyamidoamines, e.g., diamidoamines or C. for about 3 hr, at which point, bubbling ceased. The mix triamidoamines, and acetic acid as highlighted by the results ture cooled to room temperature, e.g., about 25° C., and of Examples 11-41, summarized below in Tables 2 and 3. The slowly formed a waxy Substance. cationic collectors contained varying amounts of acetic acid and water (when present) relative to a constant amount of Examples 3A-3B polyamidoamines, and also contained varying polyamidoam 0.141. The naphthenic acid-TOFA-DETA polyamidoam ine compositions within different cationic collectors. The ine was made by the following: To a 40 mL scintillation vial synergetic effects for selective phosphate flotation were due, equipped with a magnetic stir bar, about 10g of tall oil fatty at least in part, to the combination of the diamidoamines and acid and about 8.125 g of naphthenic acid were added under the acetic acid to form the cationic collectors as highlighted an air atmosphere. The mixture was stirred and warmed to by the results of Examples 42A-47D, summarized below in about 80°C., and about 3.7 g of DETA was added over about Table 4. 4 min. The mixture exothermed to a temperature of about 0.137 Beneficiation Procedure: 105°C. to about 110°C., and then the mixture was heated for 0.138. The following phosphate beneficiation procedure about 15 minto reach a temperature of about 165° C. As the was used for Examples 1A-10E and 42A-45D. About 500g of reaction mixture neared 165°C., bubbling commenced, indi phosphate rougher concentrate and about 214 g of water were cating reaction progress. The mixture was maintained at added to a 2L capacity stainless Steel beaker equipped with a about 165° C. for about 3 hr, at which point, bubbling ceased. cruciform impeller. The concentrate and water were stirred The mixture cooled to room temperature, e.g., about 25°C., for about 0.5 min and maintained at a pH value of about 7 (if and slowly formed a waxy Substance. needed, 1 NNaOH solution was added to adjust the pH value) to produce a mixture of about 70 wt % solids. For each of the Examples 4A-4B Examples 1A-10B and 42A-45D, the listed polyamidoamine at the respective dosage was added to the mixture and stirred 0142. The isostearic acid-TOFA-DETA polyamidoamine at about 400 rpm for about 5 min. The mixture was transferred was made by the following: To a 40 mL scintillation vial to stainless steel flotation cell. About 1,300 g of water was equipped with a magnetic stir bar, about 10g of tall oil fatty added to the mixture that was stirred for about 0.5 min to acid and about 10.32 g of isostearic acid were added under an produce a mixture of about 25 wt % solids. An air injection air atmosphere. The mixture was stirred and warmed to about valve on the flotation cell was opened and frothing ensued as 80°C., and about 3.7 g of DETA was added over about 4 min. air was introduced into the mixture. After about 2 min, the The mixture exothermed to a temperature of about 105°C. to froth was collected from the flotation cell. The froth concen about 110°C., and then the mixture was heated for about 15 trate and the tailings remaining in the flotation cell were minto reach a temperature of about 165° C. As the reaction separately filtered, dewatered, and weighed. The dried froth mixture neared 165° C., bubbling commenced, indicating concentrate and the tailings were separately analyzed for reaction progress. The mixture was maintained at about 165° phosphate (Bone Phosphate of Lime, BPL) content using C. for about 3 hr, at which point, bubbling ceased. The mix inductively coupled plasma (ICP) and for acid insoluble con ture cooled to room temperature, e.g., about 25° C., and tent using an acid digestion. slowly formed a waxy Substance. Examples 1A-1B Examples 5A-5B 0.139. The TOFA-DETA polyamidoamine was made by 0143. The LNI-TOFA-DETA polyamidoamine was made the following: To a 40 mL scintillation vial equipped with a by the following: To a 40 mL scintillation vial equipped with magnetic stir bar, about 20g of tall oil fatty acid was added a magnetic stir bar, about 12.5g of tall oil fatty acid, about under an air atmosphere. The mixture was stirred and warmed 1.74 g of lauric acid, about 2.22 g of naphthenic acid, and to about 80°C., and about 3.68 g of DETA was added over about 2.57 g of isostearic acid were added under an air atmo about 4 min. The mixture exothermed to a temperature of sphere. The mixture was stirred and warmed to about 80°C., about 105° C. to about 110° C., and then the mixture was and about 3.68 g of DETA was added over about 4 min. The heated for about 15 minto reach a temperature of about 165° mixture exothermed to a temperature of about 105° C. to C. As the reaction mixture neared 165° C., bubbling com about 110°C., and then the mixture was heated for about 15 menced, indicating reaction progress. The mixture was main minto reach a temperature of about 165° C. As the reaction tained at about 165° C. for about 3 hr, at which point, bubbling mixture neared 165° C., bubbling commenced, indicating ceased. The mixture cooled to room temperature, e.g., about reaction progress. The mixture was maintained at about 165° 25°C., and slowly formed a waxy substance. C. for about 3 hr, at which point, bubbling ceased. The mix US 2016/0114338 A1 Apr. 28, 2016 20 ture cooled to room temperature, e.g., about 25° C., and ture cooled to room temperature, e.g., about 25° C., and slowly formed a waxy Substance. slowly formed a waxy Substance. Examples 6A-6B Examples 10A-10B 0144. The TOFA-TEPA polyamidoamine was made by (0.148. The LNI-TOFA-TEPA polyamidoamine was made the following: To a 2 L reactor equipped with a mechanical by the following: To a 40 mL scintillation vial equipped with stirrer, thermocouple, and Barrett trap/condenser, about 600 g a magnetic stir bar, about 12.5g of tall oil fatty acid, about of tall oil fatty acid was added under an air atmosphere. The 1.74 g of lauric acid, about 2.22 g of naphthenic acid, and mixture was stirred and warmed to about 80° C., and about about 2.57 g of isostearic acid were added under an air atmo 202 g of TEPA was added over about 4 min. The mixture sphere. The mixture was stirred and warmed to about 80°C., exothermed to a temperature of about 105°C. to about 110° and about 7.12 g of TEPA was added over about 4 min. The C., and then the mixture was heated for about 15 minto reach mixture exothermed to a temperature of about 105° C. to a temperature of about 165°C. The mixture was maintained at about 110°C., and then the mixture was heated for about 15 about 165° C. for about 3 hr, at which point, the Barrett trap minto reach a temperature of about 165° C. As the reaction had collected about 23 mL of water. The mixture cooled to mixture neared 165° C., bubbling commenced, indicating room temperature, e.g., about 25°C., and slowly formed a reaction progress. The mixture was maintained at about 165° waxy yellow Substance. C. for about 3 hr, at which point, bubbling ceased. The mix ture cooled to room temperature, e.g., about 25° C., and Examples 7A-7B slowly formed a waxy Substance. 0145 The lauric acid-TOFA-TEPA polyamidoamine was 0149. In Examples 1A-10B, the flotation results listed in made by the following: To a 40 mL scintillation vial equipped Table 1, demonstrates the effectiveness of collectors having with a magnetic stir bar, about 10 g of tall oil fatty acid and diamidoamines used to remove impurities, such as acid about 6.95 g of lauric acid were added under an air atmo insolubles, e.g., sand or silicate, from phosphate ore. The low sphere. The mixture was stirred and warmed to about 80°C., acid insoluble values indicate removal of gangue from the and about 7.12 g of TEPA was added over about 4 min. The crude phosphate mineral ore. The use of a mixed acid ami mixture exothermed to a temperature of about 105° C. to doamine system (a collector containing the amidoamines about 110° C., and then the mixture was heated for about 15 having the chemical formulas (E) and (G), where R' and R' minto reach a temperature of about 165° C. As the reaction were different hydrocarbyl groups, provided the low recovery mixture neared 165° C., bubbling commenced, indicating of acid insoluble content in the phosphate concentrate. In both reaction progress. The mixture was maintained at about 165° DETA and TEPA-based collectors, incorporation of naph C. for about 3 hr, at which point, bubbling ceased. The mix thenic acid (or the naphthenate group) increased flotation of ture cooled to room temperature, e.g., about 25° C., and silicates, as shown in Table 1 for Examples 3A, 3B, 5A, 5B, slowly formed a waxy Substance. 8A, 8B, 10A, and 10B. Surprisingly, these results indicate that the collectors can provide a technical and an economic Examples 8A-8B benefit by removing impurities at lower dosages than does the 0146 The naphthenic acid-TOFA-TEPA polyamidoam traditional purely TOFA based system. ine was made by the following: To a 40 mL scintillation vial equipped with a magnetic stir bar, about 10g of tall oil fatty TABLE 1 acid and about 8.125 g of naphthenic acid were added under Phosphate Beneficiation with Diamidoamines an air atmosphere. The mixture was stirred and warmed to about 80°C., and about 7.12 g of TEPA was added over about Dosage POs A.I. Separ. 4 min. The mixture exothermed to a temperature of about (Ib?ton) Recov. Recov. Effic. 105°C. to about 110°C., and then the mixture was heated for Ex. Polyamidoamine kg/tonne (wt %) (wt %) (wt %) about 15 minto reach a temperature of about 165° C. As the 1A TOFA-DETA O.S 99.76 68.13 31.63 1B TOFA-DETA 2 92.25 14.54 77.71 reaction mixture neared 165°C., bubbling commenced, indi 2A lauric acid-TOFA- O.S 99.88 94.18 5.7 cating reaction progress. The mixture was maintained at DETA about 165° C. for about 3 hr, at which point, bubbling ceased. 2B lauric acid-TOFA- 2 92.75 11.66 81.09 The mixture cooled to room temperature, e.g., about 25°C., DETA and slowly formed a waxy Substance. 3A naphthenic acid- O.S 99.83 87.68 12.15 TOFA-DETA 3B naphthenic acid- 2 73.28 6.2 67.08 Examples 9A-9B TOFA-DETA 4A isoStearic acid- O.S 99.83 81.74 8.09 0147 The isostearic acid-TOFA-TEPA polyamidoamine TOFA-DETA was made by the following: To a 40 mL scintillation vial 4B isostearic acid- 2 89.24 11.73 77.51 equipped with a magnetic stir bar, about 10g of tall oil fatty TOFA-DETA SA LNI-TOFA-DETA O.S 99.86 86.68 13.18 acid and about 10.32 g of isostearic acid were added under an SB LNI-TOFA-DETA 2 86.66 8.13 78.53 air atmosphere. The mixture was stirred and warmed to about 6A TOFA-TEPA O.S 99.16 28.16 71 80°C., and about 7.12 g of TEPA was added over about 4 min. 6B TOFA-TEPA 2 97.95 8.57 91.38 The mixture exothermed to a temperature of about 105°C. to 7A lauric acid-TOFA- O.S 98.54 53.28 45.26 TEPA about 110° C., and then the mixture was heated for about 15 7B lauric acid-TOFA- 2 99.02 17.61 8141 minto reach a temperature of about 165° C. As the reaction TEPA mixture neared 165° C., bubbling commenced, indicating 8A naphthenic acid- O.S 99.75 86.54 13.21 reaction progress. The mixture was maintained at about 165° TOFA-TEPA C. for about 3 hr, at which point, bubbling ceased. The mix US 2016/0114338 A1 Apr. 28, 2016 21

TABLE 1-continued Example 15 Phosphate Beneficiation with Dianidoamines (O155 The TOFA-DETA polyamidoamine acetate was Dosage POs A.I. Separ. prepared as follows: About 1 g of TOFA-DETA polyami (Ib?ton) Recov. Recov. Effic. doamine was added to a 20 mL scintillation vial, then stirred Ex. Polyamidoamine kg/tonne (wt %) (wt %) (wt %) and heated to about 80°C. About 0.37 g of glacial acetic acid and about 0.1 g of water were added over a period of about 2 8B naphthenic acid- 21 94.99 7.23 87.76 TOFA-TEPA min. The reaction mixture reached a temperature of about 9A isostearic acid- 10.5 99.8 78.69 21.11 100° C., then the heating source was removed and the mixture TOFA-TEPA was cooled to about 25°C. 9B isostearic acid- 21 98.64 10.12 88.52 TOFA-TEPA 10A LNI-TOFA-TEPA 10.5 99.45 30.69 68.76 Example 16 1OB LNI-TOFA-TEPA 1. 94.97 7.1 87.87 0156 The TOFA-DETA polyamidoamine acetate was “LNI” is laurate, isostearate, and naphthenate groups prepared as follows: About 1 g of TOFA-DETA polyami doamine was added to a 20 mL scintillation vial, then stirred 0150. The TOFA-DETA polyamidoamines and the TOFA and heated to about 80°C. About 0.37 g of glacial acetic acid TEPA polyamidoamines prepared in Examples 1A-1B and and about 0.2 g of water were added over a period of about 2 6A-6B, were used in Examples 11-16 and 17-23, respec min. The reaction mixture reached a temperature of about tively. 100° C., then the heating source was removed and the mixture was cooled to about 25°C. Example 11 Example 17 0151. The TOFA-DETA polyamidoamine acetate was prepared as follows: About 1 g of TOFA-DETA polyami (O157. The TOFA-TEPA polyamidoamine acetate was pre doamine was added to a 20 mL scintillation vial, then stirred pared as follows: About 1 g of TOFA-TEPA polyamidoamine and heated to about 80°C. About 0.093 g of glacial acetic acid was added to a 20 mL scintillation vial, then stirred and heated was added over a period of about 2 min. The reaction mixture to about 80°C. About 0.23g of glacial acetic acid was added reached a temperature of about 100° C., then the heating over a period of about 2 min. The reaction mixture reached a source was removed and the mixture was cooled to about 25° temperature of about 100° C., then the heating source was C. removed and the mixture was cooled to about 25°C. Example 12 Example 18 0152 The TOFA-DETA polyamidoamine acetate was 0158. The TOFA-TEPA polyamidoamine acetate was pre prepared as follows: About 1 g of TOFA-DETA polyami pared as follows: About 1 g of TOFA-TEPA polyamidoamine doamine was added to a 20 mL scintillation vial, then stirred was added to a 20 mL scintillation vial, then stirred and heated and heated to about 80°C. About 0.19 g of glacial acetic acid to about 80°C. About 0.23g of glacial acetic acid and about was added over a period of about 2 min. The reaction mixture 0.25g of water were added over a period of about 2 min. The reached a temperature of about 100° C., then the heating reaction mixture reached a temperature of about 100°C., then source was removed and the mixture was cooled to about 25° the heating source was removed and the mixture was cooled C. to about 25° C. Example 13 Example 19 0153. The TOFA-DETA polyamidoamine acetate was 0159. The TOFA-TEPA polyamidoamine acetate was pre prepared as follows: About 1 g of TOFA-DETA polyami pared as follows: About 1 g of TOFA-TEPA polyamidoamine doamine was added to a 20 mL scintillation vial, then stirred was added to a 20 mL scintillation vial, then stirred and heated and heated to about 80°C. About 0.28g of glacial acetic acid to about 80°C. About 0.23g of glacial acetic acid and about was added over a period of about 2 min. The reaction mixture 0.5g of water were added over a period of about 2 min. The reached a temperature of about 100° C., then the heating reaction mixture reached a temperature of about 100°C., then source was removed and the mixture was cooled to about 25° the heating source was removed and the mixture was cooled C. to about 25° C. Example 14 Example 20 0154 The TOFA-DETA polyamidoamine acetate was 0160 The TOFA-TEPA polyamidoamine acetate was pre prepared as follows: About 1 g of TOFA-DETA polyami pared as follows: About 1 g of TOFA-TEPA polyamidoamine doamine was added to a 20 mL scintillation vial, then stirred was added to a 20 mL scintillation vial, then stirred and heated and heated to about 80°C. About 0.37 g of glacial acetic acid to about 80°C. About 0.23g of glacial acetic acid and about was added over a period of about 2 min. The reaction mixture 0.75 g of water were added over a period of about 2 min. The reached a temperature of about 100° C., then the heating reaction mixture reached a temperature of about 100°C., then source was removed and the mixture was cooled to about 25° the heating source was removed and the mixture was cooled C. to about 25° C. US 2016/0114338 A1 Apr. 28, 2016 22

Example 21 Example 24 0161 The TOFA-TEPA polyamidoamine acetate was pre (0164. The LNI-TOFA-DETA polyamidoamine acetate pared as follows: About 1 g of TOFA-TEPA polyamidoamine was prepared as follows: About 1 g of LNI-TOFA-DETA was added to a 20 mL scintillation vial, then stirred and heated polyamidoamine was added to a 20 mL Scintillation vial, then to about 80°C. About 0.44 g of glacial acetic acid was added stirred and heated to about 80° C. About 0.11 g of glacial over a period of about 2 min. The reaction mixture reached a acetic acid was added over a period of about 2 min. The temperature of about 100° C., then the heating source was reaction mixture reached a temperature of about 100°C., then removed and the mixture was cooled to about 25°C. the heating source was removed and the mixture was cooled to about 25° C. Example 22 0162 The TOFA-TEPA polyamidoamine acetate was pre Example 25 pared as follows: About 1 g of TOFA-TEPA polyamidoamine was added to a 20 mL scintillation vial, then stirred and heated (0165. The LNI-TOFA-DETA polyamidoamine acetate to about 80°C. About 0.44 g of glacial acetic acid and about was prepared as follows: About 1 g of LNI-TOFA-DETA 0.25g of water were added over a period of about 2 min. The polyamidoamine was added to a 20 mL Scintillation vial, then reaction mixture reached a temperature of about 100°C., then stirred and heated to about 80° C. About 0.21 g of glacial the heating source was removed and the mixture was cooled acetic acid was added over a period of about 2 min. The to about 25° C. reaction mixture reached a temperature of about 100°C., then the heating source was removed and the mixture was cooled Example 23 to about 25° C. 0163 The TOFA-TEPA polyamidoamine acetate was pre Example 26 pared as follows: About 1 g of TOFA-TEPA polyamidoamine was added to a 20 mL scintillation vial, then stirred and heated (0166 The LNI-TOFA-DETA polyamidoamine acetate to about 80°C. About 0.9 g of glacial acetic acid was added was prepared as follows: About 1 g of LNI-TOFA-DETA over a period of about 2 min. The reaction mixture reached a polyamidoamine was added to a 20 mL Scintillation vial, then temperature of about 100° C., then the heating source was stirred and heated to about 80° C. About 0.32 g of glacial removed and the mixture was cooled to about 25°C. acetic acid was added over a period of about 2 min. The TABLE 2 Cationic Collectors with Polyanidoamines and Acetic Acid Viscosity Viscosity HOAc HO at 80° C. at 25° C. Ex. Polyamidoamine (g) (g) (cP) (cP) Homogeneity 1 TOFA-DETA O.093 O HV transparent (30-125) (1,500–3,500) 2 TOFA-DETA O.19 O HV O3C (30-125) (900–2,500) 3 TOFA-DETA O.28 O HV opaque, gel 0-125) (600-2,500) 4 TOFA-DETA 0.37 O FF transparent (30-125) (40-300) S TOFA-DETA 0.37 0.1 FF V opaque, PS 30-125) (300-900) 6 TOFA-DETA 0.37 0.2 FF V opaque, gel 0-125) (600-1,250) 7 TOFA-TEPA O.23 O HV transparent (30-125) (900–2,500) 8 TOFA-TEPA O.23 0.25 FF HV O3C 30-125) (900–2,500) 9 TOFA-TEPA O.23 0.5 FF HV opaque, gel 0-125) (900–2,500) 20 TOFA-TEPA O.23 0.75 FF HV opaque, gel (30-125) (900–2,500) 21 TOFA-TEPA 0.44 O V transparent 30-125) (300-900) 22 TOFA-TEPA 0.44 0.25 FF HV O3C 0-125) (900-2500) 23 TOFA-TEPA O.9 O FF transparent (30-125) (40-300) “FF is free flowing: “V” is viscous; “HV” is highly viscous; “NF is no flow: “PS” is phase separates US 2016/0114338 A1 Apr. 28, 2016

reaction mixture reached a temperature of about 100°C., then reaction mixture reached a temperature of about 100°C., then the heating source was removed and the mixture was cooled the heating source was removed and the mixture was cooled to about 25° C. to about 25° C. Example 27 Example 33 (0167. The LNI-TOFA-DETA polyamidoamine acetate (0173 The LNI-TOFA-TEPA polyamidoamine acetate was prepared as follows: About 1 g of LNI-TOFA-DETA was prepared as follows: About 1 g of LNI-TOFA-TEPA polyamidoamine was added to a 20 mL Scintillation vial, then polyamidoamine was added to a 20 mL Scintillation vial, then stirred and heated to about 80° C. About 0.42 g of glacial stirred and heated to about 80° C. About 0.52 g of glacial acetic acid was added over a period of about 2 min. The acetic acid and about 0.25g of water were added over a period reaction mixture reached a temperature of about 100°C., then of about 2 min. The reaction mixture reached a temperature of the heating source was removed and the mixture was cooled about 100° C., then the heating source was removed and the to about 25° C. mixture was cooled to about 25°C. Example 28 Example 34 (0168 The LNI-TOFA-DETA polyamidoamine acetate (0174. The lauric acid-TOFA-TEPA polyamidoamine was prepared as follows: About 1 g of LNI-TOFA-DETA acetate was prepared as follows: About 1 g of LNI-TOFA polyamidoamine was added to a 20 mL Scintillation vial, then TEPA polyamidoamine was added to a 20 mL scintillation stirred and heated to about 80° C. About 0.42 g of glacial vial, then stirred and heated to about 80°C. About 0.52g of acetic acid and about 0.1 g of water were added over a period glacial acetic acid and about 1 g of water were added over a of about 2 min. The reaction mixture reached a temperature of period of about 2 min. The reaction mixture reached a tem about 100° C., then the heating source was removed and the perature of about 100° C., then the heating source was mixture was cooled to about 25°C. removed and the mixture was cooled to about 25°C. Example 29 Example 35 (0169. The LNI-TOFA-DETA polyamidoamine acetate (0175. The lauric acid-TOFA-TEPA polyamidoamine was prepared as follows: About 1 g of LNI-TOFA-DETA acetate was prepared as follows: About 1 g of lauric acid polyamidoamine was added to a 20 mL Scintillation vial, then TOFA-TEPA polyamidoamine was added to a 20 mL scintil stirred and heated to about 80° C. About 0.42 g of glacial lation vial, then stirred and heated to about 80°C. About 0.53 acetic acid and about 0.2 g of water were added over a period g of glacial acetic acid was added overa period of about 2 min. of about 2 min. The reaction mixture reached a temperature of The reaction mixture reached a temperature of about 100°C., about 100° C., then the heating source was removed and the then the heating Source was removed and the mixture was mixture was cooled to about 25°C. cooled to about 25° C. Example 30 Example 36 (0176) The lauric acid-TOFA-TEPA polyamidoamine (0170 The LNI-TOFA-TEPA polyamidoamine acetate acetate was prepared as follows: About 1 g of lauric acid was prepared as follows: About 1 g of LNI-TOFA-TEPA TOFA-TEPA polyamidoamine was added to a 20 mL scintil polyamidoamine was added to a 20 mL Scintillation vial, then lation vial, then stirred and heated to about 80°C. About 0.53 stirred and heated to about 80° C. About 0.26 g of glacial g of glacial acetic acid and about 0.1 g of water were added acetic acid was added over a period of about 2 min. The over a period of about 2 min. The reaction mixture reached a reaction mixture reached a temperature of about 100°C., then temperature of about 100° C., then the heating source was the heating source was removed and the mixture was cooled removed and the mixture was cooled to about 25°C. to about 25° C. Example 37 Example 31 (0177. The lauric acid-TOFA-TEPA polyamidoamine (0171 The LNI-TOFA-TEPA polyamidoamine acetate acetate was prepared as follows: About 1 g of lauric acid was prepared as follows: About 1 g of LNI-TOFA-TEPA TOFA-TEPA polyamidoamine was added to a 20 mL scintil polyamidoamine was added to a 20 mL Scintillation vial, then lation vial, then stirred and heated to about 80°C. About 0.53 stirred and heated to about 80° C. About 0.37 g of glacial g of glacial acetic acid and about 0.25g of water were added acetic acid was added over a period of about 2 min. The over a period of about 2 min. The reaction mixture reached a reaction mixture reached a temperature of about 100°C., then temperature of about 100° C., then the heating source was the heating source was removed and the mixture was cooled removed and the mixture was cooled to about 25°C. to about 25° C. Example 38 Example 32 (0178. The lauric acid-TOFA-TEPA polyamidoamine (0172. The LNI-TOFA-TEPA polyamidoamine acetate acetate was prepared as follows: About 1 g of lauric acid was prepared as follows: About 1 g of LNI-TOFA-TEPA TOFA-TEPA polyamidoamine was added to a 20 mL scintil polyamidoamine was added to a 20 mL Scintillation vial, then lation vial, then stirred and heated to about 80°C. About 0.53 stirred and heated to about 80° C. About 0.52 g of glacial g of glacial acetic acid and about 1 g of water were added over acetic acid was added over a period of about 2 min. The a period of about 2 min. The reaction mixture reached a US 2016/0114338 A1 Apr. 28, 2016 24 temperature of about 100° C., then the heating source was acid-TOFA-TEPA polyamidoamine was added to a 20 mL removed and the mixture was cooled to about 25°C. scintillation vial, then stirred and heated to about 80° C. About 0.42 g of glacial acetic acid and about 0.25 g of water Example 39 were added over a period of about 2 min. The reaction mixture reached a temperature of about 100° C., then the heating (0179 The naphthenic acid-TOFA-TEPA polyamidoam source was removed and the mixture was cooled to about 25° ine acetate was prepared as follows: About 1 g of naphthenic C. acid-TOFA-TEPA polyamidoamine was added to a 20 mL scintillation vial, then stirred and heated to about 80° C. Example 41 About 0.53 g of glacial acetic acid and about 0.25 g of water were added over a period of about 2 min. The reaction mixture 0181. The isostearic acid-TOFA-TEPA polyamidoamine reached a temperature of about 100° C., then the heating acetate was prepared as follows: About 1 g of isostearic source was removed and the mixture was cooled to about 25° acid-TOFA-TEPA polyamidoamine was added to a 20 mL C. scintillation vial, then stirred and heated to about 80° C. About 0.53 g of glacial acetic acid and about 0.25 g of water Example 40 were added over a period of about 2 min. The reaction mixture reached a temperature of about 100° C., then the heating 0180. The isostearic acid-TOFA-TEPA polyamidoamine source was removed and the mixture was cooled to about 25° acetate was prepared as follows: About 1 g of isostearic C. TABLE 3 Cationic Collectors with Polyanidoamines Viscosity Viscosity HOAc HO at 80° C. at 25° C. Ex. Polyamidoamine (g) (g) (cP) (cP) Homogeneity 24 LNI-TOFA- O.11 O NF transparent DETA (30-125) (1,500–3,500) 2S LNI-TOFA- O.21 O HV O3Cle. ETA 30-125) (900–2,500) 26 LNI-TOFA- O.32 O RR V opaque, gel ETA 30-125) (300-900) 27 LNI-TOFA- O42 O FF transparent ETA 30-125) (40-300) 28 LNI-TOFA- O42 0.1 FF V opaque, PS ETA (30-125) (300-900) 29 LNI-TOFA- O42 0.2 FF V opaque, gel ETA 30-125) (100-600) 3 O LNI-TOFA- O.26 O NF transparent TEPA 30-125) (1,500–3,500) 31 LINI-TOFA- 0.37 O NF O3Cle. TEPA 30-125) (1,500–3,500) 32 LNI-TOFA- O.S2 O HV opaque, gel E 30-125) (600-2,500) 33 LN O.S2 0.25 FF FF 8S980 E (30-125) (40-300) 34 O.S2 1 V opaque, PS (30-125) (100-600) 35 O.S3 O HV 8S980 (30-125) (600-2,500) 36 O.S3 0.1 FF V O3Cle. (30-125) (300-900) 37 O.S3 0.25 FF FF 8S980 (30-125) (40-300) 38 O.S3 1 V O3Cle. TOFA-TEPA (30-125) (100-600) 39 naphthenic acid- O.S3 0.25 FF FF 8S980 TOFA-TEPA (30-125) (40-300) 40 isostearic acid- O42 0.25 FF V gel-like TOFA-TEPA (30-125) (300-900) 41 isostearic acid- O.S3 0.25 FF FF 8S980 TOFA-TEPA (30-125) (40-300)

“laur' is lauric acid; "isos' is isostearic acid; “naph' is naphthenic acid; “LNI is laurate, isostearate, and naphthenate groups; “FF is free flowing: “V” is viscous; “HV” is highly viscous; “NF is no flow: “PS” is phase separates US 2016/0114338 A1 Apr. 28, 2016 25

Examples 42A-42C Examples 45A-45D 0182. The TOFA-TEPA polyamidoamine acetate was pre 0185. The LNI-TOFA-TEPA polyamidoamine acetate pared was prepared as follows: To a 2 L reactor, about 779 g was prepared was prepared as follows: To a 2L reactor, about of the TOFA-TEPA polyamidoamine was added, stirred, and 600 g of the LNI-TOFA-TEPA polyamidoamine was added, heated to about 80°C. About 553 g of glacial acetic acid was stirred, and heated to about 80° C. About 299 g of glacial added over a period of about 6 min. The reaction mixture acetic acid and 143 g water were added over a period of about reached a temperature of about 100° C., then the heating 6 min. The reaction mixture reached a temperature of about source was removed and the mixture was cooled to about 25° 100° C., then the heating source was removed and the mixture C. was cooled to about 25°C. Examples 43 A-43D Examples 46A-46D 0183 The TOFA-TEPA polyamidoamine acetate was pre pared was prepared as follows: To a 2 L reactor, about 779 g 0186 The TOFA-DETA monoamidoamine acetate was of the TOFA-TEPA polyamidoamine was added, stirred, and prepared was prepared as follows: To a 2 L reactor, about 600 heated to about 80°C. About 138g of glacial acetic acid was g of the TOFA-DETA monoamidoamine was added, stirred, added over a period of about 6 min. The reaction mixture and heated to about 80°C. About 210g of glacial acetic acid, reached a temperature of about 100° C., then the heating 600 g water, and 210 g Flomin 663 frother were added over a source was removed and the mixture was cooled to about 25° period of about 6 min. The reaction mixture reached a tem C. perature of about 100° C., then the heating source was removed and the mixture was cooled to about 25°C. Examples 44A-44D Examples 47A-47D 0184 The lauric acid-TOFA-TEPA polyamidoamine acetate was prepared was prepared as follows: To a 2 L 0187. The cocoamine acetate was prepared was prepared reactor, about 600g of the lauric acid-TOFA-TEPA polyami as follows: To a 2 L reactor, about 600g of the cocoamine was doamine was added, stirred, and heated to about 80°C. About added, stirred, and heated to about 80° C. About 35.2 g of 308 g of glacial acetic acid and 147 g of water were added glacial acetic acid and 473 g water were added over a period over a period of about 6 min. The reaction mixture reached a of about 6 min. The reaction mixture reached a temperature of temperature of about 100° C., then the heating source was about 100° C., then the heating source was removed and the removed and the mixture was cooled to about 25°C. mixture was cooled to about 25°C. TABLE 4 Phosphate Beneficiation Dosage POs A.I. Separ. HOAC (Ib?ton) Recov. Recov. Effic. Ex. Polyamidoamine (wt %)* kg/tonne (wt %) (wt %) (wt %)

42A TOFA-TEPA 47 10.5 99.75 49.14 SO.61 42B TOFA-TEPA 47 1.5 0.75 99.41 24.18 75.23 42C TOFA-TEPA 47 21 96.64 8.13 88.52 43A TOFA-TEPA 18 10.5 99.72 65.59 34.13 43B TOFA-TEPA 18 1.5 0.75 98.52 11.65 86.88 43C TOFA-TEPA 18 21 97.91 8.55 89.36 43D TOFA-TEPA 18 2.51.25 97.37 8.OS 89.32 44A lauric acid-TOFA- 30 10.5 99.86 98.29 1.57 TEPA lauric acid-TOFA- 30 1.5 0.75 99.54 41.75 57.79 TEPA lauric acid-TOFA- 30 21 98.84 13.48 85.36 TEPA lauric acid-TOFA- 30 2.51.25 97.85 8.32 89.53 TEPA LNI-TOFA-TEPA 30 10.5 99.55 47.79 51.76 LNI-TOFA-TEPA 30 1.5 0.75 99.46 43.17 56.29 LNI-TOFA-TEPA 30 21 96.73 7.84 88.89 LNI-TOFA-TEPA 30 2.51.25 94.91 9.18 85.73 Monoamidoamine TOFA-DETA 13 10.5 99.53 64.45 35.09 monoamidoamine TOFA-DETA 13 1.5 0.75 98.28 32.02 66.26 monoamidoamine TOFA-DETA 13 21 97.87 25.71 72.16 monoamidoamine TOFA-DETA 13 2.51.25 97.02 20.32 76.70 monoamidoamine cocoamine acetate 6 10.5 98.94 28.8O 70.14 cocoamine acetate 6 1.5 0.75 97.88 20.21 77.67 US 2016/0114338 A1 Apr. 28, 2016 26

TABLE 4-continued Phosphate Beneficiation Dosage POs A.I. Separ. HOAC (Ib?ton) Recov. Recov. Effic. Ex. Polyamidoamine (wt %)* kg/tonne (wt %) (wt %) (wt %) 47C cocoamine acetate 6 21 96.60 14.51 82.09 47D cocoamine acetate 6 2.5 (1.25 95.32 1291 82.41 *HO Acwt % values are based on the total weight of the polyamidoamine and the acetic acid.

0188 Embodiments of the present disclosure further 0194 6. A method for purifying a mineral, comprising relate to any one or more of the following paragraphs: combining crude mineral ore, water, and a polyamidoamine 0189 1. A cationic collector, comprising a polyamidoam to produce an aqueous mixture, wherein the crude mineral ore ine, wherein the polyamidoamine comprises one or more is a silicate material, and wherein the polyamidoamine com amidoamines having the chemical formula (A), wherein R' prises one or more amidoamines having the chemical formula and R are each independently a Saturated or unsaturated, (A), wherein R' and Rare each independently a saturated or substituted or unsubstituted, linear or branched, cyclic, het unsaturated, Substituted or unsubstituted, linear or branched, erocyclic, or aromatic hydrocarbyl group, and RandR are cyclic, heterocyclic, or aromatic hydrocarbyl group, and R' different hydrocarbyl groups, R and R are each indepen and Rare different hydrocarbyl groups, RandR are each dently a hydrogen or a saturated or unsaturated, Substituted or independently a hydrogen or a saturated or unsaturated, Sub unsubstituted, linear or branched, cyclic, heterocyclic, or aro stituted or unsubstituted, linear or branched, cyclic, hetero matic hydrocarbyl group, each m is an integer of 1 to 5, and in cyclic, or aromatic hydrocarbyl group, each m is an integer of is an integer of 2 to 8. 1 to 5, and n is an integer of 2 to 8, collecting a flocculated 0190. 2. An aqueous mixture of a mineral ore, comprising material comprising the silicate material and the polyami a crude mineral ore, water, and a polyamidoamine, wherein doamine from the aqueous mixture, and collecting a purified the polyamidoamine comprises one or more amidoamines mineral ore from the aqueous mixture. having the chemical formula (A), wherein R' and Rare each 0.195 7. The method according to paragraph 6, wherein n independently a saturated or unsaturated, substituted or is 2 and the polyamidoamine has a hydrophilic-lipophilic unsubstituted, linear or branched, cyclic, heterocyclic, or aro balance of about 7.5 to about 12, n is 3 and the polyamidoam matic hydrocarbyl group, and R' and Rare different hydro ine has a hydrophilic-lipophilic balance of about 16.5 to about carbyl groups, RandR are each independently a hydrogen 21, or n is 4 and the polyamidoamine has a hydrophilic or a saturated or unsaturated, Substituted or unsubstituted, lipophilic balance of about 25.5 to about 30, based on the linear or branched, cyclic, heterocyclic, or aromatic hydro Davies’ Method for hydrophilic-lipophilic balance. carbyl group, each m is an integer of 1 to 5, and n is an integer 0.196 8. The method according to paragraph 6 or 7. of 2 to 8. wherein the polyamidoamine comprises a mixture of diami 0191 3. The aqueous mixture according to paragraph 2, doamines having a hydrophilic-lipophilic balance of about wherein the crude mineral ore is a phosphorous ore, an iron 7.5 to about 30, based on the Davies Method for hydrophilic ore, an aluminum ore, a potassium ore, a sodium ore, a cal lipophilic balance, wherein the mixture of diamidoamines cium ore, potash, feldspar, bauxite, any mixture thereof. comprises a first diamidoamine, a second diamidoamine, and 0192 4. An aqueous mixture of a phosphorous containing a third diamidoamine, and wherein the first diamidoamine has material, comprising a phosphorous ore, water, and a polya a first chemical formula wherein n is 2, the second diami midoamine, wherein the polyamidoamine comprises one or doamine has a second chemical formula wherein n is 3, and more amidoamines having the chemical formula (A), wherein the third diamidoamine has a third chemical formula wherein R" and Rare each independently a saturated or unsaturated, n is 4. substituted or unsubstituted, linear or branched, cyclic, het erocyclic, or aromatic hydrocarbyl group, and RandR are 0197) 9. The method according to any one of paragraphs 6 different hydrocarbyl groups, R and R are each indepen to 8, wherein the purified mineral ore is a phosphorous ore, an dently a hydrogen or a saturated or unsaturated, Substituted or iron ore, an aluminum ore, a potassium ore, a sodium ore, a unsubstituted, linear or branched, cyclic, heterocyclic, or aro calcium ore, potash, feldspar, bauxite, any mixture thereof. matic hydrocarbyl group, each m is an integer of 1 to 5, and in 0198 10. The method according to any one of paragraphs is an integer of 2 to 8. 6 to 9, wherein the collected silicate material is about 90 wt % 0193 5. The aqueous mixture according to paragraph 4, to about 99.99 wt % of the total silicate material contained in wherein the polyamidoamine comprises one or more ami the crude mineral ore, and wherein the collected purified doamines having the chemical formula (D), wherein R' and mineral ore is about 90 wt % to about 99.99 wt % of the total Rare each independently CH2s, CH, C, shss. Cishs, purified mineral ore contained in the crude mineral ore. ClsH29, C17Hss, C17Hss, C17H31, or C17H29, and n is 2, 3, or 0199 11. The cationic collector, the aqueous mixture, or 4, and wherein n is 2 and the polyamidoamine has a hydro the method according to any one of paragraphs 1 to 10, philic-lipophilic balance of about 7.5 to about 12, n is 3 and wherein R' is a C6 to C12 chain having 0 to 3 unsaturated the polyamidoamine has a hydrophilic-lipophilic balance of bonds, R is a C13 to C24 chain having 0 to 3 unsaturated about 16.5 to about 21, or n is 4 and the polyamidoamine has bonds, Rand Rare hydrogen, each m is 2, 3, or 4, and n is a hydrophilic-lipophilic balance of about 25.5 to about 30, 2, 3, 4, or 5. based on the Davies Method for hydrophilic-lipophilic bal 0200 12. The cationic collector, the aqueous mixture, or aCC. the method according to any one of paragraphs 1 to 11, US 2016/0114338 A1 Apr. 28, 2016 27 wherein R' is a C10 to C24 chain, R is a C1 to C5 chain, each 0211 23. The cationic collector according to paragraph m is 2, 3, or 4, and n is 2, 3, or 4. 22, wherein the cationic collector comprises about 10 wt % to 0201 13. The cationic collector, the aqueous mixture, or about 60 wt % of the organic acid, based on a combined the method according to any one of paragraphs 1 to 12, weight of the polyamidoamine and the organic acid, and wherein the polyamidoamine comprises one or more ami wherein the organic acid comprises glycolic acid, lactic acid, doamines having the chemical formula (D), wherein R' and pyruvic acid, formic acid, acetic acid, propionic acid, butyric R are each independently CoHis CoH is, CH2s, CH2, acid, Valeric acid, oxalic acid, isomers thereof, hydrates ClsHss, Cls Hai, Cish 29, C17Hss, C17Hss, C17H31, or thereof, salts thereof, adducts thereof, or any mixture thereof. C7H9, and n is 2, 3, or 4. 0212 24. The cationic collector according to paragraph 0202 14. The cationic collector, the aqueous mixture, or 22, wherein the polyamidoamine is in an amount of about 40 the method according to any one of paragraphs 1 to 13, wt % to about 90 wt %, based on a combined weight of the wherein the polyamidoamine comprises one or more ami polyamidoamine and the organic acid, and wherein the doamines having the chemical formula (O), wherein R' is a organic acid is glacial acetic acid. C6 to C24 chain, and n is 2, 3, or 4. 0213 25. The cationic collector, the aqueous mixture, or 0203 15. The cationic collector according to paragraph the method according to any one of paragraphs 1 to 24, 14, wherein R' is a C10 to C24 chain having 0 to 2 unsaturated wherein the polyamidoamine comprises a product formed by bonds, and n is 2, 3, or 4. reacting a polyamine and a fatty acid, wherein the polyamine 0204 16. The cationic collector, the aqueous mixture, or comprises diethylenetriamine, triethylenetetramine, tetraeth the method according to any one of paragraphs 1 to 13, ylenepentamine, pentaethylenehexamine, or any mixture wherein the polyamidoamine comprises one or more ami doamines having the chemical formula (D), wherein R' is a thereof, and wherein the fatty acid comprises tall oil fatty C10 to C24 chain, R is a C6 to C18 chain, and n is 2, 3, or 4. acids, coconut oil fatty acids, lauric acid, Stearic acid, isos 0205 17. The cationic collector according to paragraph tearic acid, naphthenic acid, oleic acid, linoleic acid, linolenic 16, wherein R' is a C12 to C24 chain having 0 to 2 unsaturated acid, palmitic acid, isomers thereof, or any mixture thereof. bonds, R is a C6 to C11 chain having 0 to 2 unsaturated 0214, 26. A cationic collector, comprising a polyami bonds, and n is 2, 3, or 4. doamine having the chemical formula (A), wherein: R' and 0206. 18. The cationic collector, the aqueous mixture, or Rare independently a saturated or unsaturated, substituted the method according to any one of paragraphs 1 to 17. or unsubstituted, linear or branched, cyclic, heterocyclic, or wherein n is 2 and the polyamidoamine has a hydrophilic aromatic hydrocarbyl group, R' and Rare different hydro lipophilic balance of about 7.5 to about 12, n is 3 and the carbyl groups, each R is independently hydrogen or a satu polyamidoamine has a hydrophilic-lipophilic balance of rated or unsaturated, substituted or unsubstituted, linear or about 16.5 to about 21, or n is 4 and the polyamidoamine has branched, cyclic, heterocyclic, or aromatic hydrocarbyl a hydrophilic-lipophilic balance of about 25.5 to about 30, group, R is hydrogen or a saturated or unsaturated, substi based on the Davies Method for hydrophilic-lipophilic bal tuted or unsubstituted, linear or branched, cyclic, heterocy aCC. clic, or aromatic hydrocarbyl group each m is independently 0207. 19. The cationic collector, the aqueous mixture, or an integer of 1 to 5, and n is an integer of 2 to 8. the method according to any one of paragraphs 1 to 18, 0215 27. An aqueous mixture of a phosphorous contain wherein the polyamidoamine comprises a mixture of diami ing material, comprising: an ore; water; and a polyamidoam doamines having a hydrophilic-lipophilic balance of about ine having the chemical formula (A), wherein: R' and Rare 7.5 to about 30, based on the Davies Method for hydrophilic independently a saturated or unsaturated, Substituted or lipophilic balance, wherein the mixture of diamidoamines unsubstituted, linear or branched, cyclic, heterocyclic, or aro comprises a first diamidoamine, a second diamidoamine, and matic hydrocarbyl group, RandR are different hydrocarbyl a third diamidoamine, and wherein the first diamidoamine has groups, each R is independently hydrogen or a saturated or a first chemical formula wherein n is 2, the second diami unsaturated, Substituted or unsubstituted, linear or branched, doamine has a second chemical formula wherein n is 3, and cyclic, heterocyclic, or aromatic hydrocarbyl group, R is the third diamidoamine has a third chemical formula wherein hydrogen or a saturated or unsaturated. Substituted or unsub n is 4. stituted, linear or branched, cyclic, heterocyclic, or aromatic 0208. 20. The cationic collector, the aqueous mixture, or hydrocarbyl group, each m is independently an integer of 1 to the method according to any one of paragraphs 1 to 19, 5, and n is an integer of 2 to 8. wherein the polyamidoamine comprises a polyethylene dia 0216. 28. A method for purifying a mineral, comprising: midoamine, a polyethylene triamidoamine, a polyethylene combining an ore, water, and a polyamidoamine to produce polyamidoamine with four or more amido groups, or any an aqueous mixture, wherein the ore is a silicate material, and mixture thereof. wherein the polyamidoamine has the chemical formula (A), 0209 21. The cationic collector, the aqueous mixture, or wherein: RandR are independently a saturated or unsatur the method according to any one of paragraphs 1 to 20, ated, Substituted or unsubstituted, linear or branched, cyclic, wherein the polyamidoamine comprises a mixture of poly heterocyclic, or aromatic hydrocarbyl group, R' and Rare ethylene diamidoamines and polyethylene triamidoamines, different hydrocarbyl groups, each R is independently and the mixture has about 0.5 mol% to about 20 mol% of the hydrogen or a saturated or unsaturated. Substituted or unsub polyethylene triamidoamines, based on the combined moles stituted, linear or branched, cyclic, heterocyclic, or aromatic of the polyethylene diamidoamines and the polyethylene tria hydrocarbyl group, R is hydrogen or a saturated or unsatur midoamines. ated, Substituted or unsubstituted, linear or branched, cyclic, 0210 22. The cationic collector, the aqueous mixture, or heterocyclic, or aromatic hydrocarbyl group, each m is inde the method according to any one of paragraphs 1 to 21, pendently an integer of 1 to 5, and n is an integer of 2 to 8: wherein the cationic collector comprises an organic acid. collecting a flocculated material comprising the silicate mate US 2016/0114338 A1 Apr. 28, 2016 28 rial and the polyamidoamine from the aqueous mixture; and 0224 36. An aqueous mixture, comprising: an ore; water; collecting a purified ore from the aqueous mixture. and a polyamidoamine having the chemical formula: 0217 29. The cationic collector, the aqueous mixture, or the method according to any one of paragraphs 26 to 28, O wherein: R' is a C6 to C12 chain having 0 to 3 unsaturated O bonds, R is a C13 to C24 chain having 0 to 3 unsaturated bonds, Rand each R is hydrogen, each m is independently R1 s-os- l 3 r R2, 2, 3, or 4, and n is 2, 3, 4, or 5. R R4 0218. 30. The cationic collector, the aqueous mixture, or the method according to any one of paragraphs 26 to 28, wherein: R' and Rare different and selected from a saturated wherein: R' is CoH is. CoHis C, H2s. CH2, Cishss. or unsaturated, Substituted or unsubstituted, linear or Cishsi Cshao, C7Hss, C17Hss, C17H1, or C17H29, R is branched, cyclic, heterocyclic, or aromatic hydrocarbyl CoH1s. CoH13. CH23. CH2, C15Hss, C1s Hs 1, C15H29. group, RandR are independently hydrogen or a saturated or C17Hss, C17Hss, C17H3, or C7H29. Rand each R is hydro unsaturated, Substituted or unsubstituted, linear or branched, gen, each m is 2, and n is 2, 3, or 4. cyclic, heterocyclic, or aromatic hydrocarbyl group, each mis an integer of 1 to 5, and n is an integer of 2 to 8. 0219. 31. The cationic collector, the aqueous mixture, or 0225 37. A method for purifying an ore, comprising: com the method according to any one of paragraphs 26 to 28, bining an ore, water, and a polyamidoamine to produce an wherein the polyamidoamine has the chemical formula: aqueous mixture, wherein the ore comprises an impurity, and wherein the polyamidoamine has the chemical formula:

CH3, O O

1,4)- in N l R2, R3

wherein: R' and Rare different and selected from a saturated wherein: R' is a C6 to C24 chain, and n is 2, 3, 4, or 5. or unsaturated, Substituted or unsubstituted, linear or branched, cyclic, heterocyclic, or aromatic hydrocarbyl 0220 32. The cationic collector, the aqueous mixture, or group, RandR are independently hydrogenora saturated or the method according to paragraph 31, wherein R' is a C10 to unsaturated, Substituted or unsubstituted, linear or branched, C24 chain having 0 to 2 unsaturated bonds, and n is 2, 3, or 4. cyclic, heterocyclic, or aromatic hydrocarbyl group, each mis 0221 33. The cationic collector, the aqueous mixture, or an integer of 1 to 5, and n is an integer of 2 to 8: collecting a the method according to any one of paragraphs 26 to 28, flocculated material comprising the impurity and the polya midoamine from the aqueous mixture; and collecting a puri wherein: R is a C10 to C24 chain, R is a C6 to C18 chain, R fied ore having a reduced concentration of the impurity rela and each R is hydrogen, each m is 2, and n is 2, 3, or 4. tive to the ore from the aqueous mixture. 0222 34. The cationic collector, the aqueous mixture, or 0226) 38. The composition, aqueous mixture, or method the method according to paragraph 33, wherein R' is a C12 to according to any one of paragraphs 35 to 38, wherein: R' is a C6 to C12 chain having 0 to 3 unsaturated bonds, R is a C13 C24 chain having 0 to 2 unsaturated bonds and R is a C6 to to C24 chain having 0 to 3 unsaturated bonds, Rand Rare C11 chain having 0 to 2 unsaturated bonds. hydrogen, each m is 2, 3, or 4, and n is 2, 3, 4, or 5. 0223 35. A composition, comprising a polyamidoamine 0227 39. The composition, aqueous mixture, or method having the chemical formula: according to any one of paragraphs 35 to 38, wherein: R is CoHs. CoH13. C H23. CH21. ClsHss, Cls His 1. C15H29. C17Hss, C17Hss, C17H1, or C17H29, R is CoHis Co.His CH2s. CH21. Cls Hss, ClsHs 1. C15H29. C17Hss, C17H3s. C7H1, or C-Ho, Rand Rare hydrogen, each m is 2, and n is 2, 3, or 4. 0228 40. The composition, aqueous mixture, or method according to any one of paragraphs 35 to 38, wherein the polyamidoamine has the chemical formula:

CH3, wherein: R' and Rare different and selected from a saturated or unsaturated. Substituted or unsubstituted, linear or branched, cyclic, heterocyclic, or aromatic hydrocarbyl group, RandR are independently hydrogen or a saturated or unsaturated, Substituted or unsubstituted, linear or branched, cyclic, heterocyclic, or aromatic hydrocarbyl group, each mis an integer of 1 to 5, and n is an integer of 2 to 8. wherein: R' is a C6 to C24 chain, and n is 2, 3, 4, or 5. US 2016/0114338 A1 Apr. 28, 2016 29

0229 41. The composition, aqueous mixture, or method 0242 54. The cationic collector, composition, aqueous according to any one of paragraphs 35 to 38 or 40, wherein R' mixture, or method according to any one of paragraphs 51 to is a C10 to C24 chain having 0 to 2 unsaturated bonds, and n 53, wherein the mixture comprises about 40 wt % to about 90 is 2, 3, or 4. wt % of the polyamidoamine, based on a combined weight of 0230. 42. The composition, aqueous mixture, or method the polyamidoamine and the organic acid, and wherein the according to any one of paragraphs 35 to 38, wherein: R is a organic acid comprises glacial acetic acid. C10 to C24 chain, R is a C6 to C18 chain, R and R are 0243 55. The cationic collector, composition, aqueous hydrogen, each m is 2, and n is 2, 3, or 4. mixture, or method according to any one of paragraphs 26 to 0231. 43. The composition, aqueous mixture, or method 54, wherein the polyamidoamine comprises a product formed according to any one of paragraphs 35 to 38 or 42, wherein R' by reacting a polyamine and a fatty acid. is a C12 to C24 chain having 0 to 2 unsaturated bonds and R' 0244 56. The cationic collector, composition, aqueous is a C6 to C11 chain having 0 to 2 unsaturated bonds. mixture, or method according to paragraph 55, wherein the 0232) 44. The composition according to paragraph 35, polyamine comprises diethylenetriamine, triethylenetetra wherein the composition is a cationic collector. mine, tetraethylenepentamine, pentaethylenehexamine, or 0233 45. The cationic collector, composition, aqueous any mixture thereof. mixture, or method according to any one of paragraphs 26 to 0245) 57. The cationic collector, composition, aqueous 44, wherein: n is 2 and the polyamidoamine has a hydro mixture, or method according to paragraph 55 or 56, wherein philic-lipophilic balance of about 7.5 to about 12, as mea the fatty acid comprises tall oil fatty acids, coconut oil fatty sured according to the Davies' Method for hydrophilic-lipo acids, lauric acid, stearic acid, isostearic acid, naphthenic philic balance. acid, oleic acid, linoleic acid, linolenic acid, palmitic acid, 0234 46. The cationic collector, composition, aqueous isomers thereof, or any mixture thereof. mixture, or method according to any one of paragraphs 26 to 0246) 58. The cationic collector, composition, aqueous 44, whereinnis3 and the polyamidoamine has a hydrophilic mixture, or method according to any one of paragraphs 26 to lipophilic balance of about 16.5 to about 21, as measured 28 or 35 to 37, wherein R' and Rare independently C, H., according to the Davies' Method for hydrophilic-lipophilic C11H21, C1s Has ClsH31, Cish 29, C17Hss, C17Hss, C17H31. balance. or C.H., R and R is hydrogen, and m is 2. 0235 47. The cationic collector, composition, aqueous 0247 59. The cationic collector, composition, aqueous mixture, or method according to any one of paragraphs 26 to mixture, or method according to paragraph 58, wherein n is 2 44, wherein n is 4 and the polyamidoamine has a hydrophilic and the polyamidoamine has a hydrophilic-lipophilic balance lipophilic balance of about 25.5 to about 30, as measured of about 7.5 to about 12, as measured according to the Davies’ according to the Davies' Method for hydrophilic-lipophilic Method for hydrophilic-lipophilic balance. balance. 0248) 60. The cationic collector, composition, aqueous 0236) 48. The cationic collector, composition, aqueous mixture, or method according to paragraph 58, wherein n is 3 mixture, or method according to any one of paragraphs 26 to and the polyamidoamine has a hydrophilic-lipophilic balance 47, wherein the polyamidoamine comprises a polyethylene of about 16.5 to about 21, as measured according to the diamidoamine, a polyethylene triamidoamine, a polyethyl Davies' Method for hydrophilic-lipophilic balance. ene polyamidoamine with four or more amido groups, or any 0249 61. The cationic collector, composition, aqueous mixture thereof. mixture, or method according to paragraph 58, wherein n is 4 0237 49. The cationic collector, composition, aqueous and the polyamidoamine has a hydrophilic-lipophilic balance mixture, or method according to any one of paragraphs 26 to of about 25.5 to about 30, as measured according to the 48, wherein the polyamidoamine comprises a mixture of Davies' Method for hydrophilic-lipophilic balance. polyethylene diamidoamines and polyethylene triamidoam (0250) 62. The cationic collector, composition, aqueous 10S. mixture, or method according to any one of paragraphs 26 to 0238 50. The cationic collector, composition, aqueous 61, wherein the aqueous mixture further comprises acetic mixture, or method according to any one of paragraphs 26 to acid. 49, wherein the mixture comprises about 0.5 mol % to about (0251 63. The aqueous mixture or the method according to 20 mol % of the polyethylene triamidoamines, based on the any one of paragraphs 27 to 34 or 36 to 62, wherein the ore is combined moles of the polyethylene diamidoamines and the a phosphorous ore, an iron ore, an aluminum ore, a potassium polyethylene triamidoamines. ore, a sodium ore, a calcium ore, potash, feldspar, bauxite, any 0239 51. The cationic collector, composition, aqueous mixture thereof. mixture, or method according to any one of paragraphs 26 to 0252) 64. The cationic collector, composition, aqueous 50, wherein the cationic collector further comprises an mixture, or method according to any one of paragraphs 26, 29 organic acid. to 34, or 45 to 63, wherein the cationic collector has a viscos 0240 52. The cationic collector, composition, aqueous ity of about 10 cP to about 800 cp at a temperature of 25° C. mixture, or method according to paragraph 51, wherein the 0253) 65. The cationic collector, the aqueous mixture, or cationic collector comprises about 10 wt % to about 60 wt % the method according to any one of paragraphs 26, 29 to 34. of the organic acid, based on a combined weight of the polya or 45 to 63, wherein the cationic collector has a viscosity of midoamine and the organic acid. about 10 cP to about 160 cp at a temperature of 25° C. 0241 53. The cationic collector, composition, aqueous (0254 66. The cationic collector, the aqueous mixture, or mixture, or method according to paragraph 51 or 52, wherein the method according to any one of paragraphs 26, 29 to 34. the organic acid comprises glycolic acid, lactic acid, pyruvic or 45 to 63, wherein the cationic collector has a viscosity of acid, formic acid, acetic acid, propionic acid, butyric acid, about 10 cP to about 140 cF at a temperature of 25° C. Valeric acid, oxalic acid, isomers thereof, hydrates thereof, (0255 67. The cationic collector, the aqueous mixture, or salts thereof, adducts thereof, or any mixture thereof. the method according to any one of paragraphs 26, 29 to 34. US 2016/0114338 A1 Apr. 28, 2016 30 or 45 to 63, wherein the cationic collector has a viscosity of two upper values are contemplated unless otherwise indi about 10 cP to about 300 cF at a temperature of 80° C. cated. Certain lower limits, upper limits and ranges appear in 0256 68. The cationic collector, the aqueous mixture, or one or more claims below. All numerical values are “about' or the method according to any one of paragraphs 26, 29 to 34. “approximately the indicated value, and take into account or 45 to 63, wherein the cationic collector has a viscosity of experimental error and variations that would be expected by a about 10 cP to about 100 cF at a temperature of 80° C. person having ordinary skill in the art. 0257 69. The cationic collector, the aqueous mixture, or 0266 Various terms have been defined above. To the the method according to any one of paragraphs 26, 29 to 34. extent a term used in a claim is not defined above, it should be or 45 to 63, wherein the cationic collector further comprises given the broadest definition persons in the pertinent art have an organic acid and water, and wherein the cationic collector given that term as reflected in at least one printed publication has a viscosity of about 10 cp to about 800 cp at a temperature or issued patent. Furthermore, all patents, test procedures, of 25°C. when the cationic collector includes about 2 wt % to and other documents cited in this application are fully incor about 50 wt % of the organic acid, about 2 wt % to about 50 porated by reference to the extent such disclosure is not wt % of water, and about 30 wt % to about 95 wt % of the inconsistent with this application and for all jurisdictions in polyamidoamine, based on the combined weight of the polya which Such incorporation is permitted. midoamine, the organic acid, and the water. 0258 70. The cationic collector, the aqueous mixture, or 0267 While the foregoing is directed to embodiments, the method according to any one of paragraphs 26, 29 to 34. other and further embodiments of the invention can be or 45 to 63, wherein the cationic collector further comprises devised without departing from the basic scope thereof, and an organic acid and water, and wherein the cationic collector the scope thereof is determined by the claims that follow. has a viscosity of about 10 cp to about 800 cp at a temperature of 25°C. when the cationic collector includes about 20 wt % What is claimed is: to about 60 wt % of the organic acid, about 20 wt % to about 1. A composition, comprising a polyamidoamine having 60 wt % of water, and about 30 wt % to about 80 wt % of the the chemical formula: polyamidoamine, based on the combined weight of the polya midoamine, the organic acid, and the water. 0259 71. The composition according to any one of para O graphs 35 or 37 to 63, wherein the composition further com O prises an organic acid and water, and wherein the composition has a viscosity of about 10 cp to about 800 cp at a temperature 1,4)- NN ls R2, of 25°C. when the composition includes about 2 wt % to R3 about 50 wt % of the organic acid, about 2 wt % to about 50 wt % of water, and about 30 wt % to about 95 wt % of the polyamidoamine, based on the combined weight of the polya midoamine, the organic acid, and the water. wherein: 0260 72. The composition according to any one of para R" and Rare different and selected from a saturated or graphs 35 or 37 to 63, wherein the composition further com unsaturated, Substituted or unsubstituted, linear or prises an organic acid and water, and wherein the composition branched, cyclic, heterocyclic, or aromatic hydrocar has a viscosity of about 10 cp to about 800 cp at a temperature byl group, of 25°C. when the composition includes about 20 wt % to Rand Rare independently hydrogen or a saturated or about 60 wt % of the organic acid, about 20 wt % to about 60 unsaturated, Substituted or unsubstituted, linear or wt % of water, and about 30 wt % to about 80 wt % of the branched, cyclic, heterocyclic, or aromatic hydrocar polyamidoamine, based on the combined weight of the polya byl group, midoamine, the organic acid, and the water. 0261) 73. The aqueous mixture or method according to each m is an integer of 1 to 5, and any one of paragraphs 36 to 70, wherein the ore is a phospho n is an integer of 2 to 8. OUIS O. 0262 74. The aqueous mixture or method according to 2. The composition of claim 1, wherein: any one of paragraphs 36 to 70, wherein the impurity com R" is a C6 to C12 chain having 0 to 3 unsaturated bonds, prises a silicate material. 0263 75. The aqueous mixture or method according to R’ is a C13 to C24 chain having 0 to 3 unsaturated bonds, any one of paragraphs 36 to 70, 73, or 74, wherein the aqueous Rand Rare hydrogen, mixture comprises about 0.0001 wt % to about 2 wt % of the polyamidoamine, based on the weight of the ore. each m is an integer of 2, 3, or 4, and 0264 76. The aqueous mixture or method according to n is an integer of 2, 3, 4, or 5. any one of paragraphs 36 to 70, 73, or 75, wherein the aqueous 3. The composition of claim 1, wherein: mixture comprises about 0.0001 wt % to about 2 wt % of the organic acid, based on the weight of the ore. R" and R are selected from CoHis CH, C, Has. 0265 Certain embodiments and features have been CH21. Cls Hss, ClsHs 1. C15H29. C17Hss, C 71.H 1333 described using a set of numerical upper limits and a set of C17H3, or C17H29. numerical lower limits. It should be appreciated that ranges RandR are hydrogen, including the combination of any two values, e.g., the com bination of any lower value with any upper value, the combi each m is 2, and nation of any two lower values, and/or the combination of any n is 2, 3, or 4. US 2016/0114338 A1 Apr. 28, 2016

4. The composition of claim 1, wherein the polyamidoam 14. The composition of claim 1, wherein the polyami ine has the chemical formula: doamine comprises a product formed by reacting a polyamine and a fatty acid, wherein the polyamine comprises diethylen etriamine, triethylenetetramine, tetraethylenepentamine, CH pentaethylenehexamine, or any mixture thereof, and wherein O H 3. the fatty acid comprises tall oil fatty acids, coconut oil fatty l acids, lauric acid, Stearic acid, isostearic acid, naphthenic RI 1-1 acid, oleic acid, linoleic acid, linolenic acid, palmitic acid, isomers thereof, or any mixture thereof. h O 15. An aqueous mixture, comprising: an ore; wherein: water, and R" is a C6 to C24 chain, and a polyamidoamine having the chemical formula: n is 2, 3, 4, or 5. 5. The composition of claim 4, wherein R' is a C10 to C24 chain having 0 to 2 unsaturated bonds, and n is 2, 3, or 4. O 6. The composition of claim 1, wherein: O R" is a C10 to C24 chain, R’ is a C6 to C18 chain, 1,4)- in N l R2, Rand Rare hydrogen, R3 each m is 2, and R4 n is 2, 3, or 4. 7. The composition of claim 6, wherein R' is a C12 to C24 wherein: chain having 0 to 2 unsaturated bonds and R is a C6 to C11 R" and Rare different and selected from a saturated or chain having 0 to 2 unsaturated bonds. unsaturated, Substituted or unsubstituted, linear or 8. The composition of claim 1, wherein: branched, cyclic, heterocyclic, or aromatic hydrocar n is 2 and the polyamidoamine has a hydrophilic-lipophilic byl group, balance of about 7.5 to about 12, as measured according Rand Rare independently hydrogen or a saturated or to the Davies Method for hydrophilic-lipophilic bal unsaturated, Substituted or unsubstituted, linear or ance, branched, cyclic, heterocyclic, or aromatic hydrocar n is 3 and the polyamidoamine has a hydrophilic-lipophilic byl group, balance of about 16.5 to about 21, as measured accord each m is an integer of 1 to 5, and ing to the Davies’ Method for hydrophilic-lipophilic n is an integer of 2 to 8. balance; or n is 4 and the polyamidoamine has a hydrophilic-lipophilic 16. The aqueous mixture of claim 15, wherein: balance of about 25.5 to about 30, as measured accord R" and R are independently CH, C, H, CHs. ing to the Davies’ Method for hydrophilic-lipophilic Cls Hs 1, C15H29, C17Hss, C17H33, C17H31, or C17H29. balance. RandR are hydrogen, and 9. The composition of claim 1, wherein the polyamidoam each m is 2, and wherein: ine comprises a polyethylene diamidoamine, a polyethylene n is 2 and the polyamidoamine has a hydrophilic-lipo triamidoamine, a polyethylene polyamidoamine with four or philic balance of about 7.5 to about 12, as measured more amido groups, or any mixture thereof. according to the Davies Method for hydrophilic-li 10. The composition of claim 1, wherein the polyami pophilic balance; doamine comprises a mixture of polyethylene diamidoam n is 3 and the polyamidoamine has a hydrophilic-lipo ines and polyethylene triamidoamines, and wherein the mix philic balance of about 16.5 to about 21, as measured ture comprises about 0.5 mol % to about 20 mol % of the according to the Davies Method for hydrophilic-li polyethylene triamidoamines, based on the combined moles pophilic balance; or of the polyethylene diamidoamines and the polyethylene tria n is 4 and the polyamidoamine has a hydrophilic-lipo midoamines. philic balance of about 25.5 to about 30, as measured 11. The composition of claim 1, wherein the composition according to the Davies Method for hydrophilic-li further comprises an organic acid. pophilic balance. 12. The composition of claim 11, wherein the composition 17. The aqueous mixture of claim 15, wherein the aqueous comprises about 10 wt % to about 60 wt % of the organic acid, mixture further comprises acetic acid, wherein the ore is a based on a combined weight of the polyamidoamine and the phosphorous ore, an iron ore, an aluminum ore, a potassium organic acid, and wherein the organic acid comprises glycolic ore, a sodium ore, a calcium ore, potash, feldspar, bauxite, any acid, lactic acid, pyruvic acid, formic acid, acetic acid, pro mixture thereof, and wherein the aqueous mixture comprises pionic acid, butyric acid, Valeric acid, oxalic acid, isomers about 0.0001 wt % to about 2 wt % of the polyamidoamine thereof, hydrates thereof, salts thereof, adducts thereof, or any and about 0.0001 wt % to about 2 wt % of the acetic acid, mixture thereof. based on the weight of the ore. 13. The composition of claim 11, wherein the composition 18. A method for purifying an ore, comprising: comprises about 40 wt % to about 90 wt % of the polyami combining an ore, water, and a polyamidoamine to produce doamine, based on a combined weight of the polyamidoam an aqueous mixture, wherein the ore comprises an impu ine and the organic acid, and wherein the organic acid com rity, and wherein the polyamidoamine has the chemical prises glacial acetic acid. formula: US 2016/0114338 A1 Apr. 28, 2016 32

19. The method of claim 18, wherein: O O n is 2 and the polyamidoamine has a hydrophilic-lipophilic balance of about 7.5 to about 12, as measured according R -> nNN l R2, to the Davies' Method for hydrophilic-lipophilic bal R3 ance; R4 n is 3 and the polyamidoamine has a hydrophilic-lipophilic balance of about 16.5 to about 21, as measured accord wherein: R" and R are different and selected from a saturated or ing to the Davies' Method for hydrophilic-lipophilic unsaturated, substituted or unsubstituted, linear or balance; or branched, cyclic, heterocyclic, or aromatic hydrocar n is 4 and the polyamidoamine has a hydrophilic-lipophilic byl group, balance of about 25.5 to about 30, as measured accord Rand Rare independently hydrogen or a saturated or ing to the Davies' Method for hydrophilic-lipophilic unsaturated, substituted or unsubstituted, linear or balance. branched, cyclic, heterocyclic, or aromatic hydrocar byl group, 20. The method of claim 18, wherein the ore is a phospho each m is an integer of 1 to 5, and rous ore, an iron ore, an aluminum ore, a potassium ore, a n is an integer of 2 to 8: Sodium ore, a calcium ore, potash, feldspar, bauxite, any collecting a flocculated material comprising the impurity mixture thereof, wherein the impurity comprises a silicate and the polyamidoamine from the aqueous mixture; and material, and wherein the aqueous mixture comprises about collecting a purified ore having a reduced concentration of 0.0001 wt % to about 2 wt % of the polyamidoamine, based the impurity relative to the ore from the aqueous mix on the weight of the ore. ture.