Process to treat phosphate ores

Abstract

The present invention relates to a process for treating non-sulfidic ores with a collector composition containing a primary and a secondary collector, wherein the primary collector is selected from the group of amphoteric and anionic surface active compounds and the secondary collector is an ethoxylated fatty acid wherein the average degree of ethoxylation is higher than 0 and less than 2, to collector compositions suitable for use in the above process, and to pulp comprising such collector compositions.

Claims

1. A process comprising the step of treating non-sulfidic ores with a collector composition, wherein the collector composition comprises from 3 to 60 wt % of a secondary collector and from 40 to 97 wt % of at least one primary collector, the wt % being based on a total weight of the primary and secondary collectors, wherein the primary collector is selected from the group of amphoteric and anionic surface-active compounds and the secondary collector is an ethoxylated fatty acid having an average degree of ethoxylation of greater than 0 and less than 2.

2. The process of claim 1, wherein the ethoxylated fatty acid is of the formula
R—C(O)—O-(EO)n  (I), wherein R is an alkyl or alkenyl group having 7 to 23 carbon atoms; EO is an ethyleneoxy unit; and n is a number greater than 0.5 and less than 2.

3. The process of claim 2, wherein R is a hydrocarbyl group having 11 to 21 carbon atoms, is linear or branched, has 0 to 4 double bonds and is optionally substituted with up to 3 hydroxyl substituents.

4. The process of claim 3, wherein the primary collector is an N-acyl derivative of sarcosine, an N-acyl derivative of glycine, or combinations thereof.

5. The process of claim 3, wherein the primary collector is an anionic surfactant selected from the group of fatty acids, alkyl benzene sulfonates, alkyl phosphates, alkyl sulfates, alkyl sulfosuccinamates, alkyl sulfosuccinates, alkyl lactylates, alkyl hydroxamates, N-acyl neutral amino acids, and mixtures thereof.

6. The process of claim 3, wherein the primary collector is an amphoteric surfactant of the following formula ##STR00003## wherein R is a hydrocarbon group having from 10 to 18 carbon atoms; A is an oxyalkylene group having from 2 to 4 carbon atoms; R.sub.1 is selected from the group consisting of hydrogen and hydrocarbon groups having from 1 to 4 carbon atoms; Y.sup.− is selected from the group consisting of COO.sup.− and SO.sub.3.sup.−; n is a number from 0 to 1; p is a number from 0 to 5; and q is a number from 1 to 2.

7. The process of claim 2, wherein the primary collector is an N-acyl derivative of sarcosine, an N-acyl derivative of glycine, or combinations thereof.

8. The process of claim 2, wherein the primary collector is an anionic surfactant selected from the group of fatty acids, alkyl benzene sulfonates, alkyl phosphates, alkyl sulfates, alkyl sulfosuccinamates, alkyl sulfosuccinates, alkyl lactylates, alkyl hydroxamates, N-acyl neutral amino acids, and mixtures thereof.

9. The process of claim 2, wherein the primary collector is an amphoteric surfactant of the following formula ##STR00004## wherein R is a hydrocarbon group having from 10 to 18 carbon atoms; A is an oxyalkylene group having from 2 to 4 carbon atoms; R.sub.1 is selected from the group consisting of hydrogen and hydrocarbon groups having from 1 to 4 carbon atoms; Y.sup.− is selected from the group consisting of COO.sup.− and SO.sub.3.sup.−; n is a number from 0 to 1; p is a number from 0 to 5; and q is a number from 1 to 2.

10. The process of claim 2, wherein the primary collector is an amphoteric surfactant of the following formula ##STR00005## wherein R is a hydrocarbon group having from 7 to 24 carbon atoms; A is an oxyalkylene group having from 2 to 4 carbon atoms; R.sub.1 is selected from the group consisting of hydrogen and hydrocarbon groups having from 1 to 4 carbon atoms; Y.sup.− is selected from the group consisting of COO.sup.− and SO.sub.3.sup.−; n is a number from 0 to 1; p is a number from 0 to 5; and q is a number from 1 to 2.

11. The process of claim 1, wherein the primary collector is an anionic surfactant selected from the group of fatty acids, alkyl benzene sulfonates, alkyl phosphates, alkyl sulfates, alkyl sulfosuccinamates, alkyl sulfosuccinates, alkyl lactylates, alkyl hydroxamates, N-acyl neutral amino acids and mixtures thereof.

12. The process of claim 1, wherein the primary collector is an amphoteric surfactant of the following formula ##STR00006## wherein R is a hydrocarbon group having from 7 to 24 carbon atoms; A is an oxyalkylene group having from 2 to 4 carbon atoms; R.sub.1 is selected from the group consisting of hydrogen and hydrocarbon groups having from 1 to 4 carbon atoms; Y.sup.− is selected from the group consisting of COO— and SO.sub.3.sup.−—; n is a number from 0 to 1; p is a number from 0 to about 5; and q is a number from 1 to 2.

13. The process of claim 1, wherein the collector composition comprises more than one primary collector.

14. The process of claim 1, wherein the ore is phosphate ore.

15. The process of claim 1, wherein the process is a direct flotation process.

16. A process comprising the following steps: a) conditioning a pulped ore comprising a non-sulfidic mineral and optionally flotation bath adjuncts, in an aqueous solution; b) adding the collector composition of claim 1 to the aqueous solution; b) optionally adding one or more additional flotation bath adjuncts and/or one or more depressants to the pulped ore, and c) performing a froth flotation process to recover the non-sulfidic mineral.

17. The process of claim 1, wherein the primary collector is an N-acyl derivative of sarcosine, an N-acyl derivative of glycine, or combinations thereof.

18. The process of claim 1, wherein the primary collector is an amphoteric surfactant of the following formula ##STR00007## wherein R is a hydrocarbon group having from 10 to 18 carbon atoms; A is an oxyalkylene group having from 2 to 4 carbon atoms; R.sub.1 is selected from the group consisting of hydrogen and hydrocarbon groups having from 1 to 4 carbon atoms; Y.sup.− is selected from the group consisting of COO.sup.− and SO.sub.3.sup.−; n is a number from 0 to 1; p is a number from 0 to 5; and q is a number from 1 to 2.

19. The process of claim 1, wherein, the collector composition comprises more than one primary collector, one of the one or more primary collectors comprising an amphoteric surfactant of the following formula ##STR00008## wherein R is a hydrocarbon group having from 8 to 18 carbon atoms; A is an oxyalkylene group having from 2 to 4 carbon atoms; R.sub.1 is selected from the group consisting of hydrogen and hydrocarbon groups having from 1 to 4 carbon atoms; Y.sup.− is selected from the group consisting of COO.sup.− and SO.sub.3.sup.−; n is a number from 0 to 1; p is a number from 0 to 5; and q is a number from 1 to 2; and an anionic surfactant selected from the group of fatty acids, alkyl benzene sulfonates, alkyl phosphates, alkyl sulfates, alkyl sulfosuccinamates, alkyl sulfosuccinates, alkyl lactylates, alkyl hydroxamates, N-acyl neutral amino acids, and mixtures thereof; the ethoxylated fatty acid is of the formula
R—C(O)—O-(EO)n  (I), wherein R is a hydrocarbyl group having 11 to 21 carbon atoms, is linear or branched, has 0 to 4 double bonds and is optionally substituted with up to 3 hydroxyl substituents; EO is an ethyleneoxy unit; and n is a number greater than 0.5 and less than 2; the ore is apatite ore; and the process is a direct flotation process.

20. A pulp comprising crushed and ground non-sulfidic ore, and a collector composition comprising from 3 to 60 wt % of a secondary collector and from 40 to 97 wt % of a primary collector, the wt % being based on a total weight of the primary and secondary collectors, wherein the primary collector is selected from the group of amphoteric and anionic surface-active compounds and the secondary collector is an ethoxylated fatty acid having an average degree of ethoxylation of greater than 0 and less than 2.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) The present disclosure will hereinafter be described in conjunction with the following drawing figure, wherein: FIG. 1 is a schematic representation of the flotation steps that are performed and the different fractions collected as described relative to Example 1 and Comparative Examples 2 and 3 and also relative to Example 4 and Comparative Examples 5.

(2) Surprisingly, it was found that using a fatty acid ethoxylate with a low degree of ethoxylation in a combination with one or more primary anionic or amphoteric collectors improves the selectivity of the already selective primary collectors in a process to treat non-sulfidic ores.

(3) In a preferred process a fatty acid ethoxylate was found to provide improved selectivity when used in the flotation of phosphate ores, such as more preferably apatite ores.

(4) The present invention now provides a process for treating non-sulfidic ores with a collector composition containing a primary and a secondary collector, wherein the primary collector is selected from the group of amphoteric and anionic surface-active compounds and the secondary collector is an ethoxylated fatty acid wherein the average degree of ethoxylation is higher than 0 and less than 2.

(5) It may be noted that U.S. Pat. No. 2,312,466 discloses a flotation process for phosphate rocks wherein glycol oleate (i.e. monoethoxylated oleic acid) is used but combined with pine tar oil and fuel oil, neither of which can be considered anionic or amphoteric surfactants.

(6) It may furthermore be noted that U.S. Pat. No. 2,259,420 discloses a flotation process and reagents for use therein to separate minerals, particularly for the oxidized ores of manganese. The flotation process disclosed involves the use of (talloel) tall oil as a flotation reagent. The document indicates that it is beneficial to make an aqueous composition in which the tall oil is emulsified using a small amount (0.25 to 2% on total tall oil amount) of emulsifying agent. Ethylene glycol oleate is mentioned as one choice from a group of compounds that can be used as an emulsifying agent. There is no disclosure or suggestion that an emulsifying agent would also function as a secondary collector in U.S. '420, especially because the amounts in which emulsifying agents and secondary collectors are used are different in the sense that secondary collectors are commonly used in higher amounts than the emulsifying agent is used in U.S. '420. Also in U.S. '420 no ores are treated with a composition that contains, besides the tall oil, an ethylene glycol based emulsifying agent. The one example wherein an emulsifying agent is used, 1% of propylene glycol oleate on tall oil amount is employed as this emulsifying agent. Finally, in U.S. '420 manganese ore treatments are disclosed only for ores in which the amount of manganese is higher than 10 wt % on total ore weight.

(7) The invention furthermore provides a collector composition suitable for use in the above process containing between 1 and 60 wt % of secondary collector and between 40 and 99 wt % of primary collector, the wt % being based on total collector components, wherein the primary collector is selected from the group of amphoteric and anionic surface-active compounds and the secondary collector is an ethoxylated fatty acid wherein the average degree of ethoxylation is higher than 0 and less than 2, and a pulp comprising the crushed and ground non-sulfidic ore and a collector composition as described herein.

(8) In preferred embodiments the ethoxylated fatty acid in the collector composition is of the formula
R—C(O)—O-(EO)n  (I),

(9) wherein R is an alkyl or alkenyl group having 7 to 23 carbon atoms and EO is an ethyleneoxy unit; n is a number higher than 0.5 and up to 2.

(10) In a more preferred embodiment R is a hydrocarbyl group having 11 to 21 carbon atoms, can be linear or branched, contain 0 to 4 double bonds and may be substituted with up to 3 hydroxyl substituents. Even more preferably, R is a fatty acid-derived hydrocarbyl group with 15 to 18 carbon atoms containing 0, 1 or 2 double bonds. Most preferably, R is the hydrocarbyl group derived from a fatty acid from the group of soybean fatty acid, cottonseed fatty acid, linseed fatty acid, oleic acid, linoleic acid, ricinoleic acid, and tall oil fatty acid. It should be noted that it is possible to use mixtures of different ethoxylated fatty acids obtainable by ethoxylating a mixture of fatty acids with up to 2, preferably 0.5 to 2, equivalents of ethylene oxide.

(11) In another preferred embodiment the collector composition contains between 3 and 50 wt % of secondary collector(s) and between 50 and 97 wt % of primary collector(s), even more preferably between 5 and 40 wt % of secondary collector(s) and between 60 and 95 wt % of primary collector(s), most preferably between 70 and 90 wt % of primary collector(s) and between 10 and 30 wt % of secondary collector(s), wherein the primary collector comprises a collector selected from the group of amphoteric and anionic surface-active compounds, and combinations of two or more of these, and the secondary collector comprises one or more ethoxylated fatty acids wherein the average degree of ethoxylation is higher than 0 and less than 2, and the wt % is based on total collector weight.

(12) In preferred embodiments the primary collector comprises an anionic surfactant selected from the group of fatty acids, alkyl benzene sulfonates, alkyl phosphates, alkyl sulfates, alkyl sulfosuccinamates, alkyl sulfosuccinates, alkyl lactylates, alkyl hydroxamates, N-acyl neutral amino acid (alkylamido carboxylic acid), like N-acyl derivatives of sarcosine or N-acyl derivatives of glycine, or an amphoteric surfactant of the following formula

(13) ##STR00002##

(14) wherein R is a hydrocarbon group having from 7 to 24 carbon atoms, and preferably from 10 to 18 carbon atoms; A is an oxyalkylene group having from 2 to 4 carbon atoms; R1 is selected from the group consisting of hydrogen and hydrocarbon groups having from 1 to 4 carbon atoms; Y.sup.− is selected from the group consisting of COO.sup.− and SO3.sup.−; n is a number from 0 to 1; p is a number from 0 to about 5; and q is a number from 1 to 2.

(15) In even more preferred embodiments the primary collector comprises one or more anionic surfactants selected from the group of fatty acids, alkyl benzene sulfonates, alkyl phosphates, alkyl sulfates, alkyl sulfosuccinamates, alkyl sulfosuccinates, alkyl lactylates, alkyl hydroxamates, N-acyl neutral amino acid (alkylamido carboxylic acid), like N-acyl derivatives of sarcosine or N-acyl derivatives of glycine, and is substantially free of amphoteric surfactants, i.e. contains less than 5 wt % on total primary collector weight of amphoteric surfactants, yet more preferably less than 1 wt %. Most preferably, anionic surfactants are selected from the group of fatty acids, alkyl lactylates, and the N-acyl derivatives of sarcosine and glycine.

(16) In preferred processes or pulp according to the invention the ore is a non-metallic ore, more preferably it is a phosphate ore. In an even more preferred process or pulp the ore is apatite ore. A non-metallic ore is an ore in which less than 5 wt % of metallic components are present on total ore weight, preferably less than 1 wt % on total ore weight, even more preferably less than 0.3 wt %

(17) In other preferred processes or pulp according to the invention the ore is a metallic ore, more preferably it is a metallic phosphate ore, such as even more preferably an iron-containing phosphate ore, titanium-containing phosphate ore, or alkaline earth metal-containing phosphate ore (the alkaline earth metal being e.g. magnesium or barium), most preferably an apatite-containing iron ore.

(18) In further preferred processes or pulp the ore contains less than 10 wt % of manganese, more preferably less than 5 wt % of manganese, yet more preferably less than 1 wt % of manganese, most preferably less than 0.3 wt % of manganese, on total ore weight.

(19) In other preferred embodiments the process is a direct flotation process of the ore, more preferably a direct flotation process of phosphate ore, such as apatite (which includes for example the reverse flotation of iron ores wherein apatite is floated).

(20) More specifically in yet another preferred embodiment the process comprises the following steps:

(21) a) conditioning a pulped ore, wherein the ore comprises a non-sulfidic mineral, such as phosphate, and optionally a flotation bath adjunct, in an aqueous solution

(22) b) adding the collector composition as described above

(23) b) optionally adding another flotation bath adjunct or a depressant to the pulp, and

(24) c) performing a froth flotation process to recover the mineral.

(25) Depressants can suitably be biopolymers, such as celluloses or starches, or they can be silicates. The celluloses or starches and silicates can be used as such or modified, as is known to the person skilled in the art.

(26) Flotation bath adjuncts that are of use in the process of the invention include pH-regulators, frothers, and activators. For example, nonionic surfactants can be added to contribute to the activity of the primary collector and to the regulation of the froth evolution.

(27) Compounds suitable as secondary collector in accordance with the present invention may be obtained by the addition of alkylene oxide to a carboxylic acid. The value of n in the above formula (I), also referred to as the average degree of ethoxylation in this document, does not represent a pure compound which always has the same amount of EO groups to the fatty acid but indicates that the fatty acid ethoxylate has been obtained by reacting the fatty acid with n molar equivalents of ethylene glycol, giving a product mixture wherein the average EO degree is n. Consequently, n does not have to be an integer.

(28) This reaction is well-known to those skilled in the art and usually results in some by-products. Typical by-product can be unreacted carboxylic acid, dialkyl carboxylic acid ethylene glycol ester, carboxylic acid soap and ethylene glycol. Usually by-products do not affect the process of flotation, but they can contribute to the flotation or appearance of the product-formulation in a positive way. For example, the unreacted carboxylic acid and carboxylic acid soap can perform as a primary anionic collector; dialkyl carboxylic acid ethylene glycol ester and ethylene glycol can perform as solvents.

EXAMPLE 1 AND COMPARATIVE EXAMPLES 2 AND 3

(29) A phosphate ore containing 25-30% of apatite, 24-28% of silicates and ca 20% of iron oxides was crushed and ground to a desirable flotation size (K80=180 μm). 500 g of the ore was placed into a 1.4 L Denver flotation cell, 500 ml of tap water (Stenungsund municipal water with hardness 4° dH) was added and the mixing started. Then 5 minutes conditioning with 25 ml of a 1 wt % aqueous starch solution was performed, the collector was added as a 1 wt % solution, and conditioning was continued for 2.5 minutes.

(30) In Example 1 according to the invention the primary collector is an alkyl amido sarcosinate compound ex Croda sold under the tradename Crodacinic™ 0 combined with tall oil fatty acid (TOFA), and an ethoxylated tall oil fatty acid obtained by ethoxylating tall oil fatty acid with 1 molar equivalent of ethylene oxide is added as secondary collector. In Examples 2 and 3, which are comparative, the collector composition instead of tall oil contains fatty acid ethoxylated with 1 molar equivalent of ethylene oxide, the same tall oil fatty acid ethoxylated with 10 equivalents of ethylene oxide as a secondary collector, or no secondary collector. The compositions are summarized in Table 1 below.

(31) TABLE-US-00001 TABLE 1 Composition of collector mixtures used in the flotations Amount of flotation aids in the collector mixture, weight % Crodacinic TOFA O TOFA + 1EO TOFA + 10EO Example 1 40 40 20 Comparative 40 40 20 Example 2 Comparative 50 50 Example 3

(32) After the conditioning steps tap water was added, so that a total volume of 1.4 L was obtained, the pH of the flotation mixture was adjusted to 9.5 with a 5% NaOH aqueous solution, and the flotation was started. The experiment was performed at RT (20±1° C.). The rougher flotation, followed by one cleaning step, was performed. All fractions (tailings, middlings and concentrate) were collected and analyzed. The results are summarized in Tables 2 and 3 below. In FIG. 1 the flotation steps performed and the different fractions collected are illustrated schematically.

(33) Results

(34) TABLE-US-00002 TABLE 2 Flotation results presented as P.sub.2O.sub.5 recovery and grade. Collector Amount of phosphate as P.sub.2O.sub.5 composition Fraction grade, % recovery, % Example 1 Rougher tailings 26.62 90.4 Middlings 31.69 84.7 concentrate 34.29 78.4 Comparative Rougher tailings 27.54 88.8 Example 2 Middlings 32.57 82.7 concentrate 34.92 75.1 Comparative Rougher tailings 24.84 91.2 Example 3 Middlings 29.48 86.6 concentrate 32.15 81.7

(35) TABLE-US-00003 TABLE 3 selectivity factor at grade Collector Selectivity factor at grade composition 27.6% of P.sub.2O.sub.5 29.8% P.sub.2O.sub.5 Example 1 4.9 3.2 Comparative 4.5 3.2 Example 2 Comparative 4.0 2.2 Example 3

(36) The selectivity factor is calculated according to the following equation:

(37) $\mathrm{Selectivity}\mathrm{factor}=\frac{\mathrm{reduction}\mathrm{of}\mathrm{waste}\left(\%\right)}{100-\mathrm{recovery}\mathrm{of}\mathrm{apatite}\left(\%\right)},\mathrm{Where}$$\mathrm{Reduction}\mathrm{of}\mathrm{waste}\left(\%\right)=\frac{\mathrm{waste}\mathrm{in}\mathrm{fraction}\left(\%\right)}{\mathrm{waste}\mathrm{in}\mathrm{the}\mathrm{feed}\left(\%\right)}*100$

(38) The selectivity factor should be as high as possible, which is clearly the case for Example 1 according to the present invention over the scope of several P.sub.2O.sub.5 grades. Accordingly, using a fatty acid having a low degree of ethoxylation in line with the present invention as a secondary collector proves advantageous for the selectivity in a phosphate flotation process compared to using a secondary collector that has a higher degree of ethoxylation or no secondary collector.

Example 4 and Comparative Examples 5

(39) A phosphate ore containing 25-30% of apatite, 24-28% of silicates and ca 20% of iron oxides was crushed and ground to a desirable flotation size (K80=180 μm). 500 g of the ore was placed into a 1.4 L Denver flotation cell, 500 ml of tap water (Stenungsund municipal water with hardness 4° dH) was added and the mixing started. Then 5 minutes conditioning with 25 ml of a 1 wt % aqueous starch solution was performed, the collector was added as a 1 wt % solution, and conditioning was continued for 2.5 minutes.

(40) In Example 4 according to the invention the primary collector is an alkyl amido glycinate compound prepared according to WO2015/000931 combined with tall oil fatty acid (TOFA), and an ethoxylated tall oil fatty acid obtained by ethoxylating tall oil fatty acid with 1 molar equivalent of ethylene oxide is added as secondary collector. In Example 5 which is comparative, the collector composition contains no secondary collector. The compositions are summarized in Table 4 below.

(41) TABLE-US-00004 TABLE 4 Composition of collector mixtures used in the flotations Amount of flotation aids in the collector mixture, weight % TOFA alkyl amido glycinate TOFA + 1EO Example 4 40 40 20 Comparative 50 50 Example 5

(42) After the conditioning steps tap water was added so that a total volume of 1.4 L was obtained, the pH of the flotation mixture was adjusted to 9.5 with a 5% NaOH aqueous solution, and the flotation was started. The experiment was performed at RT (20±1° C.). The rougher flotation, followed by one cleaning step, was performed. All fractions (tailings, middlings and concentrate) were collected and analyzed. The results are summarized in Tables 5 and 6 below. In FIG. 1 the flotation steps performed and the different fractions collected are illustrated schematically.

(43) Results

(44) TABLE-US-00005 TABLE 5 Flotation results presented as P.sub.2O.sub.5 recovery and grade. Amount of phosphate as Recovery at Collector P.sub.2O.sub.5 grade 33% of composition Fraction grade, % recovery, % P2O5, % Example 4 Rougher 26.68 92.5 80 tailings Middlings 31.97 84.7 concentrate 34.59 73.3 Comparative Rougher 26.04 92.9 78 Example 5 tailings Middlings 31.13 86.3 concentrate 33.5 77

(45) TABLE-US-00006 TABLE 6 selectivity factor at grade Collector Selectivity factor at grade 31% composition of P2O5 Example 4 2.5 Comparative 2.0 Example 5