METHOD OF USING FLOTATION COLLECTOR CONTAINING AZOLETHIONE STRUCTURE

Abstract

The present invention relates to an azolethione flotation collector and application thereof. According to the application, an azolethione compound such as a 1,3,4-thiadiazole-2-thione compound, a 1,3,4-oxadiazole-2-thione compound, a 1,2,4-triazole-3-thione compound or a 1,2,4,5-tetrazole-3-thione compound is used as a mineral flotation collector to be applied to ores containing copper, zinc, lead, nickel, cobalt, platinum, palladium, silver or gold minerals to realize flotation recovery of valuable metal minerals. Compared with common flotation collectors in the existing technologies, the flotation collector of the present invention can effectively improve enrichment and recovery of copper, zinc, lead, nickel, cobalt, platinum, palladium, silver or gold minerals.

Claims

1. A method of using a flotation collector containing an azolethione structure, wherein the flotation collector with the azolethione compound having the structure as shown in formula 1 is applied for flotation separation of ores containing at least one of copper minerals, silver minerals and gold minerals as well as zinc minerals, lead minerals, nickel minerals, cobalt minerals, platinum minerals and palladium minerals to realize flotation recovery of valuable metal minerals, ##STR00020## wherein X is NH, O or S, and Y is ##STR00021## or, X is NH, and Y is ##STR00022## R is a C.sub.1-C.sub.17 hydrocarbyl group or an alkoxy ether group having the structure as shown in formula 2; ##STR00023## R.sup.1 is a C.sub.1-C.sub.17 hydrocarbyl group; R.sup.2 is H or a C.sub.1-C.sub.3 alkane group; and n is an integer from 2 to 5; wherein in formula 2, R.sup.4 is a C.sub.1-C.sub.17 hydrocarbyl group, R.sup.3 is an ethylidene group or a propylidene group, and m is 1-3.

2. The method of using the flotation collector containing the azolethione structure according to claim 1, wherein the flotation collector having the structure as shown in formula 1 has the structure as shown in formula 3, 4, 5 or 6: ##STR00024##

3. The method of using the flotation collector containing the azolethione structure according to claim 1, wherein R is a C.sub.1-C.sub.17 alkane group, or a C.sub.2-C.sub.17 olefinic group, or a C.sub.6-C.sub.12 aryl group.

4. The method of using the flotation collector containing the azolethione structure according to claim 2, wherein R is a C.sub.1-C.sub.17 alkane group, or a C.sub.2-C.sub.17 olefinic group, or a C.sub.6-C.sub.12 aryl group.

5. The method of using the flotation collector containing the azolethione structure according to claim 3, wherein R is a linear C.sub.1-C.sub.17 alkane group or a C.sub.10-C.sub.17 monoolefine group.

6. The method of using the flotation collector containing the azolethione structure according to claim 4, wherein R is a linear C.sub.1-C.sub.17 alkane group or a C.sub.10-C.sub.17 monoolefine group.

7. The method of using the flotation collector containing the azolethione structure according to claim 3, wherein R is propyl, pentyl, hexyl, heptyl, nonyl, n-hendecyl, n-tridecyl, n-pentadecyl, n-heptadecyl or 8-heptadecenyl.

8. The method of using the flotation collector containing the azolethione structure according to claim 4, wherein R is propyl, pentyl, hexyl, heptyl, nonyl, n-hendecyl, n-tridecyl, n-pentadecyl, n-heptadecyl or 8-heptadecenyl.

9. The method of using the flotation collector containing the azolethione structure according to claim 1, wherein in formula 2, R.sup.3 is an ethylidene group.

10. The method of using the flotation collector containing the azolethione structure according to claim 1, wherein R.sup.4 is a linear C.sub.1-C.sub.17 alkane group or a C.sub.10-C.sub.17 monoolefine group.

11. The method of using the flotation collector containing the azolethione structure according to claim 10, wherein in formula 2, R.sup.4 is propyl, pentyl, hexyl, heptyl, nonyl, n-hendecyl, n-tridecyl, n-pentadecyl, n-heptadecyl or 8-heptadecenyl.

12. The method of using the flotation collector containing the azolethione structure according to claim 1, wherein the flotation collector is the 1,2,4,5-tetrazole-3-thione compound having the structure as shown in formula 7: ##STR00025## or the 1,2,4,5-tetrazole-3-thione compound having the structure as shown in formula 8: ##STR00026##

13. The method of using the flotation collector containing the azolethione structure according to claim 12, wherein R.sup.1 is a C.sub.1-C.sub.17 alkane group, or a C.sub.2-C.sub.17 olefinic group, or a C.sub.6-C.sub.12 aryl group.

14. The method of using the flotation collector containing the azolethione structure according to claim 13, wherein R.sup.1 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-hendecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl or n-heptadecyl.

15. The method of using the flotation collector containing the azolethione structure according to claim 12, wherein R.sup.2 is H, methyl, ethyl, propyl or isopropyl.

16. The method of using the flotation collector containing the azolethione structure according to claim 12, wherein R.sup.1 is propyl, pentyl, hexyl, heptyl or nonyl, and R.sup.2 is H or methyl.

17. The method of using the flotation collector containing the azolethione structure according to claim 12, wherein n in the compound having the structure as shown in formula 8 is 3.

18. The method of using the flotation collector containing the azolethione structure according to claim 1, comprising the following steps: step (1): crushing, grinding and pulping the ore containing at least one of copper minerals, zinc minerals, lead minerals, nickel minerals, cobalt minerals, platinum minerals, palladium minerals, silver minerals and gold minerals to obtain ore pulp; step (2): adding a flotation agent to the ore pulp obtained in step (1) for flotation, and collecting a flotation concentrate, wherein the flotation agent comprises the flotation collector.

19. The method of using the flotation collector containing the azolethione structure according to claim 2, comprising the following steps: step (1): crushing, grinding and pulping the ore containing at least one of copper minerals, zinc minerals, lead minerals, nickel minerals, cobalt minerals, platinum minerals, palladium minerals, silver minerals and gold minerals to obtain ore pulp; step (2): adding a flotation agent to the ore pulp obtained in step (1) for flotation, and collecting a flotation concentrate, wherein the flotation agent comprises the flotation collector.

20. The method of using the flotation collector containing the azolethione structure according to claim 13, wherein R.sup.2 is H, methyl, ethyl, propyl or isopropyl.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0078] FIG. 1 shows 5-phenyl-1,3,4-thiadiazole-2-thione .sup.1HNMR;

[0079] FIG. 2 shows 5-heptyl-1,3,4-thiadiazole-2-thione .sup.1HNMR;

[0080] FIG. 3 shows 5-phenyl-1,3,4-oxadiazole-2-thione .sup.1HNMR;

[0081] FIG. 4 shows 5-pentyl-1,2,4-triazole-3-thione .sup.1HNMR;

[0082] FIG. 5 shows 5-heptyl-1,2,4-triazole-3-thione .sup.1HNMR; and

[0083] FIG. 6 shows 6-hexyl-1,2,4,5-tetrazole-3-thione .sup.1HNMR.

DESCRIPTION OF THE EMBODIMENTS

[0084] The following embodiments are intended to further illustrate the content of the present invention and are not intended to limit the protection scope of the present invention.

[0085] All parts and percentages in the embodiments refer to mass unless additionally specified. The froth flotation processes for minerals or ores in the embodiments are conventional processes except that a conventional collector is replaced with the azolethione compound of the present invention.

[0086] The adding weight unit of each flotation agent in the following embodiments is g/t, and is based on the ore weight (t) unless particularly specified.

Embodiment 1 Hallimond Tube Flotation Test of Pure Chalcopyrite

[0087] Under the conditions of a certain concentration of the collector and a certain pH value of the ore pulp, the concentration of methyl isobutyl carbinol (MIBC) frother is fixed on 15 mg/L, the flow rate of N.sub.2 gas is 200 mL/min, the chalcopyrite of which the particle size is from 0.076 mm to +0.038 mm is subjected to flotation for 3 min in a Hallimond tube, and the flotation recovery of the chalcopyrite is shown in table 1. The test results in table 1 show that the azolethione collector obtains a higher chalcopyrite recovery than isoamyl xanthate.

TABLE-US-00001 TABLE 1 Hallimond tube flotation test conditions and results of pure chalcopyrite pH value Concentration of ore Chalcopyrite Collector type (mol/L) pulp recovery/% Isoamyl xanthate 2 10.sup.5 9.0 87.6 5-hexyl-1,3,4-thiadiazole-2-thione 1 10.sup.5 9.0 96.7 5-heptyl-1,3,4-oxadiazole-2-thione 2 10.sup.5 9.0 97.2 5-pentyl-1,2,4-triazole-3-thione 2 10.sup.5 8.5 93.5 6-hexyl-1,2,4,5-tetrazole-3-thione 1 10.sup.5 8.5 93.2

Embodiment 2 Hallimond Tube Flotation Test of Pure Malachite

[0088] Under the conditions of a certain concentration of the collector and a certain pH value of the ore pulp, the MIBC frother is fixed on 15 mg/L, the flow rate of N.sub.2 gas is 200 mL/min, the malachite of which the particle size is from 0.076 mm to +0.038 mm is subjected to flotation for 3 min in a Hallimond tube, and the flotation recovery ratio of the malachite is shown in table 2. The test results in table 2 show that the azolethione collector returns a higher malachite flotation recovery than isoamyl xanthate and octyl hydroxamic acid.

TABLE-US-00002 TABLE 2 Hallimond tube flotation test conditions and results of pure malachite pH value Concentration of ore Malachite Collector type (mol/L) pulp recovery/% Isoamyl xanthate 2 10.sup.4 8.0 75.2 Octyl hydroxamic acid 2 10.sup.4 8.5 88.5 5-hexanol polyethylene (2) ether 1 10.sup.4 9.0 96.4 methyl-1,3,4-thiadiazole-2-thione 5-octanol polyethylene (2) ether 1 10.sup.4 8.5 94.8 methyl-1,3,4-oxadiazole-2-thione 5-hexanol polyethylene (2) ether 2 10.sup.4 8.0 98.7 methyl-1,2,4-triazole-3-thione 6,6-methylhexyl-1,2,4,5-tetrazole- 2 10.sup.4 8.5 97.6 3-thione

Embodiment 3

[0089] In a sulfide-oxide copper ore sample in Dongchuan, Yunnan, China, a raw ore contains 0.63% of Cu, and the oxidation ratio is 26.5%. Test processes include one rougher process and one scavenger process. The ore is ground to 90% passing 0.074 mm. Flotation reagent conditions include 300 g/ton sodium sulfide (pH value of ore pulp is 7.5) in rougher operation, and 800 g/ton sodium sulfide (pH value of ore pulp is 8.0) in scavenger process. Other reagent conditions and results thereof are as shown in table 3. The test results in table 3 show that the azolethione collector of the present invention achieve a higher copper recovery (scavenger concentrate) than butyl xanthate.

TABLE-US-00003 TABLE 3 Conditions and results of flotation of sulfide-oxide copper ore in Dongchuan by azolethione collector Copper Copper Flotation reagent type and dosage (g/t) Product name Yield/% grade/% recovery/% Rougher: butyl xanthate 100, MIBC 30 Rougher concentrates 2.23 20.38 72.52 Scavenger: butyl xanthate 100 Scavenger concentrates 0.70 2.87 3.18 Tailings 97.07 0.157 24.30 Raw ores 100.00 0.627 100.00 Rougher: butyl xanthate 100, MIBC 30 Rougher concentrates 2.20 20.43 72.32 Scavenger: 5-phenyl-1,3,4-thiadiazole-2- Scavenger concentrates 0.66 5.78 6.13 thione 60 Tailings 97.14 0.138 21.55 Raw ores 100.00 0.622 100.00 Rougher: butyl xanthate 100, MIBC 30 Rougher concentrates 2.19 20.86 72.31 Scavenger: 5-hexyl-1,3,4-thiadiazole-2- Scavenger concentrates 3.62 2.18 12.49 thione 60 Tailings 94.19 0.102 15.20 Raw ores 100.00 0.632 100.00 Rougher: butyl xanthate 100, MIBC 30 Rougher concentrates 2.19 21.04 72.80 Scavenger: 5-phenyl-1,3,4-oxadiazole-2- Scavenger concentrates 0.79 5.39 6.76 thione 60 Tailings 97.02 0.133 20.43 Raw ores 100.00 0.632 100.00 Rougher: butyl xanthate 100, MIBC 30 Rougher concentrates 2.23 20.42 72.86 Scavenger: 5-hexyl-1,3,4-oxadiazole-2- Scavenger concentrates 2.19 2.45 8.61 thione 60 Tailings 95.58 0.121 18.53 Raw ores 100.00 0.624 100.00 Rougher: butyl xanthate 100, MIBC 30 Rougher concentrates 2.13 21.29 72.20 Scavenger: 5-phenyl-1,2,4-triazole-3- Scavenger concentrates 0.65 6.91 7.09 thione 60 Tailings 97.22 0.134 20.71 Raw ores 100.00 0.629 100.00 Rougher: butyl xanthate 100, MIBC 30 Rougher concentrates 2.36 19.42 72.55 Scavenger: 5-pentyl-1,2,4-triazole-3- Scavenger concentrates 1.19 5.32 10.03 thione 60 Tailings 96.45 0.114 17.42 Raw ores 100.00 0.631 100.00 Rougher: butyl xanthate 100, MIBC 30 Rougher concentrates 2.08 21.93 72.92 Scavenger: 5-hendecyl-1,2,4-triazole-3- Scavenger concentrates 2.97 2.32 11.00 thione 60 Tailings 94.95 0.106 16.08 Raw ores 100.00 0.626 100.00 Rougher: butyl xanthate 100, MIBC 30 Rougher concentrates 2.11 21.94 73.14 Scavenger: 6-phenyl-1,2,4,5-tetrazole-3- Scavenger concentrates 0.62 7.25 7.09 thione 60 Tailings 97.27 0.129 19.78 Raw ores 100.00 0.634 100.00 Rougher: butyl xanthate 100, MIBC 30 Rougher concentrates 2.08 21.83 72.23 Scavenger: 6-hexyl-1,2,4,5-tetrazole-3- Scavenger concentrates 0.66 8.61 9.08 thione 60 Tailings 97.25 0.121 18.69 Raw ores 100.00 0.630 100.00

Embodiment 4

[0090] In an oxide-sulfide copper ore sample in Changdu, Tibet, a raw ore contains 3.9% of Cu, the oxidation ratio is 69.4%, and main copper oxide minerals include malachite and azurite. Test processes include one rougher process and one scavenger process. The ore is ground to 80% passing 0.074 mm. Flotation reagent conditions include 3,000 g/ton sodium sulfide (pH value of ore pulp is 8.5) in rougher process, and 1,000 g/ton sodium sulfide (pH value of ore pulp is 9.0) scavenger process. Other reagent conditions and results thereof are as shown in table 4. The test results in table 4 show that the azolethione collector obtains a higher copper recovery (scavenger concentrates) than isoamyl xanthate as well as isoamyl xanthate+octyl hydroxamic acid.

TABLE-US-00004 TABLE 4 Conditions and results of flotation of oxide-sulfide copper ore in Changdu, Tibet Copper Reagent type and dosage (g/t) Product name Yield/% Copper grade/% recovery/% Rougher: isoamyl xanthate 300, MIBC Rougher concentrates 9.54 19.51 47.70 24 Scavenger concentrates 6.10 13.82 21.61 Scavenger: butyl xanthate 100, MIBC 12 Tailings 84.35 1.42 30.69 Raw ores 100.00 3.903 100.00 Rougher: isoamyl xanthate 300, MIBC Rougher concentrates 9.68 19.31 47.74 24 Scavenger concentrates 6.29 15.02 24.14 Scavenger: isoamyl xanthate 100, octyl Tailings 84.03 1.31 28.12 hydroximic acid 50 Raw ores 100.00 3.914 100.00 Rougher: isoamyl xanthate 300, MIBC Rougher concentrates 9.40 19.64 47.51 24 Scavenger concentrates 6.43 17.85 29.54 Scavenger: 5-pentyl-1,3,4-thiadiazole-2- Tailings 84.16 1.06 22.95 thione 60 Raw ores 100.00 3.887 100.00 Rougher: isoamyl xanthate 300, MIBC Rougher concentrates 9.67 19.18 47.14 24 Scavenger concentrates 7.76 16.37 32.28 Scavenger: 5-heptyl-1,3,4-thiadiazole-2- Tailings 82.58 0.98 20.58 thione 50 Raw ores 100.00 3.933 100.00 Rougher: isoamyl xanthate 300, MIBC Rougher concentrates 9.79 19.24 47.95 24 Scavenger concentrates 6.87 16.52 28.92 Scavenger: 5-heptyl-1,3,4-oxadiazole-2- Tailings 83.34 1.09 23.13 thione 60 Raw ores 100.00 3.927 100.00 Rougher: isoamyl xanthate 300, MIBC Rougher concentrates 9.96 18.68 47.75 24 Scavenger concentrates 8.34 14.32 30.66 Scavenger: 5-hendecyl-1,3,4- Tailings 81.69 1.03 21.59 oxadiazole-2-thione 50 Raw ores 100.00 3.897 100.00 Rougher: isoamyl xanthate 300, MIBC Rougher concentrates 9.67 19.34 47.55 24 Scavenger concentrates 6.73 17.11 29.27 Scavenger: 5-pentyl-1,2,4-triazole-3- Tailings 83.61 1.09 23.18 thione 60 Raw ores 100.00 3.932 100.00 Rougher: isoamyl xanthate 300, MIBC Rougher concentrates 9.71 19.27 47.57 24 Scavenger concentrates 7.79 16.29 32.28 Scavenger: 5-(2,2,4-trimethyl)-pentyl- Tailings 82.50 0.96 20.15 1,2,4-triazole-3-thione 50 Raw ores 100.00 3.932 100.00 Rougher: isoamyl xanthate 300, MIBC Rougher concentrates 9.27 20.14 47.50 24 Scavenger concentrates 6.77 16.72 28.79 Scavenger: 6-(1,5-pentylidene)-1,2,4,5- Tailings 83.96 1.11 23.71 tetrazole-3-thione 60 Raw ores 100.00 3.931 100.00 Rougher: isoamyl xanthate 300, MIBC Rougher concentrates 9.36 19.88 47.36 24 Scavenger concentrates 8.31 15.47 32.73 Scavenger: 5-heptyl-1,2,4,5-tetrazole-3- Tailings 82.32 0.95 19.90 thione 50 Raw ores 100.00 3.929 100.00

Embodiment 5

[0091] In a porphyry copper ore sample in Shangrao, Jiangxi, a raw ore contains 0.39% of copper and 1.85% of sulfur, the content of gold is 0.21 g/t, and the content of silver is 1.18 g/t. A test process includes one rougher process. The ore is ground to 68% passing 0.074 mm. Flotation reagent conditions: the dosage of lime is 800 g/ton, and the pH value of ore pulp is 8.5. Other reagent conditions and results are as shown in table 5. The test results in table 5 show that the combined collector of azolethione compound with butyl xanthate obtains a higher copper, gold and silver flotation recoveries (rougher concentrates) than a common collector butyl xanthate as well as 3-hexyl-4-amino-1,2,4-triazole-5-thione+butyl xanthate.

TABLE-US-00005 TABLE 5 Conditions and results of flotation of porphyry copper ore in Shangrao, Jiangxi Grade Recovery ratio/% Reagent type and dosage (g/t) Product Yield/% Cu/% Au* Ag* Cu Au Ag Butyl xanthate 50, MIBC 20 Rougher 5.94 5.42 2.45 12.54 82.82 69.30 63.13 concentrates Tailings 94.06 0.071 17.18 Raw ores 100.00 0.389 0.21 1.18 100.00 100.00 100.00 Butyl xanthate 10, 3-hexyl-4-amino- Rougher 6.12 5.46 2.49 12.56 85.17 72.57 65.14 1,2,4-triazole-5-thione 25, MIBC 10 concentrates Tailings 93.88 0.062 14.83 Raw ores 100.00 0.392 0.21 1.18 100.00 100.00 100.00 Butyl xanthate 10, 5-heptyl-1,3,4- Rougher 6.21 5.56 2.53 13.35 87.62 74.82 70.26 thiadiazole-2-thione 30, MIBC 15 concentrates Tailings 93.79 0.052 12.38 Raw ores 100.00 0.394 0.21 1.18 100.00 100.00 100.00 Butyl xanthate 10, 5-pentyl-1,3,4- Rougher 6.02 5.64 2.57 13.43 86.58 73.67 68.52 oxadiazole-2-thione 30, MIBC 15 concentrates Tailings 93.98 0.056 13.42 Raw ores 100.00 0.392 0.21 1.18 100.00 100.00 100.00 Butyl xanthate 10, 5-heptyl-1,2,4- Rougher 5.73 6.05 2.76 13.77 88.24 75.31 66.87 triazole-3-thione 25, MIBC 15 concentrates Tailings 94.27 0.049 11.76 Raw ores 100.00 0.393 0.21 1.18 100.00 100.00 100.00 Butyl xanthate 10, 6-heptyl-1,2,4,5- Rougher 6.37 5.35 2.48 12.69 87.71 75.23 68.50 tetrazole-3-thione 25, MIBC 10 concentrates Tailings 93.63 0.051 12.29 Raw ores 100.00 0.389 0.21 1.18 100.00 100.00 100.00 *Unit g/t

[0092] In conclusion, the flotation collector of the present invention can effectively increase the enrichment and recovery efficiency of valuable metal minerals from their ores containing at least one of copper minerals, silver minerals and gold minerals.