Application of a 4-amino-1,2,4-triazol-3-one compound in flotation of metal ores

Abstract

The present invention belongs to the field of flotation, and specifically discloses the application of a 4-amino-1,2,4-triazole-3-one compound. The compound of formula 1#imgabs0# is used as a collector for the flotation of metal ores; in formula 1, wherein R is an alkyl group with C1 to C 24 alkane group, a cycloalkyl group with C5 to C 12 cycloalkyl group, an alkenyl group with C2 to C 17 alkenyl group or an alkoxy ether group with C1 to C 24 The 4-amino-1,2,4-triazole-3-one compound with the structure shown in formula (I) is used as a flotation collector to recover valuable metals from ores containing elements such as copper, lead, silver, rare earth, and tin. The 4-amino-1,2,4-triazole-3-one group in this flotation collector has a strong chelating effect on the metal active sites on the surface of metal minerals, enabling the 4-amino-1,2,4-triazole-3-one compound to adsorb on the mineral surface, with the hydrophobic chain facing the water, enhancing the hydrophobicity of the mineral surface, strengthening the hydrophobicity of mineral particles, effectively improving the flotation enrichment and recovery of minerals such as copper, lead, rare earth, and tin, and increasing the flotation recovery rate of valuable metal ores.

Description

Technical Field

[0001] The present invention relates to a 4-amino-1,2,4-triazole-3-one collector and its application in the flotation of metal ores, belonging to the field of metal ore beneficiation. Background Art

[0002] Flotation is the most important method for recovering metal minerals from metal ores. The flotation collector selectively regulates the hydrophobicity of the mineral interface, which is the key to realizing the flotation separation between minerals. With the increasing depletion, fineness, and complexity of metal mineral resources, the difficulty of flotation recovery of metal minerals has increased. Developing new high-selectivity flotation collectors and expanding the difference in the interfacial properties of mineral particles are of great significance for improving the comprehensive recovery rate of metal minerals.

[0003] For metal sulfide ores, the commonly used flotation collectors developed in the industry are generally mercapto collectors. For example, patent CN107029893A reports a scheme of using 4-amino-1,2,4-triazole-3-thione compounds as collectors for metal sulfide ores, which can show good collecting ability for sulfide ores, but the flotation selectivity needs to be improved. However, there is no report in the industry on the use of non-mercapto surfactants such as 4-amino-1,2,4-triazole-3-one compounds in the flotation of metal ores, especially metal sulfide ores. Summary of the Invention

[0004] The purpose of the present invention is to provide an application method of 4-amino-1,2,4-triazole-3-one compounds in the flotation of metal ores.

[0005] The purpose of the present invention is achieved by the following means:

[0006] An application of a 4-amino-1,2,4-triazole-3-one compound, which is used as a collector for the flotation collection of metal ores;

[0007] The 4-amino-1,2,4-triazole-3-one compound is a compound having the structure of formula 1;

[0008]

[0009] Wherein, R is an alkyl group with C1 to C 24 , a cycloalkyl group with C5 to C 12 , an olefin group with C2 to C 17 or an alkoxy ether group with C1 to C 24

[0010] In the present invention, the 4-amino-1,2,4-triazol-3-one group of Formula 1 has a strong chelating effect on the metal active sites on the surface of metal minerals, can be adsorbed on the mineral surface, making the hydrophobic chain face the water, enhancing the hydrophobicity of the mineral surface, strengthening the hydrophobicity of mineral particles, and improving the flotation recovery rate of valuable metal ores. Moreover, it also helps to improve the flotation selectivity.

[0011] In the present invention, the 4-amino-1,2,4-triazol-3-one compound of Formula 1 can be simply and efficiently prepared from semicarbazide and organic carboxylic acid.

[0012] In the present invention, the preferred control of R in the structure of Formula 1 helps to further improve the intramolecular synergy of the structure of Formula 1 and further synergistically improve the recovery rate and selectivity of metal ores. Preferably, R is an alkyl group with C1-C 10 Preferably, it is propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl or hexyl, and further preferably butyl or pentyl.

[0013] In the present invention, the metal ore is an oxidized ore and / or a sulfide ore containing at least one metal element of copper, lead, rare earth, tin, etc. Further, the metal ore is preferably at least one of ores such as cupric oxide, copper sulfide, lead sulfide, tin ore, rare earth ore, etc. A more typical application solution of the present invention is to use Formula 1 as a collector to selectively collect chalcopyrite from minerals containing chalcopyrite and pyrite, or to selectively collect malachite from minerals containing malachite and calcite.

[0014] In the present invention, the dosage of the collector of Formula 1 can be adjusted according to the mineral type and requirements. For example, calculated based on the mass of the metal ore, the dosage of the 4-amino-1,2,4-triazol-3-one compound is 5-500 g / t, and further can be 10-50 g / t considering the treatment effect and cost.

[0015] Preferably, the pH in the flotation collection stage is 5.5-10.5; preferably 7.5-9.

[0016] In the present invention, the basic process of using the 4-amino-1,2,4-triazol-3-one compound shown in Formula (I) as a collector in the flotation of metal ores is as follows: (a) After the ore is ground finely, it enters the flotation; (b) In the grinding and / or flotation process, flotation reagents are added to adjust the pulp, and at least one 4-amino-1,2,4-triazol-3-one compound is contained in the added reagents; (c) The useful metal minerals are floated out by foam flotation method.

[0017] In the present invention, a foaming agent can be added to the flotation reagents according to the flotation needs. The foaming agent can be a reagent with foaming ability well-known in the industry, such as 2 # oil.

[0018] In the present invention, there is no special requirement for the dosage of the foaming agent, which can be adjusted based on existing flotation requirements. For example, it can be 5 - 100 g / t.

[0019] Beneficial effects

[0020] The present invention explores a new use of the compound of formula 1 as a collector for metal ores.

[0021] The present invention has found through research that thanks to the intramolecular synergy of the structure and groups of the compound of formula 1, it helps to improve the selective flotation recovery of metal ores. Description of the drawings

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[0031] The present invention is further illustrated by the following examples, but is not limited by the specific examples. All parts and percentages in the examples refer to mass unless otherwise specified.

[0032] Example 1 Flotation Performance of 5-Propyl-4-amino-1,2,4-triazol-3-one on Chalcopyrite and Pyrite

[0033] When the concentration of 5-propyl-4-amino-1,2,4-triazol-3-one is 5×10 -7 mol / L, the pulp pH is about 7.8, the concentration of the foaming agent (MIBC) is 3×10 -4 mol / L, and the N2 gas flow rate is 200 mL / min, chalcopyrite with a particle size of -0.076 mm to +0.038 mm is flotated for 3 minutes, and the flotation recovery rate of chalcopyrite reaches 75.2%. Under the same conditions, the recovery rate of pyrite is only 4.3%. This shows that 5-propyl-4-amino-1,2,4-triazol-3-one has excellent selective collecting ability for chalcopyrite.

[0034] Example 2 Flotation Performance of 5-Butyl-4-amino-1,2,4-triazol-3-one on Chalcopyrite and Pyrite

[0035] When the concentration of 5-butyl-4-amino-1,2,4-triazol-3-one is 5×10 -7 mol / L, the pulp pH is about 8.6, the concentration of the foaming agent (MIBC) is 3×10 -4 mol / L, and the N2 gas flow rate is 200 mL / min, chalcopyrite with a particle size of -0.076 mm to +0.038 mm is flotated for 3 minutes, and the flotation recovery rate of chalcopyrite reaches 97.0%. Under the same conditions, the recovery rate of pyrite is only 4.7%. This shows that 5-butyl-4-amino-1,2,4-triazol-3-one has excellent selective collecting ability for chalcopyrite.

[0036] Example 3 Flotation Performance of 5-Propyl-4-amino-1,2,4-triazol-3-one on Malachite and Calcite

[0037] When the concentration of 5-propyl-4-amino-1,2,4-triazol-3-one is 3×10 -4 mol / L, the pulp pH is about 8.5, the concentration of the foaming agent (MIBC) is 3×10 -4 mol / L, and the N2 gas flow rate is 200 mL / min, malachite with a particle size of -0.076 mm to +0.038 mm is flotated for 3 minutes, and the flotation recovery rate of malachite reaches 67.8%. Under the same conditions, the recovery rate of calcite is only 13.3%. This shows that 5-propyl-4-amino-1,2,4-triazol-3-one has excellent selective collecting ability for malachite.

[0038] Example 4 Flotation Performance of 5-Butyl-4-amino-1,2,4-triazol-3-one on Malachite and Calcite

[0039] At a concentration of 2.5×10 -4 mol / L of 5-butyl-4-amino-1,2,4-triazol-3-one, a pulp pH of about 7.8, a concentration of 3×10 -4 mol / L of the foaming agent (MIBC), and a N2 gas flow rate of 200 mL / min, malachite with a particle size of -0.076 mm to +0.038 mm was flotation for 3 minutes, and the flotation recovery rate of malachite reached 95.3%. Under the same conditions, the recovery rate of calcite was only 14.2%. This shows that 5-butyl-4-amino-1,2,4-triazol-3-one has excellent selective collecting ability for malachite.

[0040] Example 5 Flotation performance of 5-pentyl-4-amino-1,2,4-triazol-3-one for malachite and calcite

[0041] At a concentration of 1×10 -4 mol / L of 5-pentyl-4-amino-1,2,4-triazol-3-one, a pulp pH of about 8.2, a concentration of 3×10 -4 mol / L of the foaming agent (MIBC), and a N2 gas flow rate of 200 mL / min, malachite with a particle size of -0.076 mm to +0.038 mm was flotation for 3 minutes, and the flotation recovery rate of malachite reached 88.2%. Under the same conditions, the recovery rate of calcite was only 16.3%. This shows that 5-pentyl-4-amino-1,2,4-triazol-3-one has excellent selective collecting ability for malachite.

[0042] Example 6 Flotation recovery of a copper ore in Yunnan by 5-alkyl-4-amino-1,2,4-triazol-3-one

[0043] A copper ore sample in Yunnan contains 0.213% Cu. Test process: one roughing. Grinding fineness: -0.074 mm 70%; Reagent conditions and flotation test results are shown in Table 1. The test results in Table 1 show that compared with butyl xanthate and Z-200, the collectors of 5-butyl-4-amino-1,2,4-triazol-3-one and 5-pentyl-4-amino-1,2,4-triazol-3-one achieved higher copper recovery rates and copper grades (rough concentrates) at lower reagent dosages, and the sulfur grades and recovery rates in the rough concentrates were significantly lower, indicating that 5-alkyl-4-amino-1,2,4-triazol-3-one has excellent selective collecting ability for copper minerals.

[0044] Table 1 Flotation test results of 5-alkyl-4-amino-1,2,4-triazol-3-one, butyl xanthate and Z-200

[0045]

[0046]

[0047] Example 7 Flotation Recovery of a Copper Ore in Yunnan with 5-Butyl-4-amino-1,2,4-triazol-3-one

[0048] A copper ore sample in Yunnan contains 0.215% Cu in the raw ore. Test process: one rough selection. Grinding fineness: -0.074mm 72%; Reagent conditions and flotation test results are shown in Table 2. The test results in Table 2 show that compared with 5-pentyl-4-amino-1,2,4-triazole-3-thione, at the same reagent dosage, 5-pentyl-4-amino-1,2,4-triazol-3-one has a higher copper grade in the copper rough concentrate, and the sulfur grade and recovery rate in the rough concentrate are significantly lower, indicating that 5-pentyl-4-amino-1,2,4-triazol-3-one has excellent selective collecting ability for copper minerals.

[0049] Table 2 Flotation Test Results of 5-Pentyl-4-amino-1,2,4-triazol-3-one and 5-Pentyl-4-amino-1,2,4-triazole-3-thione

[0050]

[0051] In summary, it can be seen that the 4-amino-1,2,4-triazol-3-one compounds with the structure of Formula 1 of the present invention have good collecting ability and selectivity for oxidized ores and sulfide ores.

Claims

1. Use of a 4-amino-1,2,4-triazol-3-one compound, characterized in that, It is used as a collector for the flotation of metal ores; The 4-amino-1,2,4-triazole-3-one compound is a compound having the structure of Formula 1; （Ⅰ） Among them, R is an alkyl group of C1~C 24 or an alkoxy ether group of C1~C 24 ; The metal ore is an oxidized ore and / or a sulfide ore containing copper and lead.

2. The application according to claim 1, wherein R is an alkyl group having 1 to 10 carbon atoms.

3. The application according to claim 2, wherein R is propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl or hexyl.

4. The application according to claim 1, wherein The metal ore contains at least one of copper oxide ore, copper sulfide ore, and lead sulfide ore.

5. The application according to claim 4, characterized in that, It is used as a collector to selectively collect chalcopyrite from ores containing chalcopyrite and pyrite, to selectively collect galena from ores containing galena and pyrite, or to selectively collect malachite from minerals containing malachite and calcite.

6. The application according to any one of claims 1 to 5, characterized in that, Based on the mass of the metal ore, the dosage of the 4-amino-1,2,4-triazole-3-one compound is 5 - 500 g / t.

7. The application according to any one of claims 1 to 5, characterized in that, The pH in the flotation collection stage is 5.5 - 10.

5.

8. The application according to claim 7, characterized in that, The pH in the flotation collection stage is 7.5 - 9.

9. The application according to claim 1, characterized in that, It includes the following steps: Step (1): The metal ore is crushed, ground, and slurried to obtain a pulp; Step (2): Flotation reagents are added to the pulp in Step (1) for flotation treatment, and the obtained flotation concentrate and tailings are collected; the flotation reagents contain the 4-amino-1,2,4-triazole-3-one compound.

10. The application according to claim 9, characterized in that A foaming agent is also added to the flotation reagents.

11. The application according to claim 10, characterized in that, The dosage of the foaming agent is 5 - 100 g / t.

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