Use of 2-amino-4-hydroxy-1,3,5-triazine-6-thiol collectors in the flotation of metal ores

Abstract

The application belongs to the field of mineral flotation, and particularly discloses application of 2-amino-4-hydroxy-1,3,5-triazine-6-thiol collector in metal ore flotation. The 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compound is used as a flotation collector to recover valuable metal minerals from copper, lead, nickel, cobalt, zinc and other ores. The 2-amino-4-hydroxy-1,3,5-triazine-6-thiol collector can effectively improve the flotation enrichment and recovery of copper, lead, nickel, cobalt, zinc and other minerals, significantly improve the flotation recovery rate of valuable metal ores, and has good flotation selectivity.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of metal ore dressing, in particular to a 2-amino-4-hydroxy-1,3,5-triazine-6-thiol collector and its application in metal ore flotation. BACKGROUND

[0002] 4-hydroxy-1,3,5-triazine-6-thiol compounds have good antibacterial, antiviral, insecticidal activity and good thermal stability, and are used in the fields of agriculture, medicine, materials, chemical industry, etc. (Wang Q., Liu G., Shao R., et al.. Synthesis and antivirus activity of 1,3,5-triazine derivatives. Heteroatom Chemistry, 2003, 14: 542-545; Izidor S., Bogdan Andreja K., et al.. The synthesis of novel 2,4,6-trisubstituted 1,3,5-triazines: A search for potential MurF enzyme inhibitors. Heterocycles, 2010, 81: 91-115; Gianluca G., Bartolini S., Gianluca S., et al.. 6-alkylthio-4-[1-(2,6-difluorophenyl)alkyl]-1H-[1,3,5]triazin-2-ones (ADATs): novel regulators of cell differentiation and proliferation, 2005, 48: 6776-6778). However, there is no report on the use of 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compounds as flotation collectors in the prior art. SUMMARY

[0003] The present application aims to provide an application of 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compounds in metal ore flotation, which can effectively improve the enrichment, recovery efficiency and selectivity of valuable metal minerals.

[0004] The application of 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compounds in metal ore flotation, which is used as a collector for the flotation of metal ores.

[0005] The 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compound is at least one compound having the structure of formula (I);

[0006]

[0007] In formula (I), R 1 is a C1-C 18 hydrocarbon group or a C2-C 18 alkoxy-substituted alkyl group, R 2 is H, a C1-C 18 hydrocarbon group or a C2-C 18 alkoxy-substituted alkyl group; and M is H, a sodium ion, a potassium ion or an ammonium ion.

[0008] The present application provides a novel use of 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compounds as a flotation collector. The present application has found that the sulfur, nitrogen and oxygen atoms in the 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compound are affected by the 2-amino-4-hydroxy-1,3,5-triazine-6-thiol macrocycle, and have strong coordination ability and excellent selective chelation with transition metal atoms, which can improve the flotation selectivity, increase the flotation recovery rate of metal ores and the flotation selectivity.

[0009] The hydrocarbon group is a C1-C 18 alkyl group, a C6-C 12 aryl group, a C5-C 12 five- or six-membered ring hydrocarbon group. The alkyl group may, for example, be a straight-chain or branched alkyl group, and may further be an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a neopentyl group, a n-hexyl group, etc.

[0010] The alkoxyl-substituted alkyl group according to the present application is a group having an alkoxyl substituent on an alkyl chain, and may, for example, be an alkoxy methyl group, an alkoxy ethyl group, an alkoxy propyl group, etc. Preferably, the alkoxyl-substituted alkyl group may, for example, be R 4 OCH2CH2CH2-, wherein R 4 is a C1-C 15 hydrocarbon group, preferably an alkyl group. Further, the alkoxyl-substituted alkyl group may, for example, be an ethoxy propyl group, a propoxy propyl group, an isopropoxy propyl group, a butoxy propyl group or a hexyloxy propyl group.

[0011] Preferably, R 1 is a C2-C6 alkyl group or a C1-C6 alkoxyl-substituted propyl group. R 2 is H, a C2-C6 alkyl group or a C1-C6 alkoxyl-substituted propyl group. Further preferably, R 1 is a C3-C5 alkyl group, and R2 H. The research finds that, under the synergistic structure of formula 1, further matching the preferred control of R 1 , R 2 substituents helps to further synergistically improve the flotation recovery rate and selectivity of the minerals.

[0012] In the present application, M is preferably H, ammonium, sodium or potassium ion. When M is H, thione tautomerism can exist.

[0013] In the present application, the metal ore is an oxidized ore and / or a sulfide ore containing at least one element of Cu, Pb, Zn, Ni, Co; and can further be at least one of copper ore, lead ore, nickel ore, cobalt ore or zinc ore.

[0014] In order to improve the collecting effect of metal sulfide ore, it is generally recognized in the industry that mercapto groups need to be introduced, however, the present application finds that, under the 1,3,5-triazine conjugated system, further matching the combination of 2-amino, 4-hydroxy and 6-mercapto, can unexpectedly achieve synergy, which still has excellent collecting ability for sulfide ore, and not only that, but also can exhibit excellent flotation selectivity.

[0015] In the present application, in the flotation stage, the dosage of the 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compound is more than 2 g / t (calculated based on the weight of the flotation feed ore), and considering the processing cost, it can be further preferred to be 2-1000 g / t.

[0016] In the present application, the pH of the ore slurry in the flotation stage is 5.5-11.5.

[0017] The present application also finds that, under the synergistic structure of formula 1, further matching the joint synergistic control of the pH in the flotation stage, helps to further regulate and improve the flotation behavior and selectivity of the minerals.

[0018] For example, when the pH of the ore slurry in the flotation stage is less than 8, galena and / or sphalerite are selectively collected.

[0019] Alternatively, when the pH of the ore slurry in the flotation stage is greater than or equal to 8 (preferably 9-12, and further preferably 10-12), galena is selectively collected, and further preferably, in a mixed ore containing galena and sphalerite, galena is selectively collected.

[0020] Alternatively, when the pH of the ore slurry in the flotation stage is less than 7 (preferably 4-6), pyrite is selectively collected, and further preferably, in a mixed ore containing pyrite and chalcopyrite, pyrite is selectively collected, and chalcopyrite tailings are obtained.

[0021] Alternatively, the flotation stage slurry pH is >7 (preferably 9-11, further preferably 9-10) to selectively collect chalcopyrite, further preferably in a mixed ore containing pyrite and chalcopyrite.

[0022] Alternatively, the flotation stage slurry pH is 8-10 to selectively collect bornite and / or chrysocolla.

[0023] The application is more particularly applied in the following process, the steps of which include:

[0024] Step (1): crushing and slurrying the metal ore to obtain a slurry;

[0025] Step (2): adding a flotation reagent to the slurry of step (1) to perform flotation, and collecting a flotation concentrate; the flotation reagent comprises the 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compound.

[0026] In the application, a foaming agent can be added to the flotation reagent as needed, and the foaming agent can be a foaming agent known in the industry, such as 2# oil.

[0027] In the application, the amount of the foaming agent is not particularly limited, and can be adjusted based on existing flotation requirements, for example, can be 5-100 g / t.

[0028] The application has the following beneficial effects:

[0029] The application first applies the 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compound to the flotation and collection of valuable metals in minerals. The sulfur, nitrogen, and oxygen atoms in the 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compound are affected by the large conjugated ring of 2-amino-4-hydroxy-1,3,5-triazine-6-thiol, and have strong coordination ability and excellent selective chelation with transition metal atoms. The 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compound is particularly suitable for efficient flotation and recovery of valuable metal minerals from copper, lead, zinc, or nickel-containing mineral ores, and has excellent flotation selectivity. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 The 2-ethylamino-4-hydroxy-1,3,5-triazine-6-thiol sodium is 1 H NMR chart.

[0031] Figure 2 The 2-ethylamino-4-hydroxy-1,3,5-triazine-6-thiol sodium is 13 C NMR chart.

[0032] Figure 3Flotation results of galena with 2-butylamino-4-hydroxy-1,3,5-triazine-6-thiol sodium in Example 1;

[0033] Figure 4 Flotation results of galena and sphalerite in Example 2; wherein ■, □-2-butylamino-4-hydroxy-1,3,5-triazine-6-thiol sodium, ●, ○-isopropyl xanthate; ■, ●-galena, □, ○-sphalerite;

[0034] Figure 5 Flotation results of chalcopyrite and pyrite in Example 3;

[0035] Figure 6 Flotation results of galena in Example 6. DETAILED DESCRIPTION

[0036] The following examples are intended to further illustrate the present application and are not intended to limit the scope of the present application. All parts and percentages in the examples are by mass unless otherwise specified. The flotation processes of the minerals in the examples are all conventional processes, except that the 2-amin-4-hydroxy-1,3,5-triazine-6-thiol compounds of the present application are used instead of the conventional flotation collectors.

[0037] In the present application, the 2-amin-4-hydroxy-1,3,5-triazine-6-thiol compounds of the formula (I) can be prepared by the reported methods (Nakamura, Y., Mori, M., Okazaki, J., 2-R-4,6-dimercapto-s-triazine by polysulfur chlorohydrin vulcanization. Japan Rubber Association Journal, 1973, 46(9): 779-787; Yang, N. F., Chen, D. L., Li, Q. Synthesis of S-triazine derivatives. Journal of Natural Sciences of Jilin University, 1994(1): 101-103; Yang, N. F., Ge, S. S. Synthesis of S-triazine derivatives (II). Journal of Natural Sciences of Jilin University, 1995(1): 101-103).

[0038] The following are typical cases of the flotation experiments described in the present application:

[0039] Example 1: Flotation of galena with 2-butylamino-4-hydroxy-1,3,5-triazine-6-thiol sodium

[0040] The flotation of galena with particle size of -0.076 mm + 0.038 mm was carried out for 3 minutes at pH = 8, with the concentration of the frother methyl isobutyl carbinol (MIBC) being 15 mg / L, and the N2 gas flow rate being 200 mL / min. The flotation results are shown in Table 1. Figure 3 It is shown that the dosage of 2-butylamino-4-hydroxy-1,3,5-triazine-6-thiol sodium is 8 x 10 -7At a concentration of mol / L, the recovery rate of galena can reach 93.87%. This demonstrates that 2-butylamino-4-hydroxy-1,3,5-triazine-6-thiol compounds can effectively achieve flotation enrichment of galena as collectors.

[0041] Example 2: Flotation of galena and sphalerite using sodium 2-butylamino-4-hydroxy-1,3,5-triazine-6-thiolate

[0042] At a sodium concentration of 8 × 10⁻⁶ butylamino-4-hydroxy-1,3,5-triazine-6-thiolate -7 The frothing agent methyl isobutyl methanol (MIBC) concentration was 15 mg / L, the N2 gas flow rate was 200 mL / min, and galena and sphalerite with particle sizes of -0.076 mm to +0.038 mm were each floated for 3 minutes. The flotation results are shown in the figure. Figure 4 . Figure 4 The results show that sodium 2-butylamino-4-hydroxy-1,3,5-triazine-6-thiol exhibits high recovery rates for galena and sphalerite at pH < 8, while at pH > 8, it effectively separates galena and sphalerite, with superior separation performance compared to isopropyl xanthate. Compared to isopropyl xanthate, sodium 2-butylamino-4-hydroxy-1,3,5-triazine-6-thiol not only demonstrates stronger collecting ability for galena but also better selectivity for sphalerite.

[0043] Example 3: Flotation of chalcopyrite and pyrite using sodium 2-butylamino-4-hydroxy-1,3,5-triazine-6-thiol

[0044] At a sodium concentration of 8 × 10⁻⁶ butylamino-4-hydroxy-1,3,5-triazine-6-thiolate -6 The flotation was performed at a concentration of mol / L, with the frother methyl isobutyl methanol (MIBC) at 15 mg / L and the N2 gas flow rate at 200 mL / min. Chalcopyrite or pyrite particles with a diameter of -0.076 mm to +0.038 mm were each floated for 3 minutes. The flotation results are shown in [Figure number missing]. Figure 5 This indicates that at pH < 7, sodium 2-butylamino-4-hydroxy-1,3,5-triazine-6-thiol exhibits higher recovery rates for pyrite flotation and lower recovery rates for chalcopyrite. With increasing pH, sodium 2-butylamino-4-hydroxy-1,3,5-triazine-6-thiol shows a gradually increasing collecting capacity for chalcopyrite and a gradually decreasing collecting capacity for pyrite. At pH = 9-11, efficient flotation separation of chalcopyrite and pyrite can be achieved.

[0045] Example 4: Flotation of bornite with sodium 2-butylamino-4-hydroxy-1,3,5-triazine-6-thiol

[0046] At a sodium concentration of 3 × 10⁻⁶ butylamino-4-hydroxy-1,3,5-triazine-6-thiolate -5Example 1 : 2-Butylamino-4-hydroxy-1,3,5-triazine-6-thiol sodium flotation of chalcopyrite

[0047] Example 5: 2-Butylamino-4-hydroxy-1,3,5-triazine-6-thiol sodium flotation of malachite

[0048] The flotation of malachite with a particle size of -0.076 mm + 0.038 mm was carried out for 3 minutes at a slurry pH of 9, a concentration of 15 mg / L of the frother methyl isobutyl carbinol (MIBC), and a N2 flow rate of 200 mL / min. The flotation recovery of malachite was 85.48%. -4 The flotation of malachite with a particle size of -0.076 mm + 0.038 mm was carried out for 3 minutes at a slurry pH of 9, a concentration of 15 mg / L of the frother methyl isobutyl carbinol (MIBC), and a N2 flow rate of 200 mL / min. The flotation recovery of malachite was 85.48%.

[0049] Example 6: 2-Ethylamino-4-hydroxy-1,3,5-triazine-6-thiol sodium flotation of galena

[0050] The flotation of galena with a particle size of -0.076 mm + 0.038 mm was carried out for 3 minutes at a slurry pH of 8, a concentration of 15 mg / L of the frother methyl isobutyl carbinol (MIBC), and a N2 flow rate of 200 mL / min, with 2-ethylamino-1,3,5-triazine-2(1 H)-thione-6-thiol sodium or 2- ethylamino-4-hydroxy-1,3,5-triazine-6-thiol sodium as the collector. The flotation results are shown in Table 2. Figure 6 Table 2: Flotation of galena with 2-ethylamino-1,3,5-triazine-2(1 H)-thione-6-thiol sodium and 2-ethylamino-4-hydroxy-1,3,5-triazine-6-thiol sodium -6 The flotation of galena with a particle size of -0.076 mm + 0.038 mm was carried out for 3 minutes at a slurry pH of 8, a concentration of 15 mg / L of the frother methyl isobutyl carbinol (MIBC), and a N2 flow rate of 200 mL / min, with 2-ethylamino-1,3,5-triazine-2(1 H)-thione-6-thiol sodium or 2- ethylamino-4-hydroxy-1,3,5-triazine-6-thiol sodium as the collector. The flotation results are shown in Table 2. Table 2: Flotation of galena with 2-ethylamino-1,3,5-triazine-2(1 H)-thione-6-thiol sodium and 2-ethylamino-4-hydroxy-1,3,5-triazine-6-thiol sodium

Claims

1. Use of a 2-amino-4-hydroxy-l,3,5-triazine-6-thiol compound in the flotation of metal ores, characterized in that, The 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compound is used as a collector for the flotation of metal minerals, and the metal minerals are oxidized ores and / or sulfide ores containing at least one of Cu, Pb and Zn. The 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compound is at least one compound having the structure of formula (I). Formula (I) wherein in formula (I) R 1 is a C1-C 18 hydrocarbon group or a C2-C 18 alkoxy-substituted alkyl group, R 2 is H, a C1-C 18 hydrocarbon group or a C2-C 18 alkoxy-substituted alkyl group; and M is H, sodium, potassium or an ammonium cation.

2. Use according to claim 1, characterized in that, said hydrocarbon group is a C1-C 18 alkyl group, a C6-C 12 aryl group, a C5-C 12 five- or six-membered ring hydrocarbon group.

3. Use according to claim 1, characterized in that, said alkoxy-substituted alkyl is R 4 OCH2CH2CH2-, said R 4 is a C1-C 15 hydrocarbon group.

4. Use according to claim 1, characterized in that, R 1 C2-C6alkyl or C1-C6alkoxy-substituted propyl; R 2 is H, C2-C6alkyl or C1-C6alkoxy-substituted propyl.

5. The use according to claim 1, characterized in that, R 1 is C3-C5alkyl; R 2 is H or C3-C5alkyl.

6. The use according to claim 1, characterized in that, The metal minerals are at least one of copper ore, lead ore or zinc ore.

7. Use according to claim 6, characterized in that, In the flotation stage, the dosage of the 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compound is 2-1000 g / t.

8. Use according to claim 7, characterized in that, The pH of the ore pulp in the flotation stage is 5.5-11.

5.

9. Use according to claim 8, characterized in that, When the pH of the ore pulp in the flotation stage is less than 8, galena and / or sphalerite is selectively collected. Alternatively, when the pH of the ore pulp in the flotation stage is 9-12, galena is selectively collected from a mixed ore containing galena and sphalerite. Alternatively, when the pH of the ore pulp in the flotation stage is 4-6, pyrite is selectively collected from a mixed ore containing pyrite and chalcopyrite, and chalcopyrite tailings are obtained. Alternatively, when the pH of the ore pulp in the flotation stage is 9-11, chalcopyrite is selectively collected from a mixed ore containing pyrite and chalcopyrite. Alternatively, when the pH of the ore pulp in the flotation stage is 8-10, bornite and / or malachite is selectively collected.

10. The use according to any one of claims 1 to 9, characterized in that, The steps of the flotation process include: Step (1): crushing and slurrying the metal ore to obtain an ore pulp; Step (2): adding a flotation reagent to the ore pulp of step (1) for flotation, and collecting the flotation concentrate; the flotation reagent contains the 2-amino-4-hydroxy-1,3,5-triazine-6-thiol compound.

11. Use according to claim 10, characterized in that, A foaming agent is also selectively added to the flotation reagent; The dosage of the foaming agent is 5-100 g / t.

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