Application of azacyclo-thioketone compound

Abstract

The invention discloses an application of an azacyclo-thioketone compound, and particularly relates to an application of the azacyclo-thioketone compound in preparation of a vulcanizing agent. The azacyclo-thioketone compound is stable in property, not only has a thiocarbonyl sulfur atom of a reaction center in a molecular structure, but also has atoms with electron donating capability, such as nitrogen, oxygen and sulfur, on a heterocyclic ring, and selective flotation separation of copper, lead, zinc and iron sulfide minerals can be realized. However, no report about using the azacyclo-thioketone compound as the oxidized ore vulcanizing agent exists at present.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral flotation, and in particular relates to application of nitrogen heterocyclic thione compounds. Background Art

[0002] With the development of copper, lead and zinc sulfide resources in my country, the efficient development and utilization of difficult-to-treat copper, lead and zinc oxide resources has become a research focus.

[0003] At present, the flotation recovery of difficult-to-treat copper-lead-zinc oxide minerals is mainly carried out by sulfidation flotation, and the commonly used sulfiding agent is sodium sulfide. However, sodium sulfide is highly alkaline, deliquesces in the air, and deteriorates due to carbonation, and continuously releases hydrogen sulfide gas, which has the problem of large pollution. In addition, sodium sulfide has the problems of large dosage and high cost. With the continuous use of sodium sulfide in the closed-loop system of the flotation industry, the accumulation of Chinese medicine dosage in the return water usually produces a strong inhibitory effect. Therefore, it is of great significance to develop an efficient organic sulfiding agent that has an efficient sulfidation effect on difficult-to-treat copper-lead-zinc oxide minerals, is easily degradable, and is non-toxic, in order to improve the comprehensive utilization rate of low-grade oxide ore resources. Summary of the invention

[0004] The purpose of the present invention is to provide an application of a nitrogen heterocyclic thione compound.

[0005] The object of the present invention is achieved by using the azacyclic thione compounds in the preparation of a vulcanizing agent.

[0006] Nitrogen heterocyclic thioketone compounds are stable in nature. Their molecular structure not only contains a thiocarbonylsulfide atom as a reaction center, but also nitrogen, oxygen, sulfur and other electron-donating atoms on their heterocyclic rings, which can achieve the selective flotation separation of copper, lead, zinc and iron sulfide minerals.

[0007] The sulfidation flotation method for copper-lead-zinc oxide minerals using a sulfiding agent of the present invention comprises pretreatment, activation and flotation steps, specifically comprising: A. Pretreatment: The copper-lead-zinc oxide ore to be treated is crushed, ground and slurried to obtain slurry a; B. Activation: Add the vulcanizing agent to the slurry a and stir for 3-5 minutes to obtain the slurry b after vulcanization and activation; C. Add flotation collector to the slurry b after sulfide activation to carry out flotation to obtain flotation concentrate.

[0008] The specific operations are: 1) The oxide ore is crushed, ground and slurried to obtain slurry; 2) adding the azacyclic thione vulcanizing agent to the ore pulp in step (1), stirring, and obtaining a vulcanized and activated ore pulp; 3) Adding a flotation collector to the ore pulp in step (2), performing flotation, and collecting the flotation concentrate.

[0009] In the present invention, in the flotation stage, based on the weight of the oxidized ore, the dosage of the nitrogen heterocyclic thioketone compound is 100-5000 g / t, preferably 200-2000 g / t.

[0010] In the present invention, in the flotation stage, based on the weight of the oxidized ore, the dosage of the collector is 50-5000 g / t, preferably 200-2000 g / t.

[0011] In the present invention, the collector comprises the following components by mass fraction: 10-20 parts of butyl sodium xanthate and 80-90 parts of butyl ammonium xanthate.

[0012] The present invention has the following beneficial effects: (1) The present invention is the first to apply nitrogen heterocyclic thione compounds as a sulfiding agent for copper-lead-zinc oxide minerals. The nitrogen heterocyclic molecular structure not only has a thiocarbonylsulfide atom as a reaction center, but also has nitrogen, oxygen, sulfur and other atoms with electron-donating ability on its heterocyclic ring. It can effectively form a hydrophobic film on the surface of copper-lead-zinc oxide minerals, promote the efficient flotation enrichment of copper-lead-zinc oxide minerals, and effectively realize the flotation recovery of low-grade oxide ores to obtain oxide ore concentrates of qualified grade, with significant benefits and good industrial application prospects.

[0013] (2) The nitrogen heterocyclic thione compounds provided by the present invention have strong selective adsorption effect on oxidized minerals, good stability and low toxicity, and can overcome the disadvantage of poor stability of sodium sulfide.

[0014] (3) The nitrogen heterocyclic thioketone compound sulfiding agent provided by the present invention can realize the efficient flotation recovery of oxide ore without changing the existing process equipment and process of industrial production.

[0015] The copper-lead-zinc oxide mineral contains at least one element of copper, lead and zinc; further, it can be any one of malachite, azurite, chrysocolla, cuprite, cerussite, lead alum, smithsonite, zincite, hemimorphite and willemite.

[0016] In the present invention, the mass ratio of the nitrogen heterocyclic thione compounds of formula (I), formula (II) and formula (III) is 0-100:0-100:0-100; . BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The present invention is a process flow chart of the collector flotation of pure copper, lead and zinc oxide minerals. DETAILED DESCRIPTION

[0018] The present invention is further described below in conjunction with the embodiments, but the present invention is not limited in any way. Any changes or substitutions made based on the teachings of the present invention belong to the protection scope of the present invention.

[0019] The application of the nitrogen heterocyclic thione compounds of the present invention is the application of the nitrogen heterocyclic thione compounds in the preparation of vulcanizing agents.

[0020] The azacyclic thione compound is at least one compound having the structure of formula (I), formula (II) and formula (III), and its structure is as follows: .

[0021] Among them, R 1 is hydrogen, C1-C 15 R 2 is hydrogen, C1-C 15 R 3 is hydrogen, C1-C 15 alkyl, oxygen-containing hydrocarbon group or nitrogen-containing hydrocarbon group, phenyl, benzyl or pyridine; M is sodium, potassium, ammonium or hydrogen.

[0022] The R 1 is hydrogen, a C1-C4 hydrocarbon group, an oxygen-containing hydrocarbon group or a nitrogen-containing hydrocarbon group, a C2-C4 acyl group, a phenyl group or a benzyl group; R 2 is hydrogen, a C1-C4 hydrocarbon group, an oxygen-containing hydrocarbon group or a nitrogen-containing hydrocarbon group, a C2-C4 acyl group, a phenyl group or a benzyl group; R 3 is hydrogen, sodium, a C1-C4 hydrocarbon group, an oxygen-containing hydrocarbon group or a nitrogen-containing hydrocarbon group, a phenyl group, a benzyl group or a pyridine group; and M is sodium, potassium or hydrogen.

[0023] The R 1 is hydrogen, methyl, propyl or butyl; R 2 is hydrogen, methyl, propyl or butyl; R 3 is hydrogen, sodium, phenyl or benzyl; M is sodium or potassium.

[0024] The sulfidation flotation method for copper-lead-zinc oxide minerals using a sulfiding agent of the present invention comprises pretreatment, activation and flotation steps, specifically comprising: A. Pretreatment: The copper-lead-zinc oxide ore to be treated is crushed, ground and slurried to obtain slurry a; B. Activation: Add the vulcanizing agent to the slurry a and stir for 3-5 minutes to obtain the slurry b after vulcanization and activation; C. Add flotation collector to the slurry b after sulfide activation to carry out flotation to obtain flotation concentrate.

[0025] The copper-lead-zinc oxide ore is any one of malachite, azurite, chrysocolla, cuprite, cerussite, lead alum, smithsonite, zincite, hemimorphite and willemite.

[0026] The mass percentage concentration of slurry a in step A is 20-50%.

[0027] The amount of vulcanizing agent added in step B is 100~5000g / t.

[0028] The stirring speed in step B is 1995~2000r / min.

[0029] The flotation collector described in step C is composed of sodium butyl xanthate and butyl ammonium xanthate.

[0030] The mass proportions of the sodium butyl xanthate and the ammonium butyl black medicine are as follows: 10-20 parts of the sodium butyl xanthate and 80-90 parts of the ammonium butyl black medicine.

[0031] The present invention is further described below with specific implementation cases: Example 1 Sulfide flotation of malachite using nitrogen heterocyclic thionyl compounds The flotation process and reagent system of this embodiment are as follows: Figure 1 As shown, 2g of pure malachite mineral crushed and ball-milled to a fineness of -200 mesh was weighed and added to a 40mL RK / FGC hanging tank flotation machine for flotation separation test. The stirring speed was 1998r / min, and 5-phenyl-134-oxadiazole-2-thione and 6-methyl-1,3-benzoxazole-2-thione with a mass ratio of 1:1 were used as sulfiding agents, with a total dosage of 400g / t and an action time of 3min. Butyl ammonium black medicine was used as a collector, with a dosage of 300g / t and an action time of 5min. The dosage of methyl isobutyl carbinol, a foaming agent, was 10mg / L. When the pulp pH was 8.0, the malachite was floated for 3min. The results showed that the flotation recovery rate of malachite could reach 93.6%.

[0032] Comparative Example 1 Direct flotation of malachite with ammonium butyl Compared with Example 1, the difference of this comparative example is that no sulfiding agent is added, butyl ammonium black medicine is used as a collector, and direct flotation is performed, and the dosage is also 300g / t. The results show that the flotation recovery rate of malachite is only 55.3%.

[0033] Example 2 Sulfide flotation of malachite under high dosage of nitrogen heterocyclic thioketone compounds The flotation process and reagent system of this embodiment are as follows: Figure 1As shown, 2g of pure malachite mineral crushed and ball-milled to a fineness of -200 mesh was weighed and added to a 40mL RK / FGC hanging tank flotation machine for flotation separation test. The stirring speed was 1998r / min. 5-phenyl-134-oxadiazole-2-thione and 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazine with a mass ratio of 1:1 were used as sulfiding agents, with a total dosage of 4000g / t and an action time of 5min. Butyl ammonium black medicine was used as a collector with a dosage of 300g / t and an action time of 3min. The dosage of methyl isobutyl carbinol as a foaming agent was 10mg / L. When the pulp pH was 8.0, the malachite was floated for 3min. The results showed that the flotation recovery rate of malachite could reach 97.6%.

[0034] Comparative Example 2 Sulfide flotation of malachite under high sodium sulfide dosage conditions Compared with Example 2, the difference of this comparative example is that no nitrogen heterocyclic thione compound is added as a sulfiding agent, and traditional sodium sulfide is added as an activating agent, and the amount used is also 4000 g / t. The results show that the flotation recovery rate of malachite is 50.6%.

[0035] Example 3 Sulfide flotation separation of malachite-calcite artificial mixed ore by nitrogen heterocyclic thioketone compounds The flotation process and reagent system of this embodiment are as follows: Figure 1 As shown, 1g of pure malachite and calcite crushed and ball-milled to a fineness of -200 mesh were weighed and added to a 40mL RK / FGC hanging tank flotation machine for flotation separation test. The stirring speed was 1998r / min, and 5-phenyl-134-oxadiazole-2-thione and 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazine with a mass ratio of 1:1 were used as sulfiding agents, with a total dosage of 400g / t and an action time of 5min. Butyl ammonium black medicine was used as a collector, with a dosage of 300g / t and an action time of 3min. The dosage of methyl isobutyl carbinol, a foaming agent, was 10mg / L. When the pulp pH was 8.0, the flotation was performed for 3min. The results showed that the flotation recovery rate of malachite could reach 91.4%.

[0036] Example 4 Sulfide flotation of azurite using nitrogen heterocyclic thionone compounds The flotation process and reagent system of this embodiment are as follows: Figure 1As shown, 2g of pure blue copper ore crushed and ball-milled to a fineness of -200 mesh was weighed and added to a 40mL RK / FGC hanging tank flotation machine for flotation separation test. The stirring speed was 1998r / min. 5-phenyl-134-oxadiazole-2-thione and 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazine with a mass ratio of 1:1 were used as sulfiding agents, with a total dosage of 400g / t and an action time of 3min. Butyl ammonium black medicine was used as a collector, with a dosage of 300g / t and an action time of 5min. The dosage of methyl isobutyl carbinol, a foaming agent, was 10mg / L. When the pulp pH was 8.0, the blue copper ore was floated for 3min. The results showed that the flotation recovery rate of blue copper ore could reach 90.2%.

[0037] Example 5 Sulfide flotation of cerussite with nitrogen heterocyclic thionyl compounds The flotation process and reagent system of this embodiment are as follows: Figure 1 As shown, 2g of pure white lead ore crushed and ball-milled to a fineness of -200 mesh was weighed and added to a 40mL RK / FGC hanging tank flotation machine for flotation separation test. The stirring speed was 1998r / min, and 5-methyl-2,3-dihydro-1,3-benzoxazole-2-thione and 6-methyl-1,3-benzoxazole-2-thione with a mass ratio of 1:1 were used as sulfiding agents, with a total dosage of 400g / t and an action time of 5min. Butyl ammonium black medicine was used as a collector, with a dosage of 300g / t and an action time of 3min. The dosage of methyl isobutyl carbinol, a foaming agent, was 10mg / L. When the pulp pH was 8.0, white lead ore was floated for 3min. The results showed that the flotation recovery rate of white lead ore could reach 93.5%.

[0038] Comparative Example 3 Direct flotation of cerussite with ammonium butyl Compared with Example 1, the difference of this comparative example is that no sulfiding agent is added, butyl ammonium black medicine is used as a collector, and direct flotation is performed, and the dosage is also 300g / t. The results show that the flotation recovery rate of white lead ore is only 50.1%.

[0039] Example 6 Sulfide flotation of cerussite under high dosage of nitrogen heterocyclic thionone compounds The flotation process and reagent system of this embodiment are as follows: Figure 1As shown, 2g of pure cerussite ore crushed and ball-milled to a fineness of -200 mesh was weighed and added to a 40mL RK / FGC hanging tank flotation machine for flotation separation test. The stirring speed was 1998r / min, and 5-methyl-2,3-dihydro-1,3-benzoxazole-2-thione and 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazine with a mass ratio of 1:1 were used as sulfiding agents, with a total dosage of 4000g / t and an action time of 5min. Butyl ammonium black medicine was used as a collector, with a dosage of 300g / t and an action time of 3min. The dosage of methyl isobutyl carbinol, a foaming agent, was 10mg / L. When the pulp pH was 8.0, malachite was floated for 3min. The results showed that the flotation recovery rate of cerussite could reach 94.1%.

[0040] Comparative Example 4 Sulfide flotation of cerussite under high sodium sulfide dosage conditions Compared with Example 2, the difference of this comparative example is that no nitrogen heterocyclic thione compound is added as a sulfiding agent, and traditional sodium sulfide is added as an activating agent, and the amount used is also 4000g / t. The results show that the flotation recovery rate of white lead ore is 48.2%.

[0041] Example 7 Sulfide flotation separation of cerussite-calcite artificial mixed ore by nitrogen heterocyclic thionone compounds The flotation process and reagent system of this embodiment are as follows: Figure 1 As shown, 1g of white lead ore and pure calcite crushed and ball-milled to a fineness of -200 mesh were weighed and added to a 40mL RK / FGC hanging tank flotation machine for flotation separation test. The stirring speed was 1998r / min, and 5-methyl-2,3-dihydro-1,3-benzoxazole-2-thione and 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazine with a mass ratio of 1:1 were used as sulfiding agents, with a total dosage of 400g / t and an action time of 5min. Butyl ammonium black medicine was used as a collector, with a dosage of 300g / t and an action time of 3min. The dosage of methyl isobutyl carbinol, a foaming agent, was 10mg / L. When the pulp pH was 8.0, the flotation was performed for 3min. The results showed that the flotation recovery rate of white lead ore could reach 92.6%.

[0042] Example 8 Sulfide flotation of smithsonite using nitrogen heterocyclic thionyl compounds The flotation process and reagent system of this embodiment are as follows: Figure 1As shown in the figure, 2g of pure smithsonite ore crushed and ball-milled to a fineness of -200 mesh was weighed and added to a 40mL RK / FGC hanging tank flotation machine for flotation separation test. The stirring speed was 1998r / min, and 5-methyl-2,3-dihydro-1,3-benzoxazole-2-thione and 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazine with a mass ratio of 1:1 were used as sulfiding agents, with a total dosage of 400g / t and an action time of 5min; butyl sodium xanthate was used as a collector, with an dosage of 300g / t and an action time of 3min; the dosage of methyl isobutyl carbinol as a foaming agent was 10mg / L, and the smithsonite was floated for 3min when the pulp pH was 8.0. The results showed that the flotation recovery rate of smithsonite could reach 90.1%.

[0043] Therefore, nitrogen heterocyclic thioketone compounds exhibit excellent sulfidation effect on copper-lead-zinc oxide minerals. By forming a stable sulfide film on the surface of the mineral, the sulfide flotation of copper-lead-zinc oxide minerals can be realized, which can enhance the selective flotation enrichment of lead-zinc oxide ores. The compounds have stable properties and have strong prospects for industrial application.

Claims

1. An application of a nitrogen heterocyclic thione compound, characterized in that: The application of the nitrogen heterocyclic thione compounds in the preparation of vulcanizing agents.

2. The use of the nitrogen heterocyclic thione compounds according to claim 1, characterized in that: The azacyclic thione compound is at least one compound having the structure of formula (I), formula (II) and formula (III), and its structure is as follows: Among them, R 1 is hydrogen, C1-C 15 R 2 is hydrogen, C1-C 15 R 3 is hydrogen, C1-C 15 alkyl, oxygen-containing hydrocarbon group or nitrogen-containing hydrocarbon group, phenyl, benzyl or pyridine; M is sodium, potassium, ammonium or hydrogen.

3. The use of the nitrogen heterocyclic thione compounds according to claim 2, characterized in that: The R 1 is hydrogen, a C1-C4 hydrocarbon group, an oxygen-containing hydrocarbon group or a nitrogen-containing hydrocarbon group, a C2-C4 acyl group, a phenyl group or a benzyl group; R 2 is hydrogen, a C1-C4 hydrocarbon group, an oxygen-containing hydrocarbon group or a nitrogen-containing hydrocarbon group, a C2-C4 acyl group, a phenyl group or a benzyl group; R 3 is hydrogen, sodium, a C1-C4 hydrocarbon group, an oxygen-containing hydrocarbon group or a nitrogen-containing hydrocarbon group, a phenyl group, a benzyl group or a pyridine group; and M is sodium, potassium or hydrogen.

4. The use of the nitrogen heterocyclic thione compounds according to claim 2 or 3, characterized in that: The R 1 is hydrogen, methyl, propyl or butyl; R 2 is hydrogen, methyl, propyl or butyl; R 3 is hydrogen, sodium, phenyl or benzyl; M is sodium or potassium.

5. A sulfidation flotation method for copper-lead-zinc oxide minerals based on the sulfiding agent described in claim 1, characterized in that: It includes pre-treatment, activation and flotation steps, specifically including: A. Pretreatment: The copper-lead-zinc oxide ore to be treated is crushed, ground and slurried to obtain slurry a; B. Activation: Add the vulcanizing agent to the slurry a and stir for 3-5 minutes to obtain the slurry b after vulcanization and activation; C. Add flotation collector to the slurry b after sulfide activation to carry out flotation to obtain flotation concentrate.

6. The method according to claim 5, characterized in that The copper-lead-zinc oxide ore is any one of malachite, azurite, chrysocolla, cuprite, cerussite, lead alum, smithsonite, zincite, hemimorphite and willemite.

7. The method according to claim 5, characterized in that The mass percentage concentration of slurry a in step A is 20-50%.

8. The method according to claim 5, characterized in that The amount of vulcanizing agent added in step B is 100~5000g / t.

9. The method according to claim 5, characterized in that The stirring speed in step B is 1995~2000r / min.

10. The method according to claim 5, characterized in that The flotation collector described in step C is composed of sodium butyl xanthate and butyl ammonium xanthate.

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