Application of a nitrogen heterocyclic thion compound

Abstract

This invention discloses the application of a nitrogen-containing heterocyclic thionate compound in the preparation of sulfiding agents. Nitrogen-containing heterocyclic thionates are stable and possess not only a thiocarbonyl sulfur atom as the reaction center in their molecular structure, but also electron-donating atoms such as nitrogen, oxygen, and sulfur on their heterocycles, enabling selective flotation separation of copper, lead, zinc, and iron sulfide minerals. However, there are currently no reports on the use of nitrogen-containing heterocyclic thionates as sulfiding agents for oxidized minerals.

Description

Technical Field

[0001] This invention belongs to the field of mineral flotation technology, and specifically relates to the application of a nitrogen-containing heterocyclic thionate compound. Background Technology

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

[0003] Currently, the main method for recovering refractory copper, lead, and zinc oxide minerals is sulfide flotation, with sodium sulfide being the commonly used sulfiding agent. However, sodium sulfide is highly alkaline, deliquesces in air, and deteriorates through carbonation, continuously releasing hydrogen sulfide gas, posing a significant pollution problem. Furthermore, sodium sulfide involves large dosages and high costs; with continuous use in closed-loop flotation systems, the accumulation of sodium sulfide in the reflux water often produces a strong inhibitory effect. Therefore, developing a highly efficient organic sulfiding agent that is highly effective in sulfiding refractory copper, lead, and zinc oxide minerals, is easily degradable, and non-toxic is of great significance for improving the comprehensive utilization rate of low-grade oxide mineral resources. Summary of the Invention

[0004] The purpose of this invention is to provide an application of nitrogen-containing heterocyclic thioketone compounds.

[0005] The objective of this invention is achieved by the application of the aforementioned nitrogen-containing heterocyclic thionates in the preparation of sulfiding agents.

[0006] Nitrogen heterocyclic thioketone compounds are stable and their molecular structure not only contains thiocarbonyl sulfur atoms at the reaction center, but also nitrogen, oxygen, sulfur and other electron-donating atoms on their heterocycles, enabling selective flotation separation of copper, lead, zinc and iron sulfide minerals.

[0007] The sulfidation flotation method for copper-lead-zinc oxide minerals using the sulfidating agent described in this invention includes pretreatment, activation, and flotation steps, specifically including:

[0008] A. Pretreatment: The copper-lead-zinc oxide minerals to be treated are crushed, ground, and slurry-prepared to obtain slurry a;

[0009] B. Activation: Add the sulfiding agent to slurry a and stir for 3-5 minutes to obtain sulfidated and activated slurry b;

[0010] C. Add flotation collector to the sulfidated and activated slurry b and perform flotation to obtain flotation concentrate.

[0011] The specific steps are as follows:

[0012] 1) The oxidized ore is crushed, ground, and mixed to obtain a slurry;

[0013] 2) Add the nitrogen heterocyclic thionate sulfiding agent to the slurry in step (1), stir, and obtain the sulfidated and activated slurry;

[0014] 3) Add flotation collector to the slurry described in step (2) and perform flotation to collect flotation concentrate.

[0015] In this invention, during the flotation stage, based on the weight of the oxidized ore, the dosage of the nitrogen-containing heterocyclic thioketone compound is 100-5000 g / t, preferably 200-2000 g / t.

[0016] In this invention, during 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.

[0017] In this invention, the collector comprises the following components by mass fraction: 10-20 parts of sodium butyl xanthate and 80-90 parts of butylammonium black powder.

[0018] The present invention has the following beneficial effects:

[0019] (1) This invention is the first to apply nitrogen heterocyclic thionine compounds as sulfiding agents for copper-lead-zinc oxide minerals. The nitrogen heterocyclic molecular structure not only has thiocarbonyl sulfur atoms in the reaction center, but also has nitrogen, oxygen, sulfur and other atoms with electron-donating ability on its heterocycle. 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, and obtain qualified oxide ores concentrates. It has significant benefits and good industrial application prospects.

[0020] (2) The nitrogen heterocyclic thiones provided by the present invention have strong selective adsorption of oxidized minerals, good stability and low toxicity, which can overcome the disadvantage of poor stability of sodium sulfide.

[0021] (3) The nitrogen heterocyclic thionate compound sulfiding agent provided by the present invention can achieve efficient flotation recovery of oxide ores without changing the existing industrial production process equipment and process.

[0022] The copper-lead-zinc oxide minerals mentioned herein contain at least one element selected from copper, lead, and zinc; furthermore, they may be any one of malachite, azurite, chrysocolla, cuprite, cerussite, vanadium, smithsonite, zincite, hemimorphite, and zinc siliceous mineral.

[0023] In this invention, the mass ratio of the nitrogen heterocyclic thiones of formula (I), formula (II) and formula (III) is 0-100: 0-100: 0-100;

[0024] . Attached Figure Description

[0025] Figure 1 This is a process flow diagram of the flotation of pure copper, lead, and zinc oxide minerals using the collector of this invention. Detailed Implementation

[0026] The present invention will be further described below with reference to embodiments, but this is not intended to limit the present invention in any way. Any modifications or substitutions made based on the teachings of the present invention shall fall within the protection scope of the present invention.

[0027] The application of the nitrogen-containing heterocyclic thionate compounds described in this invention is their use in the preparation of vulcanizing agents.

[0028] The aforementioned nitrogen-containing heterocyclic thiones are at least one compound having the structures of formula (I), formula (II), and formula (III), and their structures are as follows:

[0029] .

[0030] Among them, R 1 Hydrogen, C1-C 15 Hydrocarbon group, oxygen-containing hydrocarbon group or nitrogen-containing hydrocarbon group, C2-C8 acyl group, propenyl group, ethynyl group, phenyl group, benzyl group or benzyloxy group; R 2 Hydrogen, C1-C 15 Hydrocarbon group, oxygen-containing hydrocarbon group or nitrogen-containing hydrocarbon group, C2-C8 acyl group, propenyl group, ethynyl group, phenyl group, benzyl group or benzyloxy group; R 3 Hydrogen, C1-C 15 The hydrocarbon group, oxygen-containing hydrocarbon group, or nitrogen-containing hydrocarbon group, phenyl, benzyl, or pyridine; M is sodium, potassium, ammonium, or hydrogen.

[0031] The R mentioned 1 It 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 It 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 M is hydrogen, sodium, C1-C4 hydrocarbon group, oxygen-containing hydrocarbon group or nitrogen-containing hydrocarbon group, phenyl, benzyl or pyridine; M is sodium, potassium or hydrogen.

[0032] The R mentioned 1 It is hydrogen, methyl, propyl, or butyl; R 2 It is hydrogen, methyl, propyl, or butyl; R 3 It is hydrogen, sodium, phenyl, or benzyl; M is sodium or potassium.

[0033] The sulfidation flotation method for copper-lead-zinc oxide minerals using the sulfidating agent described in this invention includes pretreatment, activation, and flotation steps, specifically including:

[0034] A. Pretreatment: The copper-lead-zinc oxide minerals to be treated are crushed, ground, and slurry-prepared to obtain slurry a;

[0035] B. Activation: Add the sulfiding agent to slurry a and stir for 3-5 minutes to obtain sulfidated and activated slurry b;

[0036] C. Add flotation collector to the sulfidated and activated slurry b and perform flotation to obtain flotation concentrate.

[0037] The copper-lead-zinc oxide ore mentioned is any one of malachite, azurite, chrysocolla, cuprite, cerussite, lead oxide, smithsonite, zincite, hemimorphite, and zinc siliceous ore.

[0038] In step A, the mass percentage concentration of slurry a is 20-50%.

[0039] In step B, the amount of vulcanizing agent added is 100~5000g / t.

[0040] In step B, the stirring speed is 1995~2000 r / min.

[0041] The flotation collector described in step C consists of sodium butyl xanthate and butylammonium black powder.

[0042] The mass fractions of the sodium butyl xanthate and the butyl ammonium black powder are as follows: 10-20 parts of sodium butyl xanthate and 80-90 parts of butyl ammonium black powder.

[0043] The invention will be further illustrated below with specific implementation examples:

[0044] Example 1

[0045] Sulfide flotation of malachite from nitrogen heterocyclic thioketone compounds

[0046] The flotation process and reagent regimen in this embodiment are as follows: Figure 1 As shown, 2g of crushed and ball-milled malachite mineral to a fineness of 200 mesh was added to a 40mL RK / FGC flotation machine for flotation separation. The stirring speed was 1998 r / min. A sulfiding agent of 5-phenyl-134-oxadiazole-2-thione and 6-methyl-1,3-benzoxazole-2-thione (mass ratio 1:1) was used, with a total dosage of 400g / t and a reaction time of 3min. Butanyl butyl alcohol black was used as the collector at a dosage of 300g / t for a reaction time of 5min. The frother, methyl isobutyl methanol, was used at a dosage of 10mg / L. The flotation of malachite was carried out for 3min at a pulp pH of 8.0. The results showed that the flotation recovery rate of malachite reached 93.6%.

[0047] Comparative Example 1

[0048] Direct flotation of malachite with butylammonium black powder

[0049] Compared to Example 1, this comparative example differs in that no sulfiding agent was added; instead, butylammonium black powder was used as the collector for direct flotation, with the same dosage of 300 g / t. The results showed that the flotation recovery rate of malachite was only 55.3%.

[0050] Example 2

[0051] Sulfide flotation of malachite under high dosage of nitrogen heterocyclic thioketone compounds

[0052] The flotation process and reagent regimen in this embodiment are as follows: Figure 1 As shown, 2g of crushed and ball-milled malachite mineral to a fineness of 200 mesh was added to a 40mL RK / FGC flotation machine for flotation separation. The stirring speed was 1998 r / min. A sulfiding agent of 5-phenyl-134-oxadiazole-2-thione and 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazine (mass ratio 1:1) was used, with a total dosage of 4000g / t and a reaction time of 5min. Butanyl butylamine black was used as the collector at a dosage of 300g / t for a reaction time of 3min. The frother, methyl isobutyl methanol, was used at a dosage of 10mg / L. The flotation of malachite was carried out for 3min at a pulp pH of 8.0. The results showed that the flotation recovery rate of malachite reached 97.6%.

[0053] Comparative Example 2

[0054] Sulfide flotation of malachite under high sodium sulfide dosage conditions

[0055] Compared to Example 2, this comparative example differs in that it does not use nitrogen-containing heterocyclic thioketone compounds as sulfiding agents, but instead uses conventional sodium sulfide as an activator at the same dosage of 4000 g / t. The results show that the flotation recovery rate of malachite is 50.6%.

[0056] Example 3

[0057] Sulfide flotation separation of malachite-calcite artificial mixed minerals using nitrogen heterocyclic thioketone compounds

[0058] The flotation process and reagent regimen in this embodiment are as follows: Figure 1As shown, 1g of crushed and ball-milled malachite and calcite (fineness - 200 mesh) were added to a 40mL RK / FGC flotation machine for flotation separation. The stirring speed was 1998r / min. A sulfiding agent of 5-phenyl-134-oxadiazole-2-thione and 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazine (mass ratio 1:1) was used, with a total dosage of 400g / t and a reaction time of 5min. Butanyl butylamine black was used as the collector at a dosage of 300g / t for a reaction time of 3min. The frother, methyl isobutyl methanol, was used at a dosage of 10mg / L. The flotation was carried out for 3min at a pulp pH of 8.0. The results showed that the flotation recovery rate of malachite reached 91.4%.

[0059] Example 4

[0060] Azurite by sulfidation flotation of nitrogen-containing heterocyclic thioketone compounds

[0061] The flotation process and reagent regimen in this embodiment are as follows: Figure 1 As shown, 2g of crushed and ball-milled azurite mineral to a fineness of 200 mesh was added to a 40mL RK / FGC flotation machine for flotation separation. The stirring speed was 1998 r / min. A sulfiding agent of 5-phenyl-134-oxadiazole-2-thione and 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazine (mass ratio 1:1) was used, with a total dosage of 400g / t and a reaction time of 3min. Butanyl butylamine black was used as the collector at a dosage of 300g / t for a reaction time of 5min. The frother, methyl isobutyl methanol, was used at a dosage of 10mg / L. The flotation of azurite was carried out for 3min at a pulp pH of 8.0. The results showed that the flotation recovery rate of azurite reached 90.2%.

[0062] Example 5

[0063] Nitrogen heterocyclic thioketone compounds sulfide flotation of cerussite

[0064] The flotation process and reagent regimen in this embodiment are as follows: Figure 1 As shown, 2g of crushed and ball-milled cerussite mineral to a fineness of 200 mesh was added to a 40mL RK / FGC flotation machine for flotation separation. The stirring speed was 1998 r / min. A sulfiding agent of 5-methyl-2,3-dihydro-1,3-benzoxazole-2-thione and 6-methyl-1,3-benzoxazole-2-thione (mass ratio 1:1) was used, with a total dosage of 400g / t and a reaction time of 5min. Butanyl butyl alcohol black was used as the collector at a dosage of 300g / t for a reaction time of 3min. The frother, methyl isobutyl methanol, was used at a dosage of 10mg / L. The flotation of cerussite was carried out for 3min at a pulp pH of 8.0. The results showed that the flotation recovery rate of cerussite reached 93.5%.

[0065] Comparative Example 3

[0066] Direct flotation of cerium silicate with butylammonium black powder

[0067] Compared to Example 1, this comparative example differs in that no sulfiding agent was added; instead, butylammonium black powder was used as the collector for direct flotation, with the same dosage of 300 g / t. The results showed that the flotation recovery rate of cerussite was only 50.1%.

[0068] Example 6

[0069] Sulfide flotation of cerussite under high dosage of nitrogen-containing heterocyclic thioketone compounds

[0070] The flotation process and reagent regimen in this embodiment are as follows: Figure 1 As shown, 2g of crushed and ball-milled cerussite mineral to a fineness of 200 mesh was added to a 40mL RK / FGC flotation machine for flotation separation. The stirring speed was 1998 r / min. A sulfiding agent of 5-methyl-2,3-dihydro-1,3-benzoxazole-2-thione and 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazine (mass ratio 1:1) was used, with a total dosage of 4000g / t and a reaction time of 5min. Butanyl butylamine black was used as the collector at a dosage of 300g / t for a reaction time of 3min. The frother, methyl isobutyl methanol, was used at a dosage of 10mg / L. Malachite was floated for 3min at a pulp pH of 8.0. The results showed that the flotation recovery rate of cerussite reached 94.1%.

[0071] Comparative Example 4

[0072] Sulfide flotation of cerussite under high sodium sulfide dosage

[0073] Compared to Example 2, this comparative example differs in that it does not use nitrogen-containing heterocyclic thioketone compounds as sulfiding agents, but instead uses conventional sodium sulfide as an activator, at the same dosage of 4000 g / t. The results show that the flotation recovery rate of cerussite is 48.2%.

[0074] Example 7

[0075] Separation of artificial mixed cerussite and calcite by sulfidation flotation of nitrogen heterocyclic thioketone compounds

[0076] The flotation process and reagent regimen in this embodiment are as follows: Figure 1As shown, 1g of crushed and ball-milled cerussite and calcite (fineness - 200 mesh) were added to a 40mL RK / FGC flotation machine for flotation separation. The stirring speed was 1998r / min. A sulfiding agent of 5-methyl-2,3-dihydro-1,3-benzoxazole-2-thione and 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazine (mass ratio 1:1) was used, with a total dosage of 400g / t and a reaction time of 5min. Butanyl butylamine black was used as the collector at a dosage of 300g / t for a reaction time of 3min. The frother, methyl isobutyl methanol, was used at a dosage of 10mg / L. The flotation was carried out for 3min at a pulp pH of 8.0. The results showed that the flotation recovery rate of cerussite ore reached 92.6%.

[0077] Example 8

[0078] Nitrogen heterocyclic thioketone compounds sulfide flotation of smithsonite

[0079] The flotation process and reagent regimen in this embodiment are as follows: Figure 1 As shown, 2g of crushed and ball-milled smithsonite mineral to a fineness of 200 mesh was added to a 40mL RK / FGC flotation machine for flotation separation. The stirring speed was 1998 r / min. A sulfiding agent was prepared using 5-methyl-2,3-dihydro-1,3-benzoxazole-2-thione and 2-(dibutylamino)-4,6-dimercapto-1,3,5-triazine at a mass ratio of 1:1, with a total dosage of 400g / t and a reaction time of 5min. Sodium butyl xanthate was used as the collector at a dosage of 300g / t and a reaction time of 3min. The frother, methyl isobutyl methanol, was used at a dosage of 10mg / L. The flotation of smithsonite was carried out for 3min at a pulp pH of 8.0. The results showed that the flotation recovery rate of smithsonite reached 90.1%.

[0080] Therefore, nitrogen-containing heterocyclic thioketone compounds exhibit excellent sulfidation effects on copper-lead-zinc oxide minerals. By forming a stable sulfidation film on the mineral surface, the sulfidation flotation of copper-lead-zinc oxide minerals can be achieved, which can enhance the selective flotation enrichment of copper-lead-zinc oxide minerals. Moreover, these compounds are stable and have strong prospects for industrial application.

Claims

1. The application of a nitrogen-containing heterocyclic thionate compound, characterized in that, The application of the aforementioned nitrogen-containing heterocyclic thionates in the preparation of sulfiding agents; the method for sulfidation flotation of copper, lead, and zinc oxide minerals using the aforementioned sulfiding agent, characterized by comprising pretreatment, activation, and flotation steps, specifically including: A. Pretreatment: The copper-lead-zinc oxide minerals to be treated are crushed, ground, and slurry-prepared to obtain slurry a; B. Activation: Add the sulfiding agent to slurry a and stir for 3-5 minutes to obtain sulfidated and activated slurry b; C. Add flotation collector to the sulfidated and activated slurry b and perform flotation to obtain flotation concentrate.

2. The application of the nitrogen-containing heterocyclic thionate compound according to claim 1, characterized in that, The aforementioned nitrogen-containing heterocyclic thiones are at least one compound having the structures of formula (I), formula (II), and formula (III), and their structures are as follows: Among them, R 1 Hydrogen, C1-C 15 Hydrocarbon group, oxygen-containing hydrocarbon group or nitrogen-containing hydrocarbon group, C2-C8 acyl group, propenyl group, ethynyl group, phenyl group, benzyl group or benzyloxy group; R 2 Hydrogen, C1-C 15 Hydrocarbon group, oxygen-containing hydrocarbon group or nitrogen-containing hydrocarbon group, C2-C8 acyl group, propenyl group, ethynyl group, phenyl group, benzyl group or benzyloxy group; R 3 Hydrogen, C1-C 15 The hydrocarbon group, oxygen-containing hydrocarbon group, or nitrogen-containing hydrocarbon group, phenyl, benzyl, or pyridine; M is sodium, potassium, ammonium, or hydrogen.

3. The application of the nitrogen-containing heterocyclic thionate compound according to claim 2, characterized in that, The R mentioned 1 It 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 It 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 M is hydrogen, sodium, C1-C4 hydrocarbon group, oxygen-containing hydrocarbon group or nitrogen-containing hydrocarbon group, phenyl, benzyl or pyridine; M is sodium, potassium or hydrogen.

4. The application of the nitrogen-containing heterocyclic thioketone compounds according to claim 2 or 3, characterized in that, The R mentioned 1 It is hydrogen, methyl, propyl, or butyl; R 2 It is hydrogen, methyl, propyl, or butyl; R 3 It is hydrogen, sodium, phenyl, or benzyl; M is sodium or potassium.

5. The method according to claim 1, characterized in that, The copper-lead-zinc oxide ore mentioned is any one of malachite, azurite, chrysocolla, cuprite, cerussite, lead oxide, smithsonite, zincite, hemimorphite, and zinc siliceous ore.

6. The method according to claim 1, characterized in that, In step A, the mass percentage concentration of slurry a is 20-50%.

7. The method according to claim 1, characterized in that, In step B, the amount of vulcanizing agent added is 100~5000g / t.

8. The method according to claim 1, characterized in that, In step B, the stirring speed is 1995~2000 r / min.

9. The method according to claim 1, characterized in that, The flotation collector described in step C consists of sodium butyl xanthate and butylammonium black powder.

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