Novel double-ligand chalcopyrite collecting agent and preparation method and application thereof

Abstract

The invention belongs to the technical field of copper-sulfur ore flotation, and particularly relates to a novel double-ligand chalcopyrite collecting agent and a preparation method and application thereof. According to the collecting agent, an intermediate oxalyl diisothiocyanate is mainly prepared from oxalyl chloride and thiocyanate through a thiocyanate method, and then series amine / alcohol is added through a one-pot method to prepare the collecting agent. According to the collecting agent, more stable double-bond adsorption can be formed on the surface of chalcopyrite, and the formed double-chelate ring structure is more stable than single-bond adsorption of xanthate, black powder and the like of a traditional chalcopyrite collecting agent. The collecting agent has higher collecting capacity and excellent selectivity, efficient copper-sulfur separation can be achieved under the low-alkali condition, the preparation technology of the collecting agent has the advantages of being simple, easy to operate and the like, and chalcopyrite flotation and separation of chalcopyrite and pyrite can be promoted.

Description

Technical Field

[0001] The invention belongs to the technical field of copper-sulfur ore flotation, and in particular relates to a novel double-ligand chalcopyrite collector and a preparation method and application thereof. Background Art

[0002] Copper is defined as a modern energy metal in the global market and is one of the most widely used metals in the world. It mainly comes from chalcopyrite in copper sulfide ores. Chalcopyrite is usually associated with pyrite, so in order to obtain qualified copper minerals, it is necessary to consider the effective separation of these two minerals.

[0003] At the same time, due to the excessive mining of sulfide ores, the grade of sulfide copper ores has become increasingly lower. Therefore, obtaining high-grade copper concentrate through flotation technology has become the most common choice and one of the most effective methods to separate valuable minerals from non-target minerals in the mineral processing process.

[0004] As we all know, collectors play a vital role in copper-sulfur flotation. Collectors can be adsorbed on the surface of target minerals through chemical adsorption, van der Waals force, etc., making the target minerals hydrophobic. However, traditional collectors have only one active group to form a single bond adsorption, resulting in low flotation effect and difficulty in selective separation. For example, the traditional collector xanthate has poor selectivity for chalcopyrite and requires strong alkaline conditions to have a selective collection effect; while the xanthate derivative Z-200 collector is widely used in industry because of its high selectivity and relatively low alkaline conditions, but its collection ability is weaker than that of xanthate.

[0005] Therefore, the present invention aims to find a double bond adsorption capable of enhancing adsorption capacity and a chalcopyrite collector having strong collecting ability and high selectivity under low-alkali conditions. Summary of the invention

[0006] In view of the above problems, the present invention provides a novel dual-ligand chalcopyrite collector and its preparation method and application. The collector has a small dosage and can separate chalcopyrite from pyrite under low-alkali conditions.

[0007] The present invention is achieved through the following technical solutions: A novel dual-ligand chalcopyrite collector, wherein the novel dual-ligand chalcopyrite collector is a compound having a structure of formula (1) or a structure of formula (2): ; Wherein, R1 in formula (1) is a C1-C6 alkyl group or an aromatic group, and R2 in formula (2) is a C1-C7 alkyl group or an aromatic group.

[0008] Furthermore, R1 is any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, phenyl, and cyclohexyl; R2 is any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, phenyl, cyclohexyl, and benzyl.

[0009] Further, the method comprises: (1) Using tetrahydrofuran (THF) as solvent, oxalyl chloride and thiocyanate as raw materials, mixing and stirring at a certain temperature to obtain the intermediate oxalyl diisothiocyanate; (2) Through a one-pot reaction, any one of di-n-butylamine, diethylamine, isopropanol or isobutanol is reacted with the intermediate oxalyl diisothiocyanate under stirring at a certain temperature to prepare a new biligand chalcopyrite collector containing two C=S double bonds.

[0010] Furthermore, in step (1), the molar ratio of any one of the di-n-butylamine, the diethylamine, the isopropanol or the isobutanol to the oxalyl chloride or the thiocyanate is (2-2.1):1:(2.05-2.1).

[0011] Furthermore, in step (1), the reaction conditions are: reaction temperature is 0-5°C, reaction time is 2.5-3.5h; In step (2), when di-n-butylamine and diethylamine are used to react with the intermediate oxalyl diisothiocyanate, the reaction temperature is 15-25° C. and the reaction time is 7-8 h; In step (2), when isobutyl alcohol or isopropyl alcohol is used to react with the intermediate oxalyl diisothiocyanate, the reaction temperature is 65-85° C. and the reaction time is 5-6 h.

[0012] A novel oxalyl biligand chalcopyrite collector is used for flotation separation of chalcopyrite and pyrite. The novel biligand chalcopyrite collector is a compound having a structure of formula (1) or a structure of formula (2).

[0013] Furthermore, the pH of the pulp during the flotation stage is controlled to be 8.0-11.0; Furthermore, the frother in the flotation stage is methyl isobutyl carbinol (MIBC); the dosage of methyl isobutyl carbinol is 8-10 mg per liter of pulp.

[0014] Furthermore, when the novel dual-ligand chalcopyrite collector having the structure of formula (1) is used, the amount of collector added in the flotation stage is 1.5-2.0 mg per liter of pulp; When the novel dual-ligand chalcopyrite collector having the structure of formula (2) is used, the amount of collector added in the flotation stage is 0.6-1.0 mg per liter of slurry.

[0015] Beneficial technical effects of the present invention: (1) The two C=S double bonds of the collector provided by the present invention can form double bond adsorption on the surface of chalcopyrite, forming a double chelate ring adsorption that is more stable than single bond adsorption, which can enhance the capture capacity and selectivity of chalcopyrite. From the flotation results, the flotation separation of chalcopyrite and pyrite can also be achieved under lower alkaline conditions; (2) The collector of the present invention is prepared by a one-pot method, the reaction conditions are relatively simple, the source is wide, and it can be industrially substituted for traditional collectors such as Z-200. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is the infrared spectrum of BDBAO prepared in Example 1 of the present invention; Figure 2 The mass spectrum of BDBAO prepared in Example 1 of the present invention; Figure 3 Infrared spectrum of DBOBO prepared in Example 2 of the present invention Figure 4 This is the mass spectrum of DBOBO prepared in Example 2 of the present invention; Figure 5 This is the infrared spectrum of BDBOO prepared in Example 3 of the present invention; Figure 6 The mass spectrum of BDBOO prepared in Example 3 of the present invention; Figure 7 This is the infrared spectrum of DPOBO prepared in Example 4 of the present invention; Figure 8 The mass spectrum of DPOBO prepared in Example 4 of the present invention; Fig. 9 This is a flotation flow chart of Examples 2 to 4. DETAILED DESCRIPTION

[0017] To make the purpose, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0018] Unless otherwise defined, all the professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing the embodiments and are not intended to limit the scope of protection of the present invention.

[0019] Example 1: Preparation of an oxalyl biligand chalcopyrite collector BDBAO: Take 0.0315 mol of ammonium thiocyanate and dissolve it in THF (50 ml) and stir it at 0-5°C for 20 min; take 0.015 mol of oxalyl chloride in a 250 ml three-necked flask and add 25 ml of THF and stir it in an ice-water mixture bath at 0-5°C for 15 min, then slowly add the above ammonium thiocyanate solution to the oxalyl chloride solution at 0-5°C (about 30 min). After the addition is completed, keep the temperature at this temperature for 3 h, then remove the ice-water mixture bath, start to add 0.03 mol of di-n-butylamine (about 20 min), and the reaction solution is basically at room temperature after the addition is completed. Stir the reaction at room temperature for 8 h, and detect the reaction by thin layer chromatography (TLC) (ethyl acetate: petroleum ether: glacial acetic acid = 7.5:2.5:0.2). After the reaction is completed, the solvent is evaporated to obtain a crude product. The crude product was dissolved in 55 g of ethyl acetate, 30 g of deionized water was added, and the mixture was extracted three times. Deionized water (adjusted with hydrochloric acid) with a pH value of 4.0 was then added and extracted three times. The ethyl acetate organic phase was dried over anhydrous magnesium sulfate and evaporated under reduced pressure to obtain the target product with a yield of 83%.

[0020] The obtained product was characterized by infrared spectrum. Figure 1 , mass spectrometry see Figure 2 , infrared spectrum analysis is shown in Table 1.

[0021] Table 1 Infrared spectrum analysis of oxalyl biligand collector BDBAO

[0022] Mass spectrometry (EI): 453.2312[430.2436+Na] + .

[0023] The collector compound prepared in this example is N,N'-oxalyl-N'',N'''-dibutylbis(thiourea) (BDBAO), and its structure is shown below: ; The preparation and synthesis route of the collector (BDBAO) in this embodiment is as follows: .

[0024] Example 2: Preparation of an oxalyl biligand collector DBOBO: Take 0.0315 mol of ammonium thiocyanate and dissolve it in THF (50 ml) and stir it at 0-5°C for 20 min; take 0.015 mol of oxalyl chloride in a 250 ml three-necked flask and add 25 ml of THF and stir it in a 0-5°C ice-water mixture bath for 15 min, then slowly add the above ammonium thiocyanate solution to the oxalyl chloride solution at 0-5°C (about 30 min). After the addition is completed, keep the temperature at this temperature for 3 h, then add 0.03 mol of isobutyl alcohol (about 20 min), stir the reaction in a 75°C water bath for 6 h after the addition is completed, and detect the reaction by thin layer chromatography (TLC) (ethyl acetate: petroleum ether: glacial acetic acid = 7.5:2.5:0.2). After the reaction is completed, the solvent is evaporated to obtain a crude product. The crude product was dissolved in 55 g of ethyl acetate and extracted three times with 30 g of deionized water, then extracted three times with deionized water (adjusted with hydrochloric acid) at pH = 4.0, and the ethyl acetate organic phase was dried with anhydrous magnesium sulfate and evaporated under reduced pressure to obtain the target product with a yield of 69%. The obtained product was characterized by its structure, and the infrared spectrum showed Figure 3 , mass spectrometry see Figure 4 , infrared spectrum analysis is shown in Table 2.

[0025] Table 2 Infrared spectrum analysis of oxalyl biligand collector DBOBO

[0026] Mass spectrometry (EI): 320.0883.

[0027] The collector compound prepared in this example is O,O'-diisobutyl oxalyl dicarbamate (DBOBO), and its structure is shown below: ; The preparation and synthesis route of the trapping agent (DBOBO) in this embodiment is as follows: .

[0028] Example 3: Preparation of an oxalyl biligand collector BDBOO: Take 0.0315 mol of ammonium thiocyanate and dissolve it in THF (50 ml) and stir it at 0-5°C for 20 min; take 0.015 mol of oxalyl chloride in a 250 ml three-necked flask and add 25 ml of THF and stir it in an ice-water mixture bath at 0-5°C for 15 min, then slowly add the above ammonium thiocyanate solution to the oxalyl chloride solution at 0-5°C (about 30 min). After the addition is completed, keep the temperature at this temperature for 3 h, then remove the ice-water mixture bath, start to add 0.03 mol of diethylamine (about 20 min), and the reaction solution is basically at room temperature after the addition is completed. Stir the reaction at room temperature for 8 h, and detect the reaction by thin layer chromatography (TLC) (ethyl acetate: petroleum ether: glacial acetic acid = 7.5:2.5:0.2). After the reaction is completed, the solvent is evaporated to obtain a crude product. The crude product was dissolved in 55 g of ethyl acetate and extracted three times with 30 g of deionized water, then extracted three times with deionized water (adjusted with hydrochloric acid) at pH = 4.0, and the organic phase of ethyl acetate was dried with anhydrous magnesium sulfate and evaporated under reduced pressure to obtain the target product with a yield of 85.1%. The obtained product was characterized by infrared spectrum. Figure 5 , mass spectrometry see Figure 6 , infrared spectrum analysis is shown in Table 3.

[0029] Table 3 Infrared spectrum analysis of oxalyl biligand collector BDBOO ; Mass spectrometry (EI): 341.1080.

[0030] The collector compound prepared in this example is N,N'-oxalyl-N'',N'''-diethylbis(thiourea) (BDBOO), and its structure is shown below: .

[0031] Example 4: Preparation of an oxalyl biligand collector DPOBO: Take 0.0315 mol of ammonium thiocyanate and dissolve it in THF (50 ml) and stir it at 0-5°C for 20 min; take 0.015 mol of oxalyl chloride in a 250 ml three-necked flask and add 25 ml of THF and stir it in an ice-water mixture bath at 0-5°C for 15 min, then slowly add the above ammonium thiocyanate solution to the oxalyl chloride solution at 0-5°C (about 30 min). After the addition is completed, keep the reaction at this temperature for 3 h, then add 0.03 mol (about 20 min), stir the reaction in a 75°C water bath for 6 h after the addition is completed, and detect the reaction by thin layer chromatography (TLC) (ethyl acetate: petroleum ether: glacial acetic acid = 7.5:2.5:0.2). After the reaction is completed, the solvent is evaporated to obtain a crude product. The crude product is dissolved in 55 g of ethyl acetate, 30 g of deionized water is added, and then deionized water (adjusted with hydrochloric acid) with a pH of 4.0 is added and extracted three times. The organic phase of ethyl acetate is dried with anhydrous magnesium sulfate and evaporated under reduced pressure to obtain the target product with a yield of 69%. The obtained product was characterized by infrared spectrum. Figure 7 , mass spectrometry see Figure 8 , infrared spectrum analysis is shown in Table 4.

[0032] Table 4 Infrared spectrum analysis of oxalyl biligand collector DBOBO ;

[0033] Mass spectrometry (EI): 292.0553.

[0034] The collector compound prepared in this example is O,O'-diisopropyl oxalyl diaminocarbamate (DBOBO), and its structure is shown below: .

[0035] Example 5: Flotation of chalcopyrite using oxalyl biligand collector and comparison with traditional collector Z-200: Use Fig. 9 The process flow shown is used to flot chalcopyrite, where the tank volume is 30 ml, the fixed speed is 1758 r / min, the pulp pH is 9.0, the frother MIBC is 10.0 mg / L, and the mineral particle size of -400 mesh to -200 mesh chalcopyrite is floated for 3 minutes. The flotation results are shown in the following table: Table 5 Comparison of the recovery of chalcopyrite by dosage of BDBAO, BDBOO, DPOBO, DBOBO and Z-200 .

[0036] Example 6: Flotation of pyrite using oxalyl biligand collector and comparison with traditional collector Z-200: Use Fig. 9The process flow shown is used to flot chalcopyrite, where the cell volume is 30 ml, the fixed rotation speed is 1758 r / min, the pulp pH is 9.0, the frother MIBC is 10.0 mg / L, and the pyrite with a mineral particle size of -400 mesh to -200 mesh is floated for 3 min.

[0037] Table 6 Comparison of the recovery of pyrite by dosage of BDBAO, BDBOO, DPOBO, DBOBO and Z-200 .

[0038] Example 7: Separation of artificial mixed minerals (mass ratio of chalcopyrite to pyrite is 1:1) by flotation of oxalyl biligand collector and comparison with traditional collector Z-200: Use Fig. 9 The process flow shown in the figure is used to flot chalcopyrite, where the tank volume is 30 ml, the fixed speed is 1758 r / min, and under the conditions of pulp pH of 9.0 and 10.0, collectors (BDBAO 2.0 mg / L / DBOBO 0.8 mg / L) and frother MIBC 10.0 mg / L are added to float the mixed minerals for 3 min. Under the same conditions, the collector is changed to Z-200 for the same flotation test. The concentrate (foam product) and tailings are collected and dried and weighed. The recovery rate is calculated based on the product weight and element content test results, and the results are shown in the table below.

[0039] Table 7 Effect of BDBAO, BDBOO, DPOBO, DBOBO and Z-200 dosage on flotation separation of artificial mixed ore ; The test results show that compared with the traditional collector Z-200, the dual-ligand collector of the present invention has stronger collection ability and excellent selectivity, and can achieve efficient separation of copper and sulfur under low alkalinity conditions of pH 9.0. These findings provide a solid theoretical basis and experimental support for the development of new high-efficiency, low-alkali, and highly selective chalcopyrite collectors. The synthesis and application research of N,N'-oxalyl-N'',N'''-dibutylbis(thiourea) collector provides a new solution to the flotation problem of low-grade and complex ores, and is expected to promote the advancement of copper ore dressing technology.

[0040] The collector provided by the present invention can form a more stable double bond adsorption on the surface of chalcopyrite, and the formed double chelate ring structure is more stable than the single bond adsorption of traditional chalcopyrite collectors such as xanthate and black medicine. The collector not only has stronger collecting ability and excellent selectivity, but also can achieve efficient copper-sulfur separation under low-alkali conditions. Its preparation process has the advantages of simplicity, easy operation, etc., and can promote the flotation of chalcopyrite and its separation from pyrite.

[0041] The above description is only one of the preferred examples of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A novel dual-ligand chalcopyrite collector, characterized in that: The novel dual-ligand chalcopyrite collector is a compound having a structure of formula (1) or a structure of formula (2): ； Wherein, R1 in formula (1) is a C1-C6 alkyl group or an aromatic group, and R2 in formula (2) is a C1-C7 alkyl group or an aromatic group.

2. A novel dual-ligand chalcopyrite collector according to claim 1, characterized in that: R1 is any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, phenyl, and cyclohexyl; R2 is any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, phenyl, cyclohexyl, and benzyl.

3. A method for preparing a novel dual-ligand chalcopyrite collector, characterized in that: The method comprises: (1) Using tetrahydrofuran as solvent, oxalyl chloride and thiocyanate as raw materials, mixing and stirring at a certain temperature to obtain the intermediate oxalyl diisothiocyanate; (2) Through a one-pot reaction, any one of di-n-butylamine, diethylamine, isopropanol or isobutanol is reacted with the intermediate oxalyl diisothiocyanate under stirring at a certain temperature to prepare a new biligand chalcopyrite collector containing two C=S double bonds.

4. The preparation method according to claim 3, characterized in that: In step (1), the thiocyanate is ammonium thiocyanate or sodium thiocyanate.

5. The preparation method according to claim 3, characterized in that: The molar ratio of any one of the di-n-butylamine, the diethylamine, the isopropanol or the isobutanol to the oxalyl chloride or the thiocyanate is (2-2.1):1:(2.05-2.1).

6. The preparation method according to claim 3, characterized in that: In step (1), the reaction conditions are: reaction temperature is 0-5°C, reaction time is 2.5-3.5h; In step (2), when di-n-butylamine and diethylamine are used to react with the intermediate oxalyl diisothiocyanate, the reaction temperature is 15-25° C. and the reaction time is 7-8 h; In step (2), when isobutyl alcohol or isopropyl alcohol is used to react with the intermediate oxalyl diisothiocyanate, the reaction temperature is 65-85° C. and the reaction time is 5-6 h.

7. Application of a novel oxalyl biligand chalcopyrite collector, characterized in that: The novel dual-ligand chalcopyrite collector of claim 1 is used for flotation separation of chalcopyrite and pyrite, wherein the novel dual-ligand chalcopyrite collector is a compound having the structure of formula (1) or having the structure of formula (2).

8. The use of a novel oxalyl biligand chalcopyrite collector according to claim 7, characterized in that: The pH of the slurry during the flotation stage is controlled at 8.0~11.

0.

9. The use of a novel oxalyl biligand chalcopyrite collector according to claim 8, characterized in that: The frother in the flotation stage is methyl isobutyl carbinol; the dosage of methyl isobutyl carbinol is 8-10 mg per liter of pulp.

10. The use of a novel oxalyl biligand chalcopyrite collector according to claim 8, characterized in that: When the novel dual-ligand chalcopyrite collector having the structure of formula (1) is used, the amount of collector used in the flotation stage is 1.5-2.0 mg per liter of pulp; When the novel dual-ligand chalcopyrite collector having the structure of formula (2) is used, the amount of collector added in the flotation stage is 0.6-1.0 mg per liter of slurry.

Images