A double-ligand chalcopyrite collector and its preparation method and application

Abstract

The present invention belongs to the technical field of copper-sulfur ore flotation, and specifically relates to a novel dual-ligand chalcopyrite collector, its preparation method, and application. The collector is mainly prepared by using oxalyl chloride and thiocyanate using a thiocyanate method to prepare an intermediate oxalyl diisothiocyanate, and then adding a series of amines / alcohols through a one-pot method. 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 and easy operation, etc., and can promote the flotation of chalcopyrite and its separation from pyrite.

Description

Technical Field

[0001] The invention belongs to the technical field of copper-sulfur ore flotation, and particularly relates to a 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 and non-target minerals in the mineral processing process.

[0004] Collectors are widely known to play a crucial role in copper-sulfur flotation. Collectors can adsorb to the surface of target minerals through chemical adsorption, van der Waals forces, and other interactions, rendering them hydrophobic. However, traditional collectors, which only have a single-bond adsorption group, result in low flotation efficiency and difficulty in selective separation. For example, the traditional collector xanthate has poor selectivity for chalcopyrite and requires strong alkaline conditions for selective capture. While the xanthate derivative Z-200 is widely used industrially due to its high selectivity and relatively low alkaline conditions, its capture ability is weaker than that of xanthate.

[0005] Therefore, the present invention aims to find a chalcopyrite collector that can enhance the adsorption capacity by double bond adsorption and has strong collecting ability and high selectivity under low-alkali conditions. Summary of the Invention

[0006] To address the above problems, the present invention provides a dual-ligand chalcopyrite collector, a preparation method thereof, and applications thereof. 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:

[0008] 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):

[0009]

[0010] 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.

[0011] 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.

[0012] Furthermore, the method comprises:

[0013] (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;

[0014] (2) Through a one-pot reaction, any one of dibutylamine, diethylamine, isopropyl alcohol or isobutyl alcohol is reacted with the intermediate oxalyl diisothiocyanate at a certain temperature with stirring to prepare a new biligand chalcopyrite collector containing two C=S double bonds.

[0015] Furthermore, in step (1), the molar ratio of any one of the di-n-butylamine, the diethylamine, the isopropyl alcohol or the isobutyl alcohol to the oxalyl chloride and the thiocyanate is (2-2.1):1:(2.05-2.1).

[0016] Furthermore, in step (1), the reaction conditions are: reaction temperature of 0 to 5°C, reaction time of 2.5 to 3.5 h;

[0017] In step (2), when di-n-butylamine and diethylamine are used to react with the intermediate oxalyl diisothiocyanate, the reaction temperature is 15 to 25° C. and the reaction time is 7 to 8 hours;

[0018] In step (2), when isobutanol or isopropanol is used to react with the intermediate oxalyl diisothiocyanate, the reaction temperature is 65-85° C. and the reaction time is 5-6 h.

[0019] The invention discloses an application of a novel oxalyl biligand chalcopyrite collector, wherein the novel 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).

[0020] Furthermore, the pH of the pulp during the flotation stage is controlled to be 8.0 to 11.0;

[0021] Furthermore, the frother in the flotation stage is methyl isobutyl carbinol (MIBC); the dosage of methyl isobutyl carbinol is 8 to 10 mg per liter of pulp.

[0022] Furthermore, when the novel biligand 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;

[0023] When the novel double-ligand chalcopyrite collector having the structure of formula (2) is used, the amount of collector used in the flotation stage is 0.6-1.0 mg per liter of pulp.

[0024] Beneficial technical effects of the present invention:

[0025] (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 ability and selectivity of chalcopyrite. From the flotation results, it can also achieve the flotation separation of chalcopyrite and pyrite under lower alkaline conditions;

[0026] (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 industrialized to replace traditional collectors such as Z-200. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is the infrared spectrum of BDBAO prepared in Example 1 of the present invention;

[0028] Figure 2 This is the mass spectrum of BDBAO prepared in Example 1 of the present invention;

[0029] Figure 3 Infrared spectrum of DBOBO prepared in Example 2 of the present invention

[0030] Figure 4 This is the mass spectrum of DBOBO prepared in Example 2 of the present invention;

[0031] Figure 5 This is the infrared spectrum of BDBOO prepared in Example 3 of the present invention;

[0032] Figure 6 This is the mass spectrum of BDBOO prepared in Example 3 of the present invention;

[0033] Figure 7 This is the infrared spectrum of DPOBO prepared in Example 4 of the present invention;

[0034] Figure 8 This is the mass spectrum of DPOBO prepared in Example 4 of the present invention;

[0035] Figure 9 This is a flotation flow chart of Examples 2 to 4. DETAILED DESCRIPTION

[0036] To make the purpose, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to 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 intended to limit the present invention.

[0037] Unless otherwise defined, all technical terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The technical 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.

[0038] Example 1: Preparation of an oxalyl biligand chalcopyrite collector BDBAO:

[0039] Dissolve 0.0315 mol of ammonium thiocyanate in 50 ml of THF and stir at 0-5°C for 20 minutes. Dissolve 0.015 mol of oxalyl chloride in a 250 ml three-necked flask, add 25 ml of THF, and stir in an ice-water bath at 0-5°C for 15 minutes. Then, slowly add the ammonium thiocyanate solution dropwise to the oxalyl chloride solution at 0-5°C (approximately 30 minutes). Incubate at this temperature for 3 hours. Remove the ice-water bath and begin the dropwise addition of 0.03 mol of di-n-butylamine (approximately 20 minutes). Once the addition is complete, the reaction mixture is essentially at room temperature. Stir at room temperature for 8 hours and monitor the reaction using thin-layer chromatography (TLC) (ethyl acetate:petroleum ether:glacial acetic acid = 7.5:2.5:0.2). After completion, evaporate the solvent to obtain the 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 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%.

[0040] The obtained product was characterized by infrared spectrum. Figure 1 , mass spectrometry see Figure 2 , infrared spectrum analysis is shown in Table 1.

[0041] Table 1 Infrared spectrum analysis of oxalyl biligand collector BDBAO

[0042]

[0043] Mass spectrometry (EI): 453.2312 [430.2436 + Na] + .

[0044] The collector compound prepared in this example is N,N'-oxalyl-N",N'"-dibutylbis(thiourea) (BDBAO), and its structure is shown below:

[0045]

[0046] The preparation synthesis route of the trapping agent (BDBAO) in this embodiment is as follows:

[0047]

[0048] Example 2: Preparation of an oxalyl biligand collector DBOBO:

[0049] Dissolve 0.0315 mol of ammonium thiocyanate in 50 ml of THF and stir at 0-5°C for 20 minutes. Dissolve 0.015 mol of oxalyl chloride in a 250 ml three-necked flask, add 25 ml of THF, and stir in an ice-water bath at 0-5°C for 15 minutes. Then, slowly add the ammonium thiocyanate solution dropwise to the oxalyl chloride solution at 0-5°C (approximately 30 minutes). After the addition is complete, incubate at this temperature for 3 hours. Then, add 0.03 mol of isobutanol dropwise (approximately 20 minutes). After the addition is complete, stir in a 75°C water bath for 6 hours. Monitor the reaction by thin-layer chromatography (TLC) (ethyl acetate:petroleum ether:glacial acetic acid = 7.5:2.5:0.2). After completion, evaporate the solvent to obtain the crude product. The crude product was dissolved in 55g of ethyl acetate and extracted three times with 30g of deionized water. The product was then extracted three times with deionized water (adjusted with hydrochloric acid) at pH 4.0. The organic phase of ethyl acetate was dried over anhydrous magnesium sulfate and evaporated under reduced pressure to obtain the target product with a yield of 69%. The obtained product was structurally characterized, and the infrared spectrum showed Figure 3 , mass spectrometry see Figure 4 , infrared spectrum analysis is shown in Table 2.

[0050] Table 2 Infrared spectrum analysis of oxalyl dual ligand collector DBOBO

[0051]

[0052] Mass spectrometry analysis (EI): 320.0883.

[0053] The collector compound prepared in this example is O,O'-diisobutyloxalyl dicarbamate (DBOBO), and its structure is shown below:

[0054]

[0055] The preparation synthesis route of the trapping agent (DBOBO) in this embodiment is as follows:

[0056]

[0057] Example 3: Preparation of an oxalyl biligand collector BDBOO:

[0058] Dissolve 0.0315 mol of ammonium thiocyanate in 50 ml of THF and stir at 0-5°C for 20 minutes. Dissolve 0.015 mol of oxalyl chloride in a 250 ml three-necked flask, add 25 ml of THF, and stir in an ice-water bath at 0-5°C for 15 minutes. Then, slowly add the ammonium thiocyanate solution dropwise to the oxalyl chloride solution at 0-5°C (approximately 30 minutes). After the addition is complete, incubate at this temperature for 3 hours. Remove the ice-water bath and begin the dropwise addition of 0.03 mol of diethylamine (approximately 20 minutes). Once the addition is complete, the reaction mixture is essentially at room temperature. Stir at room temperature for 8 hours and monitor the reaction using thin-layer chromatography (TLC) (ethyl acetate:petroleum ether:glacial acetic acid = 7.5:2.5:0.2). After completion, evaporate the solvent to obtain the crude product. The crude product was dissolved in 55g of ethyl acetate and extracted three times with 30g of deionized water. The product was then extracted three times with deionized water (adjusted with hydrochloric acid) at pH 4.0. The organic phase of ethyl acetate was dried over anhydrous magnesium sulfate and evaporated under reduced pressure to obtain the target product with a yield of 85.1%. The obtained product was structurally characterized, and the infrared spectrum showed Figure 5 , mass spectrometry see Figure 6 , infrared spectrum analysis is shown in Table 3.

[0059] Table 3 Infrared spectrum analysis of oxalyl biligand collector BDBOO

[0060]

[0061] Mass spectrometry (EI):341.1080.

[0062] The collector compound prepared in this example is N,N'-oxalyl-N",N''-diethylbis(thiourea) (BDBOO), and its structure is shown below:

[0063]

[0064] Example 4: Preparation of an oxalyl biligand collector DPOBO:

[0065] Dissolve 0.0315 mol of ammonium thiocyanate in 50 ml of THF and stir at 0-5°C for 20 minutes. Dissolve 0.015 mol of oxalyl chloride in a 250 ml three-necked flask, add 25 ml of THF, and stir in an ice-water bath at 0-5°C for 15 minutes. Then, slowly add the ammonium thiocyanate solution dropwise to the oxalyl chloride solution at 0-5°C (approximately 30 minutes). After the addition is complete, incubate at this temperature for 3 hours. Then, add 0.03 mol dropwise (approximately 20 minutes). After the addition is complete, stir in a 75°C water bath for 6 hours. Monitor the reaction by thin-layer chromatography (TLC) (ethyl acetate:petroleum ether:glacial acetic acid = 7.5:2.5:0.2). After completion, evaporate the solvent to obtain the crude product. The crude product was dissolved in 55g of ethyl acetate and extracted three times with 30g of deionized water. The product was then extracted three times with deionized water (adjusted with hydrochloric acid) at pH 4.0. The organic phase of ethyl acetate was dried over anhydrous magnesium sulfate and evaporated under reduced pressure to obtain the target product with a yield of 69%. The obtained product was structurally characterized, and the infrared spectrum showed Figure 7 , mass spectrometry see Figure 8 , infrared spectrum analysis is shown in Table 4.

[0066] Table 4 Infrared spectrum analysis of oxalyl dual ligand collector DBOBO

[0067]

[0068] Mass spectrometry analysis (EI): 292.0553.

[0069] The collector compound prepared in this example is O,O'-diisopropyl oxalyl dicarbamate (DBOBO), and its structure is shown below:

[0070]

[0071] Example 5: Flotation of chalcopyrite using an oxalyl biligand collector and comparison with the traditional collector Z-200:

[0072] Use Figure 9 The process flow shown below is for flotation of chalcopyrite, with a tank volume of 30 ml, a fixed rotational speed of 1758 r / min, a slurry pH of 9.0, and a frother MIBC concentration of 10.0 mg / L. Chalcopyrite with a particle size of -400 to -200 mesh is flotated for 3 minutes. The flotation results are shown in the following table:

[0073] Table 5 Comparison of the recovery of chalcopyrite using the dosage of BDBAO, BDBOO, DPOBO, DBOBO and Z-200

[0074]

[0075] Example 6: Flotation of pyrite using oxalyl biligand collector and comparison with traditional collector Z-200:

[0076] Use Figure 9 The process flow shown is used to flotate chalcopyrite, wherein 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 minutes.

[0077] Table 6 Comparison of the recovery of pyrite using the dosage of BDBAO, BDBOO, DPOBO, DBOBO and Z-200

[0078]

[0079] Example 7: Separation of artificial mixed minerals (chalcopyrite and pyrite mass ratio of 1:1) by flotation using oxalyl biligand collector and comparison with traditional collector Z-200:

[0080] Use Figure 9 The process flow shown below was used to flotate chalcopyrite. The cell volume was 30 ml, the rotation speed was fixed at 1758 rpm, and the mixed minerals were flotated for 3 minutes using a collector (2.0 mg / L BDBAO / 0.8 mg / L DBOBO) and a frother (10.0 mg / L MIBC) at slurry pH levels of 9.0 and 10.0. The collected minerals were then flotated using Z-200 as the collector. The concentrate (foam product) and tailings were collected, dried, and weighed. The recovery was calculated based on the product weight and elemental content. The results are shown in the table below.

[0081] Table 7 Effect of BDBAO, BDBOO, DPOBO, DBOBO and Z-200 dosage on flotation separation of artificial mixed ore

[0082]

[0083]

[0084] Experimental results indicate that, compared to the traditional collector Z-200, the dual-ligand collector of this invention exhibits enhanced capture capacity and superior selectivity, enabling efficient separation of copper and sulfur even at a low alkalinity of pH 9.0. These findings provide a solid theoretical basis and experimental support for the development of novel, highly efficient, low-alkali, and highly selective chalcopyrite collectors. The synthesis and application of the N,N'-oxalyl-N",N'"'-dibutylbis(thiourea) collector offers a novel solution to the flotation of low-grade, complex ores and is expected to advance copper ore beneficiation technology.

[0085] The collector provided by the present invention can form a more stable double bond adsorption on the surface of chalcopyrite. The resulting double chelate ring structure is more stable than the single bond adsorption of traditional chalcopyrite collectors such as xanthate and nitrochlore. This collector not only has stronger capture capacity and excellent selectivity, but also can achieve efficient copper-sulfur separation under low-alkali conditions. Its preparation process is simple and easy to operate, and it can promote the flotation of chalcopyrite and its separation from pyrite.

[0086] 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 replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An application of an oxalyl biligand chalcopyrite collector, characterized in that: A biligand chalcopyrite collector is used for flotation separation of chalcopyrite and pyrite, wherein the biligand chalcopyrite collector is a compound having a structure of formula (1) or a structure of formula (2); ； Wherein, R1 is any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, and cyclohexyl; R2 is any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, and cyclohexyl.

2. The use of an oxalyl biligand chalcopyrite collector according to claim 1, characterized in that: The pH of the pulp during the flotation stage is controlled at 8.0~11.

0.

3. The use of an oxalyl biligand chalcopyrite collector according to claim 2, 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.

4. The use of an oxalyl biligand chalcopyrite collector according to claim 3, characterized in that: When a double-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 a double-ligand chalcopyrite collector having the structure of formula (2) is used, the amount of collector used in the flotation stage is 0.6-1.0 mg per liter of pulp.

5. The use of an oxalyl biligand chalcopyrite collector according to claim 1, characterized in that: The preparation method of the dual-ligand chalcopyrite collector comprises: (1) Using tetrahydrofuran as solvent, oxalyl chloride and thiocyanate as raw materials, the intermediate oxalyl diisothiocyanate is prepared by mixing and stirring at a certain temperature; (2) Through a one-pot reaction, any one of dibutylamine, diethylamine, isopropyl alcohol or isobutyl alcohol is reacted with the intermediate oxalyl diisothiocyanate at a certain temperature by stirring to prepare a biligand chalcopyrite collector containing two C=S double bonds; In step (1), the thiocyanate is ammonium thiocyanate or sodium thiocyanate; The molar ratio of any one of the di-n-butylamine, the diethylamine, the isopropyl alcohol or the isobutyl alcohol to the oxalyl chloride or the thiocyanate is (2-2.1):1:(2.05-2.1).

6. The use of an oxalyl biligand chalcopyrite collector according to claim 5, characterized in that: The reaction temperature is 0~5℃, and the 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 isobutanol and isopropanol are used to react with the intermediate oxalyl diisothiocyanate, the reaction temperature is 65-85° C. and the reaction time is 5-6 h.

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