Metal ore flotation collector and preparation method thereof

Abstract

The present application belongs to the technical field of mineral flotation, and particularly relates to a metal ore flotation collector and a preparation method thereof. The present application designs and synthesizes a metal ore flotation collector. Experimental results show that the collector can effectively adapt to the characteristics of low-grade nickel-copper sulfide ore, and significantly improves the collection effect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of mineral flotation, and particularly relates to a metal ore flotation collector and a preparation method thereof. BACKGROUND

[0002] The mineral flotation collector is a special chemical agent, and its core function is to change the physical and chemical properties of the mineral surface or adjust the floatability of the mineral by creating specific conditions. The mineral flotation collector changes the physical and chemical properties of the mineral surface, such as electrical properties and wettability, so that the mineral exhibits different floatability in the flotation process, thereby realizing the separation of the mineral.

[0003] The low-grade copper-nickel ore contains useful ores such as violar nickel ore and magnetite, and also contains silicate gangue minerals. In such ores, the industrial target is to concentrate the copper-nickel sulfide ore. However, the excessive content of magnesium oxide in the concentrate will seriously affect the flash smelting equipment. Since the melting point of the magnesium silicate mineral is higher than that of the copper-nickel sulfide ore, the slag viscosity is large, the slag phase separation is difficult, and further, the furnace body is nodular, the furnace wall is corroded, and other serious consequences of damaging the equipment.

[0004] The prior art CN103224472 discloses that cyanuric chloride is grafted with organic amine, and then reacts with carbon disulfide to prepare a dithiocarbamate heavy metal capture agent with a suitable adjustable molecular weight and high chelating capacity. The heavy metal capture agent can rapidly react with Hg 2+ , Pb 2+ , Cd 2+ , Cr 3+ , Ni 2+ , Cu 2+ and other heavy metal ions in water, so as to precipitate and separate the heavy metals and remove the heavy metals. However, the prior art does not disclose the application of cyanuric chloride compounds in the flotation enrichment process of copper-nickel ore.

[0005] Based on the above background technology, it is urgent to develop a metal ore flotation collector with high selectivity to overcome the problem that the existing collector has no obvious effect on the collection of low-grade nickel ore. SUMMARY

[0006] In order to overcome the shortcomings of the prior art, the primary purpose of the present application is to provide a metal ore flotation collector which can effectively adapt to the characteristics of low-grade nickel-copper sulfide ore and significantly improve the collection effect.

[0007] Another purpose of the present application is to provide a preparation method of the above-mentioned metal ore flotation collector, which is simple and feasible.

[0008] The purpose of the present application is achieved by the following technical solutions:

[0009] A metal ore flotation collector, a structural formula of the metal ore flotation collector is:

[0010]

[0011] Wherein, n is 4, 5 or 6.

[0012] The preparation method of the above metal ore flotation collector comprises the following steps:

[0013] (1) sodium hydroxide and omega-hydroxy fatty acid are added to water to obtain a mixed solution; the mixed solution is added to an acetone solution of cyanuric chloride at 0-5 DEG C, and the reaction is carried out under stirring; after the reaction is completed, the intermediate 1 is obtained by post-treatment;

[0014] The structural formula of the intermediate 1 and the omega-hydroxy fatty acid is:

[0015]

[0016] Wherein, n is 4, 5 or 6;

[0017] (2) the intermediate 1 and 6-(methylthio) pyridine-3-amine are added to N, N-dimethylformamide, N, N, N', N'-tetramethylchloroformamidum hexafluorophosphate and N-methylimidazole are further added at 0-5 DEG C, and then the reaction is carried out by increasing the temperature to room temperature; n-heptane is added to the reaction system, filtration is carried out, the filter residue is added to N, N-dimethylformamide, sodium ethyl sulfate is further added, and the heating reaction is carried out under stirring; after the reaction is completed, the metal ore flotation collector is obtained by post-treatment.

[0018] The intermediate 1 is prepared by using Mitsunobu reaction of cyanuric chloride and the hydroxyl group of omega-hydroxy fatty acid in the application, the carboxyl group with ether bond is introduced; the amide condensation of the carboxyl group of the intermediate 1 and the amine group of 6-(methylthio) pyridine-3-amine is carried out, the thioether bond with pyridine group and amide group is introduced, and then the thioether bond is hydrolyzed under alkaline conditions to prepare the metal ore flotation collector containing mercapto.

[0019] According to the preparation method of the above metal ore flotation collector, further, the molar ratio of the sodium hydroxide, the omega-hydroxy fatty acid and the cyanuric chloride in step (1) is (6.5-7):(3.2-3.5):1.

[0020] According to the preparation method of the above metal ore flotation collector, further, the reaction time in step (1) is 3-5 h.

[0021] According to the preparation method of the metal ore flotation collector, further, the molar ratio of the intermediate 1, 6-(methylthio)pyridine-3-amine, N,N,N',N'-tetramethylchloroformamidine hexafluorophosphate, N-methylimidazole and sodium ethylsulfate in step (2) is 1: (4-5): (6-8): (10-12): (3.5-4).

[0022] According to the preparation method of the metal ore flotation collector, further, the reaction time of the room temperature reaction in step (2) is 12-16 h.

[0023] According to the preparation method of the metal ore flotation collector, further, the reaction temperature of the heating reaction in step (2) is 110-130 DEG C, and the reaction time is 12-16 h.

[0024] According to the preparation method of the metal ore flotation collector, further, the operation of the post-treatment in step (1) is as follows: the reaction solution is poured into a 1 mol / L hydrochloric acid solution, filtered, the collected filter residue is slurried with hot water, and dried after filtering again.

[0025] The present application has the following effects relative to the prior art:

[0026] The present application designs and synthesizes a metal ore flotation collector, and the experimental results show that the collector can effectively adapt to the characteristics of low-grade sulfide nickel-copper ore and significantly improve the collection effect. Specifically, the sulfur atom of the mercapto group in the metal collector has strong affinity, can chemically adsorb with metal ions, and form a firm metal-sulfur bond; the pyridine group has good electron donor properties and can form a coordination bond with metal ions; the melamine group has multiple nitrogen atoms and can form a multi-coordination chelate with metal ions; the ether bond can increase the flexibility and polarity of the collector molecule, which helps the collector molecule to better adapt to the chemical environment of the mineral surface; and the introduced fatty chain can provide hydrophobicity and enhance the adsorption stability of the collector molecule on the mineral surface; the synergistic effect of these functional groups can significantly improve the selective collection capacity of the collector on nickel, copper and other metal minerals. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 It is a synthesis diagram of the metal ore flotation collector of the present application;

[0028] Figure 2 It is an H NMR spectrum of the intermediate 1 of example 1 of the present application; 1 H NMR spectrum;

[0029] Figure 3 It is an HRMS spectrum of the intermediate 1 of example 1 of the present application;

[0030] Figure 4H NMR spectrum of the metal ore selective collector of Example 1 of the present application 1 H NMR spectrum of the metal ore selective collector of Example 1 of the present application

[0031] Figure 5 H NMR spectrum of the metal ore selective collector of Example 1 of the present application

[0032] Figure 6 H NMR spectrum of the metal ore selective collector of Example 1 of the present application 1 H NMR spectrum of the metal ore selective collector of Example 1 of the present application

[0033] Figure 7 H NMR spectrum of the metal ore selective collector of Example 1 of the present application

[0034] Figure 8 H NMR spectrum of the metal ore selective collector of Example 1 of the present application 1 H NMR spectrum of the metal ore selective collector of Example 1 of the present application

[0035] Figure 9 H NMR spectrum of the metal ore selective collector of Example 1 of the present application

[0036] Figure 10 H NMR spectrum of the metal ore selective collector of Example 1 of the present application 1 H NMR spectrum of the metal ore selective collector of Example 1 of the present application

[0037] Figure 11 H NMR spectrum of the metal ore selective collector of Example 1 of the present application

[0038] Figure 12 H NMR spectrum of the metal ore selective collector of Example 1 of the present application 1 H NMR spectrum of the metal ore selective collector of Example 1 of the present application

[0039] Figure 13 H NMR spectrum of the metal ore selective collector of Example 1 of the present application DETAILED DESCRIPTION

[0040] The technical solutions of the present application are further described below in combination with the specific embodiments. However, those skilled in the art should understand that the following examples are only used to illustrate the present application, and should not be regarded as limiting the present application. The specific conditions not mentioned in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used, if not specifically mentioned, are conventional products obtained through market channels.

[0041] Example 1

[0042] A metal ore flotation collector has the following structural formula:

[0043] .

[0044] The present embodiment also provides a preparation method of the above-mentioned metal ore flotation collector, and the synthesis schematic diagram is as followsFigure 1 as shown, Figure 1 n = 4, specifically comprising the following steps:

[0045] (1) Sodium hydroxide (68 mmol) was added to water (12 mL), and then 5-hydroxypentanoic acid (33 mmol) was added. After the temperature was stabilized to room temperature, a mixture was obtained. The mixture was slowly added to a cyanuric chloride acetone solution (10 mmol, 10 mL) at 0°C, and reacted for 4 h under stirring. After the reaction was completed, the reaction solution was poured into 50 mL of 1M hydrochloric acid solution, and white solids were collected by filtration. The white solids were slurried with hot water until the solid part of the TLC plate had no obvious impurity points, and then dried at 80°C after filtration to obtain intermediate 1. The structure of intermediate 1 was confirmed by 1 H NMR and HRMS spectra are shown in Figure 2 and Figure 3 as shown, 1 HNMR (CDC13, 400 MHz, DMSO): δ 11.85 (s, 3H), 4.08 (t, 6H), 2.24 (t, 6H), 1.85-1.83 (m, 6H), 1.53-1.51 (m, 6H); HRMS (ESI 18 H 27 N3O9, 400 MHz, DMSO): δ 11.85 (s, 3H), 4.08 (t, 6H), 2.24 (t, 6H),1.85-1.83 (m, 6H), 1.53-1.51 (m, 6H); HRMS (ESI + ): [M+H] + Calculated 430.17, found 430.18.

[0046] (2) Intermediate 1 (10 mmol), 6-(methylthio)pyridin-3-amine (45 mmol) were added to anhydrous N,N-dimethylformamide (50 mL), and then N,N,N',N'-tetramethylchloroformamidum hexafluorophosphate (TCFH, 70 mmol) and N-methylimidazole (NMI, 110 mmol) were added after cooling to 0°C. The reaction was gradually warmed to room temperature for 14 h. N-heptane (150 mL) was added to the reaction system, and after stirring uniformly, the filter cake was dried and added to anhydrous N,N-dimethylformamide (50 mL). Sodium ethyl sulfate (38 mmol) was added, and the reaction was warmed to 120°C for 14 h under stirring. Pre-HPLC separation obtained a metal ore collector; the structure of the metal ore collector was confirmed by 1 H NMR and HRMS spectra are shown in Figure 4 and Figure 5 as shown, 1 H NMR (CDC13, 400 MHz, DMSO): δ 11.85 (s, 3H), 4.08 (t, 6H), 2.24 (t, 6H), 1.85-1.83 (m, 6H), 1.53-1.51 (m, 6H); HRMS (ESI 33 H 39N9O6S3, 400 MHz, DMSO): δ 12.46 (s, 3H), 9.95 (s, 3H), 7.93 (t, 6H), 7.47 (d, 3H),4.08 (t, 6H), 2.32 (t, 6H), 1.86-1.84 (m, 6H), 1.53-1.51 (m, 6H); HRMS (ESI + ): [M+H] + Calcd 754.22, found 754.22.

[0047] Example 2

[0048] A metal ore flotation collector, the structural formula is as follows:

[0049] .

[0050] The embodiment also provides a preparation method of the metal ore flotation collector, and a synthesis schematic diagram is as shown in Figure 1 , Figure 1 wherein n = 5, and specifically comprises the following steps:

[0051] (1) sodium hydroxide (65 mmol) is added into water (10 mL), then 6-hydroxyhexanoic acid (32 mmol) is added, the temperature is stabilized to room temperature to obtain a mixed solution; the mixed solution is slowly added into a cyanuric chloride acetone solution (10 mmol, 10 mL) at 5°C, and reaction is performed under stirring for 3 h; after the reaction is completed, the reaction solution is poured into a 50 mL 1M hydrochloric acid solution, white solids are collected by filtration, and the white solids are beaten with hot water until no obvious impurity points are found on a solid part sampling TLC plate; after filtration, the solids are dried at 80°C to obtain the intermediate 1; the 1 H NMR and HRMS spectra are as shown in Figure 6 and Figure 7 , 1 H NMR (C 21 H 33 N3O9, 400 MHz, DMSO): δ 11.85 (s, 3H), 4.08 (t, 6H), 2.24 (t, 6H), 1.82-1.80 (m, 6H), 1.55-1.53 (m, 6H), 1.31-1.29 (m, 6H); HRMS (ESI + ): [M+H] + Calcd 472.22, found 472.22.

[0052] (2) Intermediate 1 (10 mmol), 6-(methylthio)pyridin-3-amine (40 mmol) were added into anhydrous N,N-dimethylformamide (50 mL), and then TCFH (60 mmol) and NMI (100 mmol) were added after cooling to 5℃, and the reaction was carried out at room temperature for 12 h; n-heptane (150 mL) was added into the reaction system, and then the filter cake was dried and added into anhydrous N,N-dimethylformamide (50 mL), and then sodium ethyl sulfate (35 mmol) was added, and the reaction was carried out at 130℃ under stirring for 12 h, and then the metal ore flotation collector was separated by Pre-HPLC; the structure of the metal ore flotation collector is as follows: 1 H NMR and HRMS spectra are shown in Figure 8 and Figure 9 1 H NMR (C 36 H 45 N9O6S3, 400 MHz, DMSO): δ 12.46 (s, 3H), 9.95 (s, 3H),7.93 (t, 6H), 7.47 (d, 3H),4.08 (t, 6H), 2.32 (t, 6H), 1.82-1.80 (m, 6H),1.55-1.53 (m, 6H), 1.31-1.29 (m, 6H); HRMS (ESI + ): [M+H] + Calculated 796.27, found 796.27.

[0053] Example 3

[0054] A metal ore flotation collector, and the structure thereof is as follows:

[0055] .

[0056] The embodiment also provides a preparation method of the metal ore flotation collector, and a synthesis schematic diagram is shown in Figure 1 Figure 1 wherein n=6, and the method specifically comprises the following steps:

[0057] ​​(1) Sodium hydroxide (70 mmol) was added to water (15 mL), then 7-hydroxyheptanoic acid (35 mmol) was added, and the mixture was allowed to cool to room temperature. The mixture was slowly added to a cyanuric chloride solution in acetone (10 mmol, 12 mL) at 0 °C, and stirred for 5 h. After the reaction was completed, the reaction solution was poured into 50 mL of 1 M hydrochloric acid solution, and the white solid was collected by filtration. The white solid was slurried with hot water until the solid part of the TLC plate had no obvious impurity spots, and then dried at 80 °C to obtain intermediate 1. The structure of intermediate 1 was confirmed by 1 H NMR and HRMS spectra are shown in Figure 10 and Figure 11 1 H NMR (C 24 H 39 N3O9, 400 MHz, DMSO): δ 11.85 (s, 3H), 4.08 (t, 6H), 2.24 (t,6H), 1.82-1.80 (m, 6H), 1.55-1.45 (m, 18H); HRMS (ESI + ): [M+H] + Calcd 514.27, Found 514.27.

[0058] (2) Intermediate 1 (10 mmol), 6-(methylthio)pyridin-3-amine (50 mmol) were added to 50 mL of anhydrous N,N-dimethylformamide, cooled to 0 °C, then TCFH (80 mmol) and NMI (120 mmol) were added, and gradually warmed to room temperature for 16 h. n-Heptane (150 mL) was added to the reaction system, stirred uniformly, then filtered, and the filter cake was dried and added to anhydrous N,N-dimethylformamide (50 mL), then sodium ethyl sulfate (40 mmol) was added, and stirred to warm to 110 °C for 16 h. Pre-HPLC separation obtained a metal ore collector; the structure of the metal ore collector was confirmed by 1 H NMR and HRMS spectra are shown in Figure 12 and Figure 13 1 H NMR (C 39 H 51 N9O6S3, 400 MHz, DMSO): δ 12.46 (s, 3H), 9.95 (s, 3H), 7.93(t, 6H), 7.47 (d, 3H),4.08 (t, 6H), 2.32 (t, 6H), 1.82-1.80 (m, 6H), 1.55-1.45 (m, 18H); HRMS (ESI​​+ ): [M+H] + Calcd. 838.31, Found 838.31.

[0059] Test Example

[0060] The effect of the metal ore flotation collector prepared in Examples 1-3 of the present application was verified, and n-butyl sodium xanthate was set as a comparative collector, and the specific steps were as follows:

[0061] (1) 400 g of low-grade nickel-copper sulfide ore (the grade of Ni was 0.65%, and the grade of Cu was 0.36%) was weighed and ground, so that the content of materials with particle size less than 0.074 mm was 65-70%, and water was added to adjust the pulp concentration to 50%, and a first-stage flotation experiment was carried out;

[0062] (2) In the first-stage flotation experiment, 100 g / t of activator copper sulfate was first added, and after 2 min of pulp adjustment, 100 g / t of the collector prepared in Examples 1-3 or n-butyl sodium xanthate was added, and after 2 min of continuous pulp adjustment, 100 g / t of foaming agent methyl isobutyl carbinol was added, and after 2 min of pulp adjustment, 10 min of scavenging, 5 min of cleaning and 3 min of cleaning were carried out, and concentrate 1 was obtained;

[0063] (3) In the second-stage flotation experiment, the first-stage pulp was re-ground so that the content of materials with particle size less than 0.074 mm was 85%, and then 80 g / t of activator copper sulfate was added, and after 2 min of pulp adjustment, 80 g / t of the collector prepared in Examples 1-3 or n-butyl sodium xanthate was added, and after 2 min of continuous pulp adjustment, 80 g / t of foaming agent methyl isobutyl carbinol was added, and after 2 min of pulp adjustment, 8 min of scavenging, 5 min of cleaning and 4 min of cleaning were carried out, and concentrate 2 was obtained; and then two times of scavenging of 6 min and 4 min were carried out to obtain tailings;

[0064] (4) The concentrate 1 obtained in step (2) was mixed with the concentrate 2 obtained in step (3) to obtain a copper-nickel mixed concentrate.

[0065] The nickel and copper grades in the copper-nickel mixed concentrate and tailings products were detected by ICP inductively coupled ion emission spectrometer, and the results are shown in Table 1.

[0066] Table 1

[0067]

[0068] As can be seen from Table 1, compared with sodium butyl xanthate as a collector, the copper and nickel in the copper-nickel mixed concentrate selected by using the collector of the present application embodiments 1-3 have higher grade, and the recovery rate of copper and nickel is above 85%, and with the increase of the length of the introduced fatty chain, the grade and recovery rate have a small increase. The above results show that the collector molecules designed in the present application can effectively adapt to the characteristics of low-grade nickel-copper sulfide ore, and significantly improve the collection effect.

[0069] It can be known from analyzing the molecular structure of the collector that the sulfur atom of the mercapto group in the metal ore flotation collector of the present application has strong affinity, can chemically adsorb with metal ions, and form a firm metal-sulfur bond; the pyridine group has good electron donor properties, can form a coordination bond with metal ions; the melamine group has multiple nitrogen atoms, can form a multi-coordination chelate with metal ions; the ether bond can increase the flexibility and polarity of the collector molecules, which helps the collector molecules better adapt to the chemical environment of the mineral surface; and the introduced fatty chain can provide hydrophobicity, and enhance the adsorption stability of the collector molecules on the mineral surface; the synergistic effect of these functional groups can significantly improve the selective collection ability of the collector on nickel, copper and other metal minerals.

[0070] Finally, it should be pointed out that the above embodiments are only used to illustrate the technical solutions of the present application, but not to limit it. The basic principles and main features of the present application have been described above with specific embodiments, and on the basis of the present application, some modifications or replacements can be made, but these modifications or replacements do not make the essence of the corresponding technical solution deviate from the scope of the present application.

Claims

1. A metal ore flotation collector, characterized in that: The structural formula of the metal ore flotation collector is: Wherein, n is 4, 5 or 6.

2. A method for preparing a metal ore flotation collector according to claim 1, characterized in that: The following steps are involved: (1) Sodium hydroxide and ω-hydroxy fatty acid are added to water to obtain a mixed solution; the mixed solution is added to an acetone solution of cyanuric chloride at 0-5°C and reacted under stirring; after the reaction is completed, intermediate 1 is obtained through post-treatment; The structural formula of the intermediate 1 and ω-hydroxy fatty acid is: Wherein, n is 4, 5 or 6; (2) The intermediate 1 and 6-methylthiopyridin-3-amine are added to N,N-dimethylformamide, and N,N,N',N'-tetramethylchloroformamidine hexafluorophosphate and N-methylimidazole are added at 0-5°C, and then the temperature is raised to room temperature for reaction; n-heptane is added to the reaction system, filtered, the filter residue is added to N,N-dimethylformamide, and sodium ethylsulfate is added, and the reaction is heated under stirring; after the reaction is completed, the metal ore flotation collector is obtained through post-treatment.

3. The method for preparing a metal ore flotation collector according to claim 2, wherein: The molar ratio of sodium hydroxide, ω-hydroxy fatty acid and cyanuric chloride in step (1) is (6.5-7): (3.2-3.5):

1.

4. The method for preparing a metal ore flotation collector according to claim 2, wherein: The reaction time in step (1) is 3-5 h.

5. The method for preparing a metal ore flotation collector according to claim 2, wherein: The molar ratio of the intermediate 1, 6-methylthiopyridin-3-amine, N,N,N',N'-tetramethylchloroformamidine hexafluorophosphate, N-methylimidazole and sodium ethylsulfate in step (2) is 1:(4-5):(6-8):(10-12):(3.5-4).

6. The method for preparing a metal ore flotation collector according to claim 2, wherein: The reaction time at room temperature in step (2) is 12-16 h.

7. The method for preparing a metal ore flotation collector according to claim 2, wherein: The heating reaction temperature in step (2) is 110-130°C and the time is 12-16 hours.

8. The method for preparing a metal ore flotation collector according to claim 2, wherein: The post-treatment operation in step (1) is as follows: pouring the reaction solution into a 1 mol / L hydrochloric acid solution, filtering, slurrying the collected filter residue with hot water, filtering again and drying.

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