COPPER(II)-AMMONIA COMPLEX ION SULFIDIZATION ACTIVATOR, PREPARATION AND APPLICATION THEREOF

Abstract

The disclosure relates to mineral processing, and more particularly to a copper(II)-ammonia complex ion sulfidization activator, and its preparation and application. A molar ratio of NH3 to Cu.sup.2+ in the active ingredient of the copper(II)-ammonia complex ion sulfidization activator is 2:1-4:1. The preparation method includes: dropwise adding an ammonia solution to a copper salt solution; and adjusting the mixture to pH 6-7.2 with dilute sulfuric acid to obtain the copper(II)-ammonia complex ion sulfidization activator. During the sulfidization flotation for the copper oxide ore, the copper(II)-ammonia complex ion sulfidization activator is added and mixed uniformly with the ore slurry prior to the introduction of the sulfidizing agent.

Claims

1. A copper(II)-ammonia complex ion sulfidization activator, wherein a molar ratio of NH.sub.3 to Cu.sup.2+ in an active ingredient of the ammoniacal copper complex ion sulfidization activator is 2-4:1.

2. A method of preparing a copper(II)-ammonia complex ion sulfidization activator, comprising: dropwise adding an ammonia solution into a copper salt solution to produce a mixture; and adjusting the mixture to pH 6-7.2 with dilute sulfuric acid to produce the ammoniacal copper complex ion sulfidization activator; wherein a molar ratio of NH.sub.3 to Cu.sup.2+ in the mixture is 2:1-4:1

3. The method of claim 2, wherein the copper salt solution is selected from the group consisting of copper sulfate solution, copper chloride solution, copper nitrate solution and a combination thereof.

4. The method of claim 2, wherein the ammonia solution is selected from the group consisting of ammonium sulfate solution, ammonium chloride solution, ammonium nitrate solution, ammonia water and a combination thereof.

5. The method of claim 2, wherein a concentration of the copper salt solution is 0.02-0.1 mol/L.

6. The method of claim 2, wherein a concentration of the ammonia solution is 5-10 mol/L.

7. The method of claim 2, wherein the ammonia solution is dropwise added to the copper salt solution at a rate of 0.5-2 drops/second.

8. A sulfidization flotation method for a copper oxide ore using the copper(II)-ammonia complex ion sulfidization activator of claim 1, comprising: (1) introducing the copper(II)-ammonia complex ion sulfidization activator to a slurry of the copper oxide ore followed by mixing uniformly; and (2) adding a sulfidizing agent solution to perform sulfidization flotation.

9. The sulfidization flotation method of claim 8, further comprising: before step (1), mixing the copper oxide ore with a solvent to produce the slurry and adjusting pH of the slurry.

10. The sulfidization flotation method of claim 9, wherein a copper content in the copper oxide ore is 40-50%.

11. The sulfidization flotation method of claim 9, wherein the solvent is water; and a mass ratio of the copper oxide ore to water is 2:35.

12. The sulfidization flotation method of claim 9, wherein the slurry is adjusted to pH 6-8.

13. The sulfidization flotation method of claim 9, wherein an addition amount of the copper(II)-ammonia complex ion sulfidization activator is 0.5-3 mL per gram of the copper oxide ore.

14. The sulfidization flotation method of claim 9, wherein a concentration of the sulfidizing agent solution is 0.2 mol/L; and an addition amount of the sulfidizing agent solution is 0.2-1.0 mL per gram of the copper oxide ore.

15. The sulfidization flotation method of claim 9, wherein the sulfidizing agent solution is selected from the group consisting of sodium sulfide solution, sodium hydrosulfide solution, hydrogen sulfide solution and a combination thereof.

16. The sulfidization flotation method of claim 9, further comprising: adding a mixed collector and a foaming agent to the slurry obtained in step (2) followed by mixing uniformly; and subjecting the slurry to skimming to obtain concentrate and tailings.

17. The sulfidization flotation method of claim 16, wherein a concentration of the mixed collector is 810.sup.4 mol/L and an addition amount of the mixed collector is 0.6-1.5 mL per gram of the copper oxide ore.

18. The sulfidization flotation method of claim 16, wherein the mixed collector is a mixture of benzohydroxamic acid and xanthate in a molar ratio of 1:3.

19. The sulfidization flotation method of claim 18, wherein the xanthate is butyl xanthate, amyl xanthate or a combination thereof.

20. The sulfidization flotation method of claim 16, wherein the foaming agent is terpineol oil; and an addition amount of the foaming agent is 0.5-1 L per gram of the copper oxide ore.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The FIGURE is a flow chart of the flotation of copper oxide ore using a copper(II)-ammonia complex ion sulfidization activator of the disclosure.

DETAILED DESCRIPTION OF EMBODIMENTS

[0041] In order to clearly describe the technical problems to be solved, the technical solutions and the beneficial effects, the disclosure will be further illustrated with reference to the embodiments. It should be noted that these embodiments are merely illustrative of the disclosure, and are not intended to limit the disclosure.

[0042] Unless otherwise specified, the experiments in the following embodiments are performed using the well-known techniques and conditions in the art, or performed as instructed by the manufacturer. Unless otherwise specified, the reagents and instruments adopted below are all commercially available.

EXAMPLE 1

Preparation of Copper(ii)-Ammonia Complex Ion Sulfidization Activator

[0043] The preparation process of the copper(II)-ammonia complex ion sulfidization activator was specifically described as follows.

[0044] (1) A 0.02 mol/L copper sulfate solution and a 8 mol/L ammonia solution were prepared.

[0045] (2) The ammonia solution was slowly dropwise added to 10 mL of the copper sulfate solution at a rate of 1 drop/s to a final ammonia concentration of 0.04 mol/L. Then the reaction mixture was adjusted to pH 6.3 with dilute sulfuric acid, and thus the copper(II)-ammonia complex ion sulfidization activator, in which a molar ratio of NH.sub.3 to Cu.sup.2+ was 2:1, was produced.

EXAMPLE 2

Impact of the Copper(II)-Ammonia Complex Ion Sulfidization Activator on Recovery Rate of Concentrate

[0046] The flotation experiment was carried out the following conditions: a cell-type flotation machine (laboratory flotation machine); a volume of the flotation cell: 40 mL; a rotation speed: 1450 r/min; and flotation temperature: room temperature. 2.0 g of malachite and 35 mL of deionized water were poured into the flotation cell and mixed for 1 min to produce a slurry, which was adjusted to pH 7. A comparative experiment was designed, where 1 mL of the copper(II)-ammonia complex ion sulfidization activator prepared in Example 1 was applied in the experimental group, and 1 mL of deionized water was added in the control group. The reaction was performed for 2 min, and then 0.4 mL of sodium sulfide (0.2 mol/L) was added to perform sulfidization for 3 min; a mixed collector of 0.4 mL of butyl xanthate (0.06 mol/L) and 0.4 mL of benzohydroxamic acid (0.02 mol/L) was added to perform collection for 3 min; and then 1 L of terpineol oil was added to perform foaming reaction for 1 min. The two groups were respectively subjected to manual skimming for 4 min to obtain a foam product, and then the products were respectively dried in an oven at 50 C. to produce a concentrate. The concentrate was weighed and the recovery rate was calculated, and the results were shown in Table 1.

TABLE-US-00001 TABLE 1 Comparison of recovery rates between the experimental and control groups Experimental Group group Control group Recovery rate of 92.4 73.8 concentrate (%)

[0047] The results showed that compared to the deionized water, the copper(II)-ammonia complex ion sulfidization activator containing NH.sub.3 and Cu.sup.2+ in a molar ratio of 2:1 increased the recovery rate by nearly 20% and significantly strengthened the sulfidization effect.

EXAMPLE 3

Effect of Molar Ratio of Copper Ion to Ammonia in the Copper(II)-Ammonia Complex Ion Sulfidization Activator on the Recovery Rate of Concentrate

[0048] (1) Preparation of Copper(II)-Ammonia Complex Ion Sulfidization Activators with Different Molar Ratios of NH.sub.3 to Cu.sup.2+

[0049] Three copper sulfate solutions with different concentrations (each for 10 mL) were dropwise added with a 8 mol/L concentrated ammonia water respectively to pH 6.3, 6.7 and 7.2 to accordingly produce the copper(II)-ammonia complex ion solutions respectively with a NH.sub.3Cu.sup.2+ molar ratio of 2:1, 3:1 and 4:1. These copper(II)-ammonia complex ion solutions can also be prepared according to the molar ratio of NH.sub.3 to Cu.sup.2+.

[0050] (2) Flotation Experiment

[0051] The flotation experiment was carried out under the following conditions: a cell-type flotation machine; a volume of the flotation cell: 40 mL; a rotation speed: 1450 r/min; and flotation temperature: room temperature. 2.0 g of malachite and 35 mL of deionized water were poured into the flotation cell and mixed for 1 min to produce a slurry, which was adjusted to pH 7. A comparative experiment, in which four groups were designed, was carried out, where 1 mL of a copper(II)-ammonia complex ion solution with a molar ratio of NH.sub.3 to Cu.sup.2+ of 2:1 was used as the sulfidization activator in the experimental group; copper(II)-ammonia complex ion solutions with a molar ratio of NH.sub.3 to Cu.sup.2+ of 4:1, 3:1 and 1:1 were respectively used in the control groups 1-3 at the same amount. The reaction was performed for 2 min, and then 0.4 mL of sodium sulfide (0.2 mol/L) was added to perform sulfidization for 3 min; a mixed collector consisting of 0.4 mL of butyl xanthate (0.06 mol/L) and 0.4 mL of benzohydroxamic acid (0.02 mol/L) was added to perform collection for 3 min; and then 1 L of terpineol oil were added to perform foaming reaction for 1 min. After that, the four groups were subjected to manual skimming for 4 min to obtain a foam product, and the foam products were respectively dried in an oven at 50 C. to produce a concentrate. The concentrate was weighed and the recovery rate was calculated, and the results were shown in Table 2.

TABLE-US-00002 TABLE 2 Effect of molar ratio of NH.sub.3 to Cu.sup.2+ on recovery rate of concentrate Control Control Control Experimental group 1 group 2 group 3 Group group (2:1) (4:1) (3:1) (1:1) Recovery rate of 93.1 75.9 82.7 70.4 concentrate (%)

[0052] It can be concluded from Table 2 that among the four copper(II)-ammonia complex ion solutions differing in molar ratio of NH.sub.3 to Cu.sup.2+, the copper(II)-ammonia complex ion solution with a molar ratio of NH.sub.3 to Cu.sup.2+ of 2:1 allowed for the highest recovery rate (93.1%), which was about 18% higher than the recovery rate obtained in the use of the solution with a molar ratio of NH.sub.3 to Cu.sup.2+ of 4:1 and 10% higher than the recovery rate obtained in the use of the solution with a molar ratio of NH.sub.3 to Cu.sup.2+ of 3:1. In the case of the molar ratio of NH.sub.3 to Cu.sup.2+ of 1:1, the copper(II)-ammonia complex ion solution even showed a negative effect on the recovery rate.

EXAMPLE 4

Comparison Between the Copper(II)-Ammonia Complex Ion Sulfidization Activator Provided Herein and Commercially-Available Sulfidization Activators

[0053] Flotation Experiment

[0054] 2.0 g of malachite and 35 mL of deionized water were poured into the flotation cell and mixed for 1 min to produce a slurry, which was adjusted to pH 7. A comparative experiment, in which three groups were designed, was carried out, where 1 mL of the copper(II)-ammonia complex ion sulfidization activator prepared in Example 1 was added in the first group (a total concentration of the copper(II)-ammonia complex ions in the flotation system was 0.510.sup.3 mol/L); ammonium sulfate was added in the second group to an optimal concentration of 5 10.sup.3 mol/L; and diethylamine phosphate was added in the third group to an optimal final concentration of 410.sup.3 mol/L. The activation was performed for 2 min, and then 0.4 mL of sodium sulfide (0.2 mol/L) was added to perform sulfidization for 3 min; 0.8 mL of a mixed collector (consisting of 0.4 mL of butyl xanthate with a concentration of 0.06 mol/L and 0.4 mL of benzohydroxamic acid with a concentration of 0.02 mol/L) was added to perform collection for 3 min; and then 1 L of terpineol oil was added to perform foaming reaction for 1 min. After that, the three groups were subjected to skimming for 4 min to produce a foam product, and the foam products were respectively dried in an oven at 50 C. to produce a concentrate. The concentrate was weighed and the recovery rate was calculated, and the results were shown in Table 3.

TABLE-US-00003 TABLE 3 Comparison of the copper(II)-ammonia complex ion sulfidization activator prepared herein and commercially-available sulfidization activators in the recovery rate Copper(II)- Sulfidization ammonia Ammonium Diethylamine activator complex ion sulfate phosphate Recovery rate of 92.8 80.2 75.6 concentrate (%)

[0055] It can be seen from Table 3 that the copper(II)-ammonia complex ion sulfidization activator provided herein (92.8%) was 10-20% higher than the existing sulfidization activators (diethylamine phosphate (75.6%); ammonium sulfate (80.2)) in the flotation recovery rate, which indicated that the sulfidization activator provided herein can significantly improve the flotation effect. Moreover, the addition amount of the sulfidization activator was also effectively reduced.

EXAMPLE 5

Comparison Between the Copper(II)-Ammonia Complex Ion and Single Use of Copper Ion or Ammonium Ion

[0056] Flotation Experiment

[0057] 2.0 g of malachite and 35 mL of deionized water were poured into the flotation cell and mixed for 1 min to produce a slurry, which was adjusted to pH 7. A comparative experiment, in which four groups were designed, was carried out, where 1 mL of deionized water was added in group 1; 1 mL of the copper(II)-ammonia complex ion sulfidization activator prepared in Example 1 was added in group 2 (a concentration of the complex ions in the ore slurry was 0.510.sup.3 mol/L); a copper sulfate solution was added into group 3 to a final Cu.sup.2+ concentration of 0.510.sup.3 mol/L; and an sulfate solution was added in group 4 to a final ammonium ion concentration of 110.sup.3 mol/L. The activation was carried out for 2 min, and then 0.4 mL of sodium sulfide (0.2 mol/L) was added to perform sulfidization for 3 min; 0.8 mL of a mixed collector (consisting of 0.4 mL of butyl xanthate with a concentration of 0.06 mol/L and 0.4 mL of benzohydroxamic acid with a concentration of 0.02 mol/L) was added to perform collection for 3 min; and then 1 L of terpineol oil was added to perform foaming reaction for 1 min. After that, the four groups were subjected to skimming for 4 min to produce a foam product, and the foam products were respectively dried in an oven at 50 C. to produce a concentrate. The concentrate was weighed and the recovery rate was calculated, and the results were shown in Table 4.

TABLE-US-00004 TABLE 4 Recovery rates of the four groups Copper(II)- ammonia complex ion Deionized sulfidization Ammonium Group water activator Cupric ion ion Recovery rate of 72.4 93.0 66.4 76.3 concentrate (%)

[0058] The results showed that compared to deionized water, the copper(II)-ammonia complex ion sulfidization activator (0.510.sup.3 mol/L) provided herein improved the recovery rate of copper oxide by about 20%. When cupric ion (0.510.sup.3 mol/L) was used as activator alone, the recovery rate of copper oxide was even lower than the blank group (i.e., the deionized water group), indicating that the single use of copper ion showed a negative effect on the flotation effect. Though the single addition of ammonium ion (110.sup.3 mol/L) can improve the recovery rate of copper oxide to a certain extent, the effect was significantly inferior to that obtained in the use of the copper(II)-ammonia complex ion. The experimental results clearly demonstrated that the copper(II)-ammonia activator provided herein had a significant synergistic effect compared to the single use of copper ion or ammonium ion, and the synergistic effect not only enhanced the flotation effect, but also decreased the consumption of the activator.

[0059] Described above are merely preferred embodiments of the disclosure, which are not intended to limit the disclosure. It should be noted that any modifications and improvements made by those skilled in the art without departing from the spirit of the disclosure shall fall within the scope of the disclosure defined by the appended claims.