A copper sulphide ore depressant and method of use thereof

Abstract

The application discloses a copper sulfide ore inhibitor and an application method thereof, and belongs to the technical field of mineral processing. The copper sulfide ore inhibitor is prepared by the following steps: taking gum tragacanth and hydrogen peroxide by mass percentage, stirring and dissolving, and treating by ultrasonic waves at room temperature for a certain time to obtain the copper sulfide ore inhibitor. The inhibitor is high in selectivity, low in dosage, environment-friendly, non-toxic, easy to degrade, and wide in source, and has good copper-inhibiting and molybdenum-floating effects.

Description

Technical Field

[0001] This invention relates to the field of mineral processing flotation reagents, and in particular to a copper sulfide ore depressant and its application method. Background Technology

[0002] Molybdenite is a major source of molybdenum and plays a vital role in modern society. Due to hydrothermal mineralization, molybdenite is often associated with other sulfide ores (especially chalcopyrite). It is estimated that nearly 75% of the world's copper and 50% of its molybdenum originate from copper-molybdenum ores. To meet the needs of subsequent smelting, copper-molybdenum ores are typically subjected to mixed flotation to obtain a mixed copper-molybdenum concentrate, which is then separated by adding depressants. Currently, the main process used is copper-suppressing flotation of molybdenum to separate the mixed copper-molybdenum concentrate into copper and molybdenum concentrates.

[0003] In the flotation separation of copper-molybdenum mixed concentrates, commonly used depressants include sulfides (sodium sulfide, sodium hydrosulfide, etc.) and cyanides. However, sodium sulfide is used in large quantities and can generate toxic gases in acidic environments, causing environmental pollution. Cyanides are highly toxic, cyanide-containing wastewater is difficult to degrade, pose significant harm to human health and the environment, and are used in large quantities, leading to high costs in copper-molybdenum separation. Therefore, developing efficient, low-cost, and environmentally friendly copper sulfide ore depressants to replace traditional depressants such as sodium sulfide and cyanides is of significant practical importance.

[0004] In the research of copper sulfide ore inhibitors, patent CN103878073A reported "a copper-molybdenum separation flotation agent and its application method." This method uses sodium carbonate, sulfate, copper compounds, sulfide salts, and hydrosulfide salts as sulfide inhibitors, which has good effects but faces significant environmental pressure. Patent CN106583057A reported "the preparation and application of a copper-molybdenum sulfide ore separation flotation inhibitor." This method uses mercaptoacetic acid and deacetylated chitosan to prepare mercaptochitosan as a copper sulfide ore inhibitor, requiring a small dosage but incurring high costs. Patent CN109482357A reported "the preparation and application of a copper-molybdenum separation inhibitor." This method uses mercaptoacetic acid and monoethanolamine under catalytic stirring conditions to prepare N-(2-hydroxyethyl)-2-mercaptoacetamide as a copper sulfide ore inhibitor, but this method has high production costs.

[0005] Therefore, there is an urgent need to provide an economical, practical, efficient, and environmentally friendly inhibitor for copper sulfide ore. Summary of the Invention

[0006] This invention provides a copper sulfide ore inhibitor and its application method.

[0007] The solution of the present invention is:

[0008] A copper sulfide ore inhibitor comprises the following raw materials: tragacanth gum and hydrogen peroxide;

[0009] The preparation steps of the copper sulfide ore inhibitor are as follows: weigh tragacanth gum by mass percentage, add it to hydrogen peroxide, stir to dissolve, and treat with ultrasound at room temperature for a certain time to obtain the copper sulfide ore inhibitor.

[0010] As a preferred technical solution, the hydrogen peroxide and tragacanth gum are mixed and stirred at a mass ratio of 1:2 to 4.

[0011] The present invention also discloses a method for applying a copper sulfide ore inhibitor, wherein the copper sulfide ore inhibitor is applied in the separation process of copper-molybdenum mixed concentrate to obtain copper concentrate and molybdenum concentrate.

[0012] As a preferred technical solution, the following steps are included:

[0013] 1) Place the copper-molybdenum mixed concentrate into a flotation machine and add water to adjust the slurry;

[0014] 2) Adjust the pH value of the slurry;

[0015] 3) Add the copper sulfide inhibitor, collector, and foaming agent to the slurry in sequence;

[0016] 4) Aerated flotation yields copper concentrate and molybdenum concentrate.

[0017] As a preferred technical solution, the copper-molybdenum mixed concentrate is obtained by flotation of raw copper-molybdenum ore.

[0018] As a preferred technical solution, the pH adjuster is hydrochloric acid and sodium hydroxide, and the pH of the slurry is adjusted to 3-7.

[0019] As a preferred technical solution, the copper sulfide inhibitor is prepared as a solution with a concentration of 3-10% and added at a dosage of 300-1200 g / t.

[0020] As a preferred technical solution, the collector is one or more of xanthate, black powder, and ethyl thiocyanate; the collector is prepared as a solution with a concentration of 5% to 10% and added at a dosage of 50 to 200 g / t.

[0021] As a preferred technical solution, the foaming agent is No. 2 oil, and the dosage is 30-80g / t.

[0022] A copper sulfide ore inhibitor and its application method are derived by adopting the above-mentioned technical solution, which includes tragacanth gum and hydrogen peroxide. By mass percentage, tragacanth gum is weighed and added to hydrogen peroxide, stirred and dissolved, and then ultrasonically treated at room temperature for a certain period of time to obtain the copper sulfide ore inhibitor.

[0023] In this invention, the copper sulfide ore inhibitor is a combination of H2O2 and tragacanth gum. Tragacanth gum is a natural gum extracted from legumes, mainly composed of hemiaraquinone and acidic polysaccharides containing galacturonic acid groups. Its molecules contain a large number of polar groups (hydroxyl and carboxyl groups), which can bind to Fe oxides and Fe hydroxides on the surface of chalcopyrite through hydrogen bonds, increasing the hydrophilicity of the chalcopyrite surface and thus inhibiting its flotation. However, due to the weak hydrogen bonding effect, even when the amount of tragacanth gum is 2000 g / t, more than 15% of the chalcopyrite still floats.

[0024] Hydrogen peroxide (H2O2) is a colorless, transparent liquid with strong oxidizing properties, commonly used for sterilization and disinfection. Reports indicate that adding the strong oxidizing agent H2O2 during the flotation process can alter the floatability of chalcopyrite and remove collectors pre-adsorbed on the chalcopyrite surface, ultimately inhibiting chalcopyrite flotation.

[0025] Chalcopyrite pretreated with H₂O₂ exhibits surface oxidation, forming hydrophilic oxides that significantly reduce its floatability. However, H₂O₂ has a weak oxidizing effect on molybdenite, having little impact on its recovery rate. Therefore, combining H₂O₂ with tragacanth gum as a chalcopyrite inhibitor enhances the hydrophilicity of the chalcopyrite surface through H₂O₂ oxidation, thereby strengthening the inhibitory effect of the reagent and reducing the required reagent dosage.

[0026] Advantages of this invention:

[0027] 1) The raw materials for the inhibitors described in this invention are green, environmentally friendly, and readily available.

[0028] 2) The inhibitor described in this invention has strong selectivity, good inhibitory effect, small dosage, and low price, and can be applied on a large scale in actual production.

[0029] 3) The inhibitor described in this invention is safe to use and has minimal risks in actual use.

[0030] 4) The inhibitor described in this invention has a good effect on inhibiting copper flotation and molybdenum flotation, and can effectively separate copper-molybdenum mixed concentrate by flotation.

[0031] In summary, the inhibitor of the present invention is highly selective, requires a small amount, is environmentally friendly, non-toxic, easily degradable, and widely available, and has a good effect on inhibiting copper and molybdenum floating. Attached Figure Description

[0032] Figure 1 This is a flowchart illustrating the usage of this invention.

[0033] Figure 2 This is the test result of Implementation Example 1 in this invention.

[0034] Figure 3This is the test result of Implementation Example 2 in this invention.

[0035] Figure 4 This is the test result of Implementation Example 3 in this invention. Detailed Implementation

[0036] This invention provides a copper sulfide ore inhibitor and its application method to solve the problems in the background art.

[0037] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below with reference to specific embodiments.

[0038] Inhibitor preparation:

[0039] 1. The preparation steps of the copper sulfide ore inhibitor are as follows: weigh tragacanth gum by mass percentage, add it to hydrogen peroxide, stir to dissolve, and treat with ultrasound at room temperature for a certain time to obtain the copper sulfide ore inhibitor.

[0040] The hydrogen peroxide and tragacanth gum were mixed and stirred at a mass ratio of 1:2.

[0041] The No. 1 copper sulfide ore inhibitor used was prepared.

[0042] 2. The preparation steps of the copper sulfide ore inhibitor are as follows: weigh tragacanth gum by mass percentage, add it to hydrogen peroxide, stir to dissolve, and treat with ultrasound at room temperature for a certain time to obtain the copper sulfide ore inhibitor.

[0043] The hydrogen peroxide and tragacanth gum were mixed and stirred at a mass ratio of 1:3.

[0044] The No. 2 copper sulfide ore inhibitor used was prepared.

[0045] 3. The preparation steps of the copper sulfide ore inhibitor are as follows: weigh tragacanth gum by mass percentage, add it to hydrogen peroxide, stir to dissolve, and treat with ultrasound at room temperature for a certain time to obtain the copper sulfide ore inhibitor.

[0046] The hydrogen peroxide and tragacanth gum were mixed and stirred at a mass ratio of 1:4.

[0047] The No. 3 copper sulfide ore inhibitor used was prepared.

[0048] Example 1

[0049] The No. 1 copper sulfide ore inhibitor prepared in this invention was subjected to single mineral flotation tests to verify its copper inhibition and molybdenum flotation effects.

[0050] Take 2g of molybdenite with a particle size of +38-74µm and add it to a 50mL hanging flotation tank. Add 40mL of distilled water and stir to adjust the slurry at 1600r / min. The order of reagent addition is as follows: Figure 1 As shown, the inhibitor was added to adjust the pulp pH to 5. After stirring for 4 minutes, butyl xanthate and No. 2 oil were added and stirred for 3 minutes. The dosages of the inhibitor were 0, 50, 100, 200, 300, 600, and 1200 g / t, respectively; the dosage of butyl xanthate was 150 g / t; and the concentration of No. 2 oil was 50 g / t. After stirring, aeration flotation was performed to obtain froth products and products in the tank. The froth products and products in the tank were filtered, dried, and weighed separately, and the flotation rate was calculated. The results are shown in the figure. Figure 2 As shown.

[0051] As can be seen from the examples, the inhibitor has almost no inhibitory effect on molybdenite.

[0052] Example 2

[0053] The No. 2 copper sulfide ore inhibitor prepared in this invention was subjected to single mineral flotation tests to verify its copper inhibition and molybdenum flotation effects.

[0054] Take 2g of chalcopyrite with a particle size of +38-74µm and add it to a 50mL hanging flotation tank. Add 40mL of distilled water and stir to adjust the slurry at 1600r / min. The order of reagent addition is as follows: Figure 1 As shown, the inhibitor was added to adjust the pulp pH to 5. After stirring for 4 minutes, butyl xanthate and No. 2 oil were added and stirred for 3 minutes. The inhibitor concentrations were 0, 50, 100, 200, 300, 600, and 1200 g / t, respectively. The butyl xanthate dosage was 150 g / t, and the No. 2 oil concentration was 50 g / t. After stirring, aeration flotation was performed to obtain froth products and products in the tank. The froth products and products in the tank were filtered, dried, and weighed respectively, and the flotation rate was calculated. The results are shown below. Figure 3 As shown.

[0055] As can be seen from the examples, when the dosage of the inhibitor is 300-1200g / t, it has a strong inhibitory effect on chalcopyrite.

[0056] Example 3

[0057] The No. 3 copper sulfide ore inhibitor prepared in this invention was subjected to single mineral flotation tests to verify its copper inhibition and molybdenum flotation effects.

[0058] Take 2g of molybdenite and chalcopyrite with a particle size of +38-74µm respectively and add them to a 50mL hanging flotation tank. Add 40mL of distilled water and stir to adjust the slurry at 1600r / min. The order of reagent addition is as follows. Figure 1As shown, after adding the inhibitor, NaOH / HCl was added to adjust the pH of the slurry to 3, 5, 7, 9, and 11. After stirring for 4 minutes, butyl xanthate and No. 2 oil were added and stirred for 3 minutes. The dosage of the inhibitor was 600 g / t, the dosage of butyl xanthate was 150 g / t, and the concentration of No. 2 oil was 50 g / t. After stirring, aeration flotation was performed to obtain froth products and products in the tank. The froth products and products in the tank were filtered, dried, and weighed respectively, and the flotation rate was calculated. The results are shown in the figure. Figure 4 As shown.

[0059] As can be seen from the examples, the inhibitor has no inhibitory effect on molybdenite in the pH range of 3 to 7, but has a good inhibitory effect on chalcopyrite in the pH range of 3 to 11. Chalcopyrite is almost completely inhibited, with an uplift rate of less than 10%, indicating that the inhibitor has a good selective inhibitory effect on chalcopyrite.

[0060] Example 4

[0061] The prepared No. 2 copper sulfide ore inhibitor was used for the separation of artificial mixed ore to verify its effect on inhibiting copper and floating molybdenum.

[0062] Take 1g each of molybdenite and chalcopyrite with a particle size of +38-74µm, mix them in a 1:1 ratio, add them to a 50mL flotation tank, add 40mL of distilled water, and stir to adjust the slurry at 1600rpm. The order of reagent addition is as follows. Figure 1 As shown, the inhibitor was added to adjust the slurry pH to 5. After stirring for 4 minutes, butyl xanthate and No. 2 oil were added and stirred for 3 minutes. The dosage of the inhibitor was 300 g / t, the dosage of butyl xanthate was 150 g / t, and the concentration of No. 2 oil was 50 g / t. After stirring, aeration flotation was performed to obtain froth product and in-tank product. The froth product and in-tank product were filtered, dried, and weighed respectively. The molybdenum and copper content in the concentrate was analyzed, and the recovery rates of molybdenum and copper in the concentrate were calculated. The calculated flotation rate of molybdenite was 86.59%, and the flotation rate of chalcopyrite was 10.82%.

[0063] Example 5

[0064] The prepared No. 2 copper sulfide ore inhibitor was used for the separation of artificial mixed ore to verify its effect on inhibiting copper and floating molybdenum.

[0065] Take 1g each of molybdenite and chalcopyrite with a particle size of +38-74µm, mix them in a 1:1 ratio, add them to a 50mL flotation tank, add 40mL of distilled water, and stir to adjust the slurry at 1600rpm. The order of reagent addition is as follows. Figure 1As shown, the inhibitor was added to adjust the slurry pH to 5. After stirring for 4 minutes, butyl xanthate and No. 2 oil were added and stirred for 3 minutes. The dosage of the inhibitor was 600 g / t, the dosage of butyl xanthate was 150 g / t, and the concentration of No. 2 oil was 50 g / t. After stirring, aeration flotation was performed to obtain froth products and products in the tank. The froth products and products in the tank were filtered, dried, and weighed separately. The molybdenum and copper content in the concentrate was analyzed, and the recovery rates of molybdenum and copper in the concentrate were calculated. The calculated flotation rate of molybdenite was 89.18%, and the flotation rate of chalcopyrite was 5.52%.

[0066] Example 6

[0067] The prepared No. 2 copper sulfide ore inhibitor was used for the separation of artificial mixed ore to verify its effect on inhibiting copper and floating molybdenum.

[0068] Take 1g each of molybdenite and chalcopyrite with a particle size of +38-74µm, mix them in a 1:1 ratio, add them to a 50mL flotation tank, add 40mL of distilled water, and stir to adjust the slurry at 1600rpm. The order of reagent addition is as follows. Figure 1 As shown, the inhibitor was added to adjust the slurry pH to 5. After stirring for 4 minutes, butyl xanthate and No. 2 oil were added and stirred for 3 minutes. The dosage of the inhibitor was 1200 g / t, the dosage of butyl xanthate was 150 g / t, and the concentration of No. 2 oil was 50 g / t. After stirring, aeration flotation was performed to obtain froth product and in-tank product. The froth product and in-tank product were filtered, dried, and weighed respectively. The molybdenum and copper content in the concentrate was analyzed, and the recovery rates of molybdenum and copper in the concentrate were calculated. The calculated flotation rate of molybdenite was 90.64%, and the flotation rate of chalcopyrite was 5.17%.

[0069] As can be seen from Examples 4, 5 and 6, the inhibitor can achieve effective flotation separation of artificial mixed ore (molybdenite and chalcopyrite in a mass ratio of 1:1) at a dosage of 300-1200 g / t.

[0070] Example 7

[0071] The prepared No. 2 copper sulfide ore inhibitor was used for the separation of actual copper-molybdenum mixed concentrate. First, the raw copper-molybdenum ore was subjected to flotation to obtain the copper-molybdenum mixed concentrate. The obtained copper-molybdenum mixed concentrate was then subjected to copper-molybdenum flotation separation. The specific steps are as follows:

[0072] After adding the inhibitor, the slurry pH was adjusted to 5, followed by the sequential addition of ethyl thiocyanate and No. 2 oil. The inhibitor dosage was 1000 g / t, the butyl xanthate dosage was 100 g / t, and the No. 2 oil concentration was 40 g / t. After stirring, aeration flotation was performed to obtain froth product and in-tank product. The froth product and in-tank product were filtered, dried, and weighed separately. The molybdenum and copper contents in the concentrate were analyzed, and the recovery rates of molybdenum and copper in the concentrate were calculated. The froth product was molybdenum concentrate, and the in-tank product was copper concentrate. The results are shown in Table 1. The molybdenum grade of the molybdenum concentrate was 45.82%, and the copper grade was 2.18%; the molybdenum recovery rate was 83.02%, and the copper loss rate was 0.15%, achieving good copper-molybdenum separation indicators.

[0073] Table 1

[0074]

[0075] Comparative Example 1

[0076] Astragalus gum was applied to the separation of copper-molybdenum mixed concentrate. First, the raw copper-molybdenum ore was floated to obtain a mixed concentrate. The concentrate was then subjected to copper-molybdenum flotation separation. The specific steps were as follows: Astragalus gum was added as a depressant to adjust the pulp pH to 5. Then, ethyl thiocyanate and No. 2 oil were added sequentially. The depressant dosage was 1500 g / t, the butyl xanthate dosage was 100 g / t, and the No. 2 oil concentration was 40 g / t. After stirring, aeration flotation was performed to obtain a froth product and a product from the tank. The froth product and the product from the tank were filtered, dried, and weighed separately. The molybdenum and copper content in the concentrate was analyzed, and the recovery rates of molybdenum and copper in the concentrate were calculated. The froth product was the molybdenum concentrate, and the product from the tank was the copper concentrate. The results are shown in Table 2. The molybdenum grade of the molybdenum concentrate was 39.24%.

[0077] Table 2

[0078]

[0079] Comparative Example 2

[0080] The application of H2O2 to the separation of actual copper-molybdenum mixed concentrate involves first flotation of the raw copper-molybdenum ore to obtain a mixed concentrate, followed by copper-molybdenum flotation separation of the concentrate. The specific steps are as follows:

[0081] H₂O₂ was added as an inhibitor to adjust the slurry pH to 5. Then, ethyl thiocyanate and No. 2 oil were added sequentially. The inhibitor dosage was 1200 g / t, the butyl xanthate dosage was 100 g / t, and the No. 2 oil concentration was 40 g / t. After stirring, aeration flotation was performed to obtain froth products and in-tank products. The froth products and in-tank products were filtered, dried, and weighed separately. The molybdenum and copper content in the concentrate was analyzed, and the recovery rates of molybdenum and copper in the concentrate were calculated. The froth product was molybdenum concentrate, and the in-tank product was copper concentrate. The results are shown in Table 3. The molybdenum grade of the molybdenum concentrate was 44.71%, and the copper grade was 3.24%; the molybdenum recovery rate was 75.46%, and the copper loss rate was 0.21%.

[0082] Table 3

[0083]

[0084]

[0085] Comparing the results in Tables 1, 2, and 3, it can be seen that although tragacanth gum or H2O2 can effectively inhibit the flotation of chalcopyrite, they have drawbacks such as weak inhibitory effect and large dosage. The inhibitor mentioned above not only requires a small dosage but also has the best separation effect on copper-molybdenum mixed concentrate, indicating that the inhibitor is a highly efficient and selective chalcopyrite inhibitor.

[0086] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A method for applying a copper sulfide ore inhibitor, characterized in that, The copper sulfide ore inhibitor includes tragacanth gum and hydrogen peroxide; The preparation steps of the copper sulfide ore inhibitor are as follows: weigh tragacanth gum, add it to hydrogen peroxide, stir to dissolve, and treat it with ultrasound at room temperature for a certain time to obtain the copper sulfide ore inhibitor. The hydrogen peroxide and tragacanth gum are mixed and stirred at a mass ratio of 1:3 to 4. The copper sulfide ore inhibitor is applied in the separation process of copper-molybdenum mixed concentrate, including the following steps: 1) Place the copper-molybdenum mixed concentrate into a flotation machine and add water to adjust the slurry; 2) Add pH adjuster to the slurry to adjust the pH value; 3) Add the copper sulfide ore inhibitor, collector, and foaming agent to the slurry in sequence; 4) Aerated flotation yields copper concentrate and molybdenum concentrate; The copper sulfide ore inhibitor is prepared as a solution with a concentration of 3-10% and added at a dosage of 300-1200 g / t.

2. The method for applying a copper sulfide ore inhibitor as described in claim 1, characterized in that: The copper-molybdenum mixed concentrate is obtained by flotation of raw copper-molybdenum ore.

3. The method for applying a copper sulfide ore inhibitor as described in claim 1, characterized in that: The pH adjuster is hydrochloric acid and sodium hydroxide, and the pH of the slurry is adjusted to 5-7.

4. The method for applying a copper sulfide ore inhibitor as described in claim 1, characterized in that: The collector is one or more of xanthate, black powder, and ethyl thiocyanate; the collector is prepared as a solution with a concentration of 5% to 10% and added at a dosage of 50 to 200 g / t.

5. The method for applying a copper sulfide ore inhibitor as described in claim 1, characterized in that: The foaming agent is No. 2 oil, and the dosage is 30-80g / t.

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