A galena combination inhibitor and methods of use thereof

Abstract

The application discloses a galena combined inhibitor and a use method thereof, and the combined inhibitor comprises iron sulfate, sodium nitrate and jarosite, and the mass ratio of the amount of the iron sulfate, the sodium nitrate and the jarosite is 20:(4-10):(1-2). The combined inhibitor can be applied to separation of copper-lead mixed concentrate to realize lead inhibition and copper floating, and the combined inhibitor does not need to be removed. In an acid medium, after the combined inhibitor acts, not only can the combined inhibitor decompose the adsorbed reagent on the surface of the copper-lead mixed concentrate, but also can promote the galena surface to be oxidized to generate hydrophilic PbSO4 and PbO, while the chalcopyrite surface is oxidized to generate hydrophobic elemental sulfur (S 0 ), thereby expanding the floatability difference between the copper-lead sulfide, the jarosite is selectively adsorbed on the surface of the galena, further reducing floatability of the lead, and improving the copper-lead separation efficiency. The copper concentrate and the lead concentrate obtained by the application have high recovery rates, low mutual content, reusable acid liquid, low cost and environmental protection.

Description

Technical Field

[0001] This invention relates to the field of flotation separation technology for copper-lead mixed concentrates, and specifically to a galena composite depressant and its application method. Background Technology

[0002] Copper-lead separation is a challenging problem in mineral processing engineering. The main difficulties lie in the similar floatability of copper and lead sulfides, the complex solution chemistry of the flotation pulp, and the instability of the feed for flotation separation. Currently, production often employs a "lead-suppressing, copper-floating" process, which typically requires the addition of galena depressants, mainly divided into inorganic and organic depressants. Inorganic depressants primarily include dichromates, sulfites, and H₂O₂. While dichromates are effective at suppressing lead, their use is restricted due to environmental regulations; sulfites require large quantities and are unstable; and oxidants such as H₂O₂ are easily decomposed and costly. Organic depressants mainly include carboxymethyl cellulose (CMC), carboxyethyl cellulose (HEC), starch, and guar gum, but their main problems are poor selectivity, large dosage, and high cost. Existing lead depressants fail to achieve satisfactory results in copper-lead separation: severe intermingling of copper and lead affects concentrate quality and recovery rate; they are difficult to adapt to feed fluctuations, resulting in large fluctuations in indicators; and they affect the quality of recycled water and inhibit lead roughing.

[0003] Based on the above analysis, breaking through traditional processes and existing inhibitors, expanding the differences in floatability of copper-lead sulfide ores, and developing new reagents and technologies for the efficient separation of copper and lead have significant academic and commercial value. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention aims to provide a galena composite inhibitor and its application method. Utilizing the differences in oxidation products and oxidation rates of copper-lead sulfide ores under acidic conditions, this invention develops new agents and technologies for "lead suppression and copper flotation".

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A galena composite inhibitor comprises ferric sulfate, sodium nitrate and jaundice in a mass ratio of 20:(4-10):(1-2).

[0007] The present invention also provides a method for using a galena composite inhibitor, comprising the following steps:

[0008] S1. Add inhibitors to adjust the slurry: Place the copper-lead mixed concentrate powder in the flotation cell and add water to adjust the slurry; add hydrochloric acid, nitric acid or sulfuric acid to the slurry, then add ferric sulfate and sodium nitrate. At this time, the pH of the slurry is 1-2.5, and start stirring.

[0009] S2. Selective adsorption of potassium ferric sulfate: After the slurry is stirred and reacted, the pH rises to 2.5-5. Potassium ferric sulfate is added and stirred. Potassium ferric sulfate is selectively adsorbed on the surface of galena, further inhibiting its floatability.

[0010] S3. Flotation separation: Add collector Z-200, stir, then add No. 2 oil, stir, and then carry out flotation separation to obtain copper concentrate and lead concentrate.

[0011] Furthermore, in step S1, during the water addition and slurry preparation, the slurry mass concentration is adjusted to 20-25%.

[0012] Further, in step S2, based on the dry weight of each ton of copper-lead mixed concentrate powder, the amount of hydrochloric acid, nitric acid or sulfuric acid used is 10-20 kg / t, the amount of ferric sulfate used is 1 kg / t, and the amount of sodium nitrate used is 0.2-0.5 kg / t; in step S3, the amount of potassium ferrous sulfate used is 0.05-0.1 kg / t.

[0013] Furthermore, in step S2, the reaction is stirred for 30-60 minutes.

[0014] Furthermore, in step S3, the dosage of collector Z-200 and No. 2 oil is 40g / t per ton of dry weight of copper-lead mixed concentrate powder.

[0015] The beneficial effects of this invention are as follows: This invention provides a galena composite inhibitor applicable to the separation of copper-lead mixed concentrates, achieving lead suppression and copper flotation without the need for reagent removal. After acting in an acidic medium, the inhibitor not only decomposes the reagents already adsorbed on the surface of the copper-lead mixed concentrate, but also promotes the oxidation of galena surface to produce hydrophilic PbSO4 and PbO, while chalcopyrite surface oxidation produces hydrophobic elemental sulfur (S). 0 This process widens the floatability difference between copper and lead sulfides. Potassium ferroalloy selectively adsorbs onto the surface of galena, further reducing lead floatability and improving copper-lead separation efficiency. The copper and lead concentrates obtained by this invention have high recovery rates, low cross-contamination, and the acid solution can be reused, resulting in low cost and environmental friendliness. Attached Figure Description

[0016] Figure 1 The S on the chalcopyrite-galena surface obtained in Experiment 1 of this embodiment of the invention. 0 Content comparison chart. Detailed Implementation

[0017] The present invention will be further described below with reference to the accompanying drawings. It should be noted that this embodiment is based on the present technical solution and provides detailed implementation methods and specific operation processes, but the protection scope of the present invention is not limited to this embodiment.

[0018] Example 1

[0019] 100g of copper-lead mixed concentrate powder was weighed into a 500mL flotation cell. Water was added to adjust the pulp concentration to 20%. 12.8kg / t hydrochloric acid was added, followed by 1kg / t ferric sulfate and 0.5kg / t sodium nitrate inhibitors. At this point, the pH of the pulp was 2.18. After stirring at room temperature for 1 hour, the pH rose to 4.72. 0.05kg / t potassium ferric sulfate was added and stirred for 3 minutes. 40g / t collector Z-200 was added and stirred for 3 minutes. Then, 40g / t frother No. 2 oil was added. Flotation was started after 1 minute, and roughing was carried out for 8 minutes to obtain copper and lead concentrates. The flotation parameters are shown in Table 1.

[0020] Table 1

[0021]

[0022] Example 2

[0023] 100g of copper-lead mixed concentrate powder was weighed into a 500mL flotation cell. Water was added to adjust the pulp concentration to 20%. 12kg / t nitric acid was added, followed by 1kg / t ferric sulfate and 0.2kg / t sodium nitrate inhibitors. At this point, the pH of the pulp was 1.96. The mixture was stirred at room temperature for 1 hour, and the pH rose to 4.70. 0.05kg / t potassium ferric sulfate was added and stirred for 3 minutes. 40g / t collector Z-200 was added and stirred for 3 minutes. Then 40g / t frother No. 2 oil was added. Flotation was started after 1 minute, and roughing was carried out for 8 minutes to obtain copper and lead concentrates, as shown in Table 2.

[0024] Table 2

[0025]

[0026] Example 3

[0027] Weigh 100g of copper-lead mixed concentrate powder into a 500mL flotation cell, add water to adjust the pulp concentration to 20%, add 12.5kg / t sulfuric acid, then add 1kg / t ferric sulfate inhibitor and 0.5kg / t sodium nitrate. At this point, the pH of the pulp is 1.78. Stir at room temperature for 1 hour until the pH rises to 5. Continue to add 0.1kg / t jaundice, stir for 3 minutes, add 40g / t collector Z-200 and stir for 3 minutes, then add 40g / t frother No. 2 oil. After 1 minute, start flotation and roughing for 8 minutes to obtain copper concentrate and lead concentrate, as shown in Table 3.

[0028] Table 3

[0029]

[0030] Example 4

[0031] In an industrial trial conducted at a 200t / d gold-bearing polymetallic mine in Henan Province, sulfuric acid was added to a copper-lead mixed concentrate until the pH reached 1. Then, 1 kg / t of ferric sulfate and 0.5 kg / t of sodium nitrate were added as inhibitors. The mixture was stirred at room temperature for 30 minutes, followed by the addition of 0.1 kg / t of potassium ferric sulfate and stirring. Foaming agent No. 2 oil was added, and a "one roughing, one cleaning, two scavenging" process was used to beneficiate copper, producing copper and lead concentrates.

[0032] In addition, the traditional potassium dichromate method was used to separate copper and lead in a gold-bearing polymetallic mine in Henan Province. Production indicators are shown in Table 4.

[0033] Table 4

[0034]

[0035] Comparative Example 1

[0036] 100g of copper-lead mixed concentrate powder was weighed into a 500mL flotation cell. Water was added to adjust the pulp concentration to 20%, and 12kg / t sulfuric acid was added. The initial pH of the pulp was 1.83. The mixture was stirred at room temperature for 30 minutes until the pH rose to 3.73. 10kg / t dextrin was added and reacted for 3 minutes. Then, 40g / t collector Z-200 was added and stirred for 3 minutes. 40g / t frother No. 2 oil was added, and flotation was started after 1 minute. Roughing was carried out for 8 minutes to obtain copper concentrate and lead concentrate, as shown in Table 5.

[0037] Table 5

[0038]

[0039] Experiment 1

[0040] 2.0 g of chalcopyrite and 2.0 g of galena pure mineral powder (-74 ± 38 μm) were respectively stirred in 40 mL of a combined inhibitor + hydrochloric acid solution at pH 1.3 for 1 hour. Elemental sulfur (S) was then extracted from the mineral surface using an ethanol ultrasonic method. 0 S was determined by high performance liquid chromatography (HPLC). 0 Content. For example... Figure 1 As shown, S on the surface of chalcopyrite 0 The content is 12.6 times that on the surface of galena.

[0041] For those skilled in the art, various corresponding changes and modifications can be made based on the above technical solutions and concepts, and all such changes and modifications should be included within the protection scope of the claims of this invention.

Claims

1. A method for using a galena composite inhibitor, characterized in that, Includes the following steps: S1. Add inhibitors to adjust the slurry: Place the copper-lead mixed concentrate powder in the flotation cell and add water to adjust the slurry; add hydrochloric acid, nitric acid or sulfuric acid to the slurry, and then add ferric sulfate and sodium nitrate. At this time, the pH of the slurry is 1-2.5, and start stirring. S2. Selective adsorption of potassium ferric sulfate: After the slurry is stirred and reacted, the pH rises to 2.5-5. Potassium ferric sulfate is added and stirred. Potassium ferric sulfate is selectively adsorbed on the surface of galena, further inhibiting its floatability. S3. Flotation separation: Add collector Z-200, stir, then add No. 2 oil, stir again, and carry out flotation separation to "suppress lead and float copper" to obtain copper concentrate and lead concentrate.

2. The method of use according to claim 1, characterized in that, In step S1, during the water addition and slurry preparation, the slurry mass concentration is adjusted to 20-25%.

3. The method of use according to claim 1, characterized in that, In steps S1-S2, based on the dry weight of each ton of copper-lead mixed concentrate powder, the dosage of hydrochloric acid, nitric acid or sulfuric acid is 10-20 kg / t, the dosage of ferric sulfate is 1 kg / t, the dosage of sodium nitrate is 0.2-0.5 kg / t, and the dosage of potassium ferrous sulfate is 0.05-0.1 kg / t.

4. The method of use according to claim 1, characterized in that, In step S1, the reaction is stirred for 30-60 minutes.

5. The method of use according to claim 1, characterized in that, In step S3, the dosage of collector Z-200 and No. 2 oil is 40g / t per ton of dry weight of copper-lead mixed concentrate powder.

6. A galena composite inhibitor applied to the method of use according to any one of claims 1-5, characterized in that, It includes ferric sulfate, sodium nitrate and jaundice iron alum, in a mass ratio of 20:(4-10):(1-2).

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