Method for cooperatively grinding and floating silver and selenium of argyrodite acid leaching residue and activator

Abstract

The application discloses a method for cooperatively grinding and floating silver selenium by using silver vanadium ore acid leaching residue and an activating agent, and comprises the following steps: mixing the activating agent slurry with the silver vanadium ore acid leaching residue, grinding, and obtaining a grinding slurry; adding adjusting agent, collector and foaming agent into the grinding slurry in sequence, stirring, and then performing multi-stage flotation, so as to obtain silver selenium concentrate; the activating agent comprises a mixture of copper sulfide, sodium sulfide, copper sulfate and carboxymethyl starch; the silver vanadium ore acid leaching residue and the activating agent slurry are cooperatively used in combination with the grinding process, the coupling of physical-chemical effects is realized, a stable activated film is formed, the floatability of silver selenium minerals in the acid leaching residue is improved, the silver selenium minerals in the silver vanadium ore acid leaching residue can be cooperatively separated and enriched, the silver selenium concentrate after the flotation has high grade and high recovery rate, and the method is beneficial to the high value and comprehensive utilization of resources of the silver vanadium ore acid leaching residue.

Description

Technical Field

[0001] This invention relates to the field of mineral processing technology, and in particular to a method for co-grinding and flotation of silver selenium from acid leaching residue of silver vanadium ore with an activator. Background Technology

[0002] Silver-vanadium ore is an important vanadium-silver symbiotic resource, typically with low grades of valuable elements. Mineralogical studies show that silver and selenium often occur as argentite-selenosite, closely associated with pyrite. During the acid leaching process of hydrometallurgical vanadium extraction, some silver and selenium minerals undergo transformation, remaining in the leaching residue as silver selenide, silver selenate, and adsorbed forms, mixed with pyrite. Flotation is a key technology for recovering these rare and precious metals, its core being the selective hydrophobic flotation of the target minerals through efficient activation.

[0003] Existing flotation activation processes have significant limitations. For example, improper timing and methods of activator addition can significantly increase activator consumption and shorten the effective reaction time; the activator system itself may lack effectiveness, resulting in poor separation selectivity and difficulty in improving concentrate grade.

[0004] Therefore, a beneficiation scheme for acid leaching residue of silver-vanadium ore is needed to improve the grade and recovery rate of silver-vanadium ore. Summary of the Invention

[0005] In view of this, this application provides a method for co-grinding and flotation of silver and selenium in acid leaching residue of silver vanadium ore with an activator, which is used to solve the problem of how to improve the grade and recovery rate of silver and vanadium in acid leaching residue beneficiation of silver vanadium ore.

[0006] To achieve the above technical objectives, this application adopts the following technical solution: In a first aspect, this application provides a method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator to separate silver selenium, comprising the following steps: The activator slurry is mixed with the acid leaching residue of silver-vanadium ore and then ground to obtain the grinding slurry; A modifier, collector, and frother are added sequentially to the grinding slurry and stirred. Then, multi-stage flotation is carried out to obtain silver-selenium concentrate. The activator comprises a mixture of copper sulfide, sodium sulfide, copper sulfate, and carboxymethyl starch.

[0007] Preferably, the copper sulfide accounts for 15-40% of the mass of the activator (100% by mass).

[0008] Preferably, the mass ratio of copper sulfide, sodium sulfide, copper sulfate, and carboxymethyl starch is 2-7:2-7:3-6:1-10.

[0009] Preferably, the silver grade of the acid leaching residue of the silver-vanadium ore is 60-160 g / t, and the selenium grade is 60-160 g / t.

[0010] Preferably, the amount of activator used is 50-500 g / t.

[0011] Preferably, in the activator slurry, the mass ratio of activator to water is 1:1.5-20.

[0012] Preferably, the proportion of sodium sulfide particles with a diameter less than 0.074 mm is 60%-80%; the proportion of copper sulfide particles with a diameter in the range of 0.08 mm-0.045 mm is 60%-80%; the proportion of copper sulfate particles with a diameter in the range of 0.15 mm-0.25 mm is 70%-95%; and the proportion of carboxymethyl starch particles with a diameter in the range of 0.045 mm-0.075 mm is 80%-95%.

[0013] Preferably, the multi-stage flotation includes one roughing stage, three cleaning stages, and two sweeping stages.

[0014] Preferably, the modifier is sodium carbonate, with a dosage of 500-2500 g / t; the foaming agent is No. 2 oil, with a dosage of 100-1000 g / t; and the collector is butylamine black powder, with a dosage of 200-1500 g / t.

[0015] Preferably, the concentration of the grinding slurry is 20-80 wt%, and the proportion of -0.074 mm is 50-95%.

[0016] The beneficial effects of this application are as follows: This application combines the synergistic effect of acid leaching residue and activator slurry of silver-vanadium ore with grinding process to achieve the coupling of physical and chemical effects, form a stable activation film, improve the floatability of silver-selenium minerals in acid leaching residue, and enable synergistic separation and enrichment of silver-selenium minerals in acid leaching residue of silver-vanadium ore. The silver-selenium concentrate after flotation has high grade and high recovery rate, which is conducive to the high-value and comprehensive utilization of acid leaching residue of silver-vanadium ore. Attached Figure Description

[0017] Figure 1 This is a flowchart of this application. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0019] like Figure 1 As shown, this application provides a method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator to separate silver selenium, comprising the following steps: The activator slurry is mixed with the acid leaching residue of silver-vanadium ore and then ground to obtain a grinding slurry. A modifier, collector, and frother are added to the grinding slurry in sequence and stirred. Then, multi-stage flotation is carried out to obtain silver-selenium concentrate. The activator comprises a mixture of copper sulfide, sodium sulfide, copper sulfate, and carboxymethyl starch.

[0020] This application physically mixes the acid leaching residue and activator slurry of silver-vanadium ore. Under the acidic conditions provided by the acid leaching residue, sodium sulfide in the activator preferentially sulfides the oxidized surface and dissolves the oxide layer. This allows calcium and magnesium ions in the acid leaching residue to react with sodium sulfide, competitively adsorbing them and removing interfering ions from the slurry to reduce the loss of copper sulfate and copper sulfide. Specifically, the interfering ions are magnesium and calcium ions, which can react with copper sulfate to form precipitates. Removing interfering ions does not reduce starch loss, but reducing copper sulfate loss can lower costs while maintaining silver-selenium grade and recovery rate. During grinding, copper sulfide continuously and slowly releases copper source due to the grinding action, maintaining the integrity of the copper. Copper sulfate activates the film and regulates its potential, inhibiting pyrite flotation. During grinding, the newly exposed pyrite surface is covered by a hydrophilic film formed by the long chain of carboxymethyl starch molecules, which, through electrostatic attraction and hydrogen bonding, covers the hydrophobic sites on the pyrite surface and competes with black powder for collector action sites. Through the coupling of these physical and chemical effects, a stable activated film is formed. The activator improves the floatability of silver-selenium minerals in the acid leaching residue, achieving synergistic separation and enrichment of silver-selenium minerals in the silver-vanadium ore acid leaching residue. The flotation-processed silver-selenium concentrate can be sold directly, while the tailings, after dewatering, can be used to prepare building materials such as non-fired bricks, ultimately achieving high-value and comprehensive utilization of the silver-vanadium ore acid leaching residue.

[0021] In some embodiments, the copper sulfide accounts for 15-40% of the mass of 100% of the activator.

[0022] In this embodiment, excessive use of copper sulfide will release too much Cu. 2+ and S 2- The ions not only activate the target silver selenium mineral, but also activate pyrite, causing pyrite to float to the surface and resulting in a decrease in concentrate grade. If the amount of copper sulfide is too small, it cannot provide enough copper source and cannot maintain a stable copper sulfide film.

[0023] In some embodiments, the mass ratio of copper sulfide, sodium sulfide, copper sulfate, and carboxymethyl starch is 2-7:2-7:3-6:1-10.

[0024] In this embodiment, by adjusting the proportion of components in the activator, the residual acid content was effectively reduced. If the proportion of sodium sulfide is too high, although it can effectively remove interfering ions, excessive sulfide ions will inhibit the collector. If the proportion of sodium sulfide is too low, it cannot effectively remove Ca. 2+ Mg2+ Interfering ions can lead to increased loss of copper sulfate / copper sulfide and a decrease in overall activation efficiency. If the proportion of carboxymethyl starch is too high, excessive starch will coat the surface of the target mineral, hindering the adsorption of the collector and resulting in a decrease in recovery rate. If the proportion of carboxymethyl starch is too low, it will not be able to suppress gangue such as pyrite, resulting in a large amount of gangue floating to the surface and a significant decrease in concentrate grade.

[0025] In some embodiments, the mass ratio of copper sulfide, sodium sulfide, copper sulfate, and carboxymethyl starch is 4:3:3:8.

[0026] In some embodiments, the silver grade and selenium grade of the acid leaching residue of the silver-vanadium ore are 60-160 g / t.

[0027] In some embodiments, the silver grade of the acid leaching residue of the silver-vanadium ore is 89.2 g / t, and the selenium grade is 90 g / t.

[0028] In some embodiments, the amount of activator used is 50-500 g / t.

[0029] In this embodiment, limiting the amount of activator helps to optimize reagent costs while ensuring activation effect and ensuring selectivity of the flotation process. If too much activator is used, pyrite will be activated and floated, resulting in a decrease in concentrate grade and an increase in reagent cost. If too little activator is used, it will not provide sufficient activation for silver selenium minerals, and the insufficient hydrophobicity of the mineral surface will result in a large amount of valuable metals being lost in the tailings.

[0030] In some embodiments, the mass ratio of activator to water in the activator slurry is 1:1.5-20.

[0031] In some embodiments, the proportion of sodium sulfide particles with a diameter less than 0.074 mm is 60%-80%; the proportion of copper sulfide particles with a diameter in the range of 0.08 mm-0.045 mm is 60%-80%; the proportion of copper sulfate particles with a diameter in the range of 0.15 mm-0.25 mm is 70%-95%; and the proportion of carboxymethyl starch particles with a diameter in the range of 0.045 mm-0.075 mm is 80%-95%.

[0032] In this embodiment, smaller particle size is not necessarily better; if the particle size is too fine, local saturation is likely to occur, and high concentrations of ions are likely to react with impurity ions in the slurry in a short time. Furthermore, the reagent cannot form a stable and uniform activation film on the surface of silver selenium minerals, which reduces the selective adsorption efficiency of the subsequent collector.

[0033] In some embodiments, the multi-stage flotation includes one coarse flotation, three fine flotations, and two sweep flotations.

[0034] In some embodiments, after multi-stage flotation, silver-selenium concentrate, tailings I, and tailings II are finally obtained. Specifically, as shown in... Figure 1 As shown, a modifier, collector, and frother (2# oil) are added sequentially to the grinding slurry and stirred. Then, a roughing process is performed to obtain middlings and tailings. The middlings are then subjected to a primary cleaning process to obtain a primary concentrate and primary middlings tailings. The primary concentrate is then subjected to a secondary cleaning process to obtain a secondary concentrate and secondary middlings tailings. The secondary concentrate is then subjected to a tertiary cleaning process to obtain silver-selenium concentrate and tertiary middlings tailings. The secondary middlings tailings are reused in the primary cleaning process, and the tertiary middlings tailings are also reused in the secondary cleaning process. The tailings are then subjected to a primary scavenging process to obtain tailings I and primary scavenging concentrate. The primary scavenging concentrate is then subjected to a secondary scavenging process to obtain secondary scavenging concentrate and tailings II. The secondary scavenging concentrate and primary middlings tailings are then combined and reused in the roughing process.

[0035] In some embodiments, the modifier is sodium carbonate, used at a dosage of 500-2500 g / t; the foaming agent is No. 2 oil, used at a dosage of 100-1000 g / t; and the collector is butylamine black powder, used at a dosage of 200-1500 g / t.

[0036] In some embodiments, the concentration of the grinding slurry is 20-80 wt%, and the proportion of -0.074 mm is 50-95%.

[0037] The following specific embodiments further illustrate this solution.

[0038] Example 1 A method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator to separate silver and selenium includes the following steps: An activator was obtained by mixing copper sulfide, sodium sulfide, copper sulfate, and carboxymethyl starch in a ratio of 4:3:3:8. The sodium sulfide particles smaller than 0.074 mm comprised 60% of the total; the copper sulfide particles were in the range of 0.08 mm to 0.045 mm, comprising 60%; the copper sulfate particles were in the range of 0.15 mm to 0.25 mm, comprising 70%; and the carboxymethyl starch particles were in the range of 0.045 mm to 0.075 mm, comprising 80%. The activator and water were premixed at a mass ratio of 1:2 and stirred for 1 hour to obtain an activator slurry. The acid leaching residue of silver-vanadium ore with a silver grade of 89.2 g / t and a selenium grade of 90 g / t was mixed with an activator slurry and added to a mill. Water was added to obtain a slurry, and the slurry concentration was controlled at 30%. The amount of activator was 200 g / t. Then, the ore was ground for 15 minutes. After grinding and dissociation, the fineness of the slurry obtained was 95% less than 0.075 mm. Add 2000 g / t sodium carbonate as a modifier, 800 g / t No. 2 oil as a foaming agent, and 500 g / t butylamine black powder as a collector to the grinding slurry in sequence, then proceed as follows: Figure 1 The process of roughing, scavenging, and cleaning shown is carried out in a closed-circuit flotation to obtain silver-selenium concentrate.

[0039] Examples 2-4 A method for co-grinding and flotation of silver and selenium in acid leaching residue of silver-vanadium ore with activator is disclosed. The other contents are the same as those in Example 1, except that the amount of activator used is 50 g / t, 300 g / t, and 500 g / t respectively.

[0040] Examples 5-7 A method for co-grinding and flotation of silver and selenium from acid leaching residue of silver-vanadium ore with an activator is disclosed. The other contents are the same as those in Example 1, except that the dosage of the modifier is 500 g / t, 1000 g / t, and 2500 g / t respectively.

[0041] Examples 8-10 A method for co-grinding and flotation of silver and selenium in acid leaching residue of silver-vanadium ore with activator is disclosed. The other contents are the same as those in Example 1, except that the amount of frother used is 100g / t, 800g / t, and 1000g / t respectively.

[0042] Examples 11-13 A method for co-grinding and flotation of silver and selenium in acid leaching residue of silver-vanadium ore with activator is disclosed. The other contents are the same as those in Example 1, except that the amount of collector used is 100g / t, 800g / t, and 1000g / t respectively.

[0043] Example 14 A method for co-grinding and flotation of silver and selenium in acid leaching residue of silver-vanadium ore with activator is the same as in Example 1, except that the ratio of copper sulfide, sodium sulfide, copper sulfate and carboxymethyl starch in the activator is 2:3:3:8.

[0044] Example 15 A method for co-grinding and flotation of silver and selenium in acid leaching residue of silver-vanadium ore with activator is the same as in Example 1, except that the ratio of copper sulfide, sodium sulfide, copper sulfate and carboxymethyl starch in the activator is 6:3:3:8.

[0045] Example 16 A method for co-grinding and flotation of silver and selenium in acid leaching residue of silver-vanadium ore with activator is the same as in Example 1, except that the ratio of copper sulfide, sodium sulfide, copper sulfate and carboxymethyl starch in the activator is 4:1:3:8.

[0046] Example 17 A method for co-grinding and flotation of silver and selenium in acid leaching residue of silver-vanadium ore with activator is the same as in Example 1, except that the ratio of copper sulfide, sodium sulfide, copper sulfate and carboxymethyl starch in the activator is 4:5:3:8.

[0047] Example 18 A method for co-grinding and flotation of silver and selenium in acid leaching residue of silver-vanadium ore with activator is the same as in Example 1, except that the ratio of copper sulfide, sodium sulfide, copper sulfate and carboxymethyl starch in the activator is 4:3:1:8.

[0048] Example 19 A method for co-grinding and flotation of silver and selenium in acid leaching residue of silver-vanadium ore with activator is the same as in Example 1, except that the ratio of copper sulfide, sodium sulfide, copper sulfate and carboxymethyl starch in the activator is 4:3:5:8.

[0049] Example 20 A method for co-grinding and flotation of silver and selenium in acid leaching residue of silver-vanadium ore with activator is the same as in Example 1, except that the ratio of copper sulfide, sodium sulfide, copper sulfate and carboxymethyl starch in the activator is 4:3:3:6.

[0050] Example 21 A method for co-grinding and flotation of silver and selenium in acid leaching residue of silver-vanadium ore with activator is the same as in Example 1, except that the ratio of copper sulfide, sodium sulfide, copper sulfate and carboxymethyl starch in the activator is 4:3:3:10.

[0051] Comparative Example 1 A method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator to extract silver selenium is described. The other contents are the same as in Example 1, except that the activator does not include copper sulfide.

[0052] Comparative Example 2 A method for co-grinding and flotation of silver and selenium in acid leaching residue of silver-vanadium ore with an activator is described. The other contents are the same as in Example 1, except that the activator does not include sodium sulfide.

[0053] Comparative Example 3 A method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator to extract silver-selenium is described. The other contents are the same as in Example 1, except that the activator does not include copper sulfate.

[0054] Comparative Example 4 A method for co-grinding and flotation of silver and selenium in acid leaching residue of silver-vanadium ore with an activator is described. The other contents are the same as in Example 1, except that the activator does not include carboxymethyl starch.

[0055] Comparative Example 5 A method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator to separate silver and selenium is disclosed. The other contents are the same as in Example 1, except that the preparation steps of the grinding pulp are as follows: Sodium sulfide and water are ground separately to obtain sodium sulfide slurry with a slurry fineness of less than 0.075 mm accounting for 95%. Copper sulfide and water are ground separately to obtain copper sulfide slurry with a slurry fineness of less than 0.075 mm accounting for 95%. Copper sulfate and water are ground separately to obtain copper sulfate slurry with a slurry fineness of less than 0.075 mm accounting for 95%. Carboxymethyl starch and water are ground separately to obtain carboxymethyl starch slurry with a slurry fineness of less than 0.075 mm accounting for 95%. Silver vanadium ore acid leaching residue and water are ground separately to obtain silver vanadium ore acid leaching residue slurry with a slurry fineness of less than 0.075 mm accounting for 95%. The sodium sulfide slurry, copper sulfide slurry, copper sulfate slurry, and silver vanadium ore acid leaching residue slurry are mixed to obtain the ground slurry.

[0056] Testing and Evaluation The silver grade, selenium grade, silver recovery rate, and selenium recovery rate in the silver-selenium concentrate of different embodiments and comparative examples were tested by ICP. The results are shown in Table 1.

[0057] Table 1 Test Results

[0058] This application combines the synergistic effect of acid leaching residue and activator slurry with grinding process to achieve the coupling of physical and chemical effects, forming a stable activation film, improving the floatability of silver-selenium minerals in the acid leaching residue, and enabling synergistic separation and enrichment of silver-selenium minerals in the acid leaching residue. The resulting silver-selenium concentrate has a high grade and high recovery rate, which is conducive to the high-value and comprehensive utilization of the acid leaching residue of silver-vanadium ore.

[0059] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator to separate silver and selenium, characterized in that, Includes the following steps: The activator slurry is mixed with the acid leaching residue of silver-vanadium ore and then ground to obtain the grinding slurry; A modifier, collector, and frother are added sequentially to the grinding slurry and stirred. Then, multi-stage flotation is carried out to obtain silver-selenium concentrate. The activator comprises a mixture of copper sulfide, sodium sulfide, copper sulfate, and carboxymethyl starch.

2. The method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator for silver-selenium according to claim 1, characterized in that, Based on 100% of the activator mass, the copper sulfide mass percentage is 15-40%.

3. The method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator for silver-selenium according to claim 1, characterized in that, The mass ratio of copper sulfide, sodium sulfide, copper sulfate, and carboxymethyl starch is 2-7:2-7:3-6:1-10.

4. The method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator for silver-selenium according to claim 1, characterized in that, The silver grade and selenium grade of the acid leaching residue of the silver-vanadium ore are 60-160 g / t.

5. The method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator for silver-selenium according to claim 1, characterized in that, The amount of the activator used is 50-500 g / t.

6. The method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator for silver-selenium according to claim 1, characterized in that, In the activator slurry, the mass ratio of activator to water is 1:1.5-20.

7. The method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator for silver-selenium according to claim 1, characterized in that, The sodium sulfide particles with a diameter less than 0.074 mm account for 60%-80%; the copper sulfide particles with a diameter in the range of 0.08 mm-0.045 mm account for 60%-80%; the copper sulfate particles with a diameter in the range of 0.15 mm-0.25 mm account for 70%-95%; and the carboxymethyl starch particles with a diameter in the range of 0.045 mm-0.075 mm account for 80%-95%.

8. The method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator according to claim 1, characterized in that, The multi-stage flotation includes one roughing stage, three cleaning stages, and two sweeping stages.

9. The method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator for silver-selenium according to claim 1, characterized in that, The modifier is sodium carbonate, with a dosage of 500-2500 g / t; the foaming agent is No. 2 oil, with a dosage of 100-1000 g / t; and the collector is butylamine black powder, with a dosage of 200-1500 g / t.

10. The method for co-grinding and flotation of silver-vanadium ore acid leaching residue and activator for silver-selenium according to claim 1, characterized in that, The concentration of the grinding slurry is 20-80 wt%, and the proportion of -0.074 mm is 50-95%.

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