Preparation method of secondary copper sulfide-containing copper-lead-zinc ore partial mixed flotation regulator

Abstract

A preparation method of a secondary copper sulfide-containing copper-lead-zinc ore partial mixed flotation regulator, first, hexamethyl tetramine and ferrous nitrate are added into an organic solvent ethylene glycol monoethyl ether, a nitrolysis reaction is fully carried out at a temperature of 0-20 DEG C, and a strong solubility solvent A is obtained; then, sodium pyrosulfite, zinc sulfate and a catalyst ferrous ammonium sulfate are added into the solvent A, heating is carried out until the solid is completely dissolved, then the heating is stopped, a solution B is obtained; sodium hydroxide is added into the solution B, stirring is uniformly carried out, then rapid cooling is carried out to-20-0 DEG C, a solid is separated out in the cooling process, filtration is carried out, the solid is collected, the solid is repeatedly washed with deionized water, and the secondary copper sulfide-containing copper-lead-zinc ore partial mixed flotation regulator is obtained. The prepared regulator can effectively reduce the mutual inclusion of copper, lead and zinc in the partial mixed flotation, improve the separation efficiency of copper and lead from zinc and copper and lead, and thus improve the resource utilization efficiency.

Description

Technical Field

[0001] This invention belongs to the field of non-ferrous metal beneficiation technology, and relates to flotation modifiers, specifically a mixed flotation modifier for copper-lead-zinc ore containing secondary copper sulfide and its preparation method. Background Technology

[0002] The beneficiation processes for copper-lead-zinc polymetallic ores generally include three types: preferential flotation, total mixed flotation, and partial mixed flotation. Partial mixed flotation prioritizes copper and lead while suppressing zinc flotation. Commonly used reagents for partial mixed flotation include zinc sulfate, sodium sulfite, and sodium sulfide. However, for copper-lead-zinc ores containing secondary copper sulfides, the activation effect of these secondary copper sulfides on zinc often makes zinc float very easily, and even large amounts of conventional modifiers are difficult to suppress its flotation. In this case, it is necessary to reduce the amount of copper-lead collector. This reduction in collector dosage results in a high grade of tailings from the copper-lead partial mixed flotation, a lower copper-lead recovery rate, and simultaneously, a higher copper and lead content in the zinc concentrate, leading to incomplete separation of copper, lead, and zinc and resource waste. Summary of the Invention

[0003] This invention provides a partial mixed flotation modifier for copper-lead-zinc ore containing secondary copper sulfide and its preparation method, in order to improve the quality of copper-lead mixed concentrate in copper-lead-zinc partial mixed flotation operations, reduce the activation of zinc by secondary copper sulfide, reduce the amount of zinc modifier used, improve the separation efficiency of copper, lead and zinc, and solve the problem of high mutual content of copper, lead and zinc.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] A method for preparing a partially mixed flotation modifier for copper-lead-zinc ore containing secondary copper sulfide includes the following steps: the amount of compound added in each step is based on parts by weight.

[0006] Step 1: Add 1-5 parts of hexamethylenetetramine and 1-2 parts of ferrous nitrate to 5-10 parts of the organic solvent ethylene glycol monoethyl ether. Allow the reaction to proceed at 0-20°C until the reaction is complete. Once the reaction is complete, solvent A with strong solubility is obtained.

[0007] Step 2: Add 5-10 parts sodium metabisulfite and 2.5-5 parts zinc sulfate to solvent A prepared in step 1, heat to 80-100℃ to induce a catalytic reaction, and stop heating after all the solid has dissolved to obtain solution B.

[0008] Step 3: Add 3-5 parts of sodium hydroxide to solution B obtained in step 2, stir evenly, and then rapidly cool to -20 to 0℃. During the cooling process, solids precipitate out. Filter, collect the solids, and repeatedly wash the solids with deionized water to obtain a mixed flotation modifier for copper-lead-zinc ore containing secondary copper sulfide.

[0009] Preferably, the rapid cooling time in step 3 is 10-20 minutes.

[0010] The reaction in step 1 of this invention is carried out in the organic solvent ethylene glycol monoethyl ether, which reduces the intensity of the reaction and increases its safety. The solvent A prepared in step 1 has the molecular formula (NH2)2C6H8(N2O2)2 and is a colorless crystal readily soluble in water. The chemical equation for the reaction in step 1 is as follows:

[0011] C6H 12 N4+Fe(NO3)2→(NH2)2C6H8(N2O2)2(1)

[0012] The chemical equation for step 2 is:

[0013] (NH2)2C6H8(N2O2)2+ZnSO4+Na2S2O5→Na2S2O 5• (NH2)2C6H8(N2O2)2+(NH2)2C6H8(N2O2) 2• ZnSO4(2)

[0014] Solution B prepared in step 2 is a mixture of two substances, both of which readily react with alkali.

[0015] The chemical equation for step 3 is:

[0016] Na2S2O 5• (NH2)2C6H8(N2O2)2+(NH2)2C6H8(N2O2) 2• ZnSO4 + NaOH → (NH2)2C6H8(N2O2) 2• Zn(OH)₂ + Na₂SO₄ 3• (NH2)2C6H8(N2O2)2+Na2SO4 (3)

[0017] The modifier prepared in this invention is (NH2)2C6H8(N2O2). 2• Zn(OH)₂ and Na₂SO₄ 3• A mixture of (NH2)2C6H8(N2O2)2 is formed, and the proportions of the two components vary depending on the reaction conditions; both are inhibitors. The resulting modifier is a white granular solid, soluble in water, and rapidly complexes with zinc ions in water to form (NH2)2C6H8(N2O2). 2• ZnO2 and ZnSO 3• The (NH2)2C6H8(N2O2)2 colloidal compound adheres to the surface of sphalerite, thereby blocking the activation of zinc by copper ions and the collection of zinc by the collector, while increasing the hydrophilicity of the sphalerite surface to effectively inhibit zinc.

[0018] The modifier prepared by this invention can effectively reduce the mutual inclusion of copper, lead and zinc in partial mixed flotation, improve the separation efficiency of copper and lead with zinc and copper with lead, thereby improving resource utilization efficiency.

[0019] The modifier prepared by this invention has a good inhibitory effect on zinc, the preparation method is simple, the price is reasonable, and it has a wide range of application prospects. Detailed Implementation

[0020] Example 1

[0021] A method for preparing a partially mixed flotation modifier for copper-lead-zinc ore containing secondary copper sulfide includes the following steps: the amount of compound added in each step is based on parts by weight.

[0022] Step 1: Add 2.5 parts hexamethylenetetramine and 1 part ferrous nitrate to 7 parts organic solvent ethylene glycol monoethyl ether. Allow the reaction to proceed at 10°C until complete. After the reaction is complete, solvent A with strong solubility is obtained.

[0023] Step 2: Add 4.5 parts zinc sulfate and 3.5 parts ferrous ammonium sulfate catalyst to solvent A prepared in step 1, heat to 85°C, and stop heating after all the solids have dissolved to obtain solution B;

[0024] Step 3: Add 4.5 parts of sodium hydroxide to solution B obtained in step 2, stir evenly, and then rapidly cool to -10°C within 10 minutes. During the cooling process, solids precipitate out. Filter, collect the solids, and repeatedly wash the solids with deionized water to obtain a mixed flotation modifier for copper-lead-zinc ore containing secondary copper sulfide, code-named modifier G102.

[0025] The modifier G102 prepared in this embodiment was applied to a partial mixed flotation process for a copper-lead-zinc polymetallic ore in Shaanxi Province. Analysis showed that the ore had a copper grade of 0.62%, a lead grade of 1.19%, and a zinc grade of 4.55%. The secondary copper content in the copper was 26.45%, the lead was present as galena, and the zinc as sphalerite. The final closed-circuit parameters are shown in Table 1.

[0026] Table 1

[0027]

[0028] Example 2

[0029] A method for preparing a partially mixed flotation modifier for copper-lead-zinc ore containing secondary copper sulfide includes the following steps: the amount of compound added in each step is based on parts by weight.

[0030] Step 1: Add 3 parts hexamethylenetetramine and 1.5 parts ferrous nitrate to 5 parts organic solvent ethylene glycol monoethyl ether. Allow the reaction to proceed at 20°C until complete. After the reaction is complete, solvent A with strong solubility is obtained.

[0031] Step 2: Add 10 parts sodium metabisulfite, 3 parts zinc sulfate, and 4 parts ferrous ammonium sulfate catalyst to solvent A prepared in step 1. Heat to 90°C and stop heating after all the solids have dissolved to obtain solution B.

[0032] Step 3: Add 3 parts of sodium hydroxide to solution B obtained in step 2, stir evenly, and then rapidly cool to -20°C within 15 minutes. During the cooling process, solids precipitate out. Filter, collect the solids, and repeatedly wash the solids with deionized water to obtain a mixed flotation modifier for copper-lead-zinc ore containing secondary copper sulfide, code-named modifier G212.

[0033] The modifier G212 prepared in this embodiment was applied to a partial mixed flotation process for a copper-lead-zinc polymetallic ore in Gansu Province. Testing revealed that the ore contained 0.69% copper, 1.54% lead, and 4.42% zinc. Secondary copper content in the copper was 28.96%, lead existed as galena, and zinc as sphalerite. The final closed-circuit parameters are shown in Table 2.

[0034] Table 2

[0035]

[0036] Example 3

[0037] A method for preparing a partially mixed flotation modifier for copper-lead-zinc ore containing secondary copper sulfide includes the following steps: the amount of compound added in each step is based on parts by weight.

[0038] Step 1: Add 5 parts hexamethylenetetramine and 2 parts ferrous nitrate to 6 parts organic solvent ethylene glycol monoethyl ether. Allow the reaction to proceed at 15°C until complete. After the reaction is complete, solvent A with strong solubility is obtained.

[0039] Step 2: Add 7 parts sodium metabisulfite, 5 parts zinc sulfate, and 4 parts ferrous ammonium sulfate catalyst to solvent A prepared in step 1. Heat to 100°C and stop heating after all the solids have dissolved to obtain solution B.

[0040] Step 3: Add 5 parts of sodium hydroxide to solution B obtained in step 2, stir evenly, and then rapidly cool to -15°C within 20 minutes. During the cooling process, solids precipitate out. Filter, collect the solids, and repeatedly wash the solids with deionized water to obtain a mixed flotation modifier for copper-lead-zinc ore containing secondary copper sulfide, code-named modifier G219.

[0041] The modifier G219 prepared in this embodiment was applied to a partial mixed flotation process for a copper-lead-zinc polymetallic ore from abroad. This ore has a copper grade of 0.55%, a lead grade of 1.26%, and a zinc grade of 4.81%. The secondary copper content in the copper is 24.78%, the lead is mainly in the form of galena, and the zinc is in the form of sphalerite. The final closed-circuit parameters are shown in Table 3.

[0042] Table 3

[0043]

[0044] Example 4

[0045] A method for preparing a partially mixed flotation modifier for copper-lead-zinc ore containing secondary copper sulfide includes the following steps: the amount of compound added in each step is based on parts by weight.

[0046] Step 1: Add 1 part hexamethylenetetramine and 1.8 parts ferrous nitrate to 10 parts organic solvent ethylene glycol monoethyl ether. Allow the reaction to proceed at 0°C until complete. After the reaction is complete, solvent A with strong solubility is obtained.

[0047] Step 2: Add 8 parts sodium metabisulfite, 5 parts sodium metabisulfite, 2.5 parts zinc sulfate, and 3 parts ferrous ammonium sulfate catalyst to solvent A prepared in step 1. Heat to 80°C and stop heating after all the solids have dissolved to obtain solution B.

[0048] Step 3: Add 4 parts of sodium hydroxide to solution B obtained in step 2, stir evenly, and then rapidly cool to 0°C within 15 minutes. During the cooling process, solids precipitate out. Filter, collect the solids, and repeatedly wash the solids with deionized water to obtain a mixed flotation modifier for copper-lead-zinc ore containing secondary copper sulfide, code-named modifier G215.

[0049] The modifier 215 prepared in this embodiment was applied to a partial mixed flotation process for a copper-lead-zinc polymetallic ore in Gansu Province. This ore has a copper grade of 0.49%, a lead grade of 1.32%, and a zinc grade of 4.51%. The secondary copper content in the copper is 23.92%, the lead is mainly in the form of galena, and the zinc is in the form of sphalerite. The final closed-circuit parameters are shown in Table 4.

[0050] Table 4

[0051]

[0052] This invention utilizes organic and inorganic substances to generate a modifier with excellent inhibitory effect on zinc through nitration and catalytic reactions. When copper-lead-zinc ore containing secondary copper sulfide undergoes partial mixed flotation, the modifier prepared in this invention is added. The modifier rapidly reacts with the copper-lead-zinc ore containing secondary copper sulfide, generating a colloidal-like peptide. This peptide adheres to the surface of the ore, preventing the ore from undergoing activation reactions with secondary copper ions and adsorption reactions with the collectors used in partial mixed flotation. At this point, the ore exhibits strong hydrophilicity, which is strongly inhibited.

Claims

1. A method for preparing a partially mixed flotation modifier for copper-lead-zinc ore containing secondary copper sulfide, characterized in that: Includes the following steps: The amount of compound added in each step is based on parts by weight. Step 1: Add 1-5 parts of hexamethylenetetramine and 1-2 parts of ferrous nitrate to 5-10 parts of the organic solvent ethylene glycol monoethyl ether. Allow the reaction to proceed at 0-20°C until the reaction is complete. Solvent A, which has strong solubility, is obtained. Step 2: Add 5-10 parts sodium metabisulfite, 2.5-5 parts zinc sulfate, and 3-5 parts ferrous ammonium sulfate catalyst to solvent A prepared in step 1. Heat to 80-100℃ and stop heating after all the solids have dissolved to obtain solution B. Step 3: Add 3-5 parts of sodium hydroxide to solution B obtained in step 2, stir evenly, and then rapidly cool to -20 to 0℃. During the cooling process, solids precipitate out. Filter, collect the solids, and repeatedly wash the solids with deionized water to obtain a mixed flotation modifier for copper-lead-zinc ore containing secondary copper sulfide.

2. The method for preparing the modifier according to claim 1, characterized in that: The rapid cooling time in step 3 is 10-20 minutes.

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