Method for extracting copper and cobalt from copper-cobalt sulfide concentrate step by step

Abstract

The invention relates to a method for extracting copper and cobalt from copper-cobalt sulfide concentrate step by step, which comprises the following steps: placing the copper-cobalt sulfide concentrate in a reaction container, introducing mixed gas, heating and roasting to obtain roasted sand; mixing the roasted product with water for reaction, and carrying out solid-liquid separation to obtain cobalt-containing filtrate and copper-containing filter residues; mixing the copper-containing filter residues with dilute sulphuric acid for size mixing, then adding hydrogen peroxide for reaction, and performing solid-liquid separation to obtain copper-containing filtrate and filter residues; wherein the mixed gas comprises sulfur dioxide and air. According to the method, by reasonably controlling the roasting process conditions of the copper-cobalt sulfide ore, directional phase conversion of copper and cobalt is achieved, and therefore efficient extraction and utilization of valuable metal copper and cobalt are achieved through a wet leaching method.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of extraction metallurgy, and more particularly to a method for stepwise extraction of copper and cobalt from copper-cobalt sulfide concentrate. BACKGROUND

[0002] Copper-cobalt ore is the main source of cobalt, and main copper-cobalt ores include oxidized ore, sulfide ore and mixed ore, etc. For the treatment of copper-cobalt sulfide ore, the smelting process currently adopted is mainly a "roasting-leaching-extraction-electrodeposition" process. After the copper-cobalt sulfide is converted into sulfates or oxides through roasting, a mixed solution of copper sulfate and cobalt sulfate is obtained by water leaching or acid leaching; then, the separation of copper and cobalt is realized through solvent extraction, and the cathode copper is obtained through electrodeposition after further purification of the copper-containing solution. The key of this process lies in the pyro-process of roasting, which directly affects the efficient leaching of copper and cobalt in the subsequent process. If the oxidation is not complete during the roasting process, a small amount of copper and cobalt will still exist in the form of sulfide, which cannot be leached in the subsequent leaching process and causes the loss of valuable metals; if the roasting process is over-oxidized, the cobalt sulfide may be converted into Co3O4, which is difficult to dissolve in water or acid, and thus will remain in the slag in the subsequent leaching process, causing the loss of cobalt.

[0003] Therefore, how to reasonably control the roasting process to realize the efficient extraction and utilization of copper-cobalt resources has become an important problem in the development and utilization of copper-cobalt sulfide ore. SUMMARY

[0004] Based on the above technical problems existing in the prior art, the present application provides a method for stepwise extraction of copper and cobalt from copper-cobalt sulfide concentrate, which realizes the phase directional conversion of copper and cobalt by reasonably controlling the roasting process conditions of copper-cobalt sulfide ore, so as to realize the efficient extraction and utilization of valuable metals copper and cobalt through the method of wet leaching.

[0005] In order to achieve the above purpose, the technical scheme of the present application is as follows:

[0006] A method for stepwise extraction of copper and cobalt from copper-cobalt sulfide concentrate, comprising the following steps:

[0007] S1, placing the copper-cobalt sulfide concentrate in a reaction container, introducing a mixed gas, and heating to perform roasting to obtain roasted sand;

[0008] S2, mixing the roasted sand with water to perform reaction, and performing solid-liquid separation to obtain cobalt-containing filtrate and copper-containing filter residue;

[0009] S3, mixing the copper-containing filter residue with dilute sulfuric acid to perform slurry adjustment, and then adding hydrogen peroxide to perform reaction, and performing solid-liquid separation to obtain copper-containing filtrate and filter residue;

[0010] The mixed gas comprises sulfur dioxide and air.

[0011] In some embodiments, the volume ratio of sulfur dioxide and air in the mixed gas is (1-10):1.

[0012] In some embodiments, the roasting temperature in step S1 is 500-650℃.

[0013] In some embodiments, the roasting time in step S1 is 1-10h.

[0014] In some embodiments, the solid-liquid ratio of the calcined sand and water in step S2 is 1g:(1-10)mL.

[0015] In some embodiments, step S2 specifically comprises: mixing the calcined sand and water, ball milling, and then solid-liquid separation to obtain a cobalt-containing filtrate and a copper-containing filter residue; wherein the ball-to-material ratio is (2-10):1, and the ball milling speed is 50-200rpm.

[0016] In some embodiments, the ball milling time in step S2 is 10-60min.

[0017] In some embodiments, the solid-liquid ratio of the copper-containing filter residue and the dilute sulfuric acid in step S3 is 1g:(1-10)mL.

[0018] In some embodiments, the concentration of the dilute sulfuric acid is 0.05-0.5mol / L.

[0019] In some embodiments, the concentration of the hydrogen peroxide in step S3 is 5-20wt%.

[0020] In some embodiments, the time for adding hydrogen peroxide for reaction in step S3 is 10-60min.

[0021] In some embodiments, the Cu content in the copper cobalt sulfide concentrate in step S1 is ≤20wt%, and the Co content is ≤5wt%; preferably, the Cu content is 5wt%-20wt%, and the Co content is 1wt%-5wt%.

[0022] In some embodiments, the Cu content in the filter residue in step S3 is ≤0.6wt%, and the Co content is ≤0.5wt%.

[0023] Compared with the prior art, the present application has the following advantages:

[0024] The method of the present application realizes the phase directional conversion of copper and cobalt by reasonably controlling the roasting process conditions of copper-cobalt sulfide ore, so as to realize the efficient extraction and utilization of valuable metals copper and cobalt through the method of wet leaching. Unlike the traditional roasting process, the present application converts cobalt into water-soluble sulfate and converts copper into water-insoluble oxide by roasting copper-cobalt sulfide ore under specific process conditions, and at the same time, the copper is left in the form of oxide in the residue after leaching of cobalt sulfate, thereby realizing the efficient leaching of cobalt and the efficient separation of copper and cobalt; then the leaching residue is leached with dilute acid, and the copper sulfate solution obtained can be used for copper electrowinning. The method of the present application can eliminate the traditional extraction process, simplify the production process, and provide a new short process and low cost way for the utilization of copper-cobalt sulfide ore while ensuring the efficient extraction and utilization of copper and cobalt.

[0025] The copper and cobalt in the copper-cobalt sulfide ore are extracted and separated step by step by the method of the present application, without the use of extraction process, which greatly simplifies the process flow and is beneficial to reduce production cost. DETAILED DESCRIPTION

[0026] In the following description, a lot of specific details are set forth in order to provide a thorough understanding of the present application. However, the present application can be practiced in a variety of ways beyond the specific embodiments described and illustrated herein, and it is understood that it can be made with many modifications of form, without departing from the spirit and essential characteristics of the present application. Accordingly, the present application is not limited to the specific embodiments described below.

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0028] The copper-cobalt sulfide concentrate used in the following examples and comparative examples is a copper-cobalt sulfide concentrate produced in Congo (DRC), and the Cu content in the concentrate is 12.77wt%, and the Co content is 3.54wt%.

[0029] Example 1

[0030] The method for stepwise extraction of copper and cobalt from copper-cobalt sulfide concentrate in this example comprises the following steps:

[0031] S1, the copper-cobalt sulfide concentrate is loaded into a porcelain boat and placed in a tube furnace, and a mixed gas of sulfur dioxide and air is introduced at a volume ratio of V SO2 :V 空气 = 9:1, and roasting is carried out at a temperature of 600℃ for 10h, and the roasted sand is obtained after cooling in the furnace;

[0032] S2, the calcine obtained in step S1 is added to a drum ball mill, water is added at a ratio of 10 ml of water: 1 g of calcine, the ball-to-material ratio is controlled to be 10:1, the rotation speed is 100 rpm, after grinding for 60 min, solid-liquid separation is performed, to obtain a cobalt-containing filtrate and a copper-containing filter residue;

[0033] S3, the copper-containing filter residue obtained in step S2 is added to a beaker, 0.5 mol / L dilute sulfuric acid is added at a ratio of 10 mL of dilute sulfuric acid: 1 g of copper-containing filter residue for stirring and slurry preparation, after 50 min of reaction with 15 wt% hydrogen peroxide, solid-liquid separation is performed, to obtain a copper-containing filtrate and a filter residue.

[0034] Example 2

[0035] The method for step-by-step extraction of copper and cobalt from copper-cobalt sulfide concentrate in this example includes the following steps:

[0036] S1, the copper-cobalt sulfide concentrate is loaded into a porcelain boat and placed in a tube furnace, a mixed gas of sulfur dioxide and air is passed at a volume ratio V SO2 :V 空气 = 5:1, calcination is performed at a temperature of 600°C for 10 h, and the calcine is obtained after cooling in the furnace;

[0037] S2, the calcine obtained in step S1 is added to a drum ball mill, water is added at a ratio of 10 ml of water: 1 g of calcine, the ball-to-material ratio is controlled to be 10:1, the rotation speed is 100 rpm, after grinding for 60 min, solid-liquid separation is performed, to obtain a cobalt-containing filtrate and a copper-containing filter residue;

[0038] S3, the copper-containing filter residue obtained in step S2 is added to a beaker, 0.05 mol / L dilute sulfuric acid is added at a ratio of 10 mL of dilute sulfuric acid: 1 g of copper-containing filter residue for stirring and slurry preparation, after 50 min of reaction with 15 wt% hydrogen peroxide, solid-liquid separation is performed, to obtain a copper-containing filtrate and a filter residue.

[0039] Example 3

[0040] The method for step-by-step extraction of copper and cobalt from copper-cobalt sulfide concentrate in this example includes the following steps:

[0041] S1, the copper-cobalt sulfide concentrate is loaded into a porcelain boat and placed in a tube furnace, a mixed gas of sulfur dioxide and air is passed at a volume ratio V SO2 :V 空气 = 2:1, calcination is performed at a temperature of 600°C for 10 h, and the calcine is obtained after cooling in the furnace;

[0042] S2, the calcine obtained in step S1 is added to a drum ball mill, water is added at a ratio of 10 ml of water: 1 g of calcine, the ball-to-material ratio is controlled to be 10:1, the rotation speed is 100 rpm, after grinding for 60 min, solid-liquid separation is performed, to obtain a cobalt-containing filtrate and a copper-containing filter residue;

[0043] S3, the copper-containing filter residue obtained in step S2 is added into a beaker, 10 mL of dilute sulfuric acid: 1 g of copper-containing filter residue is added to dilute sulfuric acid with a concentration of 0.1 mol / L for stirring and slurry preparation, then 15wt% hydrogen peroxide is added for reaction for 50 min, followed by solid-liquid separation to obtain a copper-containing filtrate and filter residue.

[0044] Example 4

[0045] The method for step-by-step extraction of copper and cobalt from copper-cobalt sulfide concentrate in this example comprises the following steps:

[0046] S1, the copper-cobalt sulfide concentrate is loaded into a porcelain boat and placed in a tube furnace, a mixed gas of sulfur dioxide and air is passed in at a volume ratio V SO2 :V 空气 = 9:1 at a temperature of 500°C for 10 h, and the roasted sand is obtained after cooling in the furnace;

[0047] S2, the roasted sand obtained in step S1 is added to a roller ball mill, water is added at a ratio of 10 ml of water: 1 g of roasted sand, the ball-to-material ratio is controlled to be 10:1, the rotation speed is 100 rpm, and after grinding for 60 min, solid-liquid separation is performed to obtain a cobalt-containing filtrate and a copper-containing filter residue;

[0048] S3, the copper-containing filter residue obtained in step S2 is added into a beaker, 10 mL of dilute sulfuric acid: 1 g of copper-containing filter residue is added to dilute sulfuric acid with a concentration of 0.1 mol / L for stirring and slurry preparation, then 15wt% hydrogen peroxide is added for reaction for 50 min, followed by solid-liquid separation to obtain a copper-containing filtrate and filter residue.

[0049] Example 5

[0050] The method for step-by-step extraction of copper and cobalt from copper-cobalt sulfide concentrate in this example comprises the following steps:

[0051] S1, the copper-cobalt sulfide concentrate is loaded into a porcelain boat and placed in a tube furnace, a mixed gas of sulfur dioxide and air is passed in at a volume ratio V SO2 :V 空气 = 9:1 at a temperature of 600°C for 10 h, and the roasted sand is obtained after cooling in the furnace;

[0052] S2, the roasted sand obtained in step S1 is added to a roller ball mill, water is added at a ratio of 10 ml of water: 1 g of roasted sand, the ball-to-material ratio is controlled to be 10:1, the rotation speed is 100 rpm, and after grinding for 60 min, solid-liquid separation is performed to obtain a cobalt-containing filtrate and a copper-containing filter residue;

[0053] S3, the copper-containing residue obtained in step S2 is added into a beaker, 10 mL of dilute sulfuric acid is added according to the proportion of 1 g of copper-containing residue, stirring is carried out, and then 15wt% hydrogen peroxide is added for reaction for 50 min, followed by solid-liquid separation, to obtain a copper-containing filtrate and a residue.

[0054] Comparative Example 1

[0055] The method for step-by-step extraction of copper and cobalt from the copper-cobalt sulfide concentrate in the embodiment includes the following steps:

[0056] S1, the copper-cobalt sulfide concentrate is loaded into a porcelain boat and placed in a tube furnace, sulfur dioxide gas is introduced, and roasting is carried out at a temperature of 600℃ for 10 h, and then the furnace is cooled to obtain calcine;

[0057] S2, the calcine obtained in step S1 is added into a roller ball mill, water is added according to the proportion of 10 ml of water to 1 g of calcine, the ball-to-material ratio is controlled to be 10:1, the rotating speed is 100 rpm, and grinding is carried out for 60 min, followed by solid-liquid separation, to obtain a cobalt-containing filtrate and a copper-containing residue;

[0058] S3, the copper-containing residue obtained in step S2 is added into a beaker, 10 mL of dilute sulfuric acid is added according to the proportion of 1 g of copper-containing residue, stirring is carried out, and then 15wt% hydrogen peroxide is added for reaction for 50 min, followed by solid-liquid separation, to obtain a copper-containing filtrate and a residue.

[0059] Comparative Example 2

[0060] The method for step-by-step extraction of copper and cobalt from the copper-cobalt sulfide concentrate in the embodiment includes the following steps:

[0061] S1, the copper-cobalt sulfide concentrate is loaded into a porcelain boat and placed in a tube furnace, air is introduced, and roasting is carried out at a temperature of 600℃ for 10 h, and then the furnace is cooled to obtain calcine;

[0062] S2, the calcine obtained in step S1 is added into a roller ball mill, water is added according to the proportion of 10 ml of water to 1 g of calcine, the ball-to-material ratio is controlled to be 10:1, the rotating speed is 100 rpm, and grinding is carried out for 60 min, followed by solid-liquid separation, to obtain a cobalt-containing filtrate and a copper-containing residue;

[0063] S3, the copper-containing residue obtained in step S2 is added into a beaker, 10 mL of dilute sulfuric acid is added according to the proportion of 1 g of copper-containing residue, stirring is carried out, and then 15wt% hydrogen peroxide is added for reaction for 50 min, followed by solid-liquid separation, to obtain a copper-containing filtrate and a residue.

[0064] It is detected that the leaching effects of Examples 1-5 and Comparative Examples 1-2 are shown in Table 1.

[0065] Table 1 Leaching effect of Examples 1-5 and Comparative Examples 1-2

[0066]

[0067] The technical features of the above-described embodiments can be combined in any manner. For the sake of brevity, not all possible combinations are described, but it is understood that the scope of the present specification includes all possible combinations.

[0068] The above-described embodiments are merely representative of several embodiments of the present application, and the description is relatively specific and detailed, but should not be construed as limiting the scope of the application. It should be noted that, for those skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are all within the scope of the present application. Therefore, the scope of the present application should be subject to the appended claims.

Claims

1. A process for the stepwise extraction of copper and cobalt from a copper cobalt sulphide concentrate, characterised in that, The method comprises the following steps: S1, placing copper cobalt sulfide concentrate in a reaction container, passing mixed gas, heating and roasting to obtain calcine; S2, mixing the calcine with water to react, solid-liquid separation, to obtain cobalt-containing filtrate and copper-containing residue; S3, mixing the copper-containing residue with dilute sulfuric acid to adjust the pulp, then adding hydrogen peroxide to react, solid-liquid separation, to obtain copper-containing filtrate and residue; The mixed gas comprises sulfur dioxide and air.

2. The process for the stepwise extraction of copper and cobalt from copper cobalt sulphide concentrates according to claim 1, characterized in that, The volume ratio of sulfur dioxide to air in the mixed gas is (1-10):

1.

3. The process for the stepwise extraction of copper and cobalt from copper cobalt sulphide concentrates as claimed in claim 1, wherein, In step S1, the roasting temperature is 500-650℃.

4. The process for the stepwise extraction of copper and cobalt from copper cobalt sulphide concentrates as claimed in claim 1, wherein, In step S2, the solid-liquid ratio of the calcine to water is 1g:(1-10)mL.

5. The process for the stepwise extraction of copper and cobalt from copper cobalt sulphide concentrates as claimed in claim 1, wherein, In step S3, the solid-liquid ratio of the copper-containing residue to the dilute sulfuric acid is 1g:(1-10)mL.

6. The process for the stepwise extraction of copper and cobalt from copper cobalt sulphide concentrates as claimed in claim 1, wherein, In step S3, the concentration of the hydrogen peroxide is 5-20wt%.

7. The process for the stepwise extraction of copper and cobalt from copper cobalt sulphide concentrates as claimed in claim 1, wherein, In step S2, the calcine and water are mixed and ball milled, then solid-liquid separation is performed to obtain cobalt-containing filtrate and copper-containing residue; wherein the ball-to-material ratio is (2-10):1, and the ball milling speed is 50-200rpm.

8. The process for the stepwise extraction of copper and cobalt from copper-cobalt sulfide concentrates according to any one of claims 1 to 7, characterized in that, In step S1, the Cu content in the copper cobalt sulfide concentrate is ≤20wt%, and the Co content is ≤5wt%.

9. The process for the stepwise extraction of copper and cobalt from copper-cobalt sulfide concentrates according to any one of claims 1 to 7, characterized in that, In step S3, the Cu content in the residue is ≤0.6wt%, and the Co content is ≤0.5wt%.

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