Method for recovering cobalt and nickel from tungsten smelting tailings

Abstract

The method comprises the following steps that tungsten slag and dilute acid are mixed to obtain mixed slurry, the mixed slurry is added into high-temperature and high-pressure equipment to be subjected to a high-temperature and high-pressure reaction, a high-temperature and high-pressure reaction product is obtained, the high-temperature and high-pressure reaction product is subjected to solid-liquid separation, and a cobalt-nickel solution and solid waste residues are obtained. The tungsten slag is mixed with dilute acid, so that metal elements such as cobalt and nickel in the tungsten slag react with acid and are converted into soluble metal ions, the activity of the acid is improved under the high-temperature and high-pressure conditions, the reaction of the acid with cobalt and nickel is promoted, dissolution of cobalt and nickel is facilitated, and the recovery rate of cobalt and nickel reaches 85% or above.

Description

Technical Field

[0001] The invention relates to the technical field of conversion and utilization of waste cemented carbide resources, and more specifically, to a method for recovering cobalt and nickel from tungsten smelting tailings. Background Art

[0002] Tungsten smelting tailings are the solid waste remaining after the smelting process of tungsten ore. Tungsten smelting tailings contain a certain amount of valuable metal elements. Recycling them through certain technical means can not only improve resource utilization, but also reduce environmental pollution.

[0003] For tungsten slag containing metal elements such as cobalt and nickel, the existing technology uses acid leaching to recover cobalt and nickel. However, conventional acid leaching consumes a large amount of acid and the recovery rate is about 60%, which makes it difficult to achieve a good cobalt and nickel recovery effect.

[0004] Therefore, there is an urgent need to provide a method for recovering cobalt and nickel from tungsten smelting tailings to improve the recovery efficiency of cobalt and nickel. Summary of the invention

[0005] The purpose of the present invention is to overcome the above-mentioned defects of the prior art and provide a method for recovering cobalt and nickel from tungsten smelting tailings, comprising the following steps:

[0006] A method for recovering cobalt and nickel from tungsten smelting tailings, characterized in that it comprises the following steps:

[0007] (1) mixing tungsten slag with dilute acid to obtain a mixed slurry;

[0008] (2) adding the mixed slurry into a high temperature and high pressure device to carry out a high temperature and high pressure reaction to obtain a high temperature and high pressure reaction product;

[0009] (3) subjecting the high temperature and high pressure reaction product to solid-liquid separation to obtain a cobalt-nickel solution and solid waste residue.

[0010] Implementing the embodiments of the present invention will have the following beneficial effects:

[0011] In this embodiment, tungsten slag is mixed with dilute acid to obtain a mixed slurry; the mixed slurry is added to a high temperature and high pressure device for reaction, and the high temperature and high pressure reaction product is subjected to solid-liquid separation to obtain a cobalt-nickel solution and solid waste slag. The tungsten slag is mixed with dilute acid so that metal elements such as cobalt and nickel in the tungsten slag react with the acid and are converted into soluble metal ions. The activity of the acid is increased under high temperature and high pressure conditions, which promotes the reaction between the acid and cobalt and nickel, helps dissolve cobalt and nickel, and the recovery rate of cobalt and nickel reaches more than 85%. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0013] in:

[0014] Figure 1 A flow chart of a method for recovering cobalt and nickel from tungsten smelting tailings provided by the present invention. DETAILED DESCRIPTION

[0015] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0016] Reference Figure 1 The present invention discloses a method for recovering cobalt and nickel from tungsten smelting tailings, comprising the following steps:

[0017] (1) Mix tungsten slag with dilute acid to obtain a mixed slurry.

[0018] The tungsten slag is mixed with dilute acid to make the metal elements such as cobalt and nickel in the tungsten slag react with the acid and transform into soluble metal ions.

[0019] Furthermore, before the tungsten slag is mixed with the dilute acid, the tungsten slag is dried and crushed; the drying process can be carried out by hot air drying or drying equipment (such as drying furnace, dryer, etc.), and the tungsten slag is placed in the drying equipment, and the moisture and oil therein are removed by heating and ventilation to prevent affecting the treatment effect. The crushing process can be carried out by crushing equipment (such as crusher, ball mill, etc.), and the particle size of the dried tungsten waste cobalt-nickel tungsten slag is reduced to make it easier to separate and purify it in the subsequent recovery of metal elements such as cobalt and nickel; the particle size of the tungsten slag is not less than 200 mesh.

[0020] Furthermore, the cobalt oxide content in the tungsten slag is 4wt%-6wt%, and the nickel oxide content is 2wt%-3wt%.

[0021] Furthermore, the mass ratio of the dilute acid to the tungsten slag is 2.5-3:1.

[0022] Further, the dilute acid includes one or more of dilute hydrochloric acid, dilute sulfuric acid, dilute nitric acid and dilute phosphoric acid. The concentration of the dilute acid is 1 mol / L-2 mol / L.

[0023] (2) adding the mixed slurry to a high temperature and high pressure device for reaction, performing a high temperature and high pressure reaction, and obtaining a high temperature and high pressure reaction product;

[0024] Furthermore, the reaction temperature is 150°C-200°C; the reaction pressure is 0.5Mpa-1.9Mpa; and the reaction time is 4h-6h. Under high temperature and high pressure conditions, the activity of the acid is increased, and the reaction between the acid and cobalt nickel is promoted, which helps the dissolution of cobalt nickel. When the temperature is less than 150°C, high-priced cobalt nickel is difficult to dissolve in dilute acid; when the temperature is greater than 200°C, the loss of reaction equipment is accelerated.

[0025] Furthermore, the high temperature and high pressure equipment includes a high pressure reactor.

[0026] (3) The high temperature and high pressure reaction products are subjected to solid-liquid separation to obtain a cobalt-nickel solution and solid waste residue.

[0027] The high temperature and high pressure reaction product is a solid-liquid mixture, which is separated by filtration or centrifugation to obtain a cobalt-nickel solution and solid waste residue. The cobalt-nickel solution mainly contains an enriched solution of metal ions such as cobalt and nickel, while the solid waste residue is mainly an enriched slag of tungsten.

[0028] Furthermore, the cobalt-nickel solution can be further processed, such as precipitation, extraction, electrolysis, etc., to recover metal elements such as cobalt and nickel. The solid waste residue can be recycled or processed to recover the tungsten element.

[0029] It can be understood that in this embodiment, tungsten slag is mixed with dilute acid to obtain a mixed slurry, the mixed slurry is added to a high temperature and high pressure device for reaction, and then solid-liquid separation is performed to obtain a cobalt-nickel solution and solid waste slag; the high temperature and high pressure conditions increase the activity of the acid, promote the reaction between the acid and cobalt and nickel, and help the dissolution of cobalt and nickel, and the cobalt-nickel recovery rate reaches more than 85%. Specific embodiment:

[0031] Embodiment 1:

[0032] (1) 100 g of tungsten slag is mixed with 300 ml of dilute hydrochloric acid to obtain a mixed slurry. The cobalt oxide content of the tungsten slag is 4.5 wt%, the nickel oxide content is 2.8 wt%, and the concentration of the dilute hydrochloric acid is 1.2 mol / L.

[0033] (2) The mixed slurry is added into a high-pressure reactor for reaction at a reaction temperature of 150° C., a reaction pressure of 0.5 MPa, and a reaction time of 5 h to obtain a high-temperature and high-pressure reaction product.

[0034] (3) Filtering the high temperature and high pressure reaction product to obtain a cobalt-nickel solution and solid waste residue.

[0035] Embodiment 2:

[0036] (1) 100 g of tungsten slag is mixed with 300 ml of dilute hydrochloric acid to obtain a mixed slurry. The cobalt oxide content of the tungsten slag is 4.5 wt%, the nickel oxide content is 2.8 wt%, and the concentration of the dilute hydrochloric acid is 1.2 mol / L.

[0037] (2) The mixed slurry is added into a high-pressure reactor for reaction at a reaction temperature of 175° C., a reaction pressure of 0.9 MPa, and a reaction time of 5 h to obtain a high-temperature and high-pressure reaction product.

[0038] (3) Filtering the high temperature and high pressure reaction product to obtain a cobalt-nickel solution and solid waste residue.

[0039] Embodiment 3:

[0040] (1) 100 g of tungsten slag is mixed with 300 ml of dilute hydrochloric acid to obtain a mixed slurry. The cobalt oxide content of the tungsten slag is 4.5 wt%, the nickel oxide content is 2.8 wt%, and the concentration of the dilute hydrochloric acid is 1.2 mol / L.

[0041] (2) The mixed slurry is added into a high-pressure reactor for reaction at a reaction temperature of 200° C., a reaction pressure of 1.9 MPa, and a reaction time of 5 h to obtain a high-temperature and high-pressure reaction product.

[0042] (3) Filtering the high temperature and high pressure reaction product to obtain a cobalt-nickel solution and solid waste residue.

[0043] Comparative Example 1:

[0044] (1) 100 g of tungsten slag is mixed with 300 ml of dilute hydrochloric acid to obtain a mixed slurry. The cobalt oxide content of the tungsten slag is 4.5 wt%, the nickel oxide content is 2.8 wt%, and the concentration of the dilute hydrochloric acid is 1.2 mol / L.

[0045] (2) Filter the mixed slurry to obtain a cobalt-nickel solution and solid waste residue.

[0046] Comparative Example 2:

[0047] (1) mixing tungsten slag with dilute acid to obtain a mixed slurry;

[0048] (2) adding the mixed slurry to a high-pressure reactor for reaction at a reaction temperature of 110° C., a reaction pressure of 0.5 MPa, and a reaction time of 5 h to obtain a high-temperature and high-pressure reaction product;

[0049] (3) The mixed slurry after the reaction is subjected to solid-liquid separation to obtain a cobalt-nickel solution and solid waste residue.

[0050] Comparative Example 3:

[0051] (1) mixing tungsten slag with dilute acid to obtain a mixed slurry;

[0052] (2) Add the mixed slurry into a high-pressure reactor for reaction at a reaction temperature of 150° C., a reaction pressure of 0.5 MPa, and a reaction time of 2 h;

[0053] (3) The mixed slurry after the reaction is subjected to solid-liquid separation to obtain a cobalt-nickel solution and solid waste residue.

[0054] Table 1: Cobalt and nickel dissolution rates of Examples 1-3 and Comparative Examples 1-3

[0055] Cobalt and nickel dissolution rate Example 1 85％ Example 2 86％ Example 3 87％ Comparative Example 1 59％ Comparative Example 2 66％ Comparative Example 3 62％

[0056] As shown in Table 1, in Examples 1-3, by adding the mixed slurry to a high-pressure reactor for reaction, the high temperature and high pressure conditions increased the dissolution rate of cobalt and nickel, and the dissolution rate of cobalt and nickel reached more than 85%. Comparative Example 1 did not adopt high temperature and high pressure reaction, and the dissolution rate of cobalt and nickel was significantly reduced. In Comparative Example 2, the reaction temperature was too low, and the high-priced cobalt and nickel were difficult to dissolve in dilute acid, resulting in a decrease in the dissolution rate of cobalt and nickel. In Comparative Example 3, the reaction time was too short, and the cobalt and nickel did not react completely, resulting in a decrease in the dissolution rate of cobalt and nickel.

[0057] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the patent application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for recovering cobalt and nickel from tungsten smelting tailings, characterized in that: The following steps are involved: (1) mixing tungsten slag with dilute acid to obtain a mixed slurry; (2) adding the mixed slurry into a high temperature and high pressure device to carry out a high temperature and high pressure reaction to obtain a high temperature and high pressure reaction product; (3) subjecting the high temperature and high pressure reaction product to solid-liquid separation to obtain a cobalt-nickel solution and solid waste residue.

2. The method for recovering cobalt and nickel from tungsten smelting tailings according to claim 1, characterized in that: The temperature of the high temperature and high pressure reaction is 150°C-200°C.

3. The method for recovering cobalt and nickel from tungsten smelting tailings according to claim 2, characterized in that: The pressure of the high temperature and high pressure reaction is 0.5Mpa-1.9Mpa.

4. The method for recovering cobalt and nickel from tungsten smelting tailings according to claim 3, characterized in that: The high temperature and high pressure reaction time is 4h-6h.

5. The method for recovering cobalt and nickel from tungsten smelting tailings according to claim 1, characterized in that: The high temperature and high pressure equipment includes a high pressure reactor.

6. The method for recovering cobalt and nickel from tungsten smelting tailings according to claim 1, characterized in that: The mass ratio of the dilute acid to the tungsten slag is 2.5-3:

1.

7. The method for recovering cobalt and nickel from tungsten smelting tailings according to claim 6, characterized in that The cobalt oxide content in the tungsten slag is 4wt%-6wt%, and the nickel oxide content is 2wt%-3wt%.

8. The method for recovering cobalt and nickel from tungsten smelting tailings according to claim 6, characterized in that: The concentration of the dilute acid is 1 mol / L-2 mol / L.

9. The method for recovering cobalt and nickel from tungsten smelting tailings according to claim 1, characterized in that: The dilute acid includes one or more of dilute hydrochloric acid, dilute sulfuric acid, dilute nitric acid and dilute phosphoric acid.

10. The method for recovering cobalt and nickel from tungsten smelting tailings according to claim 1, characterized in that: The particle size of the tungsten slag is not less than 200 meshes.

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