CN116219197A

CN116219197A - Leaching method of intermediate product of cobalt or nickel

Info

Publication number: CN116219197A
Application number: CN202211641626.1A
Authority: CN
Inventors: 崔俊; 肖孝军; 刘文涛; 秦汝勇; 季杨; 王伟
Original assignee: Guangdong Jiana Energy Technology Co Ltd; Qingyuan Jiazhi New Materials Research Institute Co Ltd; Jiangxi Jiana Energy Technology Co Ltd
Current assignee: Guangdong Jiana Energy Technology Co Ltd; Qingyuan Jiazhi New Materials Research Institute Co Ltd; Jiangxi Jiana Energy Technology Co Ltd
Priority date: 2022-12-20
Filing date: 2022-12-20
Publication date: 2023-06-06

Abstract

The invention relates to the technical field of metal recovery, in particular to a leaching method of cobalt or nickel intermediate products. The leaching method of the cobalt or nickel intermediate product comprises the following steps: (A) Mixing cobalt or nickel intermediate with sulfuric acid solution, performing acid leaching, and performing solid-liquid separation to obtain a first leaching solution and a first leaching residue; (B) The first leaching residue is mixed with ferrous sulfate solution and then subjected to reduction leaching, and the second leaching solution and the second leaching residue are obtained through solid-liquid separation; (C) Copper extraction and back extraction are carried out on the second leaching solution to obtain back extraction solution; adding manganese powder into the strip liquor to obtain a manganese sulfate solution and sponge copper; (D) Mixing the second leaching residue with sulfuric acid solution, and then carrying out acid leaching to obtain ferric sulfate solution; and mixing the ferric sulfate solution with copper powder to obtain a ferrous sulfate solution. The leaching method greatly reduces the use of reducing agents, oxidizing agents and neutralizing agents for iron removal, and can realize the efficient leaching of cobalt and nickel intermediate products with low cost.

Description

Leaching method of intermediate product of cobalt or nickel

Technical Field

The invention relates to the technical field of metal recovery, in particular to a leaching method of cobalt or nickel intermediate products.

Background

The cobalt intermediate and the nickel intermediate are prepared by cobalt-nickel industry manufacturers by adopting a rough machining method, raw cobalt-nickel ores are processed into coarse products-cobalt and nickel intermediate products (coarse cobalt hydroxide, coarse nickel hydroxide, coarse cobalt carbonate and coarse nickel carbonate) containing cobalt and nickel, and then cobalt or nickel intermediate products are subjected to fine machining to prepare cobalt and nickel products (nickel sulfate, cobalt chloride and the like) with higher purity. Due to the characteristic of easy oxidation of nickel, cobalt and manganese, part of cobalt, nickel and manganese in the ancient nickel intermediate product can be oxidized to a high valence state in the transportation process, so that a large amount of reducing agent is needed to be used for reducing part of high valence cobalt, nickel and manganese into +2 valence state in the finish machining process, and meanwhile, due to the use of a large amount of reducing agent, impurity Fe is generated ³⁺ Is also reduced to Fe ²⁺ And requires the use of an oxidizing agent to oxidize Fe in subsequent processes ²⁺ Oxidation to Fe ³⁺ To remove impurity Fe. This process results in a large amount of reductant and oxidant usage.

The traditional leaching method of the nickel intermediate product (cobalt intermediate product is the same as the above) comprises the following steps: using sulfuric acid and a reducing agent (sodium metabisulfite, hydrogen peroxide, SO) ₂ ) Returning the nickel intermediate productCrude nickel sulfate solution is obtained by original leaching, and acid leaching slag is obtained. Wherein the acid leaching slag is discharged, and the crude nickel sulfate solution is used for subsequent processing. The crude nickel sulfate solution was treated using copper extraction to obtain a copper depleted nickel sulfate solution from the raffinate outlet and a copper sulfate solution from the strip outlet. Wherein the copper sulfate solution is treated by electrodepositing copper to obtain sulfuric acid solution and cathode copper (sold out), and the sulfuric acid solution and the cathode copper are continuously used for back extraction of copper. The copper-removed liquid is used for subsequent process treatment. And (3) carrying out chemical iron (or iron and aluminum) removal treatment on the copper-removed liquid by using a neutralizer (sodium carbonate) and an oxidant (sodium chlorate and hydrogen peroxide) to obtain iron-removed nickel sulfate liquid and iron slag. And (3) carrying out conventional extraction processes such as P204, P507, C272 and the like on the deironing nickel sulfate solution to obtain a pure nickel sulfate solution product. And (5) discharging iron slag.

In view of this, the present invention has been made.

Disclosure of Invention

The invention aims to provide a leaching method of cobalt or nickel intermediate products, which greatly reduces the use of reducing agents, oxidizing agents and neutralizing agents for iron removal and can realize the efficient leaching of the cobalt and nickel intermediate products with low cost.

In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:

the invention provides a leaching method of cobalt or nickel intermediate, which comprises the following steps:

(A) Mixing cobalt or nickel intermediate with sulfuric acid solution, performing acid leaching, and performing solid-liquid separation to obtain a first leaching solution and a first leaching residue;

(B) The first leaching residue is mixed with ferrous sulfate solution and then subjected to reduction leaching, and the second leaching solution and the second leaching residue are obtained after solid-liquid separation;

(C) Copper extraction and back extraction are carried out on the second leaching solution to obtain back extraction solution; adding manganese powder into the strip liquor to obtain a manganese sulfate solution and sponge copper;

(D) Mixing the second leaching residue with sulfuric acid solution, performing acid leaching, and performing solid-liquid separation to obtain ferric sulfate solution; and mixing the ferric sulfate solution with copper powder to obtain a ferrous sulfate solution.

Further, in the step (A), the pH of the acid leaching is 3 to 7.

Preferably, the pH of the acid leaching is 4.5-6.5.

Preferably, the temperature of the acid leaching is 80-90 ℃.

Further, in the step (B), the pH of the reductive leaching is 1 to 3.

Preferably, the temperature of the reduction leaching is 90-95 ℃.

Further, in the step (B), fe in the ferrous sulfate solution ²⁺ The concentration of (C) is 10-100 g/L.

Preferably, the pH of the ferrous sulfate solution is 0 to 2.

Further, in the step (B), fe in the leaching system of the reduction leaching end point ²⁺ The concentration of (C) is 0.1-10 g/L.

Preferably, in the leaching system of the reduction leaching end point, fe ²⁺ The concentration of (C) is 2-6 g/L.

Further, in the step (B), the final pH value of the reduction leaching is 1-2.

Preferably, the endpoint pH of the reduction leaching is between 1.3 and 1.8.

Further, in the step (C), the total molar concentration of the copper sulfate and the sulfuric acid in the stripping liquid is 1-3 mol/L.

Further, in the step (D), the pH of the acid leaching is 0.8-1.2.

Preferably, the temperature of the acid leaching is 60-70 ℃.

Further, the sponge copper is pickled to obtain copper powder, and the copper powder is used in the step (D) and mixed with ferric sulfate solution.

Further, ferrous sulfate in step (D) is used in step (B), and is mixed with the first leaching residue and subjected to reduction leaching.

Compared with the prior art, the invention has the beneficial effects that:

according to the leaching method of the cobalt or nickel intermediate product, sulfuric acid is adopted to carry out acid leaching on the cobalt or nickel intermediate product to obtain a first leaching solution and a first leaching slag; the concentration of Cu, fe and Al in the first leaching solution is low, and a pure nickel sulfate product can be obtained through a conventional extraction process; the first leaching slag is subjected to reduction leaching by adopting ferrous sulfate solution to obtain second leaching liquid and second leaching slag; copper extraction and back extraction are carried out on the second leaching solution to obtain a copper sulfate solution, and manganese powder is added into the copper sulfate solution to obtain a pure manganese sulfate solution and sponge copper; and (3) adding the acid-washed sponge copper to react after the second leaching slag is dissolved to obtain a ferrous sulfate solution, and returning the ferrous sulfate solution to the reduction leaching step for recycling. In addition to the necessary sulfuric acid, only manganese powder is additionally introduced in the whole leaching process, and a reducing agent and an oxidizing agent are not required to be additionally introduced, so that compared with the traditional leaching method, the use of the reducing agent, the oxidizing agent and the neutralizing agent for iron removal for leaching is greatly saved; the cost is obviously reduced, and the efficient leaching of cobalt or nickel intermediate products can be realized with low cost.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.

Fig. 1 is a flow chart of a leaching method of a nickel intermediate in example 1 of the present invention.

Detailed Description

The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

Referring to fig. 1, a leaching method of a cobalt or nickel intermediate according to an embodiment of the present invention will be described in detail.

(C) Copper extraction and back extraction are carried out on the second leaching solution to obtain back extraction solution; adding manganese powder into the strip liquor to obtain manganese sulfate solution and sponge copper;

In some embodiments of the invention, in step (a), the pH of the acid leach is from 3 to 7; preferably, the pH of the acid leaching is 4.5-6.5; more preferably, the pH of the acid leaching is from 4.5 to 5.5.

In some embodiments of the invention, in step (a), the acid leaching is at a temperature of 80 to 90 ℃.

In some embodiments of the invention, in step (a), the first leach solution is extracted to produce a nickel sulfate solution; preferably, the extractant employed in the extraction process comprises one or more of P204, P507 and C272.

In some embodiments of the invention, in step (a), the cobalt or nickel intermediate comprises one or more of crude hydrogen cobalt oxide, crude nickel hydroxide, crude cobalt carbonate, and crude nickel carbonate.

In the leaching method of the intermediate product of cobalt or nickel, in the step (A), sulfuric acid is used for carrying out acid leaching on the intermediate product of cobalt or nickel, and the pH of the reaction end point is controlled to be 4.5-6.5, so as to obtain a first leaching solution (leached nickel sulfate solution) and a first leaching slag. Wherein, the leached nickel sulfate solution can be directly subjected to conventional extraction processes such as P204, P507, C272 and the like to obtain a pure nickel sulfate solution product. And the content of Cu, fe and Al in the leached nickel sulfate solution is lower due to the control of the end point pH value and is far lower than that of the conventional iron-removed nickel sulfate solution.

In some embodiments of the invention, in step (B), the pH of the reductive leaching is from 1 to 3; preferably, the pH of the reduction leaching is between 1.3 and 1.8.

In some embodiments of the invention, in step (B), the temperature of the reductive leaching is from 90 to 95 ℃.

In some embodiments of the invention, in step (B), the ferrous sulfate solution, fe ²⁺ The concentration of (2) is 10-100 g/L; preferably, in the ferrous sulfate solution, fe ²⁺ The concentration of (C) is 50-80 g/L.

In some embodiments of the invention, in step (B), the pH of the ferrous sulfate solution is from 0 to 2; preferably, the pH of the ferrous sulfate solution is 1 to 1.5.

In some embodiments of the invention, in step (B), fe in the leaching system at the endpoint of the reduction leaching ²⁺ The concentration of (2) is 0.1-10 g/L; preferably, in the leaching system of the reduction leaching end point, fe ²⁺ The concentration of (C) is 2-6 g/L.

In some embodiments of the invention, in step (B), the endpoint pH of the reductive leaching is from 1 to 2; preferably, the endpoint pH of the reduction leach is between 1.3 and 1.8.

In the leaching method of cobalt or nickel intermediate, in the step (B), ferrous sulfate solution (ferrous sulfate can be obtained in the step (D) or other ferrous sulfate is adopted) is slowly added into the first leaching slag to carry out reduction leaching, the dosage of the first leaching slag and the ferrous sulfate solution is controlled in the process, the pH value of a reaction system is controlled to be maintained between 1.3 and 1.8, and Fe in the ferrous sulfate solution is reacted ²⁺ Reducing the concentration to 2-6 g/L to obtain a second leaching solution and a second leaching residue; wherein the second leaching slag comprises acid leaching slag and iron slag.

The invention needs to ensure that a certain amount of Fe exists in the solution ²⁺ ，Fe ²⁺ Is the firstReducing agents for reactions with leached residues, e.g. Fe, in the case of the first leached residues ²⁺ No excessive amount, i.e. no Fe in the solution system after reaction ²⁺ The first leaching residue may not completely react, resulting in a large amount of high-valence cobalt, nickel and manganese not being leached completely into the residue, resulting in waste.

In some embodiments of the invention, in step (C), the total molar concentration of copper sulfate and sulfuric acid in the strip liquor is 1 to 3mol/L; preferably, the total molar concentration of the copper sulfate and the sulfuric acid in the stripping liquid is 1.5-2 mol/L. The reverse quenching liquid is copper sulfate solution.

In some embodiments of the invention, in step (C), the raffinate from the copper extraction is returned to step (a) as a base liquid.

In some embodiments of the invention, in step (C), the second leach solution is subjected to copper extraction (4-stage copper extraction, 2-stage water wash) and 2-stage stripping to produce a raffinate and a strip liquor.

In some embodiments of the invention, in step (C), the temperature of the reaction of adding manganese powder to the strip liquor is 50-80 ℃; preferably, the reaction is stopped when the pH of the reaction solution is 3.0 to 5.0 and the Cu content in the reaction solution is not more than 0.002 g/L.

In some embodiments of the invention, in step (C), manganese powder is added to the counter-quench (copper sulfate solution) to obtain a pure manganese sulfate solution and copper sponge. The manganese sulfate solution can be used for preparing ternary precursors (the ternary precursors are produced in the cobalt-nickel industry at present) or are sold outside, and the sponge copper is used for subsequent processing after being pickled.

In some embodiments of the invention, in step (D), the pH of the acid leach is between 0.8 and 1.2.

In some embodiments of the invention, in step (D), the acid leaching is at a temperature of 60 to 70 ℃.

In some embodiments of the invention, the sponge copper is acid washed to provide copper powder, which is used in step (D) and mixed with the ferric sulfate solution.

The copper powder in step (D) may be obtained by pickling sponge copper, or other copper powder may be used.

In some embodiments of the invention, the ferrous sulfate in step (D) is used in step (B) and is mixed with the first leach residue prior to the reductive leach. In the step (D), the ferrous sulfate solution is returned to the step (B) for recycling.

In the whole leaching process, only manganese powder is additionally introduced except necessary sulfuric acid, and a ferrous sulfate solution, copper powder and a neutralizing agent can be prepared by the process without additionally introducing a reducing agent and an oxidizing agent; compared with the traditional leaching method, the method greatly saves the use of reducing agents for leaching, oxidizing agents for removing iron and neutralizing agents for removing iron; the cost is obviously reduced, and the efficient leaching of cobalt or nickel intermediate products can be realized with low cost.

Example 1

Referring to fig. 1, the leaching method of the nickel intermediate provided in this embodiment includes the following steps:

(A) Adding 1500ml of water into a beaker, adding 1000g of nickel intermediate into the beaker, starting stirring, reacting at 80-90 ℃, and adding concentrated sulfuric acid until the pH value of a reaction system is 4.5-5.0; the filtration gave 2000ml of a first leaching solution and 60g of a first leaching residue.

(B) Adding 1000ml of ferrous sulfate (self-made) solution into a beaker, starting stirring, reacting at 90-95 ℃, adding first leaching slag into the beaker, controlling the dosage of the first leaching slag, keeping the pH value of the system at 1.5-2, and reacting until Fe in the ferrous sulfate solution ²⁺ Reducing the weight to 2-6 g/L; filtering to obtain a second leaching solution and a second leaching residue.

(C) Taking 1000ml of second leaching solution, carrying out copper extraction (4-level copper extraction and 2-level water washing) and 2-level back extraction to obtain raffinate and back extraction solution, and returning the raffinate obtained by copper extraction into the step (A) as base solution;

taking 500ml of back extraction solution obtained after back extraction, placing the back extraction solution in a beaker, controlling the reaction temperature to be 70-80 ℃, slowly adding 110g of manganese powder into the back extraction solution, reacting until the pH value of the solution is 3.0-5.0, and filtering to obtain sponge copper and manganese sulfate solution when the Cu content in the solution is below 0.002 g/L;

the sponge copper is washed with sulfuric acid (or reextraction liquid) until the manganese content is 1wt% for subsequent use.

(D) Adding 1000ml of sulfuric acid solution with acidity of 2N into a beaker, adding 200g of second leaching residue into the beaker, controlling the reaction temperature to 60-70 ℃ and reacting until the pH value of the solution is 0.8-1.2; filtering to obtain ferric sulfate solution and acid leaching slag, wherein the acid leaching slag can be directly discharged;

adding 1000ml of ferric sulfate solution into a beaker, 50g of the sponge copper after pickling in the step (C), controlling the reaction temperature to 60-70 ℃, and reacting until the sponge copper is completely dissolved, thereby obtaining ferrous sulfate solution, wherein the ferrous sulfate solution is used for reduction leaching in the step (B).

Example 2

The leaching method of the cobalt intermediate provided in this example is different from that in example 1 only in that the nickel intermediate in step (a) is replaced with a cobalt intermediate.

Test example 1

The ion concentration was measured in each step of example 1, and the results are shown in tables 1, 2, 3, 4 and 5.

TABLE 1

	Ni	Co	Mn	Cu	Fe	Al
							First leaching solution (g/L)	110.8	4.78	4.56	0.026	0.0005	0.001
First leaching residue (wt%)	6.05	5.69	6.89	0.042	0.32	0.16

TABLE 2

	Ni	Co	Mn	Cu	Fe	Al
							Second leachate (g/L)	25.35	11.15	13.5	24.05	2.67	0.21
Second leaching residue (wt%)	0.26	0.09	0.06	0.018	27.24	0.15

TABLE 3 Table 3

	Ni	Co	Mn	Cu	Fe	Al
							Raffinate (g/L)	25.34	11.13	13.6	0.89	2.68	0.23
Back extraction liquid (g/L)	0.005	0.005	0.006	50.98	0.001	0.005

TABLE 4 Table 4

	Ni	Co	Mn	Cu	Fe	Al
							Ferric sulfate solution (g/L)	0.49	0.18	0.11	0.026	50.89	0.21
Acid leaching residue (wt%)	0.06	0.038	0.024	0.002	6.21	0.15

TABLE 5

Test example 2

The ion concentration was measured in each step of example 2, and the results are shown in tables 1, 2, 3, 4 and 5.

TABLE 1

	Co	Ni	Mn	Cu	Fe	Al
							First leaching solution (g/L)	109.5	0.31	5.63	0.024	0.0005	0.0009
First leaching residue (wt%)	12.3	0.03	11.56	0.83	1.68	0.32

TABLE 2

	Co	Ni	Mn	Cu	Fe	Al
							Second leachate (g/L)	58.63	0.15	55.28	3.95	4.25	0.63
Second leaching residue (wt%)	0.07	0.003	0.06	0.07	8.95	0.86

TABLE 3 Table 3

	Co	Ni	Mn	Cu	Fe	Al
							Raffinate (g/L)	58.61	0.12	55.35	0.06	4.21	0.66
Back extraction liquid (g/L)	0.005	0.005	0.006	52.68	0.001	0.005

TABLE 4 Table 4

	Co	Ni	Mn	Cu	Fe	Al
							Ferric sulfate solution (g/L)	0.23	0.35	0.23	0.021	53.89	0.26
Acid leaching residue (wt%)	0.09	0.018	0.024	0.002	4.32	0.12

TABLE 5

	Co	Ni	Mn	Cu	Fe	Al
							Ferrous sulfate solution (g/L)	0.41	0.26	0.09	40.015	60.68	0.39

Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims

1. A method for leaching a cobalt or nickel intermediate product, comprising the steps of:

(C) Copper extraction and back extraction are carried out on the second leaching solution to obtain back extraction solution; adding manganese powder into the strip liquor for reaction to obtain manganese sulfate solution and sponge copper;

2. The method of leaching a cobalt or nickel intermediate according to claim 1, wherein in step (a), the pH of the acid leaching is 3 to 7;

preferably, the pH of the acid leaching is 4.5-6.5;

preferably, the temperature of the acid leaching is 80-90 ℃.

3. The method of leaching a cobalt or nickel intermediate according to claim 1, wherein in step (B), the pH of the reductive leaching is between 1 and 3;

preferably, the temperature of the reduction leaching is 90-95 ℃.

4. The method according to claim 1, wherein in the step (B), fe is contained in the ferrous sulfate solution ²⁺ The concentration of (2) is 10-100 g/L;

preferably, the pH of the ferrous sulfate solution is 0 to 2.

5. The method according to claim 1, wherein in the step (B), fe is contained in the leaching system at the reduction leaching end point ²⁺ The concentration of (2) is 0.1-10 g/L;

6. The method of leaching a cobalt or nickel intermediate according to claim 1, wherein in step (B), the endpoint pH of the reductive leaching is between 1 and 2;

preferably, the endpoint pH of the reduction leaching is between 1.3 and 1.8.

7. The method according to claim 1, wherein in the step (C), the total molar concentration of copper sulfate and sulfuric acid in the strip liquor is 1 to 3mol/L.

8. The method of leaching a cobalt or nickel intermediate according to claim 1, wherein in step (D), the pH of the acid leaching is from 0.8 to 1.2;

preferably, the temperature of the acid leaching is 60-70 ℃.

9. The method of leaching a cobalt or nickel intermediate according to claim 1, wherein the sponge copper is acid washed to provide copper powder, which is used in step (D) and mixed with an iron sulphate solution.

10. The method of leaching a cobalt or nickel intermediate according to claim 1, wherein ferrous sulphate in step (D) is used in step (B) and is mixed with the first leaching residue before being subjected to a reduction leach.