CN115818739A

CN115818739A - Method for preparing nickel sulfate by using high nickel matte

Info

Publication number: CN115818739A
Application number: CN202211657783.1A
Authority: CN
Inventors: 邓海龙; 赵思佳; 肖超; 张日阳; 唐明松; 刘仕
Original assignee: Zhongwei New Materials Co ltd; Guangxi Zhongwei New Energy Technology Co ltd
Current assignee: Zhongwei New Materials Co ltd; Guangxi Zhongwei New Energy Technology Co ltd
Priority date: 2022-12-22
Filing date: 2022-12-22
Publication date: 2023-03-21

Abstract

The application provides a method for preparing nickel sulfate by using high nickel matte, and relates to the field of lithium ion batteries. A method for preparing nickel sulfate using high nickel matte, comprising: carrying out flotation on the high nickel matte to obtain nickel sulfide concentrate and a mixture of nickel oxide and nickel alloy; mixing nickel sulfide concentrate with pyrolusite and sulfuric acid, and carrying out aerobic leaching to obtain a first leaching solution; mixing the mixture of nickel oxide and nickel alloy with sulfuric acid, and leaching under normal pressure to obtain a second leaching solution; mixing the first leaching solution and the second leaching solution with an oxidant for oxidation treatment, then adjusting the pH value for deironing, and carrying out solid-liquid separation to obtain a filtrate; and extracting and deoiling the filtrate to obtain the nickel sulfate. The application provides a method for preparing nickel sulfate by using nickel matte separates nickel sulfide in the nickel matte from nickel oxide and nickel alloy, and the nickel sulfide is leached out simultaneously on two lines, so that the productivity is improved, the tail gas leakage is effectively prevented from polluting, and the operating environment is improved.

Description

Method for preparing nickel sulfate by using high nickel matte

Technical Field

The application relates to the field of lithium ion batteries, in particular to a method for preparing nickel sulfate by using high nickel matte.

Background

In the development of the current ternary battery, the tendency of high nickel is more obvious, and the high nickel is used for replacing part of cobalt to improve the energy density of the battery and reduce the cost of the battery. The high nickel matte is used as a nickel raw material and is a sulfide eutectic of metals such as nickel, copper, cobalt, iron and the like, wherein the nickel, copper and cobalt mainly exist in sulfide phases and a small amount of alloy phases. The leaching rate of the high nickel matte is low by directly adopting a normal pressure leaching method, the consumption of the oxidant is high, and the cost is high. In the prior art, the leaching rate is greatly improved by combining normal pressure with high pressure leaching, but the leaching time in the normal pressure process is long, generally about 20 hours, oxygen needs to be introduced all the time, the production efficiency is low, and hydrogen sulfide gas is generated in the normal pressure leaching process and is not environment-friendly. In addition, high-pressure leaching is needed after atmospheric leaching, which takes longer time, and the total time is more than 25 hours.

How to develop a green and safe process for producing nickel sulfate, overcoming the defects of long time consumption, high energy consumption, large discharge amount of three wastes and the like, becomes a technical problem which needs to be mainly solved by the invention.

Disclosure of Invention

The present application aims to provide a method for preparing nickel sulfate using high nickel matte to solve the above problems.

In order to achieve the purpose, the following technical scheme is adopted in the application:

a method for preparing nickel sulfate using high nickel matte, comprising:

carrying out flotation on the high nickel matte to obtain nickel sulfide concentrate and a mixture of nickel oxide and nickel alloy;

mixing the nickel sulfide concentrate with pyrolusite and sulfuric acid, and carrying out aerobic leaching to obtain a first leaching solution; mixing the mixture of the nickel oxide and the nickel alloy with sulfuric acid to carry out normal pressure leaching to obtain a second leaching solution;

mixing the first leaching solution and the second leaching solution with an oxidant for oxidation treatment, then adjusting the pH value for deironing, and performing solid-liquid separation to obtain a filtrate;

and extracting and deoiling the filtrate to obtain the nickel sulfate.

Preferably, the high nickel matte comprises a pretreatment step before flotation:

drying the high nickel matte, and then crushing and ball milling.

Preferably, the pre-treatment step results in high nickel matte particles that meet at least one of the following conditions:

a. the end point of the drying is that the water content of the material is not higher than 0.5%;

b. the proportion of the high nickel matte particles with the particle size of not more than 38 mu m is not less than 95 percent.

Preferably, the flotation step comprises preparing the high nickel matte into high nickel matte ore pulp, and the concentration of the high nickel matte ore pulp is 25-35 wt%.

Preferably, when the high grade nickel matte ore pulp is prepared, aeration stirring is adopted; the aeration quantity of the aeration stirring is 400-600L/h.

Preferably, the flotation adopts a collector, the collector is at least one of butyl xanthate, butyl ammonium nigride, ethyl xanthate or thiamine ester, and the flotation is carried out in a batch foam scraping mode.

Preferably, the usage amount of the pyrolusite is 30-60% of the mass of the nickel sulfide concentrate.

Preferably, the aerobic leaching is carried out under normal pressure, oxygen is introduced into the system in the process, and the oxygen flow is 1-5L/min.

Preferably, the liquid-solid ratio of the aerobic leaching is (3-6) mL:1g, the initial acid concentration of the aerobic leaching is 2-4mol/L, the temperature of the aerobic leaching is 80-100 ℃, and the time of the aerobic leaching is 3-5h.

Preferably, the atmospheric leaching is carried out at normal temperature, and the liquid-solid ratio is (3-8) mL:1g, the initial acid concentration of the atmospheric leaching is 13.8-18.4mol/L, and the time of the atmospheric leaching is 3-5h.

Preferably, the oxidant comprises one or more of hydrogen peroxide, ozone, oxygen and air;

the dosage of the oxidant is 1.1-1.3 times of the sum of the theoretical amount of ferrous iron in the first leaching solution and the second leaching solution.

Preferably, the method satisfies at least one of the following conditions:

c. during iron removal, the pH value is adjusted to be not less than 6.2; the iron is removed, and the mixture is stirred for 0.5 to 2.5 hours at the temperature of between 60 and 90 ℃;

d. adjusting the pH value by using nickel hydroxide, nickel carbonate or a mixture of the nickel oxide and the nickel alloy;

e. the extraction comprises the following steps: adjusting the pH value of the filtrate to 2.5-4, extracting by using P204, and separating nickel and cobalt from P204 raffinate by using P507;

f. the P204 and the P507 are saponified by ammonia water before use, the saponification rate of the P204 is controlled to be 50-70%, and the saponification rate of the P507 is controlled to be 55-70%; and the P204 is diluted to be 20-30% by volume by using sulfonated kerosene with 72-76% by volume concentration before use.

Compared with the prior art, the beneficial effect of this application includes:

according to the method for preparing nickel sulfate by using nickel matte, nickel sulfide concentrate in the nickel matte and a mixture of nickel oxide and nickel alloy are separated through flotation, and then sulfuric acid leaching is performed on two lines in a targeted manner.

The leaching solution reacts with an oxidant, the pH value is adjusted, solid-liquid separation is carried out to remove iron, and finally nickel sulfate is obtained through extraction and oil removal.

The method has the advantages of high yield, short treatment time and environmental friendliness, improves the process operation environment, and effectively avoids pollution caused by tail gas leakage.

The method can effectively remove impurities in the preparation system, and can prepare the nickel sulfate meeting the battery-grade nickel sulfate standard.

Drawings

To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.

FIG. 1 is a schematic process flow diagram of a method for preparing nickel sulfate by using high nickel matte provided by an embodiment.

Detailed Description

The terms as used herein:

"by 8230; \ 8230; preparation" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The conjunction "consisting of 823070, 8230composition" excludes any unspecified elements, steps or components. If used in a claim, this phrase shall render the claim closed except for the materials described except for those materials normally associated therewith. When the phrase "consisting of 8230' \8230"; composition "appears in a clause of the subject matter of the claims and not immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the recited range should be interpreted to include ranges of "1 to 4," "1 to 3," "1 to 2 and 4 to 5," "1 to 3 and 5," and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

In these examples, the parts and percentages are by mass unless otherwise indicated.

"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent an arbitrary unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.

"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).

Firstly, the technical scheme provided by the application is integrally explained, and specifically, the technical scheme is as follows:

a method for preparing nickel sulfate using high nickel matte, comprising:

and extracting and deoiling the filtrate to obtain the nickel sulfate.

Manganese dioxide in the pyrolusite has oxidizability, and can promote leaching of nickel in nickel sulfide. The oxidation treatment oxidizes ferrous iron into ferric iron, which is convenient for subsequent pH adjustment and conversion into ferric iron hydroxide precipitate for removal. The extraction and oil removal are to remove other impurities such as cobalt, manganese, sulfur, etc.

In an alternative embodiment, the high nickel matte comprises a pretreatment step prior to flotation:

drying the high nickel matte, and then crushing and ball milling.

Granulation and pulp mixing are convenient for subsequent reaction and leaching.

In an alternative embodiment, the pre-treatment step results in high nickel matte particles that meet at least one of the following conditions:

a. the end point of drying is that the water content of the material is not higher than 0.5%;

b. the proportion of the part of the high nickel matte particles with the particle size of not more than 38 mu m is not less than 95 percent.

In an alternative embodiment, the high nickel matte is prepared into a high nickel matte ore pulp with a concentration of 25wt% to 35wt%.

In an alternative embodiment, the high nickel matte ore pulp is prepared by aeration stirring; the aeration quantity of the aeration stirring is 400-600L/h.

Optionally, the concentration of the high nickel matte ore pulp can be 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt% or any value between 25wt% and 35 wt%; the aeration quantity of the aeration stirring can be 400L/h, 450L/h, 500L/h, 550L/h, 600L/h or any value between 400 and 600L/h.

In an alternative embodiment, the flotation is carried out by using a collector, wherein the collector is at least one of butyl xanthate, butyl ammonium nigride, ethyl xanthate or thiamine ester, and the flotation is carried out by using a batch froth scraping method.

In an alternative embodiment, the pyrolusite is used in an amount of 30-60% by mass of the nickel sulphide concentrate.

Optionally, the amount of pyrolusite may be 30%, 40%, 50%, 60%, or any value between 30% and 60% of the mass of the nickel sulfide concentrate.

Under the action of pyrolusite and oxygen, sulfur in the nickel sulfide concentrate is converted into sulfate radicals, and no hydrogen sulfide is discharged, so that the exhaust emission is reduced.

In an alternative embodiment, the aerobic leaching is carried out under normal pressure, and oxygen is introduced into the system in the process, wherein the oxygen flow rate is 1-5L/min.

Optionally, the oxygen flow rate may be any value between 1L/min, 2L/min, 3L/min, 4L/min, 5L/min, or 1-5L/min.

In an alternative embodiment, the liquid-solid ratio of the aerobic leaching is (3-6) mL:1g, the initial acid concentration of the aerobic leaching is 2-4mol/L, the leaching temperature of the aerobic leaching is 80-100 ℃, and the time of the aerobic leaching is 3-5h.

The liquid-solid ratio can influence the concentration of the main metal and the concentration of acid in the reaction process, the liquid-solid ratio is too small, the reaction is difficult to continue to occur forward after the main metal content is saturated, the liquid-solid ratio is too large, and the forward reaction can be influenced if the concentration of acid is reduced quickly in the reaction process.

Optionally, the liquid-solid ratio of the aerobic leaching may be 3mL:1g, 4mL:1g, 5mL:1g, 6mL:1g or (3-6) mL: any value between 1 g; the initial acid concentration of the aerobic leaching can be 2mol/L, 3mol/L, 4mol/L or any value between 2 and 4mol/L, the leaching temperature of the aerobic leaching can be 80 ℃,90 ℃, 100 ℃ or any value between 80 and 100 ℃, and the time of the aerobic leaching can be 3h, 4h, 5h or any value between 3 and 5h.

In an alternative embodiment, the atmospheric leaching is carried out at ambient temperature with a liquid-to-solid ratio of (3-8) mL:1g, the time is 3-5h.

In an alternative embodiment, the initial acid concentration of the atmospheric leach is 13.8 to 18.4mol/L.

Optionally, the liquid-solid ratio of the atmospheric leaching may be 3mL:1g, 4mL:1g, 5mL:1g, 6mL:1g, 7mL:1g, 8mL:1g or (3-8) mL:1g, the time can be any value between 3h, 4h, 5h or 3-5 h; the initial acid concentration of the atmospheric leach may be 13.8mol/L, 14mol/L, 15mol/L, 16mol/L, 17mol/L, 18mol/L, 18.4mol/L or any value between 13.8 and 18.4mol/L.

In an alternative embodiment, the oxidant comprises one or more of hydrogen peroxide, ozone, oxygen, air;

Hydrogen peroxide is preferably used, the operation is convenient, the price is low, the raw materials are easily obtained, and no impurity element is introduced.

In an alternative embodiment, the method satisfies at least one of the following conditions:

Optionally, the temperature for removing iron may be any value between 60 ℃,70 ℃,80 ℃,90 ℃ or 60-90 ℃, and the time may be any value between 0.5h, 1h, 1.5h, 2h, 2.5h or 0.5-2.5h; when the extraction is carried out, the pH value of the filtrate is firstly adjusted to any value of 2.5, 3, 3.5, 4 or 2.5-4; the saponification rate of the P204 can be any value between 50%, 60%, 70% or 50-70%, and the saponification rate of the P507 can be any value between 55%, 60%, 65%, 70% or 55-70%; the sulfonated kerosene volume concentration can be any value between 72%, 73%, 74%, 75%, 76% or 72-76%, and the final P204 volume concentration can be any value between 20%, 25%, 30% or 20-30%.

Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.

The typical high nickel matte composition is shown in table 1:

TABLE 1 common high nickel matte composition

Element(s)	Ni	Co	Mn	Cu	Fe	S	Ca
								Content%	40-70	0.1-1	0-0.3	0.1-0.4	1-5	20-30	0.2-0.8

The high nickel matte compositions used in the examples and comparative examples in this application are shown in table 2 below:

TABLE 2 high nickel matte composition used in examples and comparative examples of the present application

Element(s)	Ni	Co	Mn	Cu	Fe	S	Ca
								Content%	64.15	0.4	0.002	0.14	3.77	24.95	0.48

The main components of pyrolusite used in the examples and comparative examples in this application are shown in table 3 below:

TABLE 3 main components of pyrolusite used in examples and comparative examples of the present application

Element(s)	Mn	Fe	CaO	SiO ₂
					Content%	25	8.8	0.8	33

The battery grade nickel sulfate standards are shown in table 4 below:

TABLE 4 Battery grade Nickel sulfate Standard

Example 1

As shown in fig. 1, this example provides a method for preparing nickel sulfate by using high nickel matte, which includes the following steps:

(1) The high nickel matte is put in an oven at 100 ℃ for 10 hours, so that the moisture after drying is less than 0.5 percent.

(2) And (3) sending the dried high nickel matte into a jaw crusher for crushing treatment, carrying out fine crushing treatment on the roller pair, and then carrying out ball milling by using a ball mill, wherein the fine granularity is less than 38 mu m and is more than 95 percent.

(3) Taking 400g of finely ground high nickel matte, mixing the ground high nickel matte, controlling the concentration of slurry to be 30wt%, carrying out gas charging stirring, controlling the gas charging amount to be 500L/h, using butyl xanthate as a collecting agent, adopting a batch foam scraping mode, controlling the interval time of producing flotation products to be 20s, carrying out foam scraping for 1 minute, obtaining 3 groups of flotation products in total, combining the flotation products to obtain nickel sulfide concentrate, and finally obtaining 308.1g of nickel sulfide ore with the nickel grade of 70.3% and the nickel sulfide compound recovery rate of 98.4%, and 81.4g of nickel oxide and nickel alloy after separation.

(4) Adding the obtained nickel sulfide ore into pyrolusite with the mass fraction of 50%, wherein the solid-to-solid ratio of the leaching solution is 5ml:1g, under the condition that the initial acid concentration is 3.0mol/L, introducing oxygen at 90 ℃ for leaching for 4 hours, wherein the oxygen flow is 2.0L/min, and obtaining 2.0L of first leaching solution with the nickel concentration of 106.5 g/L.

(5) 34ml of sulfuric acid with the concentration of 18.4mol/L is added into the obtained nickel oxide and nickel alloy at normal pressure and temperature, and reaction is carried out for 4 hours after the addition is finished, so that 330ml of second leaching solution with the concentration of 130.4g/L and 5.4g of slag are obtained. The obtained slag can be accumulated for many times and then treated according to the dissolving method of metallic nickel.

(6) And (3) mixing the first leaching solution and the second leaching solution obtained in the steps (4) and (5), adding 30ml of hydrogen peroxide at normal temperature for reacting for about 0.5 hour, then adding the nickel oxide and the nickel alloy obtained by flotation, stirring for about 1.5 hours at 70 ℃ until the pH value is more than 6.2, and filtering to obtain 2.33L of filtrate with the nickel content of 109.9g/L.

(7) Adjusting pH of the filtrate =3.5, and extracting with P204Removing impurities such as copper, calcium and the like (P204 volume concentration is 25%, sulfonated kerosene volume concentration is 75%), saponifying P204 with ammonia water, controlling saponification rate to be 63%, separating nickel and cobalt from P204 raffinate through P507, saponifying P507 with ammonia water, controlling saponification rate to be 64%, removing oil from nickel raffinate through an oil remover to obtain 2.1L of nickel sulfate _， The recovery rate of nickel is 99.8%.

The composition of the resulting nickel sulfate is shown in table 5:

TABLE 5 Nickel sulfate component of example 1

Example 2

The embodiment provides a method for preparing nickel sulfate by using high nickel matte, which specifically comprises the following steps:

(3) Taking 400g of finely ground high nickel matte, mixing the slurry with the slurry concentration of 30wt%, carrying out gas charging stirring with the gas charging amount of 500L/h, using butyl xanthate as a collecting agent, adopting a batch foam scraping mode, wherein the interval time for generating flotation products is 20s, and foam scraping is carried out for 1 minute to obtain 3 groups of flotation products, combining the flotation products to obtain nickel sulfide concentrate, and finally obtaining 307.7g of nickel sulfide ore with the nickel grade of 69.5% and the nickel sulfide compound recovery rate of 98.3%, and 81.2g of separated nickel oxide and nickel alloy.

(4) Adding the obtained nickel sulfide ore into pyrolusite with the mass fraction of 30%, wherein the solid-to-solid ratio of the leaching solution is 5ml:1g, under the condition that the initial acid concentration is 3.5mol/L, oxygen is introduced at 80 ℃ for leaching for 4 hours, the oxygen flow is 3.0L/min, and 2.0L of first leaching solution with the nickel concentration of 90.5g/L and 62.4g of slag are obtained.

(5) 34ml of sulfuric acid with the concentration of 18.4mol/L is added into the obtained nickel oxide and nickel alloy at normal pressure and temperature, and the reaction is carried out for 5 hours after the addition is finished, so that 295ml of second leaching solution with the concentration of 129.6g/L and 5.48g of slag are obtained. The obtained slag can be accumulated for many times and then treated according to the dissolving method of metallic nickel.

(6) And (3) mixing the first leaching solution and the second leaching solution obtained in the steps (4) and (5), adding 35ml of hydrogen peroxide at normal temperature for reacting for about 1 hour, then adding nickel hydroxide, stirring for about 2 hours at 60 ℃ until the pH value is more than 6.2, and filtering to obtain 2.3L of filtrate with the nickel content of 95.5g/L.

(7) The pH of the filtrate is adjusted to be =2.5, impurities such as copper, calcium and the like are removed through P204 extraction (the volume concentration of the P204 is 20%, and the volume concentration of the sulfonated kerosene is 72%), the P204 is saponified by ammonia water, the saponification rate is controlled to be 55%, the P204 raffinate is used for separating nickel and cobalt through P507, the P507 is saponified by ammonia water, the saponification rate is controlled to be 59%, the nickel raffinate is deoiled through an oil remover to obtain 1.9L of nickel sulfate, and the nickel recovery rate is 85.4%.

The composition of the resulting nickel sulfate is shown in Table 6:

TABLE 6 Nickel sulfate component of example 2

Example 3

(1) The high nickel matte is put into an oven at 100 ℃ for 10 hours, so that the moisture after drying is less than 0.5 percent.

(3) Taking 400g of ground high nickel matte, mixing the slurry, wherein the slurry concentration is 30wt%, inflating and stirring the slurry, the inflating amount is 500L/h, the used collecting agent is ammonium butyrate black powder, the batch foam scraping mode is adopted, the interval time for generating flotation products is 20s, foam scraping is carried out for 1 min, 3 groups of flotation products are obtained in total, nickel sulfide concentrate is obtained after combination, and finally 307.8g of nickel sulfide ore with the nickel grade of 70.5% and the nickel sulfide compound recovery rate of 98.1% and 81.6g of nickel oxide and nickel alloy after separation are obtained.

(4) Adding 60% of pyrolusite into the obtained nickel sulfide ore, and adding the nickel sulfide ore into the pyrolusite ore according to the weight percentage of 5ml:1g, under the condition that the initial acid concentration is 2.5mol/L, introducing oxygen at 90 ℃ for leaching for 3 hours, wherein the oxygen flow is 3.0L/min, and obtaining 2.0L of first leaching solution with 99.9g/L of nickel concentration and 30.5g of slag.

(5) 37.5ml of sulfuric acid with the concentration of 16.7mol/L is added into the obtained nickel oxide and nickel alloy at normal pressure and temperature, and after the addition is finished, the reaction lasts for 3.5 hours, and 300ml of second leaching solution with the concentration of 128.8g/L and 5.07g of slag are obtained. The obtained slag can be accumulated for many times and then treated according to the dissolving method of metallic nickel.

(6) And (3) mixing the first leaching solution and the second leaching solution obtained in the steps (4) and (5), adding 30ml of hydrogen peroxide at normal temperature for reaction for about 0.5 hour, then adding nickel hydroxide, stirring at 90 ℃ for about 0.5 hour until the pH value is more than 6.2, and filtering to obtain 2.3L of filtrate, wherein the content of nickel is 103.7g/L.

(7) The pH of the filtrate is adjusted to be =4, impurities such as copper, calcium and the like are removed through P204 extraction (the volume concentration of P204 is 30%, the volume concentration of sulfonated kerosene is 70%), P204 is saponified by ammonia water, the saponification rate is controlled to be 50%, P204 raffinate is subjected to P507 to separate nickel and cobalt, P507 is saponified by ammonia water, the saponification rate is controlled to be 60%, nickel raffinate is subjected to oil removal through an oil remover to obtain 2.0L of nickel sulfate, and the nickel recovery rate is 93.0%.

The composition of the resulting nickel sulfate is shown in Table 7:

TABLE 7 Nickel sulfate component of example 3

Example 4

This example provides a method for preparing nickel sulfate using high nickel matte, which includes:

(3) Taking 400g of ground high nickel matte, mixing the ground high nickel matte, wherein the concentration of slurry is 30wt%, inflating and stirring the slurry, the inflating amount is 500L/h, the used collecting agent is ethyl xanthate, the interval time for generating flotation products is 20s by adopting a batch foam scraping mode, foam scraping is carried out for 1 min, 3 groups of flotation products are obtained, nickel sulfide concentrate is obtained after combination, and finally 308.7g of nickel sulfide ore with the nickel grade of 69.9% and the nickel sulfide recovery rate of 98.5% and 80.9g of nickel oxide and nickel alloy after separation are obtained.

(4) Adding the obtained nickel sulfide ore into pyrolusite with the mass fraction of 50%, wherein the solid-to-solid ratio of the leaching solution is 3ml:1g, under the condition that the initial acid concentration is 4.0mol/L, introducing oxygen at 90 ℃ for leaching for 5 hours, wherein the oxygen flow is 4.0L/min, and obtaining 1.0L of first leaching solution with the nickel concentration of 130.5g/L and 300g and 35g of leaching residues of nickel solution crystals.

(5) 41.2ml of sulfuric acid with the concentration of 15.2mol/L is added into the obtained nickel oxide and nickel alloy at normal pressure and temperature, and reaction is carried out for 3 hours after the addition is finished, so that 325ml of second leaching solution with the concentration of 129.5g/L and 5.4g of slag are obtained. The obtained slag can be accumulated for many times and then treated according to the dissolving method of metallic nickel.

(6) And (3) mixing the first leaching solution and the second leaching solution obtained in the steps (4) and (5), adding 30ml of hydrogen peroxide at normal temperature for reacting for about 1 hour, then adding nickel hydroxide, stirring for about 1 hour at 85 ℃ until the pH value is more than 6.2, and filtering to obtain 1.325L of filtrate with the nickel content of 130.3g/L.

(7) The pH of the filtrate is adjusted to be =3, impurities such as copper, calcium and the like are removed through P204 extraction (the volume concentration of P204 is 20%, the volume concentration of sulfonated kerosene is 76%), P204 is saponified by ammonia water, the saponification rate is controlled to be 70%, P204 raffinate is subjected to P507 to separate nickel and cobalt, P507 is saponified by ammonia water, the saponification rate is controlled to be 70%, nickel raffinate is subjected to oil removal through an oil remover to obtain 1.4L of nickel sulfate, and the nickel recovery rate is 90.7%.

The composition of the resulting nickel sulfate is shown in Table 8:

table 8 nickel sulfate component of example 4

Example 5

(1) Taking 400g of high nickel matte particles with the water content of less than 0.5 percent, the particle size of less than 38 mu m and the proportion of more than 95 percent, mixing the particles, the concentration of the slurry is 30wt percent, aerating and stirring the slurry, the aeration quantity is 500L/h, the used collecting agent is ammonium butyrate black powder, the interval time for generating flotation products is 20s, the foam scraping is carried out for 1 minute, 3 groups of flotation products are obtained totally, nickel sulfide concentrate is obtained after combination, and finally 307.9g of nickel sulfide ore with the nickel grade of 70.6 percent and the nickel sulfide compound recovery rate of 98.9 percent and 81.8g of nickel oxide and nickel alloy after separation are obtained.

(2) Adding the obtained nickel sulfide ore into pyrolusite with the mass fraction of 50%, wherein the solid-to-solid ratio of the leaching solution is 6ml:1g, under the condition that the initial acid concentration is 2.0mol/L, oxygen is introduced at 90 ℃ for leaching for 4 hours, the oxygen flow is 4.0L/min, and 2.3L of first leaching solution with the nickel concentration of 90.6g/L and 11.9g of leaching residue are obtained.

(3) 37.5ml of sulfuric acid with the concentration of 16.7mol/L is added into the obtained nickel oxide and nickel alloy at normal pressure and temperature, and the mixture reacts for 2 hours after the addition is finished, so that 320ml of second leaching solution with the concentration of 131.2g/L and 5.4g of slag are obtained. The obtained slag can be accumulated for many times and then treated according to the dissolving method of metallic nickel.

(4) And (3) mixing the first leaching solution and the second leaching solution obtained in the steps (2) and (3), adding 30ml of hydrogen peroxide at normal temperature for reaction for about 0.5 hour, then adding nickel hydroxide, stirring for about 1 hour at 80 ℃ until the pH value is more than 6.2, and filtering to obtain 2.62L of filtrate, wherein the nickel content is 95.6g/L.

(5) The pH of the filtrate is adjusted to be 3.5, impurities such as copper, calcium and the like are removed through P204 extraction (the volume concentration of P204 is 30%, the volume concentration of sulfonated kerosene is 73%), P204 is saponified by ammonia water, the saponification rate is controlled to be 60%, P204 raffinate is subjected to P507 to separate nickel and cobalt, P507 is saponified by ammonia water, the saponification rate is controlled to be 55%, nickel raffinate is deoiled by an oil remover to obtain 2.1L of nickel sulfate, and the recovery rate of nickel is 97.6%.

The composition of the resulting nickel sulfate is shown in Table 9:

TABLE 9 Nickel sulfate component of example 5

The method provided by the embodiments 1-5 of the present application produces battery grade nickel sulfate with more strict requirements on components.

Example 6

(3) Taking 400g of ground high nickel matte, mixing the slurry, wherein the slurry concentration is 30wt%, inflating and stirring the slurry, the inflating amount is 500L/h, the used collecting agent is ammonium butyrate black powder, the batch foam scraping mode is adopted, the interval time for generating flotation products is 20s, foam scraping is carried out for 1 min, 3 groups of flotation products are obtained in total, nickel sulfide concentrate is obtained after combination, and finally 306.9g of nickel sulfide ore with the nickel grade of 70.6% and the nickel sulfide compound recovery rate of 98.9% and 81.3g of nickel oxide and nickel alloy after separation are obtained.

(4) Adding the obtained nickel sulfide ore into pyrolusite with the mass fraction of 50%, wherein the solid-to-solid ratio of the leaching solution is 6ml:1g, under the condition that the initial acid concentration is 2.0mol/L, oxygen is introduced at 90 ℃ for leaching for 4 hours, the oxygen flow is 4.0L/min, and 2.3L of first leaching solution with the nickel concentration of 91.2g/L and 11.9g of leaching residue are obtained.

(5) 37.5ml of sulfuric acid with the concentration of 16.7mol/L is added into the obtained nickel oxide and nickel alloy at normal pressure and temperature, and the mixture reacts for 2 hours after the addition is finished, so that 330ml of second leaching solution with the concentration of 128.4g/L and 5.4g of slag are obtained. The obtained slag can be accumulated for many times and then treated according to the dissolving method of metallic nickel.

(6) And (3) mixing the first leaching solution and the second leaching solution obtained in the steps (4) and (5), adding 30ml of hydrogen peroxide at normal temperature for reaction for about 0.5 hour, then adding nickel hydroxide, stirring for about 1 hour at 80 ℃ until the pH value is more than 6.2, and filtering to obtain 2.63L of filtrate, wherein the nickel content is 95.86g/L.

(7) The pH of the filtrate is adjusted to be 3.5, impurities such as copper, calcium and the like are removed through P204 extraction (the volume concentration of the P204 is 30%, and the volume concentration of sulfonated kerosene is 73%), the P204 is saponified by ammonia water, the saponification rate is controlled to be 60%, the P204 raffinate is used for separating nickel and cobalt through P507, the P507 is saponified by ammonia water, the saponification rate is controlled to be 55%, the nickel raffinate is deoiled through an oil remover to obtain 2.7L of nickel sulfate, and the nickel recovery rate is 98.2%.

The composition of the resulting nickel sulfate is shown in Table 10:

TABLE 10 Nickel sulfate component of example 6

Comparative example 1

(3) Taking 400g of ground high nickel matte, adding 50g/L of nickel sulfate solution as bottom water, and controlling the liquid-solid ratio to be 4ml:1g, adding 90ml of sulfuric acid, blowing oxygen at 80 ℃, leaching for 20 hours until the pH of the solution is more than 5.6, wherein the air flow is 4L/min.

(4) And carrying out solid-liquid separation to obtain 1.5L of nickel sulfate solution with the nickel concentration of 115.6g/L, and extracting, removing impurities, concentrating and crystallizing to obtain a nickel sulfate product.

(5) And (4) obtaining 297.2g of leaching residues, putting the leaching residues into a pressure kettle for oxygen pressure leaching, controlling the temperature to be 185 ℃, and controlling the liquid-solid ratio to be 10ml:1g, oxygen partial pressure of 0.6Mpa, oxygen pressure leaching for 5 hours, and solid-liquid separation to obtain nickel sulfate solution with nickel concentration of 56.1g/L and oxygen pressure slag of 21.5g.

(6) The nickel sulfate solution obtained in (5) was subjected to the step (3) as a base solution, so that the recovery rate in this step was 99.7%.

It should be noted that: because the first step of single-line leaching needs to leach the alloy phase under normal pressure and then enter the high-pressure kettle for reaction, otherwise, the alloy phase enters the high-pressure kettle to generate hydrogen explosion, and the flow processing time is long; and in the double-line leaching, the alloy phase is uniformly collected for multiple times to be subjected to oxidation leaching, so that the time length is greatly shortened.

By adopting the method provided by the application, the time of the whole process flow is about 7 hours generally; whereas the comparative example took about 25 hours. The method provided by the application obviously improves the production efficiency.

Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.

Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims

1. A method for preparing nickel sulfate by using high nickel matte is characterized by comprising the following steps:

mixing the first leaching solution and the second leaching solution with an oxidant for oxidation treatment, then adjusting the pH value for deironing, and carrying out solid-liquid separation to obtain a filtrate;

and extracting and deoiling the filtrate to obtain the nickel sulfate.

2. The method according to claim 1, characterized in that the high nickel matte comprises a pretreatment step before flotation:

drying the high nickel matte, and then crushing and ball milling.

3. A method according to claim 2, wherein the pre-treatment step results in high nickel matte particles that meet at least one of the following conditions:

4. The method of claim 1, wherein the flotation step comprises preparing the high grade nickel matte into a high grade nickel matte pulp having a concentration of 25wt% to 35wt%.

5. The method as claimed in claim 4, characterized in that the high nickel matte ore pulp is prepared by aeration stirring; the aeration quantity of the aeration stirring is 400-600L/h.

6. The method according to claim 1, wherein the flotation is carried out by using a collector, the collector is at least one of butyl xanthate, butyl ammonium nigride, ethyl xanthate or thiamine ester, and the flotation is carried out by using a batch froth scraping method.

7. The method according to claim 1, characterized in that the pyrolusite is used in an amount of 30-60% by mass of the nickel sulphide concentrate.

8. The method as claimed in claim 1, wherein the aerobic leaching is carried out under normal pressure, and oxygen is introduced into the system during the process, and the oxygen flow rate is 1-5L/min.

9. The method as claimed in claim 8, wherein the liquid-solid ratio of the aerobic leaching is (3-6) mL:1g, the initial acid concentration of the aerobic leaching is 2-4mol/L, the leaching temperature of the aerobic leaching is 80-100 ℃, and the time of the aerobic leaching is 3-5h.

10. The method according to claim 1, wherein the atmospheric leaching is carried out at normal temperature, and the liquid-solid ratio is (3-8) mL:1g, the initial acid concentration of the atmospheric leaching is 13.8-18.4mol/L, and the time of the atmospheric leaching is 3-5h.

11. The method of claim 1, wherein the oxidant comprises one or more of hydrogen peroxide, ozone, oxygen, and air;

12. The method according to any one of claims 1-11, characterized in that at least one of the following conditions is fulfilled: