WO2023273264A1

WO2023273264A1 - Method for preparing high-nickel type ternary precursor by means of ferronickel production conversion and application thereof

Info

Publication number: WO2023273264A1
Application number: PCT/CN2021/142960
Authority: WO
Inventors: 余海军; 吕思洁; 谢英豪; 李爱霞; 李长东; 张学梅
Original assignee: 广东邦普循环科技有限公司; 湖南邦普循环科技有限公司; 湖南邦普汽车循环有限公司
Priority date: 2021-06-30
Filing date: 2021-12-30
Publication date: 2023-01-05
Also published as: CN113528858A; HUP2200224A1

Abstract

The present invention relates to the field of metallurgy. Disclosed are a method for preparing a high-nickel type ternary precursor by means of ferronickel production conversion and an application thereof. The method comprises the following steps: drying laterite nickel ore, carrying out a pre-reduction reaction, and then carrying out deep reduction smelting, separation and refining to obtain a nickel-iron alloy; adding a sulfur-containing material into the nickel-iron alloy for blowing, and then adding coke powder and quartz to obtain high-grade matte nickel; adding concentrated sulfuric acid into the high-grade matte nickel for reaction, and carrying out separation and pressure leaching to obtain nickel sulfate; adding a cobalt source and a manganese source into the nickel sulfate, then adding a reducing agent, a precipitator, water, and a complexing agent, and carrying out a nucleation reaction and nuclear growth to prepare a high-nickel ternary precursor. In the present invention, on the basis of an original RKEF process, the high-grade matte nickel is prepared by taking the ferronickel which is excessive in yield and low in price as an intermediate, adding the sulfur-containing material, and adding a blowing device, and then the high-grade matte nickel is used for producing the nickel sulfate, so that the nickel recovery rate is further increased while the raw material supply pressure of the nickel sulfate is relieved to a great extent.

Description

Method for preparing high-nickel type ternary precursor by conversion of ferronickel and its application

technical field

The invention belongs to the field of metallurgy, and in particular relates to a method for preparing a high-nickel type ternary precursor through conversion of ferronickel and its application.

Background technique

Nickel has excellent physical and chemical properties, and is widely used in fields such as stainless steel, electroplating and batteries. At present, the identified nickel ore resources on the earth are mainly nickel sulfide ore and nickel oxide ore, of which nickel sulfide ore accounts for 30% of the total reserves, and laterite nickel ore whose main component is nickel oxide accounts for 70%.

The current industrial development forms of lateritic nickel ore mainly include pyrometallurgy and hydrometallurgy, among which pyrometallurgy is the most widely used because of its short process flow, high nickel recovery rate and low environmental pollution. The phase composition of laterite nickel ore is complex, and the grade of nickel in laterite ore is usually low, and the atomic radius is similar to that of iron. Therefore, the main product produced by pyrotechnics is ferronickel instead of high-purity metallic nickel. Ferronickel is an important raw material in the steelmaking industry, which can be used to produce stainless steel, structural steel and heat-resistant cast steel, etc.

Common ternary precursors are composed of three metals, nickel, cobalt, and manganese. The content of each element is closely related to the thermal stability, cycleability, and specific capacity of the material. The high-nickel ternary precursor can significantly increase the capacity of the material and reduce the unit cost of the battery. It is one of the ideal development directions for ternary lithium batteries, so the demand for its raw material nickel sulfate has been increased. It is very urgent to broaden the synthesis route of nickel sulfate. High nickel matte is a metal eutectic commonly used to produce nickel sulfate and other nickel salts. The traditional way to prepare high nickel matte is to convert nickel sulfide concentrate into a converter. However, with the long-term over-exploitation of nickel sulfide resources, its earth reserves have decreased, its mining costs have increased and its average grade has decreased. Therefore, in order to solve the increasingly sharp contradiction between the supply and demand of nickel resources, it is of great significance to accelerate the development of laterite nickel ore with abundant reserves, and to prepare high-nickel matte through its main product ferronickel, and then switch to the production of high-nickel ternary precursors. There is also a traditional method of using laterite nickel ore to produce nickel sulfate and then prepare a ternary precursor, which often uses low-matte nickel as a medium and requires a special production line; but this method has high costs, cumbersome steps and high sales pressure.

Contents of the invention

The present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a kind of method and application of preparing high-nickel type ternary precursor by conversion of ferronickel, this method is on the basis of original RKEF ("rotary kiln-submerged arc furnace" method) technology, with excess output, Using low-priced ferronickel as an intermediate, adding sulfur-containing materials and adding blowing equipment to produce high-grade nickel matte, and then using high-grade nickel-matte to produce nickel sulfate can greatly relieve the pressure on the supply of nickel sulfate raw materials and increase the production of nickel. recovery rate.

To achieve the above object, the present invention adopts the following technical solutions:

A preparation method of a high-nickel type ternary precursor, comprising the following steps:

(1) The laterite nickel ore is crushed, sieved, dried, and then pre-reduced to obtain the laterite nickel ore powder;

(2) carrying out deep reduction smelting and refining to the laterite nickel ore powder to obtain nickel-iron alloy;

(3) adding sulfur-containing material to the nickel-iron alloy for blowing, then adding coke powder and quartz to obtain high matte;

(4) making the high nickel matte into powder, adding concentrated sulfuric acid to react, filtering, taking the filtrate and continuing to add concentrated sulfuric acid, leaching under pressure to obtain nickel sulfate;

(5) Part of the reducing agent and complexing agent, water and precipitating agent are used as the bottom liquid, and a cobalt source and a manganese source are added to the nickel sulfate to prepare a nickel-cobalt-manganese mixed solution and added to the bottom liquid, and then the remaining reducing agent, complexing agent, and complexing agent are added. After the mixture is mixed, nucleation reaction, nuclei growth and synthesis are carried out to obtain the high-nickel type ternary precursor.

Pre-reduction reaction: Partial selective reduction of nickel and iron is carried out on the treated laterite nickel ore through a rotary kiln to produce high-temperature laterite nickel ore powder.

Deep reduction reaction: Using coke and coal as reducing agents, put the laterite nickel ore powder into an electric furnace under a reducing atmosphere (carbon monoxide) for reduction smelting to obtain ferronickel.

Preferably, in step (1), the particle size of the crushed laterite nickel ore is 20-100mm.

Preferably, in step (1), the Ni content of the laterite nickel ore is _1-2 %, the Fe content is 12-17%, the SiO content is 35-40%, and the MgO content is 20-25%. .

Preferably, in step (1), the drying temperature is 650-850°C.

Preferably, in step (1), the temperature of the pre-reduction reaction is 900-1100°C, and the time is 2-4h.

Preferably, in step (1), the reducing agent for the pre-reduction reaction is coke or coal.

Preferably, in step (2), the ambient gas for the deep reduction smelting is CO.

Preferably, in step (2), the temperature of the deep reduction smelting is 1500-1700°C, and the time is 2-4h

Preferably, in step (2), the nickel grade of the nickel-iron alloy is 25-30%.

Preferably, in step (3), the sulfur-containing material is at least one of sulfur, pyrite or gypsum.

Preferably, in step (3), the blowing temperature is 1300-1500° C., and the atmosphere is air.

Preferably, in step (3), the added amount of the coke powder is 40-120kg.

Preferably, in step (3), the amount of quartz added is 2-10kg.

The coke powder plays the role of increasing the furnace temperature and controlling the reaction atmosphere, and the quartz is used to lower the temperature. The combination of the two can remove impurities such as Fe and S in nickel-iron.

Preferably, in step (3), the sulfur content of the high matte is 20%.

Preferably, in the step (4), before the crushing of the high nickel matte, water extraction treatment of the high nickel matte under high-pressure water is also included.

Preferably, in step (4), the particle size of the pulverized high matte is 60-120mm.

Preferably, in step (4), the particle diameter of more than 80% of the high-grade nickel matte after ball milling is less than 50 mm.

Preferably, in step (4), the pressure of the pressure leaching is 700-850kPa, and the temperature of the pressure leaching is 145-160°C.

Preferably, in step (5), the molar ratio of nickel-cobalt-manganese in the nickel sulfate, cobalt source and manganese source is (0.6-0.9):(0.05-0.2):(0.05-0.2).

Preferably, in step (5), the precipitation agent is sodium hydroxide.

Preferably, in step (5), the complexing agent is ammonia water.

Preferably, in step (5), the reducing agent is one of sodium borohydride, hydrazine hydrate or ethylene glycol.

Further preferably, the reducing agent is sodium borohydride. Sodium borohydride is highly reducing, which can strengthen the complexation of ammonia water.

Preferably, in step (5), the cobalt source is cobalt sulfate or cobalt chloride; the manganese source is manganese sulfate or manganese chloride.

Preferably, in step (5), the concentration of the configured nickel-cobalt-manganese mixed solution is 80-150 g/L.

Preferably, in step (5), the atmosphere of the nucleation reaction is an inert gas.

Further preferably, the inert gas is argon.

Preferably, in step (5), the pH is adjusted to 8-12 during the nucleation reaction, the rotational speed of the nucleation reaction is 200-400r/min, and the temperature of the nucleation reaction is 40-800°C.

Preferably, in step (5), the synthesis includes precipitating, washing, separating and drying the slurry after nuclei growth to obtain a high-nickel ternary precursor.

Preferably, in step (5), the nucleation reaction is performed in a reactor, the nuclei growth is performed in a growth tank, and the synthesis is performed in a synthesis tank.

Carrying out multiple reactors in series to separate nucleation, growth, and synthesis can avoid the formation of new nuclei when nuclei grow, so that the product has uniform appearance and stable performance.

Further preferably, the number of growth tanks is 1-2.

The present invention also provides the application of the above preparation method in the preparation of electrolytic nickel.

Preferably, the application in the preparation of electrolytic nickel is to prepare electrolytic nickel by using the matte nickel obtained in steps (1)-(3) of the preparation method.

The high nickel matte prepared by the invention can be produced electrolytic nickel by conventional electrolytic process, or can be produced by high-pressure leaching process to produce nickel sulfate and then produce electrolytic nickel. Electrolytic nickel can be used to manufacture stainless steel and various alloy steels, and is widely used in aircraft, tanks, ships, and civilian industries.

Compared with the prior art, the beneficial effects of the present invention are as follows:

1. The traditional method of using laterite nickel ore to produce nickel sulfate and then prepare ternary precursor often uses low-matte nickel as the medium, and needs to open up a special production line; but this method is costly, cumbersome and has high sales pressure. Therefore, on the basis of the original RKEF process, the present invention uses ferronickel with excess output and low price as an intermediate, adds sulfur-containing materials, and increases blowing devices to produce high-grade nickel matte, and then utilizes high-grade nickel-matte to produce nickel sulfate. While relieving the raw material supply pressure of nickel sulfate, it also improves the recovery rate of nickel.

2. The present invention adopts an improved co-precipitation method, which can strengthen the complexation of the complexing agent ammonia with the strong reducing agent sodium borohydride, and uses a multi-pot series connection mode (nucleation, growth, synthesis and separation) to effectively control and adjust The production index of the high-nickel ternary precursor is improved, that is, the particle size is reduced and the specific surface area is increased. When the particle size is small, the precursor requires a lower roasting temperature and higher production efficiency; the particle size of the precursor determines the three The particle size of the original positive electrode material, if the particle size is too large, the sphericity of the positive electrode material will deteriorate, thus improving the quality of the product.

3. The high nickel matte prepared by the method of the present invention can not only be used to prepare nickel sulfate system, but also be used to prepare products such as electrolytic nickel, which is of great significance to the development of the overall nickel industry.

4. The present invention transforms the original RKEF production line and integrates the pressurized acid leaching and the improved co-precipitation method, complements advantages and creatively constructs an efficient high-nickel ternary precursor production process.

Description of drawings

Fig. 1 is the flowchart of the method for preparing high-nickel type ternary precursor by ferronickel conversion in Example 1 of the present invention;

Fig. 2 is the SEM picture of the high-nickel ternary precursor prepared in Example 1 of the present invention;

3 is an SEM image of the high-nickel ternary precursor prepared in Comparative Example 1 of the present invention.

detailed description

The conception and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments, so as to fully understand the purpose, features and effects of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, rather than all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative efforts belong to The protection scope of the present invention.

Example 1

The method for preparing a high-nickel type ternary precursor by converting ferronickel production in this embodiment includes the following specific steps:

(1) With nickel content of 1.5%, Fe content of 15%, _SiO2 content of 39%, MgO content of 21% and water content greater than 30% of an Indonesian high-silicon magnesium type laterite nickel ore as raw material, the laterite The nickel ore is dried at 800°C to reduce the surface water content to 20%, and crushed into lumps with a diameter of 50-100mm by using a pulverizer;

(2) Put the crushed lateritic nickel ore and coal in a rotary furnace, conduct a pre-reduction reaction for 2 hours at 1000°C, and remove part of the free water in the ore, and prepare part of the ferronickel by preheating The charge saves the energy consumption of the electric furnace in the next step;

(3) Transfer the product obtained in the rotary furnace to the feeding bin of the electric furnace, and carry out 2h deep reduction smelting at 1600°C, the reducing atmosphere is CO, to reduce metallic nickel and part of iron to produce coarse ferronickel and separate slag material;

(4) carry out converter refining to the coarse ferronickel obtained by step (3), remove part sulfur, phosphorus impurity in the thick ferronickel, obtain the nickel-iron alloy that nickel grade reaches 25%;

(5) Add pyrite with a particle size of less than 100mm to the above-mentioned ferronickel alloy, and blow air with a pressure of 10kPa into the ferronickel, carry out blowing at 1350°C, add 80kg of coke powder and 4kg of Quartz sand, to remove impurities such as Fe and S in ferronickel, so that copper and nickel can be further enriched into high nickel matte with a sulfur content of 20%;

(6) Crushing the high nickel matte so that the particle size is between 60-100 mm, and then performing ball milling. At 170° C., in a turbo-stirred reactor at normal pressure, adding concentrated sulfuric acid to the high nickel matte processed by ball milling, Carry out reaction, obtain reaction solution;

(7) filter the above-mentioned reaction solution, isolate filter residues such as copper sulfide and iron sulfide, add concentrated sulfuric acid to the filtrate, and pressurize the leaching nickel sulfate solution in an autoclave with a pressure of 700kPa and a temperature of 160°C. Evaporation and crystallization to produce nickel sulfate;

(8) Mix 1/3 of sodium borohydride with a mass concentration of 1wt%, 1/3 of ammonia with a mass concentration of 6wt%, water and sodium hydroxide, and add them to the reaction kettle as the bottom liquid, according to 8:1 :1 molar ratio, add cobalt sulfate and manganese sulfate to the nickel sulfate that makes, configure the nickel-cobalt-manganese mixed solution that total concentration is 100g/L, add in the reactor after mixing with remaining ammoniacal liquor and sodium borohydride again , and pass through argon as a protective gas;

(9) adjust the pH in the reactor to be 10.5, the temperature to be 50° C., and the stirring speed to be 300 r/min, and to carry out a nucleation reaction in the reactor (the residence time is controlled by a crystal nucleator so that the reaction only generates nuclei and does not grow), and the material is obtained. Slurry, design a program of three reactors in series, overflow the prepared slurry to the growth tank, and grow the nucleus of the ternary precursor without generating new nuclei;

(10) The slurry in the growth tank is overflowed to the synthesis tank (the reaction tank used in the synthesis process), and the high-nickel ternary precursor is obtained through precipitation, washing, separation and drying.

In Example 1, when laterite nickel ore smelts nickel sulfate, the comprehensive recovery rate of nickel is 93% (nickel recovery rate = nickel amount in the product/nickel amount in the input ore * 100%), and the cost is about 16,000 US dollars/ton of nickel (In terms of nickel content, the price from nickel ore to ferronickel is 12,000 US dollars/ton, from ferronickel to high nickel matte is 1,000 US dollars/ton, from high nickel matte to nickel sulfate is 3,000 US dollars/ton). However, in the existing related technologies, the comprehensive recovery rate of nickel is lower than 90%.

Fig. 1 is the flow chart of the method for preparing high-nickel type ternary precursor by ferronickel conversion of embodiment 1, as can be seen from Fig. 1, utilize laterite nickel ore to prepare nickel-iron alloy, then blow into high nickel matte, utilize high nickel matte to prepare sulfuric acid Nickel, add cobalt source and manganese source to nickel sulfate, then add reducing agent, precipitating agent and complexing agent for co-precipitation to prepare high-nickel ternary precursor.

Fig. 2 is an SEM image of the high-nickel ternary precursor of Example 1. It can be seen from Fig. 2 that the high-nickel ternary precursor has a small particle size, a large surface area, and a regular shape.

Example 2

(1) With nickel content of 1.5%, Fe content of 15%, _SiO2 content of 39%, MgO content of 21% and water content greater than 30% of an Indonesian high-silicon magnesium type laterite nickel ore as raw material, the laterite The nickel ore is dried at 700°C to reduce the surface water content to 20%, and crushed into lumps with a diameter of 50-100mm by using a crusher;

(2) Put the crushed lateritic nickel ore in a rotary furnace, conduct a pre-reduction reaction at 900°C for 2 hours, and remove part of the free water in the ore. While producing part of ferronickel, save by preheating the charge The energy consumption of the electric furnace in the next step;

(3) Transfer the product obtained in the rotary furnace to the feeding bin of the electric furnace, and carry out 3h deep reduction smelting at 1500°C, the reducing atmosphere is CO, to reduce metallic nickel and part of iron to produce coarse ferronickel and separate slag material;

(4) carry out converter refining to the laterite nickel ore obtained by step (3), remove part of the sulfur and phosphorus impurities in the thick ferronickel, and obtain ferronickel with a nickel grade of 25%;

(5) Add gypsum with a particle size of less than 100mm to the above-mentioned ferronickel alloy, and blow air with a pressure of 10kPa into the ferronickel, carry out blowing at 1350°C, add 80kg of coke powder and 4kg of quartz sand , to remove impurities such as Fe and S in ferronickel, so that copper and nickel can be further enriched into high nickel matte with a sulfur content of 20%;

(7) Separating the reaction solution, adding concentrated sulfuric acid to the remaining solution, to pressurize the leaching nickel sulfate solution in an autoclave with a pressure of 800kPa and a temperature of 160°C, and finally obtain nickel sulfate through evaporative crystallization;

(8) Sodium hydroxide, 1/3 of sodium borohydride with a mass concentration of 1wt%, 1/3 of ammonia with a mass concentration of 6wt%, and water are mixed and added to the reactor, according to the ratio of 8:1:1 Molar ratio, adding cobalt sulfate and manganese sulfate to the prepared nickel sulfate, configuring a nickel-cobalt-manganese mixed solution with a concentration of 80g/L, and then adding the remaining ammonia and sodium borohydride to the reactor, and feeding argon as a protective gas;

(9) adjust the pH in the reactor to be 9.5, the temperature to be 80° C., and the stirring speed to be 400 r/min, to carry out a nucleation reaction to obtain a slurry, and to design a program in which three kettles are connected in series to overflow the obtained slurry to the growth kettle, Allows the nuclei of the ternary precursor to grow without generating new nuclei;

(10) The slurry in the growth tank is overflowed to the synthesis tank, and after precipitation, washing, separation and drying, a high-nickel ternary precursor product is obtained.

In Example 2, when laterite nickel ore smelts nickel sulfate, the comprehensive recovery rate of nickel is 94% (nickel recovery rate = nickel amount in the product/nickel amount in the input ore * 100%), and the cost is about 16,500 US dollars/ton of nickel ($12,000 from nickel ore to ferronickel, $1,000 from ferronickel to high nickel matte, and $3,500 from high nickel matte to nickel sulfate).

Example 3

(2) Put the crushed laterite nickel ore in a rotary furnace, conduct a pre-reduction reaction at 1000°C for 2 hours, and remove part of the free water in the ore. The energy consumption of the electric furnace in the next step;

(5) Add pyrite with a particle size of less than 100mm to the above-mentioned ferronickel alloy, and blow air with a pressure of 10kPa into the ferronickel, carry out blowing at 1450°C, add 80kg of coke powder and 4kg of Quartz sand, to remove impurities such as Fe and S in ferronickel, so that copper and nickel can be further enriched into high nickel matte with a sulfur content of 20%;

(7) Separating the reaction solution, adding concentrated sulfuric acid to the remaining solution, to pressurize the leaching nickel sulfate solution in an autoclave with a pressure of 700kPa and a temperature of 160°C, and finally obtain nickel sulfate through evaporative crystallization;

(8) Sodium hydroxide, 1/3 of sodium borohydride with a mass concentration of 1wt%, 1/3 of ammonia with a mass concentration of 6wt%, and water are mixed and added to the reactor, according to the ratio of 8:1:1 Molar ratio, adding cobalt sulfate and manganese sulfate to the prepared nickel sulfate, configuring a nickel-cobalt-manganese mixed solution with a concentration of 100g/L, and then adding the remaining ammonia and sodium borohydride to the reaction kettle, and feeding argon as a protective gas;

(9) Adjust the pH in the reactor to be 11.5, the temperature to be 50° C., and the stirring speed to be 300 r/min, to carry out a nucleation reaction to obtain a slurry, and to design a program in which three kettles are connected in series, and overflow the prepared slurry to the growth kettle, Allows the nuclei of the ternary precursor to grow without generating new nuclei;

(10) The slurry in the growth tank is overflowed to the synthesis tank, and the nickel-rich ternary precursor is obtained through precipitation, washing, separation and drying.

In Example 3, when lateritic nickel ore smelts nickel sulfate, the comprehensive recovery rate of nickel is 95% (nickel recovery rate = nickel amount in the product/nickel amount in the input ore * 100%), and the cost is about 16,000 US dollars/ton of nickel ($12,000 from nickel ore to ferronickel, $1,000 from ferronickel to high nickel matte, and $3,000 from high nickel matte to nickel sulfate).

Comparative example 1

A method for preparing a high-nickel type ternary precursor by converting ferronickel into production, comprising the following specific steps:

The difference from Example 1 is that in Comparative Example 1, a high-nickel ternary precursor was directly prepared by a simple co-precipitation method, rather than an improved co-precipitation method, and the method of connecting multiple reactors in series was not used.

Comparative example 2

The difference with Example 1 is: Comparative Example 2 does not add sodium borohydride.

Comparative example 3

(1) With nickel content of 1.5%, Fe content of 15%, _SiO2 content of 39%, MgO content of 21% and water content of 33.5% in an Indonesian high-silicon magnesium type laterite nickel ore as raw material, the laterite The nickel ore is dried at 800°C to reduce the surface water content to 20%, and crushed into lumps with a diameter of 50-100mm by using a pulverizer;

(2) Mix the lump ore and gypsum powder and put them in the brick making machine to make bricks, then crush the bricks to a particle size of 40mm-100mm, gradually add coke into the blast furnace, and then put in 49kg of limestone and quartz sand in turn 1. After the broken bricks are blown into air to start blowing, the air volume is 70m ³ /(m ² ·min). After the reaction, low-matte slag is released;

(3) After raising the temperature of the continuous converting furnace to 1150°C, feed the low nickel matte into the continuous converting furnace from the feeding pipe of the blast furnace. The liquid level of the melt is about 95mm higher than the distance from the tuyere, and the temperature is kept for 1 hour to stabilize the melt. Take 35kg of quartz sand, divide the quartz sand into three basic equal parts, and add them into the converting furnace every 90 minutes;

(4) Inject air into the furnace, measure the oxygen volume percentage in the air as 20.9%, the injection pressure is 0.1MPa, and the injection volume is 33m ³ /(m ² ·min). After the reaction is carried out for 5 hours, measure The iron content in the high nickel matte is 5.3%, and the smelting is finished to obtain the high nickel matte;

(5) Crushing the high nickel matte so that the particle size is between 60-100 mm, and then performing ball milling, at 170° C., in a turbo-stirred reactor at normal pressure, adding concentrated sulfuric acid to the high nickel matte processed by ball milling, Carry out reaction, obtain reaction solution;

(6) Separating the reaction solution, adding concentrated sulfuric acid to the remaining solution, to pressurize the leaching nickel sulfate solution in an autoclave with a pressure of 700kPa and a temperature of 160°C, and finally obtain nickel sulfate through evaporative crystallization;

(7) Mix part of sodium hydroxide, sodium borohydride, water and ammonia water, add to the reaction kettle, add cobalt sulfate and manganese sulfate to the prepared nickel sulfate according to the molar ratio of 8:1:1, and configure the concentration 100g/L nickel-cobalt-manganese mixed solution, and the remaining ammonia and sodium borohydride are added to the reactor, and argon is introduced as a protective gas;

(8) Adjust the pH in the reactor to be 10.5, the temperature to be 50° C., and the stirring speed to be 300 r. Perform a nucleation reaction to obtain a slurry. Design a program in which three kettles are connected in series to overflow the obtained slurry to the growth kettle. In the case of generating new nuclei, the nuclei of the ternary precursor are grown;

(9) The slurry in the growth tank is overflowed to the synthesis tank, and after precipitation, washing, separation and drying, a high-nickel ternary precursor product is obtained.

In comparative example 1, when laterite nickel ore smelts nickel sulfate, the comprehensive recovery rate of nickel is 89% (nickel recovery rate = nickel amount in the product/nickel amount in the input ore * 100%), and the cost is about 14,800 US dollars/ton of nickel ($12,000 from nickel ore to ferronickel, $1,000 from ferronickel to high nickel matte, and $1,800 from high nickel matte to nickel sulfate).

The difference between Example 1 and Comparative Example 1 is that in Comparative Example 1, a high-nickel ternary precursor was directly prepared by a simple co-precipitation method, instead of an improved co-precipitation method, without using multiple reactors in series. The high-nickel ternary precursor produced under the simple co-precipitation process, as shown in Figure 3, has problems such as irregular shape, low production efficiency, poor dispersion and batch stability. As shown in table 1 and table 2, the ICP data, particle size distribution situation (D50) and specific surface area of embodiment 1-3 and comparative example 1-3 have been compared in detail, compared with comparative example 1, embodiment 1- 3 The content of impurity elements in the prepared high-nickel ternary precursor is low, the particle size is small and the specific surface area is large.

Table 1 The content of each element in the high-nickel ternary precursor

元素含量(％)Element content (%)	NiNi	Coco	Mnmn	FeFe	CrCr	MgMg	CaCa	CuCu
实施例1Example 1	48.5848.58	6.106.10	5.945.94	0.00050.0005	0.00030.0003	0.00290.0029	0.00570.0057	0.00140.0014
实施例2Example 2	50.3750.37	6.756.75	6.626.62	0.00030.0003	0.00010.0001	0.00170.0017	0.00610.0061	0.00150.0015
实施例3Example 3	50.0250.02	6.426.42	6.206.20	0.00120.0012	0.00040.0004	0.00430.0043	0.00930.0093	0.00210.0021
对比例1Comparative example 1	48.6348.63	6.286.28	5.935.93	0.00290.0029	0.00260.0026	0.00580.0058	0.00550.0055	0.00230.0023
对比例2Comparative example 2	50.4250.42	6.076.07	6.216.21	0.00480.0048	0.00120.0012	0.00540.0054	0.00750.0075	0.00460.0046
对比例3Comparative example 3	49.7549.75	6.356.35	5.865.86	0.00550.0055	0.00390.0039	0.00810.0081	0.00920.0092	0.00350.0035

Table 2 Comparison of particle size and specific surface area of high-nickel ternary precursor

It can be seen from Table 2 that the high-nickel ternary precursor prepared in Examples 1-3 of the present invention has a small particle size and a large surface area, so the required calcination temperature of the precursor is lower and the production efficiency is higher.

The embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned embodiments, and within the scope of knowledge of those of ordinary skill in the art, various modifications can be made without departing from the spirit of the present invention. Variety. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other if there is no conflict.

Claims

A preparation method of high-nickel type ternary precursor, is characterized in that, comprises the following steps:

(1) The laterite nickel ore is crushed, sieved, dried, and then pre-reduced to obtain the laterite nickel ore powder;

(2) carrying out deep reduction smelting and refining to the laterite nickel ore powder to obtain nickel-iron alloy;

(3) adding sulfur-containing material to the nickel-iron alloy for blowing, then adding coke powder and quartz to obtain high matte;

(4) making the high nickel matte into powder, adding concentrated sulfuric acid to react, filtering, taking the filtrate and continuing to add concentrated sulfuric acid, leaching under pressure to obtain nickel sulfate;

(5) Part of the reducing agent and complexing agent, water and precipitating agent are used as the bottom liquid, and a cobalt source and a manganese source are added to the nickel sulfate to prepare a nickel-cobalt-manganese mixed solution and added to the bottom liquid, and then the remaining reducing agent, complexing agent, and complexing agent are added. After the mixture is mixed, nucleation reaction, nuclei growth and synthesis are carried out to obtain the high-nickel type ternary precursor.
The preparation method according to claim 1, characterized in that, in step (1), the Ni content of the laterite nickel ore is 1-2 %, the Fe content is 12-17%, and the SiO content is 35-40% , MgO content is 20-25%.
The preparation method according to claim 1, characterized in that, in step (1), the temperature of the pre-reduction reaction is 900-1100°C, and the time of the pre-reduction reaction is 2-4h.
The preparation method according to claim 1, characterized in that, in step (2), the ambient gas of the deep reduction smelting is CO, the temperature of the deep reduction smelting is 1500-1700°C, and the time of the deep reduction smelting is 2- 4h.
The preparation method according to claim 1, characterized in that, in step (3), the sulfur-containing material is at least one of sulfur, pyrite or gypsum.
The preparation method according to claim 1, characterized in that, in step (3), the blowing temperature is 1300-1500° C., and the blowing atmosphere is air.
The preparation method according to claim 1, characterized in that, in step (5), the reducing agent is one of sodium borohydride, hydrazine hydrate or ethylene glycol.
The preparation method according to claim 1, characterized in that, in step (5), the cobalt source is cobalt sulfate or cobalt chloride; the manganese source is manganese sulfate or manganese chloride.
preparation method according to claim 1, is characterized in that, in step (5), in the process of described nucleation reaction, adjust pH to be 8-12, the rotating speed of nucleation reaction is 200-400r/min, the temperature of nucleation reaction is 40-800°C.
Application of the preparation method described in claim 1 in the preparation of electrolytic nickel.