阅读说明：本技术 一种硫化矿加压酸浸制备镍锌铁氧体的方法 (Method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore ) 是由 罗文波 罗勋 甘胤 郑凯 张琼 周东波 洪开发 谢瑶 于 2021-06-10 设计创作，主要内容包括：本发明公开了一种硫化矿加压酸浸制备镍锌铁氧体的方法,包括以下步骤：第一步,按照产品镍锌铁氧体中镍、锌、铁三种成分的质量比称取一定比例的硫化镍精矿、硫化锌精矿两种矿物,将两种矿物及一定量硫酸溶液加入到加压釜内,通入氧气,进行加压加热搅拌。本发明是一种工艺先进、有价金属镍、锌和铁浸出率高,成本低、操作简便、生产连续化、环境污染小,热利用率高的由原矿直接制备镍锌铁氧体的方法,本发明适用于各种含量的硫化镍精矿和硫化锌精矿,特别适用于含铁高的,镍铁、锌铁难分离的高铁硫化镍精矿和高铁硫化锌精矿,变原矿中废弃物铁为原料,大大提高资源利用率,缩短了净化流程,增加了经济效益。(The invention discloses a method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore, which comprises the following steps: firstly, weighing two minerals of nickel sulfide concentrate and zinc sulfide concentrate according to the mass ratio of nickel, zinc and iron in the product nickel-zinc ferrite, adding the two minerals and a certain amount of sulfuric acid solution into a pressure kettle, introducing oxygen, pressurizing, heating and stirring. The invention is a method for directly preparing nickel-zinc ferrite from raw ore, which has advanced process, high leaching rate of valuable metals of nickel, zinc and iron, low cost, simple and convenient operation, continuous production, small environmental pollution and high heat utilization rate.)

1. A method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore is characterized by comprising the following steps:

firstly, weighing two minerals of nickel sulfide concentrate and zinc sulfide concentrate according to the mass ratio of nickel, zinc and iron in the product nickel-zinc ferrite, adding the two minerals and a certain amount of sulfuric acid solution into a pressure kettle, introducing oxygen, and carrying out pressure heating and stirring;

step two, filtering the ore pulp obtained by the acid leaching under oxygen pressure in the step one to respectively obtain filter residues and a leaching solution, washing the filter residues and piling up the filter residues, returning washing water to the acid leaching under oxygen pressure process, reducing ferric iron in the leaching solution into ferrous iron, reducing the ferric iron in the leaching solution by using a raw material sulfide ore as a reducing agent, returning the reduced filter residues to the pressure leaching process for leaching, and obtaining a filtrate as a reducing solution;

thirdly, purifying and decontaminating the reducing liquid in the second step, wherein the decontamination process is divided into a primary purification section and a deep purification section, the primary purification section is characterized in that lime milk is added into the reducing liquid as a neutralizer, the solution is neutralized until the pH value of the solution is 2.0-6.0, the temperature is controlled to be 30-95 ℃, the time is 0.5-2 h, a certain amount of flocculant PMA is added to remove silicon and aluminum, a certain amount of ammonium sulfide is added to remove copper and cadmium, a certain amount of ammonium fluoride is added to remove calcium and magnesium, the obtained primary purified liquid is subjected to deep purification, a certain amount of ammonium sulfate is added into the solution, most of nickel, zinc and iron generate double sulfate precipitates, impurity elements are remained in the solution, most of impurities in the solution can be removed, the double sulfate precipitates are added into a sulfuric acid solution to be dissolved, and simultaneously a certain amount of nickel sulfate, zinc sulfate and ferrous sulfate solution are added according to the proportion of nickel, zinc and iron of ferrite of the nickel and the product, finally, adding a little excessive ammonium oxalate for coprecipitation to obtain oxalate precipitates of nickel, zinc and iron.

2. The method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore according to claim 1, wherein in the first step, the pressure acid leaching conditions are as follows: the liquid-solid ratio is 3-10: 1.

3. The method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore according to claim 1, wherein in the first step, the pressure acid leaching conditions are as follows: the initial sulfuric acid concentration is 100g/L to 300 g/L.

4. The method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore according to claim 1, wherein in the first step, the pressure acid leaching conditions are as follows: the time is 0.5h-2.0 h.

5. The method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore according to claim 1, wherein in the first step, the pressure acid leaching conditions are as follows: the temperature is controlled between 110 ℃ and 200 ℃.

6. The method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore according to claim 1, wherein in the first step, the pressure acid leaching conditions are as follows: the pressure is 0.4MPa-2.0 MPa.

7. The method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore according to claim 1, wherein in the first step, the pressure acid leaching conditions are as follows: the stirring speed is 300r/min-700 r/min.

8. The method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore according to claim 1, wherein in the second step, the reduction conditions are as follows: the usage amount of the sulphide ore is 1 to 4 times of the theoretical amount.

9. The method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore according to claim 1, wherein in the second step, the reduction conditions are as follows: the temperature is 40-95 ℃ and the time is 0.5-3 h.

10. The method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore according to claim 1, wherein in the second step, the reduction conditions are as follows: the stirring speed is 300r/min-700 r/min.

Technical Field

The invention relates to the technical field of preparation methods of nickel-zinc ferrite, in particular to a method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ores.

Background

The soft magnetic ferrite is a nonmetal magnetic material which is most widely applied in ferrite and has the largest production capacity, and is mainly characterized by high resistivity, lower residual magnetic flux density and coercive force and good high-frequency property. Nickel zinc ferrite is one of soft magnetic ferrites, which has the advantages of excellent high frequency characteristics, good temperature stability, large nonlinearity, and the like, compared with the most commonly used manganese zinc ferrite. The high-frequency resonant transformer is widely applied to medium-frequency transformers, magnetic heads, short-wave antenna rods, tuning inductance reactors and magnetic saturation amplifiers. At present, the mainstream production process of the nickel-zinc ferrite comprises an oxide method (ceramic method) and a chemical coprecipitation method:

1. the oxide method uses metal oxide or easily decomposed metal salt as raw materials, firstly mixes various materials according to a product formula, puts the weighed raw materials into a ball milling tank for ball milling and mixing, presinteres the uniformly mixed powder at a temperature lower than the sintering temperature to generate a preliminary solid phase reaction, and then carries out ball milling mixing, granulation, molding, sintering and grinding on the presintered sample to obtain the nickel-zinc ferrite product. The method is mature, has the advantages of wide raw material source, small equipment investment, simple process and the like, is the method for preparing the soft magnetic ferrite which is developed most mature at the earliest application, and has the following defects: the raw materials are mixed in a granular form, the raw materials are difficult to be mixed uniformly, the granules greatly influence the solid phase reaction,

2. the chemical coprecipitation method is to dissolve pure metal as raw material in acid or alkali to form nitrate, sulfate or hydroxide solution of metal, after filtering, measure solution according to formula proportion and mix. Adding proper precipitant to coprecipitate metal ions, filtering and roasting to form coprecipitate material, and pre-sintering, ball milling, granulating, molding, sintering and grinding the coprecipitate sample to obtain the nickel-zinc ferrite product. The precipitates obtained by the method are mixed in a molecular or ionic state, are uniform in uniformity and good in activity, and can be used for preparing high-performance soft magnetic ferrite materials. But the method has higher production cost compared with the oxide method;

in conclusion, the oxide method of nickel-zinc ferrite has the disadvantages of high reaction temperature, difficult material mixing, large powder particles which are not beneficial to sintering, poor activity, large pollution and the like, and the chemical coprecipitation method of nickel-zinc ferrite has the disadvantages of high production cost and the like due to the requirement of pure metal or metal compounds as raw materials.

Disclosure of Invention

The invention aims to provide a method for preparing nickel-zinc ferrite by pressure acid leaching of sulphide ore, which aims to solve the problems in the background technology.

In order to achieve the purpose, the invention adopts the following technical scheme:

a method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore comprises the following steps:

firstly, weighing two minerals of nickel sulfide concentrate and zinc sulfide concentrate according to the mass ratio of nickel, zinc and iron in the product nickel-zinc ferrite, adding the two minerals and a certain amount of sulfuric acid solution into a pressure kettle, introducing oxygen, and carrying out pressure heating and stirring;

step two, filtering the ore pulp obtained by the acid leaching under oxygen pressure in the step one to respectively obtain filter residues and a leaching solution, washing the filter residues and piling up the filter residues, returning washing water to the acid leaching under oxygen pressure process, reducing ferric iron in the leaching solution into ferrous iron, reducing the ferric iron in the leaching solution by using a raw material sulfide ore as a reducing agent, returning the reduced filter residues to the pressure leaching process for leaching, and obtaining a filtrate as a reducing solution;

thirdly, purifying and decontaminating the reducing liquid in the second step, wherein the decontamination process is divided into a primary purification section and a deep purification section, the primary purification section is characterized in that lime milk is added into the reducing liquid as a neutralizer, the solution is neutralized until the pH value of the solution is 2.0-6.0, the temperature is controlled to be 30-95 ℃, the time is 0.5-2 h, a certain amount of flocculant PMA is added to remove silicon and aluminum, a certain amount of ammonium sulfide is added to remove copper and cadmium, a certain amount of ammonium fluoride is added to remove calcium and magnesium, the obtained primary purified liquid is subjected to deep purification, a certain amount of ammonium sulfate is added into the solution, most of nickel, zinc and iron generate double sulfate precipitates, impurity elements are remained in the solution, most of impurities in the solution can be removed, the double sulfate precipitates are added into a sulfuric acid solution to be dissolved, and simultaneously a certain amount of nickel sulfate, zinc sulfate and ferrous sulfate solution are added according to the proportion of nickel, zinc and iron of ferrite of the nickel and the product, finally, adding a little excessive ammonium oxalate for coprecipitation to obtain oxalate precipitates of nickel, zinc and iron.

As a further improvement scheme of the technical scheme: in the first step, the pressure acid leaching conditions are as follows: the liquid-solid ratio is 3-10: 1.

As a further improvement scheme of the technical scheme: in the first step, the pressure acid leaching conditions are as follows: the initial sulfuric acid concentration is 100g/L to 300 g/L.

As a further improvement scheme of the technical scheme: in the first step, the pressure acid leaching conditions are as follows: the time is 0.5h-2.0 h.

As a further improvement scheme of the technical scheme: in the first step, the pressure acid leaching conditions are as follows: the temperature is controlled between 110 ℃ and 200 ℃.

As a further improvement scheme of the technical scheme: in the first step, the pressure acid leaching conditions are as follows: the pressure is 0.4MPa-2.0 MPa.

As a further improvement scheme of the technical scheme: in the first step, the pressure acid leaching conditions are as follows: the stirring speed is 300r/min-700 r/min.

As a further improvement scheme of the technical scheme: in the second step, the reduction conditions are as follows: the usage amount of the sulphide ore is 1 to 4 times of the theoretical amount.

As a further improvement scheme of the technical scheme: in the second step, the reduction conditions are as follows: the temperature is 40-95 ℃ and the time is 0.5-3 h.

As a further improvement scheme of the technical scheme: in the second step, the reduction conditions are as follows: the stirring speed is 300r/min-700 r/mi.

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

(1) the leaching rate of the valuable metals of nickel, zinc and iron is high, and the cost is low. Compared with the traditional nickel-zinc ferrite preparation process, the invention takes sulfide concentrate of nickel, zinc and iron as raw materials, and utilizes the favorable conditions of high temperature, high pressure, strong oxidizing atmosphere and the like of the pressure acid leaching process, the leaching rate of nickel and zinc is up to more than 95 percent, the leaching rate of iron is up to more than 80 percent, and the leaching rate of valuable metals such as nickel, zinc, iron and the like is high. Compared with the traditional oxide method and coprecipitation method, the process takes sulfide concentrate as a raw material, the raw material is cheap and has wide sources, and the production cost can be greatly reduced.

(2) High utilization of iron and short technological process. In the smelting process of the nickel sulfide concentrate and the zinc sulfide concentrate, iron is removed as harmful impurities and is used for preparing the nickel-zinc ferrite material, and the iron is used as one of raw materials, so that the harmful impurities can be changed into useful metals, the iron removal process is reduced, the economic benefit is increased, and the process flow is shortened.

(3) Simple operation, reduced labor intensity and continuous production. Compared with the traditional nickel-zinc ferrite preparation process, the autoclave of the oxygen pressure acid leaching process adopted by the invention basically realizes automation, so that the operation is simpler and more convenient, the labor intensity can be reduced, and the production continuity is realized.

(4) Little environmental pollution and high heat utilization rate. The reaction of the invention is carried out in a pressurized reaction kettle, no toxic and harmful gas is generated, and no environmental pollution is caused basically. The autoclave has good tightness, and is provided with a heat insulation sleeve, so that the heat dissipation is small. The traditional nickel-zinc ferrite preparation process is open, a large amount of polluted gas is discharged, and heat is also dissipated greatly.

In conclusion, the method for directly preparing the nickel-zinc ferrite from the raw ore has the advantages of advanced process, high leaching rates of valuable metals of nickel, zinc and iron, low cost, simple and convenient operation, continuous production, small environmental pollution and high heat utilization rate. The method is suitable for nickel sulfide concentrate and zinc sulfide concentrate with various contents, in particular to high-iron nickel sulfide concentrate and high-iron zinc sulfide concentrate which have high iron content and are difficult to separate nickel iron and zinc iron, changes waste iron in raw ore into raw material, greatly improves the resource utilization rate, shortens the purification process and increases the economic benefit.

The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings. The detailed description of the present invention is given in detail by the following examples and the accompanying drawings.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:

FIG. 1 is a flow chart of a preferred embodiment of a method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore according to the present invention;

FIG. 2 is a process flow chart of a method for preparing nickel-zinc ferrite by pressure acid leaching of sulphide ore according to the present invention.

Detailed Description

The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention. The invention is described in more detail in the following paragraphs by way of example with reference to the accompanying drawings. Advantages and features of the present invention will become apparent from the following description and from the claims. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention.

It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When a component is referred to as being "connected" to another component, it can be directly connected to the other component or intervening components may also be present. When a component is referred to as being "disposed on" another component, it can be directly on the other component or intervening components may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

Referring to fig. 1-2, in an embodiment of the present invention, a method for preparing nickel-zinc ferrite by pressure acid leaching of sulfide ore includes the following steps:

firstly, weighing two minerals of nickel sulfide concentrate and zinc sulfide concentrate according to the mass ratio of nickel, zinc and iron in the product nickel-zinc ferrite, adding the two minerals and a certain amount of sulfuric acid solution into a pressure kettle, introducing oxygen, and carrying out pressure heating and stirring;

step two, filtering the ore pulp obtained by the acid leaching under oxygen pressure in the step one to respectively obtain filter residues and a leaching solution, washing the filter residues and piling up the filter residues, returning washing water to the acid leaching under oxygen pressure process, reducing ferric iron in the leaching solution into ferrous iron, reducing the ferric iron in the leaching solution by using a raw material sulfide ore as a reducing agent, returning the reduced filter residues to the pressure leaching process for leaching, and obtaining a filtrate as a reducing solution;

thirdly, purifying and decontaminating the reducing liquid in the second step, wherein the decontamination process is divided into a primary purification section and a deep purification section, the primary purification section is characterized in that lime milk is added into the reducing liquid as a neutralizer, the solution is neutralized until the pH value of the solution is 2.0-6.0, the temperature is controlled to be 30-95 ℃, the time is 0.5-2 h, a certain amount of flocculant PMA is added to remove silicon and aluminum, a certain amount of ammonium sulfide is added to remove copper and cadmium, a certain amount of ammonium fluoride is added to remove calcium and magnesium, the obtained primary purified liquid is subjected to deep purification, a certain amount of ammonium sulfate is added into the solution, most of nickel, zinc and iron generate double sulfate precipitates, impurity elements are remained in the solution, most of impurities in the solution can be removed, the double sulfate precipitates are added into a sulfuric acid solution to be dissolved, and simultaneously a certain amount of nickel sulfate, zinc sulfate and ferrous sulfate solution are added according to the proportion of nickel, zinc and iron of ferrite of the nickel and the product, finally, adding a little excessive ammonium oxalate for coprecipitation to obtain oxalate precipitates of nickel, zinc and iron.

Preferably, in the first step, the pressure acid leaching conditions are as follows: the liquid-solid ratio is 3-10: 1.

Preferably, in the first step, the pressure acid leaching conditions are as follows: the initial sulfuric acid concentration is 100g/L to 300 g/L.

Preferably, in the first step, the pressure acid leaching conditions are as follows: the time is 0.5 h-2.0.

Preferably, in the first step, the pressure acid leaching conditions are as follows: the temperature is controlled between 110 ℃ and 200 ℃.

Preferably, in the first step, the pressure acid leaching conditions are as follows: the pressure is 0.4MPa-2.0 MPa.

Preferably, in the first step, the pressure acid leaching conditions are as follows: the stirring speed is 300r/min-700 r/min.

Preferably, in the second step, the reduction conditions are: the usage amount of the sulphide ore is 1 to 4 times of the theoretical amount.

Preferably, in the second step, the reduction conditions are: the temperature is 40-95 ℃ and the time is 0.5-3 h.

Preferably, in the second step, the reduction conditions are: the stirring speed is 300r/min-700 r/mi.

The following explains a method for preparing a precursor of a positive electrode material by using a waste ternary lithium battery according to the present invention by using a specific embodiment:

example 1

According to the formula Ni of nickel-zinc ferrite_0.6Zn_0.4Fe₂O₄Nickel sulfide concentrate (Ni content 6.56%, Fe content 26.19%) and zinc sulfide concentrate (Zn content 50.08%, Fe content 6) were weighed in a certain proportion.77%) two minerals, adding the two minerals and a certain amount of sulfuric acid solution into a pressurized kettle, introducing oxygen, and controlling the conditions of pressurized acid leaching as follows: the liquid-solid ratio is 6:1, the initial sulfuric acid concentration is 180g/L, the time is 1.5h, the temperature is controlled at 160 ℃, and the stirring speed is 600r/min under the pressure of 0.8 MPa. The leaching rates of nickel, zinc and iron were 95.54%, 99.42% and 82.05%, respectively.

Filtering the leached ore pulp, washing and piling filter residues, returning washing water to the oxygen pressure acid leaching process, reducing ferric iron in the solution by using the raw material sulfide ore as a reducing agent, and returning the reduced filter residues to the pressure leaching process for leaching. The reduction conditions were controlled as follows: the usage amount of the sulphide ore is 2.2 times of the theoretical amount, the temperature is 90 ℃, the time is 1.5h, and the stirring speed is 600 r/min. The reduction rate of ferric iron in the solution is 95.07 percent, lime milk is firstly added into the reduction solution as a neutralizer, the solution is neutralized until the pH value of the solution is 4.5, the temperature is controlled to be 60 ℃, the reaction time is 1 hour, a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide are added for primary impurity removal and purification, and ammonium sulfate is added into the solution for deep purification after the primary purification. Adding ammonium oxalate for coprecipitation after the solution preparation to obtain oxalate precipitates of nickel, zinc and iron.

Example 2

According to the formula Ni of nickel-zinc ferrite_0.6Zn_0.4Fe₂O₄Weighing two minerals of nickel sulfide concentrate (Ni content 6.56%, Fe content 26.19%) and zinc sulfide concentrate (Zn content 50.08%, Fe content 6.77%) according to a certain proportion, adding the two minerals and a certain amount of sulfuric acid solution into a pressurized kettle, introducing oxygen, and controlling the conditions of pressurized acid leaching as follows: the liquid-solid ratio is 5:1, the initial sulfuric acid concentration is 220g/L, the time is 2h, the temperature is controlled at 200 ℃, the pressure is 1.2MPa, and the stirring speed is 600 r/min. The leaching rates of nickel, zinc and iron are respectively 98.78%, 99.61% and 81.67%.

Filtering the leached ore pulp, washing and piling filter residues, returning washing water to the oxygen pressure acid leaching process, reducing ferric iron in the solution by using the raw material sulfide ore as a reducing agent, and returning the reduced filter residues to the pressure leaching process for leaching. The reduction conditions were controlled as follows: the usage amount of the sulphide ore is 3 times of the theoretical amount, the temperature is 70 ℃, the time is 1.5h, and the stirring speed is 600 r/min. The reduction rate of ferric iron in the solution is 96.33%, lime milk is firstly added into the reduction solution as a neutralizer, the solution is neutralized until the pH value of the solution is 4.5, the temperature is controlled at 70 ℃, the reaction time is 1.5h, a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide are added for primary impurity removal and purification, and ammonium sulfate is added into the solution for deep purification after the primary purification. Adding ammonium oxalate for coprecipitation after the solution preparation to obtain oxalate precipitates of nickel, zinc and iron.

Example 3

According to the formula Ni of nickel-zinc ferrite_0.35Zn_0.65Fe₂O₄Weighing two minerals of nickel sulfide concentrate (Ni content 6.56%, Fe content 26.19%) and zinc sulfide concentrate (Zn content 50.08%, Fe content 6.77%) according to a certain proportion, adding the two minerals and a certain amount of sulfuric acid solution into a pressurized kettle, introducing oxygen, and controlling the conditions of pressurized acid leaching as follows: the liquid-solid ratio is 6:1, the initial sulfuric acid concentration is 200g/L, the time is 1.5h, the temperature is controlled at 160 ℃, and the stirring speed is 600r/min under the pressure of 1.0 MPa. The leaching rates of nickel, zinc and iron were 97.73%, 99.78% and 83.16%, respectively.

Filtering the leached ore pulp, washing and piling filter residues, returning washing water to the oxygen pressure acid leaching process, reducing ferric iron in the solution by using the raw material sulfide ore as a reducing agent, and returning the reduced filter residues to the pressure leaching process for leaching. The reduction conditions were controlled as follows: the usage amount of the sulphide ore is 2.5 times of the theoretical amount, the temperature is 50 ℃, the time is 2.0h, and the stirring speed is 600 r/min. The reduction rate of ferric iron in the solution is 96.18%, lime milk is firstly added into the reduction solution as a neutralizer, the solution is neutralized until the pH value of the solution is 4.0, the temperature is controlled to be 80 ℃, the reaction time is 2 hours, a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide are added for primary impurity removal and purification, and ammonium sulfate is added into the solution for deep purification after the primary purification. Adding ammonium oxalate for coprecipitation after the solution preparation to obtain oxalate precipitates of nickel, zinc and iron.

Example 4

According to the formula Ni of nickel-zinc ferrite_0.35Zn_0.65Fe₂O₄Weighing two minerals of nickel sulfide concentrate (Ni content 4.47%, Fe content 35.36%) and zinc sulfide concentrate (Zn content 45.47%, Fe content 9.03%) according to a certain proportion, adding the two minerals and a certain amount of sulfuric acid solution into a pressurized kettle, introducing oxygen, and controlling the conditions of pressurized acid leaching as follows: liquid for treating urinary tract infectionThe solid ratio is 7:1, the initial sulfuric acid concentration is 160g/L, the time is 2.0h, the temperature is controlled at 200 ℃, and the stirring speed is 600r/min under the pressure of 1.5 MPa. The leaching rates of nickel, zinc and iron were 95.75%, 99.55% and 80.31%, respectively.

Filtering the leached ore pulp, washing and piling filter residues, returning washing water to the oxygen pressure acid leaching process, reducing ferric iron in the solution by using the raw material sulfide ore as a reducing agent, and returning the reduced filter residues to the pressure leaching process for leaching. The reduction conditions were controlled as follows: the usage amount of the sulphide ore is 2.0 times of the theoretical amount, the temperature is 60 ℃, the time is 1.0h, and the stirring speed is 600 r/min. The reduction rate of ferric iron in the solution is 94.73%, lime milk is firstly added into the reduction solution as a neutralizer, the solution is neutralized until the pH value of the solution is 4.0, the temperature is controlled to be 80 ℃, the reaction time is 2 hours, a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide are added for primary impurity removal and purification, and ammonium sulfate is added into the solution for deep purification after the primary purification. Adding ammonium oxalate for coprecipitation after the solution preparation to obtain oxalate precipitates of nickel, zinc and iron.

Example 5

According to the formula Ni of nickel-zinc ferrite_0.35Zn_0.65Fe₂O₄Weighing two minerals of nickel sulfide concentrate (Ni content 4.47%, Fe content 35.36%) and zinc sulfide concentrate (Zn content 45.47%, Fe content 9.03%) according to a certain proportion, adding the two minerals and a certain amount of sulfuric acid solution into a pressurized kettle, introducing oxygen, and controlling the conditions of pressurized acid leaching as follows: the liquid-solid ratio is 6:1, the initial sulfuric acid concentration is 210g/L, the time is 2.0h, the temperature is controlled at 200 ℃, the pressure is 1.5MPa, and the stirring speed is 500 r/min. The leaching rates of nickel, zinc and iron are respectively 98.84%, 99.86% and 84.22%.

Filtering the leached ore pulp, washing and piling filter residues, returning washing water to the oxygen pressure acid leaching process, reducing ferric iron in the solution by using the raw material sulfide ore as a reducing agent, and returning the reduced filter residues to the pressure leaching process for leaching. The reduction conditions were controlled as follows: the usage amount of the sulphide ore is 3.0 times of the theoretical amount, the temperature is 90 ℃, the time is 2.0h, and the stirring speed is 600 r/min. The reduction rate of ferric iron in the solution is 96.36%, lime milk is firstly added into the reduction solution as a neutralizer, the solution is neutralized until the pH value of the solution is 4.5, the temperature is controlled at 50 ℃, the reaction time is 1.5h, a certain amount of flocculating agents PMA, ammonium fluoride and ammonium sulfide are added for primary impurity removal and purification, and ammonium sulfate is added into the solution for deep purification after the primary purification. Adding ammonium oxalate for coprecipitation after the solution preparation to obtain oxalate precipitates of nickel, zinc and iron.

The working principle of the invention is as follows:

the proper pressure acid leaching condition with the temperature of 110-200 ℃ and the pressure of 0.4-2.0 MPa is controlled, and the following reaction mainly occurs, (1) NiS +1/2O₂+H₂SO₄＝NiSO₄+S+H₂O；

(2)FeS+1/2O₂+H₂SO₄＝FeSO₄+S+H₂O；

(3)ZnS+1/2O₂+H₂SO₄＝ZnSO₄+S+H₂O；

(4)4FeSO₄+O₂+2H₂SO₄＝2Fe₂(SO₄)₃+2H₂And O. The reaction rate is accelerated under the high-temperature high-pressure strong oxidizing condition of the pressurized kettle, so that the leaching rate of the valuable metals of nickel, zinc and iron is greatly improved. And then, the raw material sulphide ore is used as a reducing agent, and ferric ions in the reduction leachate are ferrous ions, so that the iron in the solution cannot be neutralized and precipitated in the subsequent impurity removal process, and the iron in the nickel-zinc ferrite prepared by subsequent coprecipitation can be better precipitated by coprecipitation with nickel and zinc. The reducing liquid contains valuable metal ions of nickel, zinc and iron, and also contains impurities of silicon, aluminum, copper, cadmium, calcium, magnesium and the like, lime milk is firstly added into the reducing liquid for neutralization and precipitation to remove silicon and aluminum, ammonium sulfide is then added for precipitation to remove copper and cadmium, ammonium fluoride is then added for precipitation to remove calcium and magnesium for primary purification, finally, a deep purification process of sulfate double salt precipitation is carried out to obtain pure nickel, zinc and iron sulfate solution, and a pure sulfate solution is added. Adding a precipitator ammonium oxalate into the prepared solution to obtain a coprecipitation powder product of nickel, zinc and iron.

The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; the present invention may be readily implemented by those of ordinary skill in the art as illustrated in the accompanying drawings and described above; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the scope of the invention as defined by the appended claims; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.