CN113584314A - High nickel matte normal pressure leaching method and nickel sulfate - Google Patents
High nickel matte normal pressure leaching method and nickel sulfate Download PDFInfo
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- CN113584314A CN113584314A CN202110863150.5A CN202110863150A CN113584314A CN 113584314 A CN113584314 A CN 113584314A CN 202110863150 A CN202110863150 A CN 202110863150A CN 113584314 A CN113584314 A CN 113584314A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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Abstract
The application provides a high nickel matte normal pressure leaching method and nickel sulfate, the method comprises a first normal pressure leaching process and a second normal pressure leaching process, ultrasonic waves and oxygen are applied in the first normal pressure leaching process and the second normal pressure leaching process, on one hand, no hydrogen peroxide water is consumed, the leaching cost is low, and no transportation, storage and process control risks exist; on the other hand, the stability of the raw materials in the leaching process is damaged, the raw materials are prevented from being wrapped by the leaching liquid, the activity is reduced, the leaching rate of Ni in the normal-pressure leaching process is improved, the material throughput of a high-pressure leaching system is greatly reduced, the volume design amount of a pressure kettle is small, and the production management and control are safer; and finally, the oxygen is promoted to efficiently contact with the raw material and the hydrogen sulfide generated in the leaching process, the hydrogen sulfide can be quickly converted into sulfuric acid, the treatment risk of the hydrogen sulfide gas is effectively reduced, and the leaching process is safer.
Description
Technical Field
The application relates to the technical field of hydrometallurgy, in particular to a high nickel matte normal pressure leaching method and nickel sulfate.
Background
In the development of the current ternary battery, the tendency of high nickel is more obvious, and the high nickel and cobalt reduction can improve the energy density of the battery and also can reduce the cost of the battery. The high nickel matte is used as a nickel raw material, belongs to sulfide eutectic of metals such as nickel, copper, cobalt, iron and the like, and mainly exists in sulfide phases and a small amount of alloy phases. In the prior art, although normal pressure and high pressure leaching are mentioned, the leaching rate in the normal pressure process is low and is only 30-50%, the material throughput of a subsequent high pressure leaching system is still very large, the equipment volume is large, the manufacturing cost is high, and the safety is low.
Disclosure of Invention
The application aims to provide a high nickel matte normal-pressure leaching method, and aims to improve the leaching rate of normal-pressure leaching before high nickel matte high-pressure leaching.
In order to achieve the above object, the present application provides a high nickel matte atmospheric pressure leaching method, comprising:
carrying out first normal-pressure leaching on the nickel matte by using a first acid solution to obtain a first leaching solution and first leaching residues;
performing second normal-pressure leaching on the first leaching residue by using a second acid solution to obtain a second leaching solution and second leaching residue;
wherein, ultrasonic waves and oxygen are applied in the first atmospheric leaching process and the second atmospheric leaching process.
Preferably, in the first atmospheric pressure leaching process, adding acid to maintain the pH value of the first acid solution at 0.5-1.5; 5-10 liters of the first acid solution is used for each kilogram of the high nickel matte.
Preferably, in the second acid solution, the initial H2SO4The concentration is 150-250 g/L; and 1.5-4 liters of second acid solution is used for each kilogram of first leaching residues.
Preferably, the frequency of the ultrasonic waves is 20-100 kHz; the flux of oxygen is 5-50 m3V (h) ton dry material), oxygen concentration is 50-95%.
Preferably, the leaching time of the first atmospheric leaching and the leaching time of the second atmospheric leaching are respectively and independently 1-10 h.
Preferably, in the first atmospheric pressure leaching process and the second atmospheric pressure leaching process, the first acid solution and the second acid solution are respectively leached in a circulating mode through the sanding equipment.
Preferably, the second leach solution is returned to the first atmospheric leach process for use as the first acid liquor.
Preferably, the leaching temperatures of the first atmospheric leaching and the second atmospheric leaching are respectively 70-100 ℃.
Preferably, the first atmospheric pressure leaching further comprises: the high nickel matte is crushed and ground to a particle size of 80-400 meshes.
The application also provides nickel sulfate obtained by the high nickel matte normal pressure leaching method.
Compared with the prior art, the beneficial effect of this application includes:
the application provides a high nickel matte normal pressure leaching method, ultrasonic waves and oxygen are applied in a first normal pressure leaching process and a second normal pressure leaching process, on one hand, no hydrogen peroxide water is consumed, the leaching cost is low, and no transportation, storage and process control risks exist; on the other hand, the solution is subjected to the violently changed pressure in the process of propagation by the ultrasonic waves, so that strong stirring can be formed, the diffusion resistance of the solute is obviously reduced, and the mass transfer efficiency is improved. The inclusions generated before and during the reaction of the raw materials under the conventional conditions can be removed under the action of ultrasound, so that the stability of the raw materials in the leaching process is damaged, the raw materials are prevented from being wrapped by the leaching solution, the activity is reduced, the leaching rate of Ni in the normal-pressure leaching process is improved, the material throughput of a high-pressure leaching system is greatly reduced, the design volume of a pressure kettle is small, and the production management and control are safer; finally, under the vibration of ultrasonic waves and the pushing of ultrasonic air volume, leachate and oxygen radicals are continuously collided and quickly react, tens of thousands of tiny bubbles, namely cavitation bubbles, are generated, the bubbles grow in a negative pressure area formed by the longitudinal propagation of the ultrasonic waves, and are quickly closed in a positive pressure area, so that the bubbles are compressed and stretched under the alternate positive and negative pressure, the oxygen is promoted to efficiently contact with raw materials and the oxygen and hydrogen sulfide generated in the leaching process, the hydrogen sulfide can be quickly converted into sulfuric acid, the treatment risk of the hydrogen sulfide gas is effectively reduced, and the leaching process is safer.
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 flow diagram of the high nickel matte atmospheric pressure leaching method of the present invention;
FIG. 2 is a specific process flow diagram of the high nickel matte atmospheric pressure leaching method of the invention.
Detailed Description
The terms as used herein:
"prepared from … …" 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 … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than 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 the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 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 any 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).
The application provides a high nickel matte normal-pressure leaching method, which can improve the leaching rate of high nickel matte in the normal-pressure leaching process, so that the volume of a used high-pressure kettle is reduced in the subsequent high-pressure leaching process of the high nickel matte, and the safety is higher. Please refer to fig. 1, which includes:
s101: and (3) carrying out first atmospheric leaching on the nickel matte by using a first acid solution, and applying ultrasonic waves and oxygen in the first atmospheric leaching process to obtain a first leaching solution and first leaching residues.
Specifically, the first acid solution may be, for example, a sulfuric acid solution, and for example, high nickel matte is slurried with water and supplemented with concentrated sulfuric acid, thereby obtaining the first acid solution. In the first atmospheric pressure leaching process, the elemental nickel reacts with sulfuric acid to generate nickel sulfate, so that the sulfuric acid is continuously consumed, and therefore, the sulfuric acid is continuously supplemented in the first atmospheric pressure leaching process to maintain the pH value of the first acid solution to be 0.5-1.5 and ensure that the pH value of the first leaching solution after the first atmospheric pressure leaching is finished is also 0.5-1.5. Specifically, the pH of the first acid solution may be maintained at any value (0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5) or between 0.5 and 1.5. More preferably, the pH value of the first acid solution is maintained at 0.5-1.0.
Specifically, at the beginning of the first atmospheric leaching, the usage amount of the first acid solution and the high nickel matte should meet the requirement that 5-10 liters of the first acid solution is used per kilogram of the high nickel matte. For example, 5, 6, 7, 8, 9, or 10 liters of the first acid solution per kilogram of nickel matte, or any value between 5 and 10 liters, may be used.
Optionally, the temperature of the first atmospheric leaching is 70-100 ℃, for example, (70, 75, 80, 85, 90, 95 or 100) ℃ or any value between 70-100 ℃. More preferably, the temperature of the first atmospheric leach is 85 ℃.
Optionally, the leaching time of the first atmospheric leaching is 1-10 h, for example, (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) h, or any value between 1-10 h. Preferably, the leaching time of the first atmospheric leaching is 6-8 h.
Oxygen is applyed at first ordinary pressure leaching process to this application scheme, oxidizes through oxygen, and no hydrogen peroxide solution consumes, leaches low cost, and no transportation, storage, process management and control risk, reaction process are mainly as follows.
Ni+H2SO4→NiSO4+H2↑
Because fine unreacted nickel matte raw materials can be quickly leached by NiSO generated in the leaching solution in the normal pressure leaching process4And (3) the activity is greatly reduced by wrapping. Thus ultrasonic waves are also applied during the first atmospheric leaching. The solution is subjected to the pressure which is changed violently in the process of propagation by ultrasonic waves, so that strong stirring can be formed, the diffusion resistance of solute is obviously reduced, the mass transfer efficiency is improved, and NiSO generated on the surface of the raw material is removed4And the covering material prevents the raw material from being wrapped by the leaching solution, reduces the activity and improves the leaching rate of Ni in the normal pressure leaching process.
Under the vibration of ultrasonic waves and the pushing of the ultrasonic air quantity, the leachate and the oxygen radicals continuously collide and rapidly react to generate tens of thousands of micro bubbles, namely cavitation bubbles. The bubbles grow in the negative pressure area formed by the longitudinal propagation of the ultrasonic waves, and are quickly closed in the positive pressure area, so that the bubbles are compressed and stretched under the alternate positive and negative pressure, oxygen is fully fused and reacted with the leaching solution, and the leaching rate of nickel is improved.
In addition, the nickel matte directly reacts with sulfuric acid to release toxic hydrogen sulfide gas, ultrasonic oxygen is assisted in the first normal-pressure leaching process to oxidize and leach, oxygen is enabled to be in efficient contact with raw materials, oxygen and hydrogen sulfide, hydrogen sulfide can be rapidly converted into sulfuric acid, the disposal risk of hydrogen sulfide gas is effectively reduced, and the leaching process is safer.
Specifically, the ultrasonic wave and the oxygen gas may be applied, for example, by inserting an ultrasonic probe into the first atmospheric leaching tank and introducing oxygen gas into the first atmospheric leaching tank.
Specifically, the frequency of the ultrasonic waves applied in the first atmospheric leaching process is 20 to 100kHz, and may be (20, 30, 40, 50, 60, 70, 80, 90, or 100) kHz or any value between 20 and 100kHz, for example.
The flux of oxygen applied in the first atmospheric pressure leaching process is 5-50 m3/(h) tons of dry matter), e.g. may be (5, 10, 20, 30, 40 or 50) m3V (h) ton of dry material, or 5 to 50m3Any value between/(h dry matter). The concentration of oxygen applied is 50 to 95%, and may be, for example, (50, 60, 70, 80, 90, or 95)%, or any value between 50 and 95%.
More preferably, referring to fig. 2 together, in order to further improve the activity of nickel matte in the leaching process, in the first atmospheric pressure leaching process, the first acid solution, i.e. the leaching slurry, may be returned to the leaching tank after passing through the sanding device, and leaching is continuously circulated, and the stability of the raw material in the leaching process may be further destroyed through the sanding device, so that more nickel reacts with sulfuric acid, and the leaching rate of elemental nickel is further improved.
Referring to fig. 2, the first atmospheric leaching further comprises crushing: the high nickel matte is crushed and ground to a particle size of 80-400 meshes. The contact area of the crushed nickel matte, oxygen and sulfuric acid is increased, the reaction is easier, and the leaching rate of nickel is improved.
Referring to fig. 2, after the first atmospheric pressure leaching is completed, a first leaching solution and first leaching residues are obtained through solid-liquid separation, the first leaching solution comprises leached elemental nickel, the first leaching solution enters a subsequent purification and impurity removal process, and the first leaching residues enter a subsequent second atmospheric pressure leaching process.
S102: and performing second normal-pressure leaching on the first leaching slag by using a second acid solution, and applying ultrasonic waves and oxygen in the second normal-pressure leaching process to obtain a second leaching solution and second leaching slag.
Specifically, the first leaching residue is mainly sulfide nickel, and under the condition of high-concentration acid, part of the residue is activated again to promote sulfuric acid to further diffuse into the particles of the first leaching residue, so that unreacted residue is digested. The second acid liquor may be, for example, a high-concentration sulfuric acid, and the first leach residue may be slurried with water and supplemented with concentrated sulfuric acid to obtain the second acid liquor. In the second acid solution, the initial H should be ensured2SO4The concentration is 150-250 g/L to ensure that the second atmospheric leaching is completed, and the leaching solution has higher acid concentration. For example, the concentration may be (150, 160, 170, 180, 190, 200, 210, 220, 230, 240, or 250) g/L, or any value between 150 and 250 g/L.
Specifically, the second atmospheric leaching starts with 1.5 to 4 liters of the second acid solution per kilogram of the first leaching residue, and may be (1.5, 2.0, 2.5, 3.0, 3.5, or 4.0) liters, or any value between 1.5 and 4 liters, for example.
Optionally, the temperature of the second atmospheric leaching is 70-100 ℃, for example, (70, 75, 80, 85, 90, 95 or 100) ℃ or any value between 70-100 ℃. More preferably, the temperature of the first atmospheric leach is 85 ℃. The temperature of the second atmospheric leach may or may not be the same as the temperature of the first atmospheric leach.
Optionally, the leaching time of the second atmospheric leaching is 1-10 h, for example, (1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) h, or any value between 1-10 h. Preferably, the leaching time of the first atmospheric leaching is 5-9 h. The leaching time of the second atmospheric leaching may be the same as or different from the leaching time of the first atmospheric leaching.
Oxygen is also applyed at the second ordinary pressure in-process of leaching to this application scheme, oxidizes through oxygen, and no hydrogen peroxide water consumes, leaches low cost, and no transportation, storage, process management and control risk, reaction process are as follows.
As the fine unreacted first leaching residue raw material can be quickly leached by the NiSO generated in the leaching solution in the normal pressure leaching process4And (3) the activity is greatly reduced by wrapping. Ultrasonic waves are thus also applied during the second atmospheric leaching. The solution is subjected to the pressure which is changed violently in the process of propagation by ultrasonic waves, so that strong stirring can be formed, the diffusion resistance of solute is obviously reduced, the mass transfer efficiency is improved, and NiSO generated on the surface of the first leaching residue raw material is removed4And the covering material prevents the raw material from being wrapped by the leaching solution, reduces the activity and improves the leaching rate of the sulfide Ni in the normal pressure leaching process. Through two times of normal pressure leaching, the leaching rate of the normal pressure leaching nickel can reach 70%, the material throughput of a high pressure leaching system is greatly reduced, the design volume of a pressure kettle is small, and the production management and control are safer.
Under the vibration of ultrasonic waves and the pushing of the ultrasonic air quantity, the leachate and the oxygen radicals continuously collide and rapidly react to generate tens of thousands of micro bubbles, namely cavitation bubbles. The bubbles grow in a negative pressure area formed by the longitudinal propagation of the ultrasonic waves, and are quickly closed in a positive pressure area, so that the bubbles are compressed and stretched under the alternate positive and negative pressure, oxygen is fully fused and reacted with the leaching solution, and the leaching rate of the nickel in a sulfide state is improved.
In addition, the sulfuration state nickel reacts with sulfuric acid to release toxic gas of hydrogen sulfide, ultrasonic oxygen is assisted in the second normal-pressure leaching process to oxidize and leach, so that oxygen is enabled to be in efficient contact with the raw material, the oxygen and the hydrogen sulfide, the hydrogen sulfide can be quickly converted into the sulfuric acid, the disposal risk of the hydrogen sulfide gas is effectively reduced, and the leaching process is safer.
Specifically, the ultrasonic wave and the oxygen gas may be applied, for example, by inserting an ultrasonic probe into the second atmospheric leaching tank and introducing oxygen gas into the second atmospheric leaching tank.
Ultrasonic waves and oxygen are applied in the second atmospheric pressure leaching process, no hydrogen peroxide water (fire hazard substances of type A) is consumed, the leaching cost is low, and no transportation, storage and process control risks exist. The second normal pressure leaching process is assisted with ultrasonic oxygen oxidation leaching, so that oxygen is enabled to be in high-efficiency contact with the raw material, the oxygen and hydrogen sulfide generated in the leaching process, the hydrogen sulfide can be quickly converted into sulfuric acid, the treatment risk of hydrogen sulfide gas is effectively reduced, and the leaching process is safer.
Specifically, the frequency of the ultrasonic waves applied in the second atmospheric leaching process is 20 to 100kHz, for example, (20, 30, 40, 50, 60, 70, 80, 90, or 100) kHz, or any value between 20 and 100 kHz. The wavelength of the applied ultrasonic wave is 0.02 to 0.1cm, and may be (0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.1) cm, or any value between 0.02 to 0.1cm, for example.
The oxygen flux applied in the second atmospheric pressure leaching process is 5-50 m3/(h) tons of dry matter), e.g. may be (5, 10, 20, 30, 40 or 50) m3V (h) ton of dry material, or 5 to 50m3Any value between/(h dry matter). The concentration of oxygen applied is 50 to 95%, and may be, for example, (50, 60, 70, 80, 90, or 95)%, or any value between 50 and 95%.
It is understood that the ultrasonic waves and oxygen applied in the first atmospheric leaching process may or may not be the same as the ultrasonic waves and oxygen applied in the second atmospheric leaching process. Preferably, the ultrasonic waves and the oxygen applied in the first atmospheric leaching process are the same as those applied in the second atmospheric leaching process, so that only one application parameter needs to be adjusted in two leaching processes, and the process is simpler.
More preferably, referring to fig. 2 together, in order to further improve the activity of the raw material in the leaching process, in the second atmospheric pressure leaching process, the second acid solution, i.e. the leaching slurry, is returned to the leaching tank through the sanding device, and is continuously and circularly leached, and the stability of the raw material in the leaching process can be further destroyed through the sanding device, so that more nickel reacts with sulfuric acid, and the leaching rate of nickel in a sulfide state is further improved.
Specifically, referring to fig. 2, after the second atmospheric pressure leaching is completed, a second leaching solution and a second leaching residue are obtained through solid-liquid separation. And the second leaching slag enters a subsequent high-pressure leaching system to further leach nickel at high pressure.
The second leaching solution can be returned to the first atmospheric leaching process to be used as the first acid solution, and the circulation is carried out, so that the nickel leached by the first atmospheric leaching solution and the nickel leached by the second atmospheric leaching solution are both in the first leaching solution, and the high-pressure leaching solution and the first leaching solution only need to be purified and purified subsequently.
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 conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Grinding: 5kg of high nickel matte (purchased from Jilin Jien Nickel industries, Ltd.) was ground to 150 mesh by a ball mill, and the results of the detection of the high nickel matte component are shown in Table 1.
TABLE 1 high nickel matte content test results
| Co％ | Mn％ | Ni％ | Cu％ | Fe％ | Al％ |
| 1.17 | 0.0028 | 60.29 | 12.59 | 3.28 | 0.0005 |
| Ca％ | Mg％ | As％ | S％ | Zn％ | H2O％ |
| 0.0014 | 0.0011 | 0.055 | 12.53 | 0.0003 | 0.93 |
First atmospheric leaching: the ratio of the mass (kg) of the high nickel matte to the volume (L) of the water in the ground high nickel matte is 1: 8 pulping (water 40L), supplementing concentrated sulfuric acid after pulping to control leaching pH value to be maintained at 1.0, leaching with ultrasonic oxygen, returning leaching liquor from leaching tank to leaching tank after passing through sanding equipment, and continuously and circularly leaching with ultrasonic frequency of 40kHz and oxygen flux of 30m3And v, performing solid-liquid separation to obtain a first leaching solution and first leaching slag after leaching for 6 hours, wherein the leaching rate of nickel after the first normal pressure leaching reaches 55.3% after accounting of nickel in the slag.
Second atmospheric leaching: the first leaching residue is extracted by water according to the ratio of the mass (kg) of the first leaching residue to the volume (L) of the water of 1: 2.5 carrying out the pulpAfter slurrying is finished, adding concentrated sulfuric acid to the initial H2SO4The concentration is 220g/L, the leaching tank is assisted with ultrasonic oxygen for leaching, during the leaching, leaching liquor in the leaching tank returns to the leaching tank after passing through sanding equipment, and is continuously and circularly leached, the ultrasonic frequency is 40kHz, and the oxygen flux is 30m3And (h) t dry material), the oxygen concentration is 90.5%, after the leaching time is 8h, the solid-liquid separation is carried out to obtain a second leaching solution and second leaching slag, the second leaching solution can be returned to be used as the bottom water of the first normal-pressure leaching tank, and the second leaching slag enters a high-pressure leaching system. After the second atmospheric pressure leaching, the leaching rate of the nickel reaches 40.6 percent.
Through two-stage normal pressure leaching, the comprehensive leaching rate of nickel reaches 73.4 percent, and the normal pressure leaching rate of the high nickel matte is greatly improved.
Example 2
The only difference from example 1 is:
first atmospheric leaching: the ratio of the mass (kg) of the high nickel matte to the volume (L) of the water in the ground high nickel matte is 1: 6 slurrying (30L of water), supplementing concentrated sulfuric acid after slurrying to control the leaching pH value to be maintained at 1.2, supplementing ultrasonic oxygen to the leaching tank for leaching, returning leaching liquor from the leaching tank to the leaching tank after passing through sanding equipment, and continuously and circularly leaching, wherein the ultrasonic frequency is 50kHz, and the oxygen flux is 20m3And (h) ton of dry material), the oxygen concentration is 88%, the first leaching liquid and the first leaching slag are obtained by solid-liquid separation after 9h of leaching, the nickel is contained in the slag by accounting, and the leaching rate of the nickel after the first normal pressure leaching reaches 53.29%.
Second atmospheric leaching: the first leaching residue is extracted by water according to the ratio of the mass (kg) of the first leaching residue to the volume (L) of the water of 1: 3, slurrying, and adding concentrated sulfuric acid to the initial H after slurrying2SO4The concentration is 250g/L, the leaching tank is assisted with ultrasonic oxygen for leaching, during the leaching, leaching liquor in the leaching tank returns to the leaching tank after passing through sanding equipment, and is continuously and circularly leached, the ultrasonic frequency is 50kHz, and the oxygen flux is 40m3And (h) ton of dry materials), the oxygen concentration is 88%, solid-liquid separation is carried out after 9h of leaching time to obtain a second leaching solution and second leaching residues, the second leaching solution can be returned to be used as bottom water of the first normal-pressure leaching tank, and the second leaching residues enter a high-pressure leaching system. After the second atmospheric pressure leaching, the second leaching residueThe leaching rate of the nickel in the nickel reaches 41.18 percent.
Through two-stage normal pressure leaching, the comprehensive leaching rate of nickel reaches 72.53%, and the normal pressure leaching rate of the high nickel matte is greatly improved.
Example 3
The difference from example 1 is that:
first atmospheric leaching: the ratio of the mass (kg) of the high nickel matte to the volume (L) of the water in the ground high nickel matte is 1: 10 pulping (50L of water), supplementing concentrated sulfuric acid after pulping to control the pH value of leaching to be maintained at 0.5, leaching with ultrasonic oxygen in a leaching tank, returning leaching liquor from the leaching tank to the leaching tank after passing through a sanding device, continuously and circularly leaching, wherein the ultrasonic frequency is 80kHz, and the oxygen flux is 50m3And v, the oxygen concentration is 95%, the first leaching liquid and the first leaching slag are obtained through solid-liquid separation after leaching for 6 hours, the nickel in the slag is calculated, and the leaching rate of the nickel after the first normal pressure leaching reaches 55.52%.
Second atmospheric leaching: the first leaching residue is extracted by water according to the ratio of the mass (kg) of the first leaching residue to the volume (L) of the water of 1: 2, slurrying, and adding concentrated sulfuric acid to the initial H after slurrying2SO4The concentration is 150g/L, the leaching tank is assisted with ultrasonic oxygen for leaching, during the leaching, leaching liquor in the leaching tank returns to the leaching tank after passing through sanding equipment, and is continuously and circularly leached, the ultrasonic frequency is 80kHz, and the oxygen flux is 50m3And h, the oxygen concentration is 95%, after leaching for 5h, solid-liquid separation is carried out to obtain a second leaching solution and second leaching residues, the second leaching solution can be returned to be used as bottom water of the first normal-pressure leaching tank, and the second leaching residues enter a high-pressure leaching system. After the second normal pressure leaching, the leaching rate of the nickel in the second leaching residue reaches 39.61%.
Through two-stage normal pressure leaching, the comprehensive leaching rate of nickel reaches 73.14%, and the normal pressure leaching rate of the high nickel matte is greatly improved.
Example 4
The only difference from example 1 is: in the first atmospheric leaching process and the second atmospheric leaching process, leaching liquor in the leaching tank does not return to the leaching tank after passing through sanding equipment, and continuous cyclic leaching is not carried out.
In the atmospheric leaching method of example 4, the leaching rate of nickel in the nickel matte after the first atmospheric leaching process was 43.36%, the leaching rate of nickel in the first leaching residue after the second atmospheric leaching process was 32.43%, and the combined leaching rate of nickel after the two atmospheric leaching processes was 61.83%. Therefore, the leaching tank leaching slurry is not returned to the leaching tank after passing through the sanding equipment, and continuous circulating leaching is not carried out, so that the normal pressure leaching rate of the nickel is influenced, but compared with the normal pressure leaching method in the prior art, the leaching rate of the nickel in the scheme of the embodiment 4 is also improved.
Comparative example 1
The only difference from example 1 is: comparative example 1 only performed the first atmospheric leaching process, and did not perform the second atmospheric leaching process, and the leaching rate of nickel after the last first atmospheric leaching was the comprehensive nickel leaching rate, which was only 46.17%, compared to the technical scheme of the present application, the leaching rate of nickel was greatly reduced.
Comparative example 2
The only difference from example 1 is: the water for high nickel matte is prepared by mixing water with high nickel matte according to the ratio of the mass (kg) of the high nickel matte to the volume (L) of the water of 1: 8, directly adding concentrated sulfuric acid to the initial H after slurrying2SO4The concentration was 220g/L and the second atmospheric leaching was carried out without the first atmospheric leaching process. And finally, the leaching rate of the nickel after the second normal pressure leaching is the comprehensive leaching rate of the nickel, which is only 50.66%, and compared with the technical scheme of the application, the leaching rate of the nickel is greatly reduced.
Comparative example 3
The only difference from example 1 is: neither the first atmospheric leaching process nor the second atmospheric leaching process applied ultrasonic waves and oxygen.
The leaching rate of nickel after the first atmospheric leaching of comparative example 3 is only 16.14%, the leaching rate of nickel after the second atmospheric leaching is only 5.28%, and the leaching rate of comprehensive nickel is only 20.57%, which indicates that the leaching rate of nickel is greatly influenced by ultrasonic waves and oxygen.
Comparative example 4
The only difference from example 1 is: neither the first atmospheric leaching process nor the second atmospheric leaching process applied ultrasonic waves, but only oxygen.
The leaching rate of nickel after the first atmospheric leaching of comparative example 4 was 43.75%, the leaching rate of nickel after the second atmospheric leaching was 37.21%, and the leaching rate of total nickel was 64.68%. Thus, the ultrasonic wave can promote the reaction of oxygen and the raw material and the leaching rate of nickel by dispersing the oxygen into fine bubbles.
Comparative example 5
The only difference from example 1 is: neither the first atmospheric leaching process nor the second atmospheric leaching process applied ultrasonic waves nor oxygen, nor returned the leaching tank leaching liquor to the leaching tank after passing through the sanding equipment, and did not perform continuous cycle leaching.
The leaching rate of nickel after the first atmospheric leaching of comparative example 5 was 12.51%, the leaching rate of nickel after the second atmospheric leaching was 4.67%, and the leaching rate of total nickel was 16.59%. Therefore, only acid leaching is adopted, and the leaching rate of nickel is lowest.
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 (10)
1. A high nickel matte atmospheric pressure leaching method is characterized by comprising the following steps:
carrying out first normal-pressure leaching on the nickel matte by using a first acid solution to obtain a first leaching solution and first leaching residues;
performing second normal-pressure leaching on the first leaching slag by using a second acid solution to obtain a second leaching solution and second leaching slag;
wherein ultrasonic waves and oxygen are applied in both the first atmospheric leaching and the second atmospheric leaching.
2. The method for leaching nickel matte under normal pressure according to claim 1, wherein in the first normal pressure leaching process, acid is supplemented to maintain the pH value of the first acid solution at 0.5-1.5; 5-10 liters of the first acid solution is used per kilogram of the high nickel matte.
3. The atmospheric leaching method for nickel matte according to claim 1, wherein in the second acid solution, initial H is added2SO4The concentration is 150-250 g/L; and 1.5-4 liters of the second acid solution is used for every kilogram of the first leaching residues.
4. The high nickel matte atmospheric pressure leaching method according to claim 1, wherein the ultrasonic frequency is 20-100 kHz; the flux of the oxygen is 5-50 m3V (h) ton dry material), oxygen concentration is 50-95%.
5. The nickel freematte atmospheric leaching method according to claim 1, wherein the leaching time of the first atmospheric leaching and the leaching time of the second atmospheric leaching are respectively 1-10 h independently.
6. The method of claim 1, wherein the first and second acid solutions are separately circulated through a sand mill during the first and second atmospheric leaching.
7. A nickel freematte atmospheric leach process according to claim 1, wherein the second leach solution is returned to the first atmospheric leach process for use as the first acid liquor.
8. The nickel freematte atmospheric leaching method according to claim 1, wherein the leaching temperatures of the first atmospheric leaching and the second atmospheric leaching are respectively 70-100 ℃.
9. The method of claim 1, wherein the first atmospheric leach is preceded by: and crushing and grinding the high nickel matte to the granularity of 80-400 meshes.
10. Nickel sulphate obtainable by the nickel freematte atmospheric leaching process according to any one of claims 1 to 9.
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