CN111424172A - Wet treatment process of laterite-nickel ore - Google Patents
Wet treatment process of laterite-nickel ore Download PDFInfo
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- CN111424172A CN111424172A CN202010486605.1A CN202010486605A CN111424172A CN 111424172 A CN111424172 A CN 111424172A CN 202010486605 A CN202010486605 A CN 202010486605A CN 111424172 A CN111424172 A CN 111424172A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
- C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
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Abstract
The invention provides a wet treatment process of laterite-nickel ore. The wet processing technology comprises the following steps: step S1, carrying out acid leaching treatment on the laterite-nickel ore to obtain iron-containing acid leaching slag and acid leaching liquid; step S2, adjusting the pH value of the pickle liquor to 1.5-1.8 by using steel slag powder to perform preneutralization to obtain paste slag and preneutralized liquor; step S3, adjusting the pH value of the preneutralized liquid to 3.5-4.8 by using steel slag powder to remove iron and aluminum to obtain iron-containing aluminum slag and iron-removed aluminum liquid; and step S4, adjusting the pH value of the molten iron-removed aluminum to 3.5-5.5 by using sulfuric acid, and then replacing nickel and cobalt in the molten iron-removed aluminum by using metal powder to obtain lean solution after nickel and cobalt removal and precipitates containing nickel and cobalt, wherein the metal powder is metal powder with the particle size of 1 nm-100 mu m. The nickel and cobalt in the molten iron-removed aluminum are removed by adopting a replacement mode, so that the nickel and cobalt are separated from the molten iron-removed aluminum in the form of metal simple substances.
Description
Technical Field
The invention relates to the field of nickel-cobalt material production, in particular to a wet treatment process for laterite-nickel ore.
Background
With the rapid development of the battery industry, the demand of nickel and cobalt in the world rises sharply, the price of nickel and cobalt rises greatly, high-grade nickel and cobalt resources are depleted day by day, people focus on developing low-grade laterite-nickel ore with complex components, and the adopted process is generally a high-pressure acid leaching process to produce nickel and cobalt raw materials for batteries.
In the existing hydrometallurgical process of the laterite-nickel ore, lime, limestone and the like are generally adopted as neutralizing agents, and sulfide, magnesium oxide and sodium hydroxide are adopted as nickel-cobalt precipitants to produce MHP (nickel-cobalt hydroxide intermediate product). The traditional method has the advantages of large consumption of the neutralizing agent, large quantity of substance of produced MHP products, high water content and high transportation cost.
Disclosure of Invention
The invention mainly aims to provide a wet treatment process for laterite-nickel ore, which aims to solve the problem that in the prior art, the treatment cost is increased due to the fact that a large amount of MHP is produced by the hydrometallurgy of laterite-nickel ore.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a wet treatment process of lateritic nickel ore, the wet treatment process including: step S1, carrying out acid leaching treatment on the laterite-nickel ore, and carrying out solid-liquid separation to obtain iron-containing acid leaching slag and acid leaching liquid; step S2, adjusting the pH value of the pickle liquor to 1.5-1.8 by using steel slag powder for preneutralization, and performing solid-liquid separation to obtain paste slag and preneutralized liquor; step S3, adjusting the pH value of the preneutralized liquid to 3.5-4.8 by using steel slag powder to remove iron and aluminum, and performing solid-liquid separation to obtain iron-containing aluminum slag and iron-removed aluminum liquid; step S4, after the pH value of the molten iron-removed aluminum is adjusted to 3.5-5.5 by sulfuric acid, nickel and cobalt in the molten iron-removed aluminum are replaced by metal powder, and after solid-liquid separation, lean solution after nickel and cobalt removal and nickel-containing precipitate are obtained, wherein the metal powder is metal powder with the particle size of 1 nm-100 mu m; step S5, removing iron from the lean solution after removing nickel and cobalt by adopting a chemical oxidation precipitation method, wherein steel slag powder is adopted as a neutralizer, and solid-liquid separation is carried out to obtain ferrite-containing slag and iron-removed solution; and step S6, oxidizing the liquid after iron removal, and then removing manganese by using steel slag powder as a neutralizer to obtain manganese-containing slag and a liquid after manganese removal.
Further, the metal powder is a metal powder having a particle size of 100nm to 50 μm, the substitution reaction time in step S4 is preferably 0.5 to 5.0 hours, and the molar ratio of the metal powder to nickel cobalt is preferably 1.0 to 5.0.
Further, the metal powder is any one or more of iron powder, magnesium powder, aluminum powder, manganese powder and zinc powder.
Further, the solid-liquid separation process of step S2 includes performing counter-current washing on the slurry obtained after the pre-neutralization to obtain the cream slag and the pre-neutralization solution in the form of underflow, or includes filtering the slurry obtained after the pre-neutralization to obtain the cream slag and the pre-neutralization solution in the form of filter cake.
Further, the pH of the iron-removed liquid is controlled to be 7.5 to 8.5 in step S5, and at least a part of the iron-removed liquid is used as washing water for counter-current washing or filtered washing water.
Further, the pH value of the obtained demanganized liquid is controlled to be 7.5-8.5 in step S6, and at least part of demanganized liquid is used as washing water for countercurrent washing or filtered washing water.
Further, the countercurrent washing is multistage countercurrent washing, and preferably 4-8 stages of countercurrent washing.
Further, the wet treatment process also comprises the step of carrying out magnetic separation treatment on the nickel-cobalt-containing precipitate to obtain nickel-cobalt enriched intermediate powder.
Further, the step S3 includes: adjusting the pH value of the preneutralized liquid to 3.5-3.8 by using steel slag powder to remove iron and aluminum, and performing solid-liquid separation to obtain iron-aluminum-containing slag and iron-removed aluminum liquid, or the step S3 comprises the following steps: adjusting the pH value of the preneutralized liquid to 3.5-3.8 by using steel slag powder to perform primary iron and aluminum removal, and performing solid-liquid separation to obtain primary iron-aluminum-containing slag and primary iron and aluminum-removed liquid; and adjusting the pH value of the first-stage iron-removed aluminum liquid to 4.4-4.8 by using steel slag powder to remove iron and aluminum, performing solid-liquid separation to obtain iron-containing aluminum slag and iron-removed aluminum liquid, and returning the iron-containing aluminum slag to the step S1 to perform acid leaching treatment together with the laterite-nickel ore.
Further, the step S5 includes: adjusting the pH value of the lean solution after nickel and cobalt removal to 7.5-8.5 by using steel slag powder as a neutralizer, heating the lean solution after nickel and cobalt removal to 40-60 ℃, and introducing compressed air into the heated lean solution after nickel and cobalt removal for oxidation to obtain ore pulp containing ferrite; and carrying out solid-liquid separation on the ore pulp containing the ferrite to obtain ferrite-containing slag and iron-removed liquid.
Further, the step S5 is to control the pH of the obtained iron-removed liquid to be 7.5 to 8.5, and the step S6 includes: mixing at least part of the iron-removed liquid with paste slag, iron-containing aluminum slag and manganese-containing slag to form tailing slurry; and neutralizing the tailing slurry by using the steel slag powder, and introducing compressed air into the tailing slurry to perform oxidation demanganization to obtain manganese-containing slag and demanganization solution.
By applying the technical scheme of the invention, after removing the aluminum, the nickel and cobalt in the molten aluminum without the iron are removed in the step S4 in a replacement mode, so that the nickel and cobalt are separated from the molten aluminum without the iron in the form of metal simple substances. In order to ensure that the nickel and cobalt in the molten iron-removed aluminum are completely replaced as much as possible by the replacement reaction in the step S4, metal powder with the particle size of 1 nm-100 microns is used as reducing metal, the replacement reaction efficiency is improved by specifically utilizing the higher contact area of the metal powder and the nickel and cobalt, and the deposition of the replaced nickel and cobalt on the reducing metal is effectively avoided by utilizing the high reaction efficiency of the small particle size. In addition, the steel slag powder is used as the neutralizing agent in the steps S2, S3, S5 and S6, so that the effective recycling of resources is realized.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art of the present application, in the prior art, lime, limestone, etc. are generally used as a neutralizing agent, and sulfide, magnesium oxide and sodium hydroxide are used as a nickel-cobalt precipitant to produce a nickel-cobalt hydroxide intermediate product, which has a large physical quantity, high water content and high freight cost, resulting in an increase in the treatment cost of laterite-nickel ore, in order to solve the problem, the present application provides a wet treatment process for laterite-nickel ore, which includes: step S1, carrying out acid leaching treatment on the laterite-nickel ore, and carrying out solid-liquid separation to obtain iron-containing acid leaching slag and acid leaching liquid; step S2, adjusting the pH value of the pickle liquor to 1.5-1.8 by using steel slag powder for preneutralization, and performing solid-liquid separation to obtain paste slag and preneutralized liquor; step S3, adjusting the pH value of the preneutralized liquid to 3.5-4.4 by using steel slag powder to remove iron and aluminum, and performing solid-liquid separation to obtain iron-containing aluminum slag and iron-removed aluminum liquid; step S4, after the pH value of the molten iron-removed aluminum is adjusted to 3.5-5.5 by sulfuric acid, nickel and cobalt in the molten iron-removed aluminum are replaced by metal powder, and after solid-liquid separation, lean solution after nickel and cobalt removal and nickel-containing precipitate are obtained, wherein the metal powder is metal powder with the particle size of 1 nm-100 mu m; step S5, removing iron from the lean solution after removing nickel and cobalt by adopting a chemical oxidation precipitation method, wherein steel slag powder is adopted as a neutralizer, and solid-liquid separation is carried out to obtain ferrite-containing slag and iron-removed solution; and step S6, oxidizing the liquid after iron removal, and then removing manganese by using steel slag powder as a neutralizer to obtain manganese-containing slag and a liquid after manganese removal.
After deironing, step S4 adopts the mode of replacement to get rid of the nickel cobalt in the deironing aluminium liquid for nickel cobalt separates out from deironing aluminium liquid with the form of metal simple substance, and because its constitution characteristics, the water content in the obtained nickel cobalt containing precipitate is very little, consequently is convenient for transport. In order to ensure that the nickel and cobalt in the molten iron-removed aluminum are completely replaced as much as possible by the replacement reaction in the step S4, metal powder with the particle size of 1 nm-100 microns is used as reducing metal, the replacement reaction efficiency is improved by specifically utilizing the higher contact area of the metal powder and the nickel and cobalt, and the deposition of the replaced nickel and cobalt on the reducing metal is effectively avoided by utilizing the high reaction efficiency of the small particle size. In addition, the steel slag powder is used as the neutralizing agent in the steps S2, S3, S5 and S6, so that the effective recycling of resources is realized.
In order to further improve the substitution efficiency, the metal powder has a particle size of 100nm to 50 μm, the substitution reaction time in the step S4 is preferably 0.5 to 5.0 hours, and the molar ratio of the metal powder to nickel cobalt is preferably 1.0 to 5.0.
In principle, metals having better reducing properties than nickel and cobalt are considered to be used as the metal powder in this application, and in order to save costs and avoid the introduction of impurity metals that are not easily removed, it is preferable that the metal powder be any one or more of iron powder, magnesium powder, aluminum powder, manganese powder, and zinc powder.
The wet treatment process is applicable to various grades of nickel-containing laterites, including limonite types and eluvial ore types, or transition layer laterite-nickel ores, or mixed ores of a plurality of types, and the like, the acid leaching treatment in the step S1 can be conventional normal pressure leaching or high pressure leaching, and a person skilled in the art can select a proper acid leaching process according to the existing equipment conditions and capital conditions, and details are not repeated herein.
After the pre-neutralization in step S2 is completed, the solid-liquid separation in the formed pulp may be performed by conventional solid-liquid separation methods, such as filtration, sedimentation, centrifugation, etc., and in one embodiment, the solid-liquid separation in step S2 includes counter-current washing of the pulp obtained after the pre-neutralization to obtain the sludge and the pre-neutralization solution in the form of underflow. The countercurrent washing can realize effective washing of ore pulp, and is more suitable for industrial production. In order to reduce the influence of solid impurities in the preneutralized solution, the countercurrent washing is preferably multistage countercurrent washing, and more preferably 4-8 stages of countercurrent washing. In another embodiment, the solid-liquid separation process comprises filtering the slurry obtained after pre-neutralization to obtain a sludge in the form of a filter cake and a pre-neutralization solution. The process of filtration is suitable for small batch production and laboratory applications.
In order to further realize comprehensive utilization of water resources, it is preferable that the pH value of the iron-removed liquid is controlled to be 7.5 to 8.5 in step S5, and at least part of the iron-removed liquid is used as washing water for countercurrent washing or filtered washing water. Or preferably, the pH value of the solution after manganese removal is controlled to be 7.5-8.5 in the step S6, and at least part of the solution after manganese removal is used as washing water for countercurrent washing or filtered washing water. And (3) controlling the pH value of the liquid after iron removal or manganese removal within 7.5-8.5 to precipitate metal ions in the liquid so as to recycle the liquid, wherein the pH value can be controlled by adopting steel slag powder, lime milk, sodium hydroxide or sodium carbonate as a neutralizing agent.
In the nickel-cobalt-containing precipitate obtained in the above step S4, nickel and cobalt mainly exist in the form of a metal simple substance, so that the magnetism of the simple substance can be fully utilized to separate nickel and cobalt from the nickel and cobalt, and preferably, the wet processing process further includes performing magnetic separation on the nickel-cobalt-containing precipitate to obtain nickel and cobalt enriched intermediate powder. When iron powder is used as the metal powder in step S4, the metal powder is generally added in an excessive amount, so that unreacted iron powder is present in the nickel-cobalt-containing precipitate at the same time, and then iron and nickel cobalt are simultaneously separated in the form of an iron-cobalt-nickel alloy during the magnetic separation treatment, that is, the main component of the nickel-cobalt-enriched intermediate powder is the iron-cobalt-nickel alloy.
The step of removing iron and aluminum may be a first step of removing iron and aluminum, and may be a second step of removing iron and aluminum, in an embodiment, the step S3 includes: and adjusting the pH value of the preneutralized liquid to 3.5-3.8 by using steel slag powder to remove iron and aluminum, and performing solid-liquid separation to obtain the iron-aluminum-containing slag and the iron-aluminum-removed liquid. In the process, ferric iron is mainly removed so as to avoid the consumption of metal powder due to the oxidation of the ferric iron when the nickel cobalt is replaced by the metal powder.
In another embodiment, the step S3 includes: adjusting the pH value of the preneutralized liquid to 3.5-3.8 by using steel slag powder to perform primary iron and aluminum removal, and performing solid-liquid separation to obtain primary iron-aluminum-containing slag and primary iron and aluminum-removed liquid; and adjusting the pH value of the first-stage iron-removed aluminum liquid to 4.4-4.8 by using steel slag powder to remove iron and aluminum, performing solid-liquid separation to obtain iron-containing aluminum slag and iron-removed aluminum liquid, and returning the iron-containing aluminum slag to the step S1 to perform acid leaching treatment together with the laterite-nickel ore. The first stage de-ironing of the aluminum is mainly used for removing ferric iron, the second stage de-ironing of the aluminum further removes the residual ferric iron, ferrous iron and aluminum, meanwhile, part of nickel and cobalt in the second stage de-ironing of the aluminum is precipitated, and in order to further recover the part of nickel and cobalt, the slag containing iron and aluminum obtained by the second stage de-ironing of the aluminum is returned to the step S1 for acid leaching so that the nickel and cobalt are leached into acid leaching solution.
In an embodiment of the present application, the step S5 includes: adjusting the pH value of the lean solution after nickel and cobalt removal to 7.5-8.5 by using steel slag powder as a neutralizer, heating the lean solution after nickel and cobalt removal to 40-60 ℃, and introducing compressed air into the heated lean solution after nickel and cobalt removal for oxidation to obtain ore pulp containing ferrite; and carrying out solid-liquid separation on the ore pulp containing the ferrite to obtain ferrite-containing slag and iron-removed liquid. In the process, the steel slag powder is used for adjusting the pH value of the barren solution after removing the nickel and cobalt, and the metal elements such as iron in the barren solution are oxidized to form ferrite, so that the economic value of the laterite-nickel ore is further improved.
In another embodiment of the present application, the step S5 is to control the pH of the iron-removed solution to be 7.5-8.5, and the step S6 includes: mixing at least part of the iron-removed liquid with paste slag, iron-containing aluminum slag and manganese-containing slag to form tailing slurry; and neutralizing the tailing slurry by using the steel slag powder, and introducing compressed air into the tailing slurry to perform manganese removal through oxidation. The tailing slurry is oxidized to oxidize manganese into high-valence manganese, and then the steel slag powder is used for adjusting the pH value of the oxidized system to precipitate and separate the high-valence manganese in the forms of MnOOH, manganese sesquioxide, manganic oxide and manganese dioxide.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
100Kg of limonite type laterite-nickel ore is adopted as a raw material, wherein the nickel content is 1.2 wt% and the cobalt content is 0.2 wt%, the raw material is prepared into ore pulp with the concentration of 22-25%, the ore pulp is subjected to high-pressure sulfuric acid leaching treatment, the leaching temperature is 250 ℃, the leaching time is 1h, the sulfuric acid concentration is 98.5%, the acid-ore ratio is 250Kg/t ore, and iron-containing acid leaching slag and acid leaching liquid are obtained after solid-liquid separation;
adjusting the pH value of the pickle liquor to 1.5 by using steel slag powder as a neutralizer, carrying out preneutralization, washing preneutralized ore pulp by adopting 7-grade countercurrent, and removing iron and aluminum in the preneutralized liquid in the next step;
adjusting the pH value of the preneutralized liquid to 3.5-3.8 by using steel slag powder, and performing solid-liquid separation to obtain a section of iron-containing aluminum slag and a section of iron-removed aluminum liquid; adjusting the pH value of the first-stage iron-removed aluminum liquid to 4.4-4.8 by using steel slag powder to remove iron and aluminum, performing solid-liquid separation to obtain iron-containing aluminum slag and iron-removed aluminum liquid, and returning the iron-containing aluminum slag to perform acid leaching treatment together with the laterite-nickel ore;
adopting 400-mesh metal iron powder as a reducing metal, adding a small amount of sulfuric acid into iron-removed aluminum liquid in a replacement process to control the pH value to be 3.5-4.0, wherein the molar ratio of the iron powder to nickel and cobalt in the iron-removed aluminum liquid is 2.5, the reaction time is 5.0h, carrying out solid-liquid separation to obtain lean solution after removing the nickel and cobalt and a nickel and cobalt-containing precipitate, selecting Fe-Co-Ni alloy in the nickel and cobalt-containing precipitate in a magnetic separation mode, washing to obtain 4.3kg of nickel and cobalt enriched powder intermediate product, further analyzing the nickel and cobalt enriched powder intermediate product, wherein the weight of nickel is 1.045g and the weight of cobalt is 0.166g, and calculating the nickel recovery rate to be 87% and the cobalt recovery rate to be 83%, wherein the intermediate product can be used as an iron alloy smelting raw material and can also be used as a wet refining raw material;
adding steel slag powder as a neutralizer into the lean solution after nickel and cobalt removal, introducing compressed air into the lean solution for oxidation to form ferrite, controlling the pH value of ore pulp to be about 8.0, performing solid-liquid separation to obtain a liquid after iron removal and manganese-containing slag, using part of the liquid after iron removal as washing water of the countercurrent washing, adding the other part of the liquid together with underflow of the last stage (seventh stage) after the countercurrent washing and iron-containing aluminum slag for neutralization, introducing compressed air for oxidation demanganization, controlling the pH value of the ore pulp to be about 8.0, performing solid-liquid separation after the oxidation demanganization is finished to obtain manganese-containing slag and a liquid after manganese removal, and using part of the liquid after manganese removal as washing water of the countercurrent washing.
Example 2
The difference from the embodiment 1 is that:
the method comprises the steps of adopting metal iron powder of 400 meshes as reducing metal, adding a small amount of sulfuric acid into iron-removed aluminum liquid in a replacement process to control the pH value to be 4.0-5.0, enabling the molar ratio of the iron powder to nickel and cobalt in the iron-removed aluminum liquid to be 2.5, enabling the reaction time to be 5.0h, carrying out solid-liquid separation to obtain barren solution and nickel-cobalt-containing precipitate after removing the nickel and cobalt, selecting Fe-Co-Ni alloy in the nickel-cobalt-containing precipitate in a magnetic separation mode, washing to obtain 3.9kg of nickel-cobalt enriched powder intermediate product, further analyzing the nickel-cobalt enriched powder intermediate product to calculate the nickel recovery rate to be 81% and the cobalt recovery rate to be 73%.
Example 3
The difference from the embodiment 1 is that: the method comprises the steps of adopting metal iron powder of 400 meshes as reducing metal, adding a small amount of sulfuric acid into iron-removed aluminum liquid in a replacement process to control the pH value to be 5.0-5.5, enabling the molar ratio of the iron powder to nickel and cobalt in the iron-removed aluminum liquid to be 2.5, enabling the reaction time to be 5.0h, carrying out solid-liquid separation to obtain barren solution and nickel-cobalt-containing precipitate after removing the nickel and cobalt, selecting Fe-Co-Ni alloy in the nickel-cobalt-containing precipitate in a magnetic separation mode, washing to obtain 3.6kg of nickel-cobalt enriched powder intermediate product, further analyzing the nickel-cobalt enriched powder intermediate product to calculate that the weight of nickel is 1.007g and the weight of cobalt is 0.155g, and accordingly calculating the nickel recovery rate to be 84% and the cobalt recovery rate to be 78.
Example 4
The difference from the embodiment 1 is that: the method comprises the steps of adopting 1000-mesh metal iron powder as reducing metal, adding a small amount of sulfuric acid into iron-removed aluminum liquid in a replacement process to control the pH value to be 3.5-4.0, enabling the molar ratio of the iron powder to nickel and cobalt in the iron-removed aluminum liquid to be 2.5, enabling the reaction time to be 5.0h, carrying out solid-liquid separation to obtain lean solution after nickel and cobalt removal and nickel-containing precipitate, selecting Fe-Co-Ni alloy in the nickel and cobalt-containing precipitate in a magnetic separation mode, washing to obtain 4.7kg of nickel and cobalt enriched powder intermediate product, further analyzing the nickel and cobalt enriched powder intermediate product to calculate that the weight of nickel is 1.104g and the weight of cobalt is 0.177g, and calculating the nickel recovery rate to be 92% and the cobalt recovery rate to be 88%.
Example 5
The difference from the embodiment 1 is that: the method comprises the steps of adopting 50-mesh metal iron powder as reducing metal, adding a small amount of sulfuric acid into iron-removed aluminum liquid in a replacement process to control the pH value to be 3.5-4.0, enabling the molar ratio of the iron powder to nickel and cobalt in the iron-removed aluminum liquid to be 2.5, enabling the reaction time to be 5.0h, carrying out solid-liquid separation to obtain lean solution after nickel and cobalt removal and nickel-containing precipitate, selecting Fe-Co-Ni alloy in the nickel and cobalt-containing precipitate in a magnetic separation mode, washing to obtain 3.1kg of nickel and cobalt enriched powder intermediate product, further analyzing the nickel and cobalt enriched powder intermediate product to calculate the nickel recovery rate to be 72% and the cobalt recovery rate to be 70%.
Example 6
The difference from the embodiment 1 is that: the method comprises the steps of adopting metal iron powder of 400 meshes as reducing metal, adding a small amount of sulfuric acid into iron-removed aluminum liquid in a replacement process to control the pH value to be 3.5-4.0, enabling the molar ratio of the iron powder to nickel and cobalt in the iron-removed aluminum liquid to be 1.0, enabling the reaction time to be 7.0h, carrying out solid-liquid separation to obtain lean solution after nickel and cobalt removal and nickel-containing precipitate, selecting Fe-Co-Ni alloy in the nickel and cobalt-containing precipitate in a magnetic separation mode, washing to obtain 3.3kg of nickel and cobalt enriched powder intermediate product, further analyzing the nickel and cobalt enriched powder intermediate product to calculate that the weight of nickel is 0.936g and the weight of cobalt is 0.15g, and accordingly calculating the nickel recovery rate to be 78% and the cobalt recovery rate to be 75%.
Example 6
The difference from the embodiment 1 is that: the method comprises the steps of adopting 1000-mesh metal iron powder as reducing metal, adding a small amount of sulfuric acid into iron-removed aluminum liquid in a replacement process to control the pH value to be 3.5-4.0, enabling the molar ratio of the iron powder to nickel and cobalt in the iron-removed aluminum liquid to be 5.0, enabling the reaction time to be 0.5h, carrying out solid-liquid separation to obtain lean solution after nickel and cobalt removal and nickel-containing precipitate, selecting Fe-Co-Ni alloy in the nickel and cobalt-containing precipitate in a magnetic separation mode, washing to obtain 4.7kg of nickel and cobalt enriched powder intermediate product, further analyzing the nickel and cobalt enriched powder intermediate product to calculate that the weight of nickel is 1.056g and the weight of cobalt is 0.164g, and calculating that the nickel recovery rate is 88% and the cobalt recovery rate is 82%.
Example 7
The difference from the embodiment 1 is that: the method comprises the steps of adopting 1000-mesh metal aluminum powder as reducing metal, adding a small amount of sulfuric acid into iron-removed aluminum liquid in a replacement process to control the pH value to be 3.5-4.0, enabling the molar ratio of aluminum powder to nickel and cobalt in the iron-removed aluminum liquid to be 2.5, enabling the reaction time to be 5.0h, carrying out solid-liquid separation to obtain lean solution after nickel and cobalt removal and nickel-containing precipitate, selecting Al-Co-Ni alloy in the nickel-cobalt-containing precipitate in a magnetic separation mode, washing to obtain 4.7kg of nickel and cobalt enriched powder intermediate product, further analyzing the nickel and cobalt enriched powder intermediate product to obtain 1.08g of nickel and 0.165g of cobalt, and calculating the nickel recovery rate to be 90% and the cobalt recovery rate to be 83%.
Example 8
The difference from the embodiment 1 is that: the method comprises the steps of adopting 1000-mesh metal manganese powder as reducing metal, adding a small amount of sulfuric acid into iron-removed aluminum liquid in a replacement process to control the pH value to be 3.5-4.0, enabling the molar ratio of the manganese powder to nickel and cobalt in the iron-removed aluminum liquid to be 2.5, enabling the reaction time to be 5.0h, carrying out solid-liquid separation to obtain lean liquid and nickel-cobalt-containing precipitate after removing the nickel and cobalt, selecting Mn-Co-Ni alloy in the nickel-cobalt-containing precipitate in a magnetic separation mode, washing to obtain 4.7kg of nickel-cobalt enriched powder intermediate product, further analyzing the weight of nickel in the nickel-cobalt enriched powder intermediate product to be 1.068g and 0.158g, and calculating the nickel recovery rate to be 89% and the cobalt recovery rate to be 79%.
Comparative example 1
The difference from the embodiment 1 is that: the method comprises the steps of adopting metal iron powder with the particle size of 0.2-1 mm as reducing metal, adding a small amount of sulfuric acid into iron-removed aluminum liquid in a replacement process to control the pH value to be 3.5-4.0, enabling the molar ratio of the iron powder to nickel and cobalt in the iron-removed aluminum liquid to be 2.5, enabling the reaction time to be 5.0h, carrying out solid-liquid separation to obtain lean solution after nickel and cobalt are removed and nickel-containing precipitate, selecting Fe-Co-Ni alloy in the nickel and cobalt-containing precipitate in a magnetic separation mode, washing to obtain 1.3kg of nickel and cobalt enriched powder intermediate product, further analyzing the nickel and cobalt enriched powder intermediate product to calculate that the nickel recovery rate is 43% and the cobalt recovery rate is 37%, wherein the weight of nickel is 0.516g and the weight of cobalt is 0.074 g.
Comparative example 2
The difference from the embodiment 1 is that: the method comprises the steps of adopting metal iron powder of 400 meshes as reducing metal, adding a small amount of sulfuric acid into iron-removed aluminum liquid in a replacement process to control the pH value to be 2.0-3.0, enabling the molar ratio of the iron powder to nickel and cobalt in the iron-removed aluminum liquid to be 2.5, enabling the reaction time to be 5.0h, carrying out solid-liquid separation to obtain barren solution and nickel-cobalt-containing precipitate after removing the nickel and cobalt, selecting Fe-Co-Ni alloy in the nickel-cobalt-containing precipitate in a magnetic separation mode, washing to obtain 3.3kg of nickel-cobalt enriched powder intermediate product, further analyzing the nickel-cobalt enriched powder intermediate product to calculate that the weight of nickel is 0.672g and the weight of cobalt is 0.098g, and calculating that the nickel recovery rate is 56% and the cobalt recovery rate is 49%.
Comparative example 3
The difference from the embodiment 1 is that: the method comprises the steps of adopting metal iron powder of 400 meshes as reducing metal, adding a small amount of sulfuric acid into iron-removed aluminum liquid in a replacement process to control the pH value to be 6.0-6.5, enabling the molar ratio of the iron powder to nickel and cobalt in the iron-removed aluminum liquid to be 2.5, enabling the reaction time to be 5.0h, carrying out solid-liquid separation to obtain barren solution and nickel-cobalt-containing precipitate after removing the nickel and cobalt, selecting Fe-Co-Ni alloy in the nickel-cobalt-containing precipitate in a magnetic separation mode, washing to obtain 2.7kg of nickel-cobalt enriched powder intermediate product, further analyzing the nickel-cobalt enriched powder intermediate product to calculate that the weight of nickel is 0.601g and the weight of cobalt is 0.088g, and calculating that the nickel recovery rate is 50% and the cobalt recovery rate is 44%.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
after deironing, step S4 adopts the mode of replacement to get rid of the nickel cobalt in the deironing aluminium liquid for nickel cobalt separates out from deironing aluminium liquid with the form of metal simple substance, and because its constitution characteristics, the water content in the obtained nickel cobalt containing precipitate is very little, consequently is convenient for transport. In order to ensure that the nickel and cobalt in the molten iron-removed aluminum are completely replaced as much as possible by the replacement reaction in the step S4, metal powder with the particle size of 1 nm-100 microns is used as reducing metal, the replacement reaction efficiency is improved by specifically utilizing the higher contact area of the metal powder and the nickel and cobalt, and the deposition of the replaced nickel and cobalt on the reducing metal is effectively avoided by utilizing the high reaction efficiency of the small particle size. In addition, the steel slag powder is used as the neutralizing agent in the steps S2, S3, S5 and S6, so that the effective recycling of resources is realized.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A wet treatment process for laterite-nickel ore is characterized by comprising the following steps:
step S1, carrying out acid leaching treatment on the laterite-nickel ore, and carrying out solid-liquid separation to obtain iron-containing acid leaching slag and acid leaching liquid;
step S2, adjusting the pH value of the pickle liquor to 1.5-1.8 by using steel slag powder for preneutralization, and performing solid-liquid separation to obtain paste slag and preneutralized liquor;
step S3, adjusting the pH value of the pre-neutralization solution to 3.5-4.8 by using steel slag powder to remove iron and aluminum, and performing solid-liquid separation to obtain iron-containing aluminum slag and iron-removed aluminum liquid;
step S4, after the pH value of the molten iron-removed aluminum is adjusted to 3.5-5.5 by sulfuric acid, replacing nickel and cobalt in the molten iron-removed aluminum by metal powder, and after solid-liquid separation, obtaining lean solution after nickel and cobalt removal and nickel-containing precipitates, wherein the metal powder is metal powder with the particle size of 1 nm-100 mu m;
step S5, removing iron from the lean solution after removing nickel and cobalt by adopting a chemical oxidation precipitation method, wherein steel slag powder is adopted as a neutralizer, and solid-liquid separation is carried out to obtain ferrite-containing slag and iron-removed solution; and
and step S6, oxidizing the liquid after iron removal, and then removing manganese by using steel slag powder as a neutralizer to obtain manganese-containing slag and a liquid after manganese removal.
2. The wet processing process according to claim 1, wherein the metal powder has a particle size of 100nm to 50 μm, the substitution reaction time of step S4 is preferably 0.5 to 5.0h, and the molar ratio of the metal powder to the nickel cobalt is preferably 1.0 to 5.0.
3. The wet processing process of claim 1, wherein the metal powder is any one or more of iron powder, magnesium powder, aluminum powder, manganese powder and zinc powder.
4. The wet treatment process according to claim 1, wherein the solid-liquid separation process of step S2 includes counter-current washing of the slurry obtained after the pre-neutralization to obtain a sludge in the form of underflow and a pre-neutralization solution,
or filtering the ore pulp obtained after the pre-neutralization to obtain the paste residue and the pre-neutralization liquid in the form of filter cakes.
5. The wet processing process according to claim 4, wherein the pH value of the deironing solution is controlled to be 7.5-8.5 in step S5, and at least a part of the deironing solution is used as the washing water for the counter-current washing or the filtered washing water.
6. The wet processing process according to claim 4, wherein the pH value of the obtained demanganized liquid is controlled at step S6 to be 7.5-8.5, and at least part of the demanganized liquid is used as the washing water of the counter-current washing or the filtered washing water.
7. The wet treatment process according to claim 4, wherein the counter-current washing is a multi-stage counter-current washing, preferably a 4-8 stage counter-current washing.
8. The wet processing process according to claim 1, further comprising magnetically separating the nickel-cobalt-containing precipitate to obtain a nickel-cobalt-enriched intermediate powder.
9. The wet processing process according to claim 1, wherein the step S3 comprises:
adjusting the pH value of the preneutralized liquid to 3.5-3.8 by using steel slag powder to remove iron and aluminum, performing solid-liquid separation to obtain the iron-aluminum-containing slag and the iron-aluminum-removed liquid,
or the step S3 includes:
adjusting the pH value of the preneutralized liquid to 3.5-3.8 by using steel slag powder to perform primary iron and aluminum removal, and performing solid-liquid separation to obtain primary iron-containing aluminum slag and primary iron and aluminum removed liquid;
adjusting the pH value of the first-stage iron-removed aluminum liquid to 4.4-4.8 by using steel slag powder to remove iron and aluminum, performing solid-liquid separation to obtain the iron-containing aluminum slag and the iron-removed aluminum liquid,
and returning the iron-containing aluminum slag to the step S1 to be subjected to acid leaching treatment together with the laterite-nickel ore.
10. The wet processing process according to claim 1, wherein the step S5 comprises:
adjusting the pH value of the lean solution after nickel and cobalt removal to 7.5-8.5 by using steel slag powder as a neutralizer, heating the lean solution after nickel and cobalt removal to 40-60 ℃, and introducing compressed air into the heated lean solution after nickel and cobalt removal for oxidation to obtain ore pulp containing ferrite;
and carrying out solid-liquid separation on the ore pulp containing the ferrite to obtain ferrite-containing slag and iron-removed liquid.
11. The wet processing process according to claim 1, wherein the step S5 is to control the pH of the iron-removed liquid to be 7.5-8.5, and the step S6 includes:
mixing at least part of the deironing liquid with the paste slag, the iron-containing aluminum slag and the manganese-containing slag to form tailing slurry;
and neutralizing the tailing slurry by using steel slag powder, and introducing compressed air into the tailing slurry to perform oxidation demanganization to obtain manganese-containing slag and demanganization solution.
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