A method for treating high-pressure leaching residue of nickel-cobalt hydroxide

Abstract

The application discloses a treatment method of nickel-cobalt hydroxide high-pressure leaching residue and relates to the technical field of valuable metal resource regeneration. The treatment method of the nickel-cobalt hydroxide high-pressure leaching residue comprises the following steps: S1, mixing the nickel-cobalt hydroxide high-pressure leaching residue with an alkali solution, washing and filtering to obtain alkali washing residue and alkali washing solution; S2, mixing the alkali washing residue with solid alkali, sequentially performing roasting and water leaching to obtain water leaching residue; and S3, mixing the water leaching residue with an acid solution, performing acid leaching and filtering to obtain acid leaching solution and acid leaching residue; and the alkali solution comprises at least one of a sodium hydroxide solution and an ammonia water solution. The application has the advantages of simple process, environmental friendliness, high safety, high economic benefit, high production efficiency, high recovery rate and the like, realizes resource utilization of the nickel-cobalt hydroxide high-pressure leaching residue and improves economic benefit.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of valuable metal resource regeneration, in particular to a treatment method of high-pressure leaching residue of nickel-cobalt hydroxide. BACKGROUND

[0002] At present, sulfide ore and laterite nickel ore are two common nickel ore resources. In recent years, with the continuous development and utilization of sulfide nickel ore resources leading to their exhaustion, and the rapid development of new energy industries of high-nickel ternary lithium-ion batteries, the development of more than 60% of the global nickel resource reserves in laterite nickel ore has attracted widespread attention. However, the nickel and cobalt content in laterite nickel ore is low, and it is an oxidized mineral, so the enrichment of nickel and cobalt cannot be economically realized through beneficiation process. Pyrometallurgical process is suitable for processing residual laterite nickel ore with nickel content higher than 1.8%, while brown iron type laterite nickel ore with about 1% nickel is currently mainly developed by using hydrometallurgical process. The hydrometallurgical process for treating laterite nickel ore mainly adopts reduction roasting-ammonia leaching process (RRAL) and high-pressure sulfuric acid leaching process (HPAL). Among the global annual nickel metal production, laterite type nickel ore accounts for about 30%. At present, most of the main processes of the 10 large-scale nickel laterite mines being constructed or expanded in the world are HPAL. The nickel content of the nickel-cobalt-containing solution produced by this method is generally 3-5 g / L, so the treatment capacity of the production system is limited, and further enrichment is needed before nickel-cobalt refining.

[0003] At present, there are three methods for treating low-concentration nickel-cobalt-containing solution after removing iron and aluminum from laterite nickel ore: 1) preparing hydroxide precipitate: adding sodium hydroxide or magnesium oxide as neutralizing precipitant to the solution, so that the nickel and cobalt ions in the solution form hydroxide precipitate (MHP) under certain pH conditions. 2) preparing sulfide precipitate: passing hydrogen sulfide as a precipitate reaction gas and nitrogen as a protective gas into the low-concentration nickel-cobalt-containing solution, so that the nickel and cobalt ions in the solution form sulfide precipitate (MSP). 3) ion exchange enrichment: the liquid after removing iron and aluminum is subjected to resin adsorption, washing, and elution to obtain a high-concentration nickel-cobalt-containing solution, and then nickel sulfate and cobalt sulfate are obtained by extraction-evaporation crystallization.

[0004] The hydrogen sulfide gas used in the MSP process is highly toxic and poses a safety risk, and due to technical monopoly, the industrialized sulfidation precipitation technology has not been able to be implemented. The resin adsorption method is prone to adsorption capacity decline due to fouling during production, and the refining system of the method has a large processing capacity and is still in the laboratory research stage. The MHP process gradually becomes the industry mainstream due to small investment, low operating cost and high safety. The main valuable metals in MHP are nickel and cobalt, and the manganese content is also high, generally in the form of manganese dioxide and manganese hydroxide. With the development of the power battery industry, the demand for ternary precursors increases, which leads to an increase in the demand for battery-grade manganese sulfate. The leaching behavior of manganese in the raw material is studied, and whether the manganese in the raw material is recovered can be determined according to the fluctuation of the market situation, which can improve the adaptability of enterprises to the product market.

[0005] However, the manganese dioxide in the existing process is generally treated as waste slag together with iron and aluminum slag, causing waste of resources. Therefore, there is an urgent need for a process method that simplifies the process, consumes less auxiliary materials, and can recycle and utilize high-pressure leaching slag, to solve the above problems. SUMMARY

[0006] The purpose of the present application is to provide a process method that simplifies the process, consumes less auxiliary materials, and can recycle and utilize high-pressure leaching slag.

[0007] The first aspect of the present application is:

[0008] A treatment method for high-pressure leaching slag of nickel-cobalt hydroxide is provided.

[0009] The second aspect of the present application is:

[0010] Application of the treatment method for high-pressure leaching slag of nickel-cobalt hydroxide.

[0011] Specifically, the technical scheme adopted according to the first aspect of the present application is:

[0012] A treatment method for high-pressure leaching slag of nickel-cobalt hydroxide, comprising the following steps:

[0013] S1 mixing high-pressure leaching slag of nickel-cobalt hydroxide with an alkali solution, washing and filtering to obtain alkali washing slag and alkali washing solution;

[0014] S2 mixing the alkali washing slag with solid alkali, and sequentially roasting and water leaching to obtain water leaching slag;

[0015] S3 mixing the water leaching slag with an acid solution, acid leaching and filtering to obtain acid leaching solution and acid leaching slag;

[0016] The alkali solution includes at least one of a sodium hydroxide solution and an ammonia solution.

[0017] According to the embodiment of the present application, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0018] 1. The treatment method of the nickel-cobalt hydroxide high-pressure leaching residue, the nickel-cobalt hydroxide high-pressure leaching residue is mixed with an alkali solution, washed and filtered to obtain alkali washing residue and alkali washing solution; first, the alkali washing of the alkali solution is used to wash away the Al element in the nickel-cobalt hydroxide high-pressure leaching residue to obtain a NaAlO2 solution, and to wash away a small part of Si element; when the purity of the alkali washing solution is high enough, the NaAlO2 product can be prepared by adding aluminum sulfate to the solution to generate economic benefits; second, the alkali washing method is used to separate the Al in the nickel-cobalt hydroxide high-pressure leaching residue from other elements, thereby reducing the cost of subsequent treatment of the Al as iron-aluminum slag into solid waste or hazardous waste.

[0019] 2. The treatment method of the nickel-cobalt hydroxide high-pressure leaching residue, the alkali washing residue is mixed with solid alkali and then subjected to roasting and water leaching and filtration, and the main purpose is to remove the silicon dioxide in the high-pressure leaching residue; on the one hand, the roasting method can be used to remove the silicon dioxide, thereby avoiding the difficulty in filtration caused by the formation of sol or gel of Si in the wet separation process, saving the treatment time and the cost of flocculant consumption; on the other hand, the direct product of the roasting of the alkali washing residue and the solid alkali can become Na2SiO3 and water vapor, which is environmentally friendly and can turn waste into treasure to generate relatively pure Na2SiO3 product.

[0020] 3. The present application has the advantages of simple process, environmental friendliness, high safety, high economic benefit, high production efficiency and high recovery rate, and can realize the resource utilization of the nickel-cobalt hydroxide high-pressure leaching residue and improve the economic benefit.

[0021] According to one embodiment of the present application, when the alkali solution comprises a sodium hydroxide solution, the relevant reaction equation after the mixing of the nickel-cobalt hydroxide high-pressure leaching residue and the alkali solution is as follows:

[0022]

[0023] According to one embodiment of the present application, the alkali solution comprises at least one of a sodium hydroxide solution and an ammonia water solution, the mass percentage of sodium hydroxide in the sodium hydroxide solution is 5% to 25%, and the mass percentage of ammonia in the ammonia water solution is 5% to 25%.

[0024] According to one embodiment of the present application, the alkali solution comprises at least one of a sodium hydroxide solution and an ammonia water solution, the mass percentage of sodium hydroxide in the sodium hydroxide solution is 10% to 25%, and the mass percentage of ammonia in the ammonia water solution is 10% to 25%.

[0025] According to an embodiment of the present application, the alkali solution is an ammonia solution, and the mass percentage of the ammonia solution is 5%-25%.

[0026] According to an embodiment of the present application, the alkali solution is a sodium hydroxide solution, and the mass percentage of the sodium hydroxide solution is 5%-25%.

[0027] According to an embodiment of the present application, in step S1, the following step is further included: first mixing the nickel-cobalt hydroxide high-pressure leaching residue with the ammonia solution, and then adding the sodium hydroxide solution.

[0028] According to an embodiment of the present application, in step S1, when washing and filtering, the temperature is 60-80°C.

[0029] According to an embodiment of the present application, the solid alkali includes a first solid alkali and a second solid alkali, and in step S2, the following step is further included: sequentially stacking the first solid alkali, the alkali washing residue, and the second solid alkali, and then performing roasting.

[0030] According to an embodiment of the present application, when the solid alkali includes a sodium hydroxide solid, and after mixing the alkali washing residue with the solid alkali and performing roasting and water immersion filtering, the related reaction equations are as follows:

[0031]

[0032] According to an embodiment of the present application, from the above related reaction equations, it can be known that, during the roasting process after mixing the alkali washing residue with the solid alkali, if the temperature is higher than 530°C, MnO2 decomposition will occur.

[0033] According to an embodiment of the present application, the first solid alkali, the alkali washing residue, and the second solid alkali are sequentially solid sodium hydroxide, the alkali washing residue, and solid sodium hydroxide.

[0034] According to an embodiment of the present application, the weight ratio of the first solid alkali, the alkali washing residue, and the second solid alkali is sequentially 0.8-1:1:0.8-1.

[0035] According to an embodiment of the present application, the weight ratio of the first solid alkali, the alkali washing residue, and the second solid alkali is sequentially 0.9-1:1:0.9-1.

[0036] According to an embodiment of the present application, the roasting temperature is greater than or equal to 350°C.

[0037] According to an embodiment of the present application, the roasting temperature is 350°C-950°C.

[0038] According to an embodiment of the present application, the roasting temperature is 450-550°C.

[0039] According to an embodiment of the present application, the roasting temperature is 500-550℃.

[0040] According to an embodiment of the present application, the roasting temperature is 350-500℃.

[0041] According to an embodiment of the present application, the roasting is performed in a muffle furnace for 2-4 hours.

[0042] According to an embodiment of the present application, in step S2, the water immersion temperature is 60-100℃.

[0043] According to an embodiment of the present application, in step S2, the water immersion temperature is 80-100℃.

[0044] According to an embodiment of the present application, the preparation method of the high-pressure leaching residue of nickel-cobalt hydroxide comprises the following steps:

[0045] A1 adding the nickel-cobalt hydroxide residue into the first acid solution, and performing leaching filtration to obtain a first leaching solution and a first leaching residue;

[0046] A2 mixing the first leaching residue and a second acid solution, and performing high-pressure leaching filtration to obtain the high-pressure leaching residue of nickel-cobalt hydroxide.

[0047] According to an embodiment of the present application, at least one of the technical solutions has one of the following advantages or beneficial effects:

[0048] According to an embodiment of the present application, in step A1, when the first acid solution comprises sulfuric acid, the nickel-cobalt hydroxide residue is added into the first acid solution, the pH is controlled to be 3-4, and after the leaching filtration, the first leaching solution is obtained, the battery-grade nickel-cobalt sulfate product is obtained by extraction, and the first leaching residue is subjected to high-pressure leaching.

[0049] According to an embodiment of the present application, in step A1, the following step is further included: crushing the nickel-cobalt hydroxide residue to wash the magnesium with water to obtain a magnesium-washed residue, and adding the magnesium-washed residue into the first acid solution.

[0050] According to an embodiment of the present application, in step A1, in the leaching filtration operation, the pH of the first leaching solution is maintained to be 3-4.

[0051] According to an embodiment of the present application, in step A1, the following step is further included: continuously adding the nickel-cobalt hydroxide into the first leaching solution, and performing leaching filtration operation again to obtain a relatively pure nickel-cobalt-manganese solution, and performing extraction operation to obtain the battery-grade nickel-cobalt-manganese solution.

[0052] According to an embodiment of the present application, the concentration of the first acid solution is 100-200 g / L.

[0053] According to an embodiment of the present application, the second acid solution has a concentration of 100-980 g / L.

[0054] According to an embodiment of the present application, in step A1, the temperature during the leaching filtration is 60-100℃.

[0055] According to an embodiment of the present application, in step A1, the temperature during the leaching filtration is 80-100℃.

[0056] According to an embodiment of the present application, in step A1, the temperature during the leaching filtration is 60-65℃.

[0057] According to an embodiment of the present application, the other aspect of the present application further relates to the application of the treatment method of the high-pressure leaching residue of nickel-cobalt hydroxide in the recycling of valuable metal resources. The treatment method of the high-pressure leaching residue of nickel-cobalt hydroxide is as described in the above first aspect embodiment. Since the application adopts all the technical solutions of the treatment method of the high-pressure leaching residue of nickel-cobalt hydroxide, it at least has all the beneficial effects brought by the technical solutions of the above embodiments.

[0058] Other features and advantages of the present application will be set forth in the description that follows, and in part will become apparent to those skilled in the art upon examination of the following or can be learned by practice of the present application. BRIEF DESCRIPTION OF DRAWINGS

[0059] The above and / or additional aspects and advantages of the present application will become apparent and be readily understood from the following description, taken in conjunction with the accompanying drawings, in which:

[0060] Figure 1 The flow chart of the treatment method of the high-pressure leaching residue of nickel-cobalt hydroxide in Example 1.

[0061] Figure 2 The XRD spectrum of the acid leaching residue obtained in Example 1.

[0062] Figure 3 The XRD spectrum of the acid leaching residue obtained in Example 15. DETAILED DESCRIPTION

[0063] In the description of the present application, if there is a description of first, second, etc., it is only for the purpose of distinguishing technical features, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features or the sequence of indicated technical features.

[0064] When a numerical range is disclosed herein, the range is to be construed as having been recited to the full extent of the range, including every value within the range. Further, when a range is provided, it is intended to include the maximum and minimum values of the range, as well as every value therebetween. Additionally, when a plurality of ranges is provided, it is intended to include every range that is a combination of the provided ranges. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all sub-ranges subsumed therein. Still further, when a range is provided, it is intended to include the maximum and minimum values of the range, as well as every integer within the range. Additionally, when a plurality of ranges is provided, it is intended to include every range that is a combination of the provided ranges.

[0065] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of the present application.

[0066] The reagents, methods and devices used in the present application are conventional reagents, methods and devices in the technical field unless otherwise specified.

[0067] In the examples and comparative examples, the determination method of the content of residual components in the acid leaching residue is as follows: the residue sample is first digested, and then the content of each element is determined by using ICP-MS / ICP-OES. When the content of each element determined by ICP-MS / ICP-OES is 0.0001 wt.%, it represents that the detection limit of the instrument has been reached.

[0068] Example 1

[0069] A preparation method of a high-pressure leaching residue of nickel-cobalt hydroxide includes the following steps:

[0070] A1 adds 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% into 200 g / L sulfuric acid, and obtains a first leaching liquid with a pH value of 3.05 and a first leaching residue through leaching and filtration;

[0071] A2 mixes the first leaching residue and sulfuric acid with a concentration of 98% at a mass ratio of 4:1, and obtains the high-pressure leaching residue of nickel-cobalt hydroxide through high-pressure leaching and filtration operation.

[0072] In the high-pressure leaching residue of nickel-cobalt hydroxide, the mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon are 0.014%, 0.0137%, 58.38%, 1.07%, 0.26% and 9.127%, respectively.

[0073] A treatment method of a high-pressure leaching residue of nickel-cobalt hydroxide, the flow chart is as shown in Figure 1 Specifically, the treatment method includes the following steps:

[0074] S1 0.2 kg of nickel-cobalt hydroxide high-pressure leaching residue was added to 1 L of water at a solid-liquid ratio of 1:5 (kg), 25 mL of 5% sodium hydroxide solution was added, the temperature was controlled at 60°C, the stirring speed was 400 rpm, and after 2 h, filtration was performed to obtain alkali washing liquid and alkali washing residue, and the mass percentage of Al in the alkali washing residue was 0.06 wt.%;

[0075] S2 sodium hydroxide solid (bottom), alkali washing residue (middle) and sodium hydroxide solid (top) were stacked in a mass ratio of 1:1:1, the temperature was controlled at 350°C, and the calcination time was 2 h, then the obtained calcined residue was subjected to water leaching at a solid-liquid ratio of 1 g:4 g and a temperature of 60°C for 30 min to obtain water leaching residue, and the Si content in the water leaching residue was 0.0002 wt.%;

[0076] S3 the water leaching residue was added to water to prepare a slurry with a solid content of 25%, 20 mL of 2 mol / L sulfuric acid was added for acid leaching, the temperature was controlled at 60°C, and after 30 min, filtration was performed to obtain acid leaching liquid and acid leaching residue (manganese dioxide), and the XRD spectrum of the acid leaching residue is shown in Figure 2 , wherein 2Theta (deg) represents the 2θ angle, and Intensity (a.u.) represents the intensity of the diffraction peak. The residual component content in the acid leaching residue was Ni 0.0001 wt.%, Co 0.0001 wt.%, MnO2 99.41 wt.%, Al 0.0015 wt.%, Fe 0.0001 wt.% and Si 0.0002 wt.%.

[0077] Example 2

[0078] The difference between Example 2 and Example 1 includes that in step S1, Example 2 uses 5% ammonia water instead of 5% sodium hydroxide solution in Example 1.

[0079] A preparation method of a nickel-cobalt hydroxide high-pressure leaching residue includes the following steps:

[0080] A1 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% was added to 200 g / L sulfuric acid, and after leaching and filtration, a first leaching liquid with a pH value of 3.32 and a first leaching residue were obtained;

[0081] A2 the first leaching residue and sulfuric acid with a concentration of 98% were mixed at a mass ratio of 4:1, and after high-pressure leaching and filtration, a nickel-cobalt hydroxide high-pressure leaching residue was obtained.

[0082] In the nickel-cobalt hydroxide high-pressure leaching residue, the mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon are 0.014%, 0.021%, 43.94%, 1.3537%, 0.0402% and 10.292%, respectively.

[0083] A treatment method of a nickel-cobalt hydroxide high-pressure leaching residue, specifically, comprising the following steps:

[0084] S1 take 0.2 kg of nickel-cobalt hydroxide high-pressure leaching residue, add 1 L of water according to a solid-liquid ratio of 1:5 (kg), then add 25 mL of 5% ammonia water, control the temperature at 60°C, and stir at a speed of 400 rpm; after 2 h, filter to obtain alkali washing liquid and alkali washing residue; the Al content in the alkali washing residue is 0.041 wt.%;

[0085] S2 according to a mass ratio of 1:1:1, respectively stack sodium hydroxide solid (bottom), alkali washing residue (middle) and sodium hydroxide solid (top), control the temperature at 350°C, and calcine for 2 h; then perform water leaching on the obtained calcined residue, control the solid-liquid ratio at 1 g:4 g, control the temperature at 60°C, and react for 30 min to obtain water leaching residue; the Si content in the water leaching residue is 0.0002 wt.%.

[0086] S3 add water to the water leaching residue to prepare a slurry with a solid content of 25%, add 20 mL of 2 mol / L sulfuric acid to perform acid leaching, control the temperature at 60°C, and filter after 30 min to obtain acid leaching liquid and acid leaching residue (manganese dioxide).

[0087] Example 3

[0088] The difference between Example 3 and Example 1 includes that in step S1, the mass percentage of the sodium hydroxide solution is 10%.

[0089] A preparation method of a nickel-cobalt hydroxide high-pressure leaching residue comprises the following steps:

[0090] A1 add 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% to 200 g / L sulfuric acid, perform leaching and filtration to obtain first leaching liquid with a pH value of 3.05 and first leaching residue;

[0091] A2 mix the first leaching residue and sulfuric acid with a concentration of 98% according to a mass ratio of 4:1, perform high-pressure leaching and filtration to obtain nickel-cobalt hydroxide high-pressure leaching residue.

[0092] In the nickel-cobalt hydroxide high-pressure leaching residue, the mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon are 0.014%, 0.0137%, 58.38%, 1.07%, 0.26% and 9.127%, respectively.

[0093] A treatment method of a nickel-cobalt hydroxide high-pressure leaching residue, specifically, comprising the following steps:

[0094] S1 take 0.2 kg of nickel-cobalt hydroxide high-pressure leaching residue, add 1 L of water according to a solid-liquid ratio of 1:5 (kg), then add 25 mL of a sodium hydroxide solution with a mass percentage of 10%, control the temperature at 60 DEG C, and stir at a speed of 400 rpm; after 2 h, filter to obtain an alkali washing liquid and an alkali washing residue; the alkali washing residue is detected to have an aluminum mass percentage of 0.033 wt.%;

[0095] S2 stack sodium hydroxide solids (bottom), alkali washing residues (middle) and sodium hydroxide solids (top) according to a mass ratio of 1:1:1, control the temperature at 350 DEG C, and calcine for 2 h; then perform water leaching on the obtained calcined residue according to a solid-liquid ratio of 1 g:4 g at a temperature of 60 DEG C for 30 min to obtain a water leaching residue; the water leaching residue has a silicon content of 0.0001 wt.%;

[0096] S3 add water to the water leaching residue to prepare a slurry with a solid content of 25%, add 20 mL of sulfuric acid with a concentration of 2 mol / L to perform acid leaching, control the temperature at 60 DEG C, and filter after 30 min to obtain an acid leaching liquid and an acid leaching residue (manganese dioxide); the acid leaching residue has residual contents of Ni 0.008 wt.%, Co 0.0005 wt.%, MnO2 98.7 wt.%, Al 0.0001 wt.%, Fe 0.0001 wt.% and Si 0.0001 wt.%.

[0097] Example 4

[0098] The difference between Example 4 and Example 3 includes that in step S1, the mass percentage of the sodium hydroxide solution is 15%.

[0099] A preparation method of a nickel-cobalt hydroxide high-pressure leaching residue includes the following steps:

[0100] A1 add 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% to 200 g / L of sulfuric acid, perform leaching and filtration to obtain a first leaching liquid with a pH value of 3.05 and a first leaching residue;

[0101] A2 mix the first leaching residue and sulfuric acid with a concentration of 98% according to a mass ratio of 4:1, perform high-pressure leaching and filtration to obtain a nickel-cobalt hydroxide high-pressure leaching residue.

[0102] In the nickel-cobalt hydroxide high-pressure leaching residue, the mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon are 0.014%, 0.0137%, 58.38%, 1.07%, 0.26% and 9.127%, respectively.

[0103] A treatment method of a nickel-cobalt hydroxide high-pressure leaching residue, specifically, includes the following steps:

[0104] S1 take 0.2 kg of nickel-cobalt hydroxide high-pressure leaching residue, add 1 L of water according to a solid-liquid ratio of 1:5 (kg), then add 25 mL of a sodium hydroxide solution with a mass percentage of 15%, control the temperature at 60 DEG C, and stir at a speed of 400 rpm; after 2 h, filter to obtain an alkali washing liquid and an alkali washing residue; the alkali washing residue is detected to have an aluminum mass percentage of 0.0001 wt.%;

[0105] S2 stack sodium hydroxide solid (bottom), alkali washing residue (middle) and sodium hydroxide solid (top) according to a mass ratio of 1:1:1, control the temperature at 350 DEG C, and calcine for 2 h; then perform water leaching on the obtained calcined residue according to a solid-liquid ratio of 1 g:4 g at a temperature of 60 DEG C for 30 min to obtain a water leaching residue; the water leaching residue has a silicon content of 0.0001 wt.%;

[0106] S3 add water to the water leaching residue to prepare a slurry with a solid content of 25%, add 20 mL of 2 mol / L sulfuric acid to perform acid leaching, control the temperature at 60 DEG C, and filter after 30 min to obtain an acid leaching liquid and an acid leaching residue (manganese dioxide); the acid leaching residue has a residual content of Ni 0.008 wt.%, Co 0.0005 wt.%, MnO2 98.7 wt.%, Al 0.0001 wt.%, Fe 0.0001 wt.% and Si 0.0001 wt.%.

[0107] Example 5

[0108] The difference between Example 5 and Example 3 includes that in step S1, the mass percentage of the sodium hydroxide solution is 20%.

[0109] A preparation method of a nickel-cobalt hydroxide high-pressure leaching residue includes the following steps:

[0110] A1 add 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% to 200 g / L sulfuric acid, perform leaching and filtration to obtain a first leaching liquid with a pH value of 3.05 and a first leaching residue;

[0111] A2 mix the first leaching residue and sulfuric acid with a concentration of 98% according to a mass ratio of 4:1, perform high-pressure leaching and filtration to obtain a nickel-cobalt hydroxide high-pressure leaching residue.

[0112] In the nickel-cobalt hydroxide high-pressure leaching residue, the mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon are 0.014%, 0.0137%, 58.38%, 1.07%, 0.26% and 9.127%, respectively.

[0113] A treatment method of a nickel-cobalt hydroxide high-pressure leaching residue, specifically, includes the following steps:

[0114] S1 take 0.2 kg of nickel-cobalt hydroxide high-pressure leaching residue, add 1 L of water according to a solid-liquid ratio of 1:5 (kg), then add 25 mL of a sodium hydroxide solution with a mass percentage of 20%, control the temperature at 60 DEG C, and stir at a speed of 400 rpm; after 2 h, filter to obtain an alkali washing liquid and an alkali washing residue; the alkali washing residue is detected to have an aluminum mass percentage of 0.002 wt.%;

[0115] S2 stack sodium hydroxide solids (bottom), alkali washing residues (middle) and sodium hydroxide solids (top) according to a mass ratio of 1:1:1, control the temperature at 350 DEG C, and calcine for 2 h; then perform water leaching on the obtained calcined residue according to a solid-liquid ratio of 1 g:4 g at a temperature of 60 DEG C for 30 min to obtain a water leaching residue; the water leaching residue has a silicon content of 0.0001 wt.%;

[0116] S3 add water to the water leaching residue to prepare a slurry with a solid content of 25%, add 20 mL of 2 mol / L sulfuric acid to perform acid leaching, control the temperature at 60 DEG C, and filter after 30 min to obtain an acid leaching liquid and an acid leaching residue (manganese dioxide); the acid leaching residue has residual contents of Ni 0.008 wt.%, Co 0.0005 wt.%, MnO2 98.7 wt.%, Al 0.0001 wt.%, Fe 0.0001 wt.% and Si 0.0001 wt.%.

[0117] Example 6

[0118] The difference between Example 6 and Example 3 includes that in step S1, the mass percentage of the sodium hydroxide solution is 25%.

[0119] A preparation method of a nickel-cobalt hydroxide high-pressure leaching residue includes the following steps:

[0120] A1 add 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% to 200 g / L sulfuric acid, perform leaching and filtration to obtain a first leaching liquid with a pH value of 3.05 and a first leaching residue;

[0121] A2 mix the first leaching residue and concentrated sulfuric acid with a concentration of 98% according to a mass ratio of 4:1, perform high-pressure leaching and filtration to obtain a nickel-cobalt hydroxide high-pressure leaching residue.

[0122] In the nickel-cobalt hydroxide high-pressure leaching residue, the mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon are 0.014%, 0.0137%, 58.38%, 1.07%, 0.26% and 9.127%, respectively.

[0123] A treatment method of a nickel-cobalt hydroxide high-pressure leaching residue, specifically, includes the following steps:

[0124] S1 take 0.2 kg of nickel-cobalt hydroxide high-pressure leaching residue, add 1 L of water according to a solid-liquid ratio of 1:5 (kg), then add 25 mL of a sodium hydroxide solution with a mass percentage of 25%, control the temperature at 60 DEG C, and stir at a speed of 400 rpm; after 2 h, filter to obtain an alkali washing liquid and an alkali washing residue; the alkali washing residue is detected to have an Al mass percentage of 0.026 wt.%;

[0125] S2 stack sodium hydroxide solids (bottom), alkali washing residues (middle) and sodium hydroxide solids (top) according to a mass ratio of 1:1:1, control the temperature at 350 DEG C, and calcine for 2 h; then perform water leaching on the obtained calcined residue according to a solid-liquid ratio of 1 g:4 g at a temperature of 60 DEG C for 30 min to obtain a water leaching residue; the Si content in the water leaching residue is 0.0001 wt.%;

[0126] S3 add water to the water leaching residue to prepare a slurry with a solid content of 25%, add 20 mL of 2 mol / L sulfuric acid to perform acid leaching, control the temperature at 60 DEG C, and filter after 30 min to obtain an acid leaching liquid and an acid leaching residue (manganese dioxide); the residual component content in the acid leaching residue is Ni 0.008 wt.%, Co 0.0005 wt.%, MnO2 98.7 wt.%, Al 0.0001 wt.%, Fe 0.0001 wt.%, and Si 0.0001 wt.%.

[0127] Example 7

[0128] The difference between Example 7 and Example 1 includes that in step S1, 15 mL of a sodium hydroxide solution with a mass percentage of 5% is first added, and then 5 mL of an ammonia water solution with a mass percentage of 5% is added.

[0129] A preparation method of a nickel-cobalt hydroxide high-pressure leaching residue includes the following steps:

[0130] A1 add 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% to 200 g / L sulfuric acid, perform leaching and filtration to obtain a first leaching liquid with a pH value of 3.65 and a first leaching residue;

[0131] A2 mix the first leaching residue and concentrated sulfuric acid with a concentration of 98% according to a mass ratio of 4:1, perform high-pressure leaching and filtration to obtain a nickel-cobalt hydroxide high-pressure leaching residue.

[0132] In the nickel-cobalt hydroxide high-pressure leaching residue, the mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon are 0.016%, 0.0035%, 55.82%, 1.77%, 0.256% and 13.272%, respectively.

[0133] A treatment method of a nickel-cobalt hydroxide high-pressure leaching residue, specifically, includes the following steps:

[0134] S1 take 0.2 kg of nickel-cobalt hydroxide high-pressure leaching residue, add 1 L of water according to a solid-liquid ratio of 1:5 (kg), then add 15 mL of a 5% by mass sodium hydroxide solution, and then add 5 mL of a 5% by mass ammonia water, control the temperature at 60 DEG C, and stir at a speed of 400 rpm, and after 2 h, filter to obtain an alkali washing liquid and an alkali washing residue, and the alkali washing residue is detected to have an aluminum content of 0.03% by mass;

[0135] S2 according to a mass ratio of 1:1:1, respectively stack sodium hydroxide solid (bottom), alkali washing residue (middle) and sodium hydroxide solid (upper part), control the temperature at 350 DEG C, and calcine for 2 h, then perform water leaching on the obtained calcined residue according to a solid-liquid ratio of 1 g:4 g at a temperature of 60 DEG C for 30 min to obtain a water leaching residue;

[0136] S3 add water to the water leaching residue to prepare a slurry with a solid content of 25%, add 20 mL of 2 mol / L sulfuric acid to perform acid leaching, control the temperature at 60 DEG C, and after 30 min, filter to obtain an acid leaching liquid and an acid leaching residue, and the acid leaching residue has residual contents of Ni 0.002% by mass, Co 0.0011% by mass, MnO2 86.2% by mass, Al 0.03% by mass, Fe 0.0001% by mass, and Si 3.9% by mass.

[0137] Example 8

[0138] The difference between Example 8 and Example 7 includes that in step S1, 5 mL of 5% by mass ammonia water is first added, and then 15 mL of 5% by mass sodium hydroxide solution is added.

[0139] A preparation method of a nickel-cobalt hydroxide high-pressure leaching residue includes the following steps:

[0140] A1 add 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% to 200 g / L sulfuric acid, perform leaching and filtration to obtain a first leaching liquid with a pH value of 3.65 and a first leaching residue;

[0141] A2 mix the first leaching residue and 98% by mass sulfuric acid according to a mass ratio of 4:1, perform high-pressure leaching and filtration to obtain a nickel-cobalt hydroxide high-pressure leaching residue.

[0142] In the nickel-cobalt hydroxide high-pressure leaching residue, the mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon are 0.016%, 0.0035%, 55.82%, 1.77%, 0.256% and 13.272%, respectively.

[0143] A treatment method of a nickel-cobalt hydroxide high-pressure leaching residue, specifically, includes the following steps:

[0144] S1 take 0.2 kg of nickel-cobalt hydroxide high-pressure leaching residue, add 1 L of water according to a solid-liquid ratio of 1:5 (kg), then add 5 mL of 5% ammonia water, and then add 15 mL of 5% sodium hydroxide solution, control the temperature at 60 DEG C, and stir at a speed of 400 rpm; after 2 h, filter to obtain alkali washing liquid and alkali washing residue; the alkali washing residue is detected to have an aluminum content of 0.0001 wt. %;

[0145] S2 stack sodium hydroxide solid (bottom), alkali washing residue (middle) and sodium hydroxide solid (top) according to a mass ratio of 1:1:1, control the temperature at 350 DEG C, and calcine for 2 h; then perform water leaching on the obtained calcined residue according to a solid-liquid ratio of 1 g:4 g at a temperature of 60 DEG C for 30 min to obtain water leaching residue;

[0146] S3 add water to the water leaching residue to prepare a slurry with a solid content of 25%, add 20 mL of 2 mol / L sulfuric acid to perform acid leaching, control the temperature at 60 DEG C, and filter after 30 min to obtain acid leaching liquid and acid leaching residue (manganese dioxide); the acid leaching residue has a residual content of Ni 0.002 wt. %, Co 0.0012 wt. %, MnO2 98.6 wt. %, Al 0.0001 wt. %, Fe 0.0001 wt. % and Si 0.009 wt. %.

[0147] Example 9

[0148] The difference between Example 9 and Example 7 includes that in step S1, 5 mL of 5% ammonia water and 15 mL of 5% sodium hydroxide solution are simultaneously added in Example 9.

[0149] A preparation method of a nickel-cobalt hydroxide high-pressure leaching residue includes the following steps:

[0150] A1 add 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% to 200 g / L sulfuric acid, perform leaching and filtration to obtain first leaching liquid with a pH value of 3.65 and first leaching residue;

[0151] A2 mix the first leaching residue and 98% sulfuric acid according to a mass ratio of 4:1, perform high-pressure leaching and filtration to obtain nickel-cobalt hydroxide high-pressure leaching residue.

[0152] In the nickel-cobalt hydroxide high-pressure leaching residue, the mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon are 0.016%, 0.0035%, 55.82%, 1.77%, 0.256% and 13.272%, respectively.

[0153] A treatment method of a nickel-cobalt hydroxide high-pressure leaching residue, specifically, includes the following steps:

[0154] S1 take 0.2kg of nickel-cobalt hydroxide high-pressure leaching residue, add 1L of water according to the solid-liquid ratio of 1:5 (kg), then simultaneously add 5mL of 5% ammonia water and 15mL of 5% sodium hydroxide solution, control the temperature at 60℃, and stir at a speed of 400rpm, and after 2h, filter to obtain alkali washing liquid and alkali washing residue, and the mass percentage of Al in the alkali washing residue is 0.022wt.%;

[0155] S2 according to the mass ratio of 1:1:1, respectively stack sodium hydroxide solid (bottom), alkali washing residue (middle) and sodium hydroxide solid (upper), control the temperature at 350℃, and calcine for 2h, then perform water leaching on the obtained calcined residue, the solid-liquid ratio is 1g:4g, the temperature is 60℃, and the reaction time is 30min, and obtain water leaching residue;

[0156] S3 add water to the water leaching residue to prepare a slurry with a solid content of 25%, add 20mL of 2mol / L sulfuric acid to perform acid leaching, control the temperature at 60℃, and after 30min, filter to obtain acid leaching liquid and acid leaching residue (manganese dioxide), and the residual content in the acid leaching residue is Ni 0.0019wt.%, Co 0.003wt.%, MnO2 96.3wt.%, Al 0.0025wt.%, Fe 0.0001wt.%, and Si 0.03wt.%.

[0157] Example 10

[0158] The difference between Example 10 and Example 8 includes that in step S2, Example 10 respectively stacks sodium hydroxide solid (bottom), alkali washing residue (middle) and sodium hydroxide solid (upper) according to the mass ratio of 0.8:1:0.8.

[0159] A preparation method of a nickel-cobalt hydroxide high-pressure leaching residue includes the following steps:

[0160] A1 add 2kg of nickel-cobalt hydroxide residue with a water content of 53.4% to 200g / L sulfuric acid, perform leaching and filtration, and obtain first leaching liquid with a pH value of 3.50 and first leaching residue;

[0161] A2 mix the first leaching residue and sulfuric acid with a concentration of 98% according to a mass ratio of 4:1, perform high-pressure leaching and filtration, and obtain nickel-cobalt hydroxide high-pressure leaching residue.

[0162] In the nickel-cobalt hydroxide high-pressure leaching residue, the mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon are 0.0953%, 0.1021%, 43.94%, 1.7329%, 0.0451% and 12.6592% respectively.

[0163] A treatment method of a nickel-cobalt hydroxide high-pressure leaching residue, specifically, includes the following steps:

[0164] S1 take 0.2 kg of nickel-cobalt hydroxide high-pressure leaching residue, add 1 L of water according to a solid-liquid ratio of 1:5 (kg), then add 5 mL of 5% ammonia water, and then add 15 mL of 5% sodium hydroxide solution, control the temperature at 60 DEG C, and stir at a speed of 400 rpm; after 2 h, filter to obtain alkali washing liquid and alkali washing residue; the alkali washing residue contains 0.0001 wt.% of Al.

[0165] S2 stack sodium hydroxide solid (bottom), alkali washing residue (middle) and sodium hydroxide solid (top) according to a ratio of 0.8:1:0.8, control the temperature at 350 DEG C, and calcine for 2 h; then perform water leaching on the obtained calcined residue according to a solid-liquid ratio of 1 g:4 g at a temperature of 60 DEG C for 30 min to obtain water leaching residue; the Si content in the water leaching residue is 0.9 wt.% and the silicon removal rate is 92.89%.

[0166] S3 add water to the water leaching residue to prepare a slurry with a solid content of 25%, add 20 mL of 2 mol / L sulfuric acid to perform acid leaching, control the temperature at 60 DEG C, and filter after 30 min to obtain acid leaching liquid and acid leaching residue (manganese dioxide); the residual content in the acid leaching residue is Ni 0.0021 wt.%, Co 0.0005 wt.%, MnO2 98.9 wt.%, Al 0.0001 wt.%, Fe 0.0001 wt.% and Si 0.9 wt.%.

[0167] Example 11

[0168] The difference between Example 11 and Example 10 includes that in step S2, Example 11 stacks sodium hydroxide solid (bottom), alkali washing residue (middle) and sodium hydroxide solid (top) according to a ratio of 0.9:1:0.9.

[0169] A preparation method of a nickel-cobalt hydroxide high-pressure leaching residue includes the following steps:

[0170] A1 add 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% to 200 g / L sulfuric acid, perform leaching and filtration to obtain first leaching liquid with a pH value of 3.50 and first leaching residue;

[0171] A2 mix the first leaching residue and 98% sulfuric acid according to a mass ratio of 4:1, perform high-pressure leaching and filtration to obtain nickel-cobalt hydroxide high-pressure leaching residue.

[0172] In the nickel-cobalt hydroxide high-pressure leaching residue, the mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon are 0.0953%, 0.1021%, 43.94%, 1.7329%, 0.0451% and 12.6592%, respectively.

[0173] A treatment method of a nickel-cobalt hydroxide high-pressure leaching residue, specifically comprising the following steps:

[0174] S1 0.2 kg of nickel-cobalt hydroxide high-pressure leaching residue is taken, 1 L of water is added according to a solid-liquid ratio of 1:5 (kg), then 5 mL of 5% ammonia water is added, then 15 mL of 5% sodium hydroxide solution is added, the temperature is controlled at 60 DEG C, the stirring speed is 400 rpm, after 2 h, filtration is performed to obtain alkali washing liquid and alkali washing residue, and it is detected that the mass percentage of Al in the alkali washing residue is 0.0001 wt.%;

[0175] S2 sodium hydroxide solid (bottom), alkali washing residue (middle) and sodium hydroxide solid (upper) are respectively stacked according to 0.9:1:0.9, the temperature is controlled at 350 DEG C, and roasting is performed for 2 h, then the obtained roasting residue is subjected to water immersion, the solid-liquid ratio is 1 g:4 g, the temperature is 60 DEG C, and reaction is performed for 30 min to obtain water immersion residue; the Si content in the water immersion residue is 0.21 wt.%, and the silicon removal rate is 98.34%.

[0176] S3 the water immersion residue is added with water to prepare a slurry with a solid content of 25%, 20 mL of 2 mol / L sulfuric acid is added for acid immersion, the temperature is controlled at 60 DEG C, and after 30 min, filtration is performed to obtain acid immersion liquid and acid immersion residue (manganese dioxide), and the residual component content in the acid immersion residue is Ni 0.001 wt.%, Co 0.0012 wt.%, MnO2 99.07 wt.%, Al 0.0001 wt.%, Fe 0.0001 wt.% and Si 0.25 wt.%.

[0177] Example 12

[0178] The difference between example 12 and example 10 includes that in step S2, example 12 respectively stacks sodium hydroxide solid (bottom), alkali washing residue (middle) and sodium hydroxide solid (upper) according to 1:1:1.

[0179] A preparation method of a nickel-cobalt hydroxide high-pressure leaching residue includes the following steps:

[0180] A1 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% is added into 200 g / L sulfuric acid, and after leaching and filtration, a first leaching liquid with a pH value of 3.48 and a first leaching residue are obtained;

[0181] A2 the first leaching residue and sulfuric acid with a concentration of 98% are mixed according to a mass ratio of 4:1, and after high-pressure leaching and filtration operation, a nickel-cobalt hydroxide high-pressure leaching residue is obtained.

[0182] In the nickel-cobalt hydroxide high-pressure leaching residue, the mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon are 0.004%, 0.0025%, 53.25%, 1.68%, 0.0635% and 10.0189% respectively.

[0183] A treatment method of a high-pressure leaching residue of nickel-cobalt hydroxide, specifically comprising the following steps:

[0184] S1 Take 0.2 kg of high-pressure leaching residue of nickel-cobalt hydroxide, add 1 L of water according to a solid-liquid ratio of 1:5 (kg), then add 5 mL of 5% ammonia water, and then add 15 mL of 5% sodium hydroxide solution, control the temperature at 60°C, and stir at a speed of 400 rpm. After 2 h, filter to obtain alkali washing liquid and alkali washing residue. The content of Al in the alkali washing residue is 0.0001 wt.%.

[0185] S2 Stack sodium hydroxide solid (bottom), alkali washing residue (middle), and sodium hydroxide solid (top) according to a mass ratio of 1:1:1, control the temperature at 350°C, and calcine for 2 h. Then, perform water leaching on the obtained calcined residue according to a solid-liquid ratio of 1 g:4 g at a temperature of 60°C for 30 min to obtain water leaching residue. The content of Si in the water leaching residue is 0.009 wt.%, and the silicon removal rate is 99.91%.

[0186] S3 Add water to the water leaching residue to prepare a slurry with a solid content of 25%, add 20 mL of 2 mol / L sulfuric acid for acid leaching, control the temperature at 60°C, and filter after 30 min to obtain acid leaching liquid and acid leaching residue (manganese dioxide). The content of residual components in the acid leaching residue is Ni 0.0018 wt.%, Co 0.0011 wt.%, MnO2 98.15 wt.%, Al 0.0001 wt.%, Fe 0.0001 wt.%, and Si 0.009 wt.%.

[0187] Example 13

[0188] The difference between Example 13 and Example 8 includes that, in step S2, the calcination temperature of Example 13 is 450°C.

[0189] A preparation method of a high-pressure leaching residue of nickel-cobalt hydroxide includes the following steps:

[0190] A1 Add 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% to 200 g / L sulfuric acid, perform leaching and filtration to obtain first leaching liquid with a pH value of 3.40 and first leaching residue.

[0191] A2 Mix the first leaching residue and sulfuric acid with a concentration of 98% according to a mass ratio of 4:1, perform high-pressure leaching and filtration, and obtain the high-pressure leaching residue of nickel-cobalt hydroxide.

[0192] In the high-pressure leaching residue of nickel-cobalt hydroxide, the mass percentages of nickel, cobalt, manganese, iron, aluminum, and silicon are 0.063%, 0.1019%, 45.64%, 1.629%, 0.0433%, and 11.65%, respectively.

[0193] The application discloses a treatment method of a high-pressure leaching residue of nickel-cobalt hydroxide, and particularly comprises the following steps.

[0194] S1 0.2 kg of the high-pressure leaching residue of nickel-cobalt hydroxide is taken, 1 L of water is added according to a solid-liquid ratio of 1:5 (kg), 5 mL of 5% ammonia water is further added, 15 mL of 5% sodium hydroxide solution is further added, the temperature is controlled to be 60 DEG C, the stirring speed is 400 rpm, and after 2 h, filtration is performed to obtain alkali washing liquid and alkali washing residue; the alkali washing residue is detected, and the mass percentage of Al in the alkali washing residue is 0.0001 wt.%.

[0195] S2 sodium hydroxide solid (bottom), alkali washing residue (middle) and sodium hydroxide solid (upper) are respectively stacked according to a mass ratio of 1:1:1, the temperature is controlled to be 450 DEG C, the roasting time is 2 h, then the obtained roasting residue is subjected to water immersion, the solid-liquid ratio is 1 g:4 g, the temperature is 60 DEG C, and the reaction time is 30 min, so as to obtain water immersion residue; the Si content in the water immersion residue is 0.001 wt.%.

[0196] S3 the water immersion residue is added with water to prepare a slurry with a solid content of 25%, 20 mL of 2 mol / L sulfuric acid is added for acid immersion, the temperature is controlled to be 60 DEG C, and after 30 min, filtration is performed to obtain acid immersion liquid and acid immersion residue (manganese dioxide); the residual component content in the acid immersion residue is as follows: Ni 0.0035 wt.%, Co 0.002 wt.%, MnO2 98.66 wt.%, Al 0.0015 wt.%, Fe 0.0037 wt.% and Si 0.001 wt.%.

[0197] Example 14

[0198] The difference between example 14 and example 8 comprises that in step S2, the roasting temperature of example 14 is 500 DEG C.

[0199] A preparation method of the high-pressure leaching residue of nickel-cobalt hydroxide comprises the following steps:

[0200] A1 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% is added into 200 g / L sulfuric acid, and after leaching and filtration, a first leaching residue and a first leaching liquid with a pH value of 4.00 are obtained;

[0201] A2 the first leaching residue and sulfuric acid with a concentration of 98% are mixed according to a mass ratio of 4:1, and after high-pressure leaching and filtration, the high-pressure leaching residue of nickel-cobalt hydroxide is obtained.

[0202] In the high-pressure leaching residue of nickel-cobalt hydroxide, the mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon are 0.08%, 0.25%, 46.60%, 1.88%, 0.023% and 8.5759% respectively.

[0203] A treatment method of a high-pressure leaching residue of nickel-cobalt hydroxide, specifically comprising the following steps:

[0204] S1 0.2 kg of the high-pressure leaching residue of nickel-cobalt hydroxide is taken, 1 L of water is added according to a solid-liquid ratio of 1:5 (kg), then 5 mL of 5% ammonia water is added, and then 15 mL of 5% sodium hydroxide solution is added, the temperature is controlled at 60 DEG C, the stirring speed is 400 rpm, and after 2 h, filtration is performed to obtain alkali washing liquid and alkali washing residue, and it is detected that the mass percentage of Al in the alkali washing residue is 0.0001 wt.%.

[0205] S2 sodium hydroxide solid (bottom), alkali washing residue (middle) and sodium hydroxide solid (upper) are respectively stacked according to a mass ratio of 1:1:1, the temperature is controlled at 500 DEG C, and the roasting time is 2 h, then the obtained roasting residue is subjected to water leaching, the solid-liquid ratio is 1 g:4 g, the temperature is 60 DEG C, and the reaction time is 30 min, and the water leaching residue is obtained, and the Si content in the water leaching residue is 0.001 wt.%.

[0206] S3 the water leaching residue is added with water to prepare a slurry with a solid content of 25%, 20 mL of 2 mol / L sulfuric acid is added for acid leaching, the temperature is controlled at 60 DEG C, and after 30 min, filtration is performed to obtain acid leaching liquid and acid leaching residue (manganese dioxide), and the residual component content in the acid leaching residue is Ni 0.0018 wt.%, Co 0.0005 wt.%, MnO2 99.37 wt.%, Al 0.0001 wt.%, Fe 0.0001 wt.% and Si 0.0001 wt.%.

[0207] Example 15

[0208] The difference between Example 15 and Example 8 includes that in step S2, the roasting temperature of Example 15 is 550 DEG C.

[0209] A preparation method of a high-pressure leaching residue of nickel-cobalt hydroxide comprises the following steps:

[0210] A1 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% is added into 200 g / L sulfuric acid, and after leaching and filtration, a first leaching liquid with a pH value of 3.70 and a first leaching residue are obtained;

[0211] A2 the first leaching residue and sulfuric acid with a concentration of 98% are mixed according to a mass ratio of 4:1, and after high-pressure leaching and filtration, a high-pressure leaching residue of nickel-cobalt hydroxide is obtained.

[0212] In the high-pressure leaching residue of nickel-cobalt hydroxide, the mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon are 0.083%, 0.09%, 48.36%, 1.83%, 0.096% and 9.75%, respectively.

[0213] A kind of processing method of nickel-cobalt hydroxide high-pressure leaching residue, specifically, including the following steps:

[0214] S1 takes nickel-cobalt hydroxide high-pressure leaching residue 0.2 kg, adds 1L water according to solid-liquid ratio 1:5 (kg), then adds 5 mL, mass percentage 5% ammonia water, then adds 15 mL, mass percentage 5% sodium hydroxide solution, temperature control is 60 DEG C, stirring speed 400 rpm, after 2h, filter to obtain alkali wash liquid and alkali wash residue, by detection, the mass percentage of Al in alkali wash residue is 0.0001wt.%;

[0215] S2 according to the mass ratio of 1:1:1, respectively, superimposed sodium hydroxide solid (bottom), alkali wash residue (middle) and sodium hydroxide solid (upper), temperature control is at 550 DEG C, calcination time 2h, then the obtained calcined slag is immersed in water, solid-liquid ratio 1g:4g, temperature 60 DEG C, reaction 30min, obtain water immersion residue;Si content in water immersion residue is 0.0001wt.%.

[0216] S3 water immersion residue is added to water to prepare slurry with solid content 25%, add 20 mL of 2mol / L sulfuric acid for acid leaching, temperature control is 60 DEG C, 30min after filtration to obtain acid leaching liquid and acid leaching residue (manganese dioxide and manganese sesquioxide mixture), residual component content in acid leaching residue is Ni 0.002wt.%, Co 0.0003wt.%, Al 0.0001wt.%, Fe 0.0001wt.%, Si 0.0001wt.% and 97.1521wt.% manganese dioxide and manganese sesquioxide mixture.The XRD diagram of acid leaching residue is shown in Figure 3 , wherein, 2Theta (deg) represents 2 theta angle, intensity (a.u.) represents the intensity of diffraction peak.

[0217] At 550 DEG C, the product is mainly a mixture of MnO2 and Mn2O3, by controlling calcination temperature, the product type can be regulated in example 15.

[0218] Example 16

[0219] The difference between example 16 and example 14 includes: in step S2, example 16 superimposes Na2CO3 solid (bottom), alkali wash residue (middle) and Na2CO3 solid (upper) for calcination.

[0220] A kind of preparation method of nickel-cobalt hydroxide high-pressure leaching residue includes the following steps:

[0221] A1 adds 2kg of nickel-cobalt hydroxide residue with water content 53.4% to 200g / L sulfuric acid, after leaching filtration, obtains the first leaching liquid with pH value 3.80 and the first leaching residue;

[0222] A2 mixed the first leaching residue and sulfuric acid with a concentration of 98% in a mass ratio of 4:1, and obtained the nickel-cobalt hydroxide high-pressure leaching residue through high-pressure leaching filtration operation.

[0223] In the nickel-cobalt hydroxide high-pressure leaching residue, the mass percentages of nickel, cobalt, manganese, iron, aluminum, and silicon are 0.07%, 0.035%, 46.72%, 1.85%, 0.0411%, and 11.556%, respectively.

[0224] A method for processing a nickel-cobalt hydroxide high-pressure leaching residue, specifically comprising the following steps:

[0225] S1 takes 0.2 kg of nickel-cobalt hydroxide high-pressure leaching residue, adds 1 L of water according to a solid-liquid ratio of 1:5 (kg), then adds 5 mL of ammonia water with a mass percentage of 5%, and then adds 15 mL of sodium hydroxide solution with a mass percentage of 5%, controls the temperature at 60°C, and stirs at a speed of 400 rpm. After 2 hours, filter to obtain alkali washing liquid and alkali washing residue. The mass percentage of Al in the alkali washing residue is 0.0001 wt.% after detection.

[0226] S2 adds Na2CO3 solid (bottom), alkali washing residue (middle), and Na2CO3 solid (top) according to a mass ratio of 1:1:1, controls the temperature at 500°C, and roasts for 2 hours. Then, the obtained roasted residue is subjected to water immersion at a solid-liquid ratio of 1 g:4 g and a temperature of 60°C for 30 minutes to obtain a water immersion residue. The Si content in the water immersion residue is 9.33 wt.%.

[0227] S3 adds water to the water immersion residue to prepare a slurry with a solid content of 25%, adds 20 mL of 2 mol / L sulfuric acid for acid immersion, controls the temperature at 60°C, and filters after 30 minutes to obtain acid immersion liquid and acid immersion residue (manganese dioxide).

[0228] Example 17

[0229] The difference between Example 17 and Example 16 includes that in step S2, the roasting temperature of Example 17 is 850°C.

[0230] A method for preparing a nickel-cobalt hydroxide high-pressure leaching residue includes the following steps:

[0231] A1 adds 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% to 200 g / L sulfuric acid, and obtains first leaching liquid with a pH value of 3.80 and first leaching residue through leaching filtration.

[0232] A2 mixes the first leaching residue and sulfuric acid with a concentration of 98% in a mass ratio of 4:1, and obtains the nickel-cobalt hydroxide high-pressure leaching residue through high-pressure leaching filtration operation.

[0233] The mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon in the high-pressure leaching residue of nickel-cobalt hydroxide are 0.07%, 0.035%, 46.72%, 1.85%, 0.0411% and 11.556%, respectively.

[0234] A treatment method of a high-pressure leaching residue of nickel-cobalt hydroxide, specifically, comprising the following steps:

[0235] S1: 0.2 kg of the high-pressure leaching residue of nickel-cobalt hydroxide is taken, 1 L of water is added according to a solid-liquid ratio of 1:5 (kg), then 5 mL of 5% ammonia water and 15 mL of 5% sodium hydroxide solution are added, the temperature is controlled at 60°C, the stirring speed is 400 rpm, and after 2 h, filtration is performed to obtain alkali washing liquid and alkali washing residue, and the mass percentage of Al in the alkali washing residue is 0.0001 wt.%.

[0236] S2: Na2CO3 solid (bottom), alkali washing residue (middle) and Na2CO3 solid (upper) are stacked according to a mass ratio of 1:1:1, the temperature is controlled at 850°C, and the roasting time is 2 h, then the obtained roasting residue is subjected to water leaching at a solid-liquid ratio of 1 g:4 g and a temperature of 60°C for 30 min to obtain water leaching residue, and the Si content in the water leaching residue is 1.29 wt.%.

[0237] S3: The water leaching residue is added with water to prepare a slurry with a solid content of 25%, 20 mL of 2 mol / L sulfuric acid is added for acid leaching, the temperature is controlled at 60°C, and after 30 min, filtration is performed to obtain acid leaching liquid and acid leaching residue (a mixture of manganese dioxide and dimanganese trioxide).

[0238] Example 18

[0239] The difference between Example 18 and Example 16 includes that in step S2, the roasting temperature of Example 18 is 950°C.

[0240] A preparation method of a high-pressure leaching residue of nickel-cobalt hydroxide comprises the following steps:

[0241] A1: 2 kg of nickel-cobalt hydroxide residue with a water content of 53.4% is added into 200 g / L sulfuric acid, and after leaching and filtration, a first leaching liquid with a pH value of 3.80 and a first leaching residue are obtained.

[0242] A2: The first leaching residue and sulfuric acid with a concentration of 98% are mixed according to a mass ratio of 4:1, and after high-pressure leaching and filtration, a high-pressure leaching residue of nickel-cobalt hydroxide is obtained.

[0243] The mass percentages of nickel, cobalt, manganese, iron, aluminum and silicon in the high-pressure leaching residue of nickel-cobalt hydroxide are 0.07%, 0.035%, 46.72%, 1.85%, 0.0411% and 11.556%, respectively.

[0244] A treatment method of a nickel-cobalt hydroxide high-pressure leaching residue, specifically comprising the following steps:

[0245] S1Take 0.2 kg of nickel-cobalt hydroxide high-pressure leaching residue, add 1 L of water according to a solid-liquid ratio of 1:5 (kg), then add 5 mL of 5% ammonia water, and then add 15 mL of 5% sodium hydroxide solution, control the temperature at 60°C, and stir at a speed of 400 rpm, filter after 2 h to obtain alkali washing liquid and alkali washing residue, and detect that the mass percentage of Al in the alkali washing residue is 0.0001 wt.%.

[0246] S2According to a mass ratio of 1:1:1, respectively stack Na2CO3 solid (bottom), alkali washing residue (middle) and Na2CO3 solid (upper part), control the temperature at 950°C, and calcine for 2 h, then perform water immersion on the obtained calcined residue according to a solid-liquid ratio of 1 g:4 g at a temperature of 60°C for 30 min to obtain water immersion residue; the Si content in the water immersion residue is 0.0035 wt.%.

[0247] S3Add water to the water immersion residue to prepare a slurry with a solid content of 25%, add 20 mL of 2 mol / L sulfuric acid to perform acid immersion, control the temperature at 60°C, and filter after 30 min to obtain acid immersion liquid and acid immersion residue (a mixture of manganese dioxide and dimanganese trioxide).

[0248] Performance test:

[0249] Part of the element contents in the nickel-cobalt hydroxide high-pressure leaching residue, alkali washing residue and water immersion residue in Examples 1-18 are taken out for comparison, and the comparison results are shown in Table 1.

[0250] Table 1

[0251]

[0252]

[0253] In Example 1, sodium hydroxide is used to wash the nickel-cobalt hydroxide high-pressure leaching residue, and through detection of the Al content in the alkali washing residue, it is shown that sodium hydroxide can wash away Al in the nickel-cobalt hydroxide high-pressure leaching residue.

[0254] In Example 2, ammonia water is used instead of sodium hydroxide to wash the nickel-cobalt hydroxide high-pressure leaching residue, and through detection of the Al content in the alkali washing residue, it is shown that ammonia water is difficult to dissolve Al in the nickel-cobalt hydroxide high-pressure leaching residue. The mass percentage of Al in the alkali washing residue of Example 2 is slightly higher than that in the nickel-cobalt hydroxide high-pressure leaching residue, because there is a certain error in the two detection results, and the error is within a reasonable range.

[0255] Examples 3-6 differ in the concentration of sodium hydroxide. Among them, Example 4 (corresponding to the mass percentage concentration of sodium hydroxide is 15%) achieves an Al removal rate of 99.96%.

[0256] In Examples 7-9, the difference lies in the order of adding sodium hydroxide and ammonia. Among them, Example 8 achieves an Al removal rate of 99.96%, indicating that adding 5 mL of 5% ammonia first and then adding 15 mL of 5% sodium hydroxide has the best effect, because although ammonia cannot dissolve the hydrated alunite in the high-pressure slag into the solution, it can first generate aluminum hydroxide, which then reacts with sodium hydroxide to form sodium metaaluminate, thereby improving the aluminum removal rate. In Example 7, the aluminum is not completely removed because sodium hydroxide is added first, and then ammonia is added. This also affects the subsequent silicon removal. Moreover, due to the presence of a portion of sodium-silicon slag in the slag, the content of manganese dioxide in the acid leaching slag is also reduced.

[0257] In Examples 10-12, the difference lies in the amount of alkali used during the calcination of the alkali washed slag. In Example 12, during calcination, NaOH solid (upper layer): alkali washed slag (middle): NaOH solid (lower layer) are placed in the order of 1:1:1, and the Si removal rate reaches 99.91%.

[0258] In Examples 13-15, the difference lies in the calcination temperature. Although the Si removal rates in Examples 13-15 are not far apart, from Figure 3 It can be known that when the temperature is higher than 530 degrees, such as 550 degrees, the product of calcination is mainly a mixture of MnO2 and Mn2O3.

[0259] In Examples 16-18, Na2CO3 is added for calcination, and Examples 16-18 differ in calcination temperature. The results show that for Examples 16-17, since the calcination temperature is lower than or equal to 850℃, the melting point of Na2CO3 (850℃) is not reached, resulting in the inability to remove or completely remove silicon. In addition, in Example 18, the calcination temperature is 950℃, and the product contains manganese sesquioxide. Since when the calcination temperature is between 350℃ and 500℃, the product is mainly MnO2, and when the calcination temperature is greater than 530℃, the product contains manganese sesquioxide, therefore, by adjusting the calcination temperature, the desired product can be obtained.

[0260] The above are only examples of the present application, and do not limit the patent scope of the present application. Any equivalent transformation or direct or indirect application in related technical fields using the content of the present application specification is also included in the patent protection scope of the present application.

Claims

1. A method for treating high-pressure leaching residue of nickel-cobalt hydroxide, characterized in that: Includes the following steps: S1. Mixed nickel-cobalt hydroxide high-pressure leaching residue and alkaline solution are washed and filtered to obtain alkaline washing residue and alkaline washing solution. The alkaline solution includes sodium hydroxide solution or sodium hydroxide solution and ammonia solution. The mass percentage of sodium hydroxide in the sodium hydroxide solution is 5%-25%, and the mass percentage of ammonia in the ammonia solution is 5%-25%. S2 The alkaline washing residue and solid alkali are mixed and then successively roasted and water-leached to obtain water-leached residue and silicon-containing water-leached liquid. The roasting temperature is 450-550℃. S3. The water-leached residue and acid solution are mixed, and after acid leaching and filtration, an iron-containing acid leaching solution and a manganese-containing acid leaching residue are obtained.

2. The method according to claim 1, characterized in that: The alkaline solution includes at least one of sodium hydroxide solution or sodium hydroxide solution and ammonia solution, wherein the sodium hydroxide solution contains 10%-25% sodium hydroxide by mass and the ammonia solution contains 10%-25% ammonia by mass.

3. The method according to claim 1, characterized in that: Step S1 also includes the following steps: first, mix the high-pressure leaching residue of nickel-cobalt hydroxide with an ammonia solution, and then add a sodium hydroxide solution.

4. The method according to claim 1, characterized in that: The solid alkali includes a first solid alkali and a second solid alkali. In step S2, the following steps are also included: stacking the first solid alkali, alkali washing residue, and second solid alkali in sequence, and then roasting them.

5. The method according to claim 4, characterized in that: The weight ratio of the first solid alkali, the alkali washing residue, and the second solid alkali is 0.8-1:1:0.8-1, respectively.

6. The method according to claim 5, characterized in that: The weight ratio of the first solid alkali, the alkali washing residue, and the second solid alkali is 0.9-1:1:0.9-1, respectively.

7. The method according to claim 1, characterized in that: The preparation method of the nickel-cobalt hydroxide high-pressure leaching residue includes the following steps: A1 Add nickel-cobalt hydroxide slag to the first acid solution, and after leaching and filtration, obtain the first leachate and the first leaching residue; A2 is mixed with the first leaching residue and the second acid solution, and then subjected to high-pressure leaching and filtration to obtain nickel-cobalt hydroxide high-pressure leaching residue.

8. The application of the method for treating high-pressure leaching residue of nickel-cobalt hydroxide as described in any one of claims 1 to 7 in the regeneration of valuable metal resources.

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