A method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw material

Abstract

The invention belongs to the field of hydrometallurgy or chemical technology, and particularly relates to a method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials. First, the nickel-cobalt hydroxide is subjected to ripening leaching instead of direct leaching with sulfuric acid to separate silicon and nickel-cobalt; then, part of silicon and metal elements are separated, and NiCO3 is recycled to neutralize the leached pulp to reach a certain pH value, so that elements such as iron and aluminum are precipitated into iron-aluminum slag; during the leaching process of the iron-aluminum slag, the silicon is removed by mixing with acid leaching to well solve the problem of excessive silicon content in the subsequent process of the iron-aluminum slag, and the separation of nickel, cobalt and iron-aluminum is also realized; then, Na2CO3 is used for two-stage iron removal and aluminum precipitation, and the obtained NiCO3 can be recycled to the first stage iron removal process, and Na2SO4 can be evaporated and crystallized to produce by-products. The nickel-cobalt solution obtained after the first stage iron removal is then separated from nickel, cobalt and manganese by P204 and P507 to obtain nickel solution, cobalt solution and manganese solution, and no interphase pollution is generated during the separation process, and efficient nickel-cobalt-manganese separation can be realized.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrometallurgy or chemical engineering, and particularly relates to a method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials. Background Art

[0002] Nickel cobalt hydroxide is a kind of product made from laterite nickel ore through high pressure acid leaching technology (HPAL). However, nickel cobalt hydroxide contains impurities such as iron, aluminum, manganese, magnesium, and silicon in addition to nickel and cobalt. The current treatment method is to slurry and dissolve the nickel cobalt hydroxide material, extract and remove impurities, and then purify it for reuse. However, flocculants are often added to the nickel cobalt hydroxide produced from laterite nickel ore during the front-end treatment process, resulting in a large amount of flocculants in the nickel cobalt hydroxide product; and a large amount of reducing agent sodium pyrosulfite is added in the leaching process of nickel cobalt hydroxide, resulting in too high COD concentration in the pre-extraction liquid, which seriously affects the quality of subsequent products; at the same time, in order to remove iron and aluminum, the pH value of the impurity removal process solution will be adjusted to 5.0-5.2 or higher, resulting in a large amount of nickel precipitation and reducing the nickel recovery rate. Moreover, a large amount of silicon is dissolved in the process of treatment, which affects the subsequent process. When the leaching liquid is extracted, the silicate in the liquid forms a large amount of interphase dirt, and the interphase dirt will make the extraction and stripping phase separation difficult and cause phase entrainment, and the extraction production will fall into chaos. In severe cases, it will lead to shutdown, and it is difficult to separate nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials. For example, CN105274332A discloses a separation technology and process for extracting nickel and cobalt from nickel-containing high-cobalt hydroxide, but silicon is not removed in the process, and only conventional leaching-extraction separation is performed. The presence of silicon not only forms a large amount of interphase dirt when the leaching liquid is extracted, making extraction and stripping phase separation difficult, but also affects the leaching rate in the subsequent leaching and reuse process of iron-aluminum slag. CN110551905A discloses a method for treating nickel-cobalt hydroxide, which mainly includes aging and reduction leaching processes. However, this method only describes the removal method of Si, Na, and COD, and does not remove impurities such as aluminum and iron, and does not explain the separation of nickel, cobalt, and manganese in the raw materials. In addition, this patent removes silicon at the front end of the nickel-cobalt hydroxide, the material volume is large, and the removed silica gel is viscous, which is not easy to filter.

[0003] Nickel cobalt hydroxide contains a large amount of elements such as nickel, cobalt, and manganese. However, in the actual application and production of nickel cobalt hydroxide, combinations of nickel, cobalt, and manganese ternary materials with different ratios can form ternary materials with different properties. Among them, cobalt can stabilize the layered structure of the material and improve the cycle and rate performance of the material, but too high a cobalt content will lead to a decrease in the actual capacity; nickel can increase the volume energy density of the new material, but ternary materials with a high nickel content (i.e., high nickel) will also lead to lithium-nickel mixing, thereby causing lithium precipitation; manganese has good electrochemical inertness, which allows the material to always maintain a stable structure, while reducing material costs, improving material safety and structural stability, but too high a manganese content will destroy the layered structure of the material and reduce the specific capacity of the material; therefore, it is particularly important to obtain nickel-cobalt-manganese ternary materials with different properties in a suitable ratio while keeping the structure unchanged to meet the lithium-ion battery market for different purposes. However, the methods used in the prior art for treating nickel, cobalt and manganese in the raw materials all have defects. For example, CN106319228A discloses a method for simultaneously recovering nickel, cobalt and manganese from a sulfuric acid leachate containing nickel, cobalt and manganese waste slag. The method first removes iron and aluminum from the leachate by an oxidative precipitation method, then extracts copper, then extracts zinc, and finally uses tributyl phosphate and saponified neodecanoic acid to simultaneously extract nickel, cobalt and manganese. This method can achieve simultaneous extraction and recovery of nickel, cobalt and manganese in the nickel, cobalt and manganese waste slag leachate, and calcium and magnesium in the raw material liquid will not affect the extraction process. However, this method is not a separation of nickel-cobalt hydroxide raw materials and cannot achieve the separation of the three elements of nickel, cobalt and manganese.

[0004] Therefore, it is worth considering proposing a method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials. Summary of the invention

[0005] In order to solve the above technical problems or at least partially solve the above technical problems, the present invention provides a method for separating nickel, cobalt and manganese from a nickel-cobalt hydroxide raw material, the method comprising the following steps:

[0006] The nickel-cobalt hydroxide raw material is subjected to ripening leaching and a first-stage iron and aluminum removal in sequence to obtain a primary filter residue and a nickel-cobalt filtrate;

[0007] The nickel-cobalt filtrate is subjected to phase separation after extracting manganese and impurities with P204 to obtain an extracted organic phase and a raffinate;

[0008] The extracted organic phase is subjected to a manganese removal treatment using stripping manganese acid, and after phase separation, an impurity-containing organic phase and a manganese-containing liquid are obtained; the raffinate is subjected to cobalt extraction using P507, and after phase separation, a cobalt-containing organic phase and a nickel-containing liquid are obtained;

[0009] The cobalt-containing organic phase is subjected to a cobalt-removal treatment by using a cobalt-removal acid, and a regenerated organic phase and a cobalt-containing liquid are obtained after phase separation.

[0010] Furthermore, the ripening and leaching is specifically:

[0011] The nickel cobalt hydroxide raw material and concentrated sulfuric acid are mixed at a ratio of 500-1000 kg / t of mixed acid to ore, water is added to a liquid-solid ratio of 1.5-3:1, stirred at 300-800 r / min at 80-95 ° C for 1-3 hours, and then water is added to a liquid-solid ratio of 8-12:1, the first reducing agent is added, reduced for 0.3-1 hour, and then filtered to obtain a primary silicon slag and a first filtrate.

[0012] Further, the first reducing agent is selected from H 2 O 2 、SO 2 、Na 2 S 2 O 6 Any one or a mixture of two or three;

[0013] The coefficient of the first reducing agent is: the amount of the first reducing agent / the amount of Mn contained in the nickel-cobalt hydroxide raw material is 0.5-1.5 mol / mol.

[0014] Furthermore, the first stage of iron and aluminum removal is specifically:

[0015] Add a neutralizing agent to the first filtrate to adjust the pH to 4.5-4.8, then use air as an oxidant to oxidize at a temperature of 60-80° C. and a stirring speed of 300-800 r / min for 3-5 hours;

[0016] The solution obtained by oxidation is subjected to solid-liquid separation to obtain a primary filter residue and a nickel-cobalt filtrate;

[0017] Wherein, the flow rate of the air is 50-200mL / min;

[0018] The neutralizing agent is NiCO 3 , and then used after being adjusted into slurry, the solid content in the slurry is 30-60%.

[0019] Furthermore, the nickel-cobalt filtrate is subjected to P204 extraction for manganese and impurities as follows:

[0020] P204 and sulfonated kerosene are mixed and then saponified with alkali solution; wherein the volume content of P204 is 10-30% and the saponification rate is 50-80%;

[0021] The nickel-cobalt filtrate is extracted according to the conditions of extraction phase ratio O / A of 1:1-3, extraction pH of 2-4, extraction temperature of 25°C, and extraction time of 1-5min;

[0022] The phase separation time is 2-4 minutes, and the extraction levels are 5-8.

[0023] Further, the extracted organic phase is subjected to a manganese removal treatment using stripping manganese acid:

[0024] The stripping manganese acid is sulfuric acid with a concentration of 1-2.5 mol / L, an O / A ratio of 1-3:1, a temperature of 25° C., and a mixing time of 1-5 min;

[0025] The phase separation time is 2-4 minutes, and the number of stages is 4-8.

[0026] Further, the extraction of cobalt from the raffinate by using P507 is specifically as follows:

[0027] P507 and sulfonated kerosene are mixed and then saponified with alkali solution; wherein the volume content of P507 is 10-30% and the saponification rate is 50-70%;

[0028] The nickel-cobalt filtrate is extracted according to the conditions of extraction phase ratio O / A of 1:1-3, extraction pH of 2-4, extraction temperature of 25°C, and extraction time of 1-5min;

[0029] The phase separation time is 2-4 minutes, and the extraction levels are 3-6.

[0030] Furthermore, the cobalt-containing organic phase is subjected to a cobalt-reversal treatment using cobalt-reversal acid as follows:

[0031] The transcobalt acid concentration is 1-2.5 mol / L sulfuric acid, the O / A ratio is 1-5:1, the temperature is 25°C, and the mixing time is 1-5 min;

[0032] The phase separation time is 2-4 minutes, and the level is 3-8.

[0033] Further, the impurity-containing organic phase is treated with 3-5 mol / L sulfuric acid; wherein the O / A ratio is 2-5:1, the temperature is 25° C., and the mixing time is 1-5 min;

[0034] After phase separation with a phase separation time of 2-4 minutes and a stage number of 4-8, regenerated organic and impurity-containing liquid are obtained, and the regenerated organic can be reused.

[0035] Furthermore, the method further comprises treating the primary filter residue, specifically comprising the following steps:

[0036] Acid leaching: mixing the primary filter residue with concentrated sulfuric acid, adding a second reducing agent, stirring and reacting, and performing solid-liquid separation on the reduced solution to obtain secondary silicon residue and desiliconization filtrate;

[0037] Second stage iron and aluminum removal: adding a neutralizing agent to the desiliconization filtrate, adjusting the pH to 4.8-5.2, and reacting for 3-5 hours, and performing solid-liquid separation on the reaction liquid to obtain iron and aluminum slag and impurity removal filtrate;

[0038] Nickel precipitation: add the neutralizing agent NaCO to the impurity removal filtrate3 , adjust the pH to 7-8, react at 40-70℃ for 2-4h, separate the reaction liquid into solid and liquid to obtain the residue NiCO 3 and filtrate Na 2 SO 4 .

[0039] Furthermore, during the acid leaching process:

[0040] The acid-ore ratio of nickel-cobalt hydroxide raw material and concentrated sulfuric acid is 800-1400kg / t. When mixing, stir for 2-5 minutes and then place for 1-2 hours, then add water to a liquid-solid ratio of 8-12:1 and stir for 0.5-2 hours.

[0041] The second reducing agent added is selected from H 2 O 2 、SO 2 Or one of them or a mixture of the two, the dosage of the second reducing agent / Mn content of the ore is 0.5-1.5 mol / mol, the reduction time is 0.3-1h, the temperature is 80-95°C, and the stirring speed is 300-800r / min.

[0042] Beneficial effects of the present invention:

[0043] The present invention first uses ripening leaching of nickel-cobalt hydroxide instead of direct leaching of sulfuric acid to separate silicon and nickel-cobalt, while improving the direct yield of nickel-cobalt; then separates part of silicon and metal elements, and reuses NiCO 3 The leached slurry is neutralized to a certain pH value, so that elements such as iron and aluminum are precipitated into iron-aluminum slag. In the process of iron-aluminum slag leaching, the use of acid leaching to remove silicon effectively solves the problem of excessive silicon content in the subsequent process of iron-aluminum slag, thereby realizing the separation of nickel, cobalt and iron and aluminum. The iron-aluminum slag is mixed with acid and matured to obtain a desiliconized solution; then Na 2 CO 3 The two-stage iron and aluminum removal and nickel precipitation are carried out to obtain NiCO 3 And Na 2 SO 4 solution. NICO 3 It can be recycled to the first iron and aluminum removal process, and Na 2 SO 4 The by-product can be produced by evaporation and crystallization. The nickel-cobalt solution obtained after the first stage of iron and aluminum removal is then separated into nickel, cobalt and manganese by P204 and P507 to obtain nickel solution, cobalt solution and manganese solution. No interphase contamination is generated during the separation process, and efficient nickel-cobalt-manganese separation can be achieved.

[0044] Other features and advantages of the present invention will be described in the following description, and partly become apparent from the description, or understood by practicing the present invention. The purpose and other advantages of the present invention can be realized and obtained by the structures pointed out in the description, claims and drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0046] Figure 1 A flow chart showing the method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials proposed by the present invention is shown;

[0047] Figure 2 A detailed flow chart of the method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials proposed in an embodiment of the present invention is shown. DETAILED DESCRIPTION

[0048] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0049] The present invention proposes a process for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials. First, the nickel-cobalt hydroxide is aged with sulfuric acid to leach nickel, cobalt and other elements, separate part of silicon and metal elements, and then reuse NiCO 3 The leached pulp is neutralized to a certain pH value, so that elements such as iron and aluminum are precipitated into iron-aluminum slag. After filtration, nickel-cobalt solution and iron-aluminum slag are obtained, thereby realizing the separation of nickel-cobalt and iron-aluminum. The iron-aluminum slag is mixed with acid and matured to obtain a desiliconized solution, which is then treated with Na 2 CO 3 Secondary iron and aluminum removal and nickel precipitation are carried out to obtain NiCO 3 And Na 2 SO 4 solution. NICO 3 Can be reused in the previous process, and Na 2 SO 4 The byproduct can be produced by evaporation and crystallization. The nickel-cobalt solution obtained after the iron and aluminum are removed once is then separated into nickel, cobalt and manganese by P204 and P507 to obtain nickel solution, cobalt solution and manganese solution. The process of the present invention is simple, the desiliconization effect is good, and efficient nickel-cobalt-manganese separation can be achieved.

[0050] The P204 used is di(2-ethylhexyl) phosphate, which is an acidic extractant. It exists in kerosene in the form of a hydrogen-bonded dimer structure to cover its polar phosphate group, and usually participates in the reaction in the form of a dimer when complexing with metal ions.

[0051] P507 is 2-ethylhexyl mono-2-ethylhexyl phosphate, which can separate the main metal ions and impurity metal ions, enrich the concentration of main metal ions, purify metal ions, and change the type of anions.

[0052] The specific steps are as follows Figure 1 As shown:

[0053] The nickel-cobalt hydroxide raw material is subjected to ripening leaching and a stage of iron and aluminum removal in sequence to obtain a primary filter residue and a nickel-cobalt filtrate; wherein the ripening leaching is specifically as follows: the nickel-cobalt hydroxide raw material and concentrated sulfuric acid are mixed at a ratio of 500-1000 kg / t, water is added to a liquid-solid ratio of 1.5-3:1, stirred at 300-800 r / min for 1-3 hours at 80-95°C, and then water is added to a liquid-solid ratio of 8-12:1, a first reducing agent is added, reduced for 0.3-1 hours, and then filtered to obtain a primary silicon slag and a first filtrate. The first reducing agent is selected from H 2 O 2 、SO 2 、Na 2 S 2 O 6 Any one or a mixture of two or three of the above; the coefficient of the first reducing agent is: the amount of the first reducing agent / the amount of Mn in the nickel cobalt hydroxide raw material is 0.5-1.5 mol / mol. The first stage of iron and aluminum removal is specifically as follows: add a neutralizing agent to the first filtrate to adjust the pH to 4.5-4.8, then use air as an oxidant to oxidize at a temperature of 60-80°C and a stirring speed of 300-800r / min for 3-5h; perform solid-liquid separation on the oxidized solution to obtain a primary filter residue and a nickel cobalt filtrate; wherein the flow rate of the air is 50-200mL / min; the neutralizing agent is NiCO 3 , and then used after being adjusted into slurry, the solid content in the slurry is 30-60%.

[0054] The nickel-cobalt filtrate is subjected to phase separation after extracting manganese and impurities with P204 to obtain an extracted organic phase and a raffinate; specifically, P204 and sulfonated kerosene are mixed and saponified with alkali solution, and the alkali solution can be ammonia water, sodium hydroxide, etc., preferably ammonia water; wherein the volume content of P204 is 10-30%, and the saponification rate is 50-80%; the nickel-cobalt filtrate is extracted under the conditions of an extraction phase O / A ratio of 1:1-3, an extraction pH of 2-4, an extraction temperature of 25°C, and an extraction time of 1-5min; the phase separation time is 2-4min, and the extraction level is 5-8 levels;

[0055] The extracted organic phase is subjected to a manganese removal treatment by using a manganese stripping acid, specifically, the acid and the extracted organic phase are fully mixed, and then the impurity-containing organic phase and the manganese-containing liquid are obtained after standing and phase separation; the manganese stripping acid is sulfuric acid with a concentration of 1-2.5 mol / L, the phase O / A is 1-3:1, the temperature is 25°C, and the mixing time is 1-5 min; the phase separation time is 2-4 min, and the number of stages is 4-8; the raffinate is subjected to cobalt extraction by using P507, and after phase separation, a cobalt-containing organic phase and a nickel-containing liquid are obtained; P507 and sulfonated kerosene are mixed and then saponified with alkali solution; wherein the volume content of P507 is 1 0-30%, saponification rate 50-70%; extract the nickel-cobalt filtrate under the conditions of extraction phase O / A of 1:1-3, extraction pH of 2-4, extraction temperature of 25°C, and extraction time of 1-5min; the phase separation time is 2-4min, and the extraction level is 3-6 levels; further, the impure organic phase is treated with 3-5mol / L sulfuric acid; wherein the phase O / A is 2-5:1, the temperature is 25°C, and the mixing time is 1-5min; after phase separation with a phase separation time of 2-4min and a level of 4-8, the regenerated organic phase and the impure liquid are obtained, and the regenerated organic phase can be reused;

[0056] The cobalt-containing organic phase is subjected to a cobalt-removal treatment by using a cobalt-removal acid, the acid and the extracted organic phase are fully mixed, and then the phases are allowed to stand for phase separation to obtain a regenerated organic phase and a cobalt-containing liquid; the cobalt-removal acid is 1-2.5 mol / L sulfuric acid, the phase O / A ratio is 1-5:1, the temperature is 25°C, the mixing time is 1-5 min; the phase separation time is 2-4 min, and the number of stages is 3-8.

[0057] Furthermore, the primary filter residue can be treated in the following ways:

[0058] Acid leaching: the primary filter residue is mixed with concentrated sulfuric acid, and then a second reducing agent is added to stir and react, and the solution obtained by reduction is subjected to solid-liquid separation to obtain secondary silicon slag and desiliconization filtrate; wherein the acid-ore ratio of the nickel-cobalt hydroxide raw material and the concentrated sulfuric acid is 800-1400 kg / t, and when mixing, the mixture is stirred for 2-5 minutes and then placed for 1-2 hours, and then water is added to a liquid-solid ratio of 8-12:1 and then stirred for 0.5-2 hours; the second reducing agent added is selected from H 2 O 2 、SO 2 Or one of them or a mixture of the two, the dosage of the second reducing agent / Mn content of the ore is 0.5-1.5 mol / mol, the reduction time is 0.3-1h, the temperature is 80-95°C, and the stirring speed is 300-800r / min.

[0059] Second stage iron and aluminum removal: adding a neutralizing agent to the desiliconization filtrate, adjusting the pH to 4.8-5.2, and reacting for 3-5 hours, and performing solid-liquid separation on the reaction liquid to obtain iron and aluminum slag and impurity removal filtrate;

[0060] Nickel precipitation: add the neutralizing agent NaCO to the impurity removal filtrate 3 , adjust the pH to 7-8, react at 40-70℃ for 2-4h, separate the reaction liquid into solid and liquid to obtain the residue NiCO 3 and filtrate Na 2 SO 4 .

[0061] The manganese-containing solution, nickel-containing extract and cobalt-containing solution obtained in the above process can be further purified by other means, specifically by continuous extraction or by segmented crystallization.

[0062] The following is combined with specific embodiments and Figure 2 The above method and the reaction conditions of each step are described in detail, which mainly includes several steps: ripening leaching, primary iron and aluminum removal, acid leaching, secondary iron and aluminum removal, nickel precipitation, manganese extraction, impurity extraction and nickel and cobalt separation.

[0063] Example 1

[0064] Ripening leaching: Mix the nickel-cobalt hydroxide raw material with concentrated sulfuric acid, with an acid-ore ratio of 800 kg / t, add water to a liquid-solid ratio of 2:1, stir for 2 hours, then add water to a liquid-solid ratio of 8:1, add a reducing agent, and the reduction time is 0.5 hours. Then perform solid-liquid separation to obtain primary silicon slag and the first filtrate.

[0065] One-stage iron and aluminum removal: Add neutralizing agent NiCO to the first filtrate 3 , adjust the pH to 4.8, use air as the oxidant, and react for 4 hours. Then perform solid-liquid separation to obtain a primary filter residue and a nickel-cobalt filtrate. The components of the nickel-cobalt filtrate are shown in Table 1:

[0066] Table 1 Composition of nickel-cobalt filtrate

[0067]

[0068] Acid leaching: Mix the primary filter residue obtained from the first stage of iron and aluminum removal with concentrated sulfuric acid, with an acid-ore ratio of 1000 kg / t, stir for 5 minutes, leave for 2 hours, then add water to a liquid-solid ratio of 8:1, stir for 1 hour, and then add the second reducing agent H 2 O 2 , the reduction time is 0.5h. Then solid-liquid separation is performed to obtain secondary silicon slag and desiliconization filtrate. The components of the desiliconization filtrate are shown in Table 2:

[0069] Table 2 Composition of desiliconization filtrate

[0070]

[0071] It can be seen from the results in Tables 1 and 2 that by separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials according to the method proposed in the present invention, more nickel, cobalt and manganese elements can be retained for subsequent extraction in a process of removing iron and aluminum.

[0072] Second stage iron and aluminum removal: add neutralizing agent NaCO to the desiliconization filtrate obtained by acid leaching 3 , adjust the pH to 5.2, react for 4 hours, and then separate the solid and liquid to obtain iron-aluminum slag and impurity-removed filtrate.

[0073] Nickel precipitation: Add the neutralizing agent NaCO to the impurity-removing filtrate obtained in the second stage of iron and aluminum removal. 3 , adjust pH to 7.6, react for 2h, and the reaction temperature is 70℃. After solid-liquid separation, filter residue NiCO 3 and filtrate Na 2 SO 4 Filter residue NiCO 3 Reuse in the first iron and aluminum removal process, the filtrate Na 2 SO 4 Evaporation and crystallization are carried out to obtain the by-product Glauber's salt.

[0074] Extraction of manganese and impurities: The nickel-cobalt solution obtained from the step of removing iron and aluminum is extracted with P204 for manganese and impurities. The organic phase is a mixture of P204 and sulfonated kerosene. The volume content of P204 is 20%, and then saponified with ammonia water. The saponification rate is 60%, and the extraction phase O / A is 1:1. The extraction pH is 3. The extraction temperature is 25°C, the extraction time is 3min, the phase separation time is 3min, the extraction level is 8, and the phase is separated after extraction to obtain an extracted organic phase and a raffinate. The extracted organic phase is used for demanganese treatment, and the demanganese acid concentration is 2mol / L sulfuric acid, the phase O / A is 1:1, the temperature is 25°C, the mixing time is 3min, the phase separation time is 3min, and the level is 6. After demanganese extraction and phase separation, an impure organic phase and a manganese-containing liquid are obtained. This manganese-containing liquid continues to be extracted and purified by P204. The impure organic phase obtained in the stripping process of manganese was used for stripping treatment, the impurity acid concentration was 3.5 mol / L sulfuric acid, the phase O / A ratio was 1:1, the temperature was 25°C, the mixing time was 3 minutes, the phase separation time was 3 minutes, and the number of stages was 8. The regenerated organic phase and the impurity liquid were obtained, and the regenerated organic phase can be reused.

[0075] Nickel-cobalt separation process: The raffinate obtained in the manganese extraction process is extracted with P507 for cobalt extraction. The organic phase is a mixture of P507 and sulfonated kerosene. The volume content of P507 is 20%. It is then saponified with liquid alkali, the saponification rate is 60%, and the extraction phase O / A is 1:1. The extraction pH is 3. The extraction temperature is 25°C, the extraction time is 3min, the phase separation time is 3min, the extraction level is 5, and the phases are separated after extraction to obtain a cobalt-containing organic phase and a nickel-containing liquid. The cobalt-containing organic phase is used for reverse cobalt treatment. The reverse cobalt acid concentration is 2mol / L sulfuric acid, the phase O / A is 1:1, the temperature is 25°C, the mixing time is 3min, the phase separation time is 3min, and the level is 6. After reverse cobalt extraction and phase separation, a regenerated organic phase and a cobalt-containing liquid are obtained, and the regenerated organic phase can be reused.

[0076] The compositions of the manganese-containing solution, nickel-containing solution and cobalt-containing solution after extraction are shown in Table 3:

[0077] Table 3 Extraction liquid composition

[0078]

[0079] Example 2

[0080] The difference from Example 1 is that the acid-ore ratio in the mature leaching step is 1000 kg / t, and the other conditions remain unchanged. The components of the nickel-cobalt filtrate after the first stage of iron and aluminum removal are shown in Table 4:

[0081] Table 4 Composition of nickel-cobalt filtrate

[0082]

[0083] Example 3

[0084] The difference from Example 1 is that the pH is adjusted to 4.5 in the first iron and aluminum removal step, and the operation is carried out under the other conditions unchanged.

[0085] The components of the nickel-cobalt filtrate after the first stage of iron and aluminum removal are shown in Table 5:

[0086] Table 5 Composition of nickel-cobalt filtrate

[0087]

[0088] Example 4

[0089] The difference from Example 1 is that the saponification rate of P204 in the manganese extraction and impurity extraction steps is 70%, and the composition of the liquid after extraction is shown in Table 6.

[0090] Table 6 Extraction liquid composition

[0091]

[0092] Example 5

[0093] The difference from Example 1 is that in the nickel-cobalt separation step, the saponification rate is 70%, the extraction phase ratio O / A is 1:2, and the composition of the liquid after extraction is shown in Table 7. As the extraction phase ratio changes, the ion content in the extract changes.

[0094] Table 7 Extraction liquid composition

[0095]

[0096] Comparative Example 1

[0097] The difference from Example 1 is that the acid-ore ratio in the mature leaching step is 300 kg / t, and the other conditions remain unchanged. The components of the nickel-cobalt filtrate after the first stage of iron and aluminum removal and the desiliconization filtrate after the mixed acid leaching are shown in Table 8:

[0098] Table 8 Composition of nickel-cobalt filtrate

[0099]

[0100] Comparative Example 2

[0101] The difference from Example 1 is that the pH is adjusted to 4 in the first iron and aluminum removal step, and the operation is carried out under the other conditions unchanged.

[0102] The components of the nickel-cobalt filtrate after the first stage of iron and aluminum removal and the desiliconization filtrate after acid leaching are shown in Table 9:

[0103] Table 9 Composition of nickel-cobalt filtrate

[0104]

[0105] Comparative Example 3

[0106] The difference from Example 1 is the nickel-cobalt separation process: the organic phase saponification rate is 30%, and the composition of the liquid after extraction is shown in Table 10:

[0107] Table 10 Extraction liquid composition

[0108]

[0109] Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent substitutions for some of the technical features therein; and these modifications or substitutions do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials, characterized in that: The method comprises the following steps: The nickel-cobalt hydroxide raw material is subjected to ripening leaching and a first-stage iron and aluminum removal in sequence to obtain a primary filter residue and a nickel-cobalt filtrate; the ripening leaching specifically comprises: the nickel-cobalt hydroxide raw material and concentrated sulfuric acid are mixed at a ratio of 500-1000 kg / t of mixed acid to ore, water is added to a liquid-solid ratio of 1.5-3:1, stirred at 300-800 r / min for 1-3 hours at 80-95°C, then water is added to a liquid-solid ratio of 8-12:1, a first reducing agent is added, reduced for 0.3-1h, and then filtered to obtain a primary silicon slag and a first filtrate; the first-stage iron and aluminum removal specifically comprises: a neutralizing agent is added to the first filtrate to adjust the pH to 4.5-4.8, and then air is used as an oxidant to oxidize at a temperature of 60-80°C and a stirring speed of 300-800 r / min for 3-5 hours; the solution obtained by oxidation is subjected to solid-liquid separation to obtain a primary filter residue and a nickel-cobalt filtrate; The nickel-cobalt filtrate is subjected to phase separation after extracting manganese and impurities with P204 to obtain an extracted organic phase and a raffinate; The extracted organic phase is subjected to a manganese removal treatment by using a manganese stripping acid, and an impurity-containing organic phase and a manganese-containing liquid are obtained after phase separation; the raffinate is subjected to a cobalt extraction by using P507, and a cobalt-containing organic phase and a nickel-containing liquid are obtained after phase separation; the manganese stripping acid is sulfuric acid with a concentration of 1-2.5 mol / L, a phase O / A ratio of 1-3:1, a temperature of 25° C., a mixing time of 1-5 min, a phase separation time of 2-4 min, and a level of 4-8; The cobalt-containing organic phase is subjected to a cobalt-removal treatment by using a cobalt-removal acid, and a regenerated organic phase and a cobalt-containing liquid are obtained after phase separation; The method further comprises treating the primary filter residue, specifically comprising the following steps: Acid leaching: mixing the primary filter residue with concentrated sulfuric acid, adding a second reducing agent, stirring and reacting, and performing solid-liquid separation on the reduced solution to obtain secondary silicon residue and desiliconization filtrate; Second stage iron and aluminum removal: add a neutralizer to the desiliconization filtrate, adjust the pH to 4.8-5.2, and then react for 3-5 hours, and separate the reaction liquid into solid and liquid to obtain iron and aluminum slag and impurity removal filtrate; Nickel precipitation: add the neutralizing agent Na2CO3 to the impurity removal filtrate, adjust the pH to 7-8 and react at 40-70°C for 2-4h, separate the reaction liquid into solid and liquid to obtain the filter residue NiCO3 and the filtrate Na2SO4.

2. The method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials according to claim 1, characterized in that: The first reducing agent is selected from any one of H2O2, SO2, and Na2S2O6 or a mixture of two or three thereof; The coefficient of the first reducing agent is: the amount of the first reducing agent / the amount of Mn contained in the nickel-cobalt hydroxide raw material is 0.5-1.5 mol / mol.

3. The method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials according to claim 2, characterized in that: In the one-stage iron and aluminum removal process, the air flow rate is 50-200 mL / min; the neutralizing agent is NiCO3, which is used after being adjusted into slurry, and the solid content in the slurry is 30-60%.

4. The method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials according to claim 1, characterized in that: The nickel-cobalt filtrate is subjected to P204 extraction of manganese and impurities as follows: P204 and sulfonated kerosene are mixed and then saponified with alkali solution; wherein the volume content of P204 is 10-30% and the saponification rate is 50-80%; The nickel-cobalt filtrate is extracted under the conditions of an extraction phase ratio O / A of 1:1-3, an extraction pH of 2-4, an extraction temperature of 25°C, and an extraction time of 1-5 min; The phase separation time is 2-4 minutes, and the extraction levels are 5-8.

5. The method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials according to claim 1, characterized in that: The method of extracting cobalt from the raffinate by using P507 is as follows: P507 and sulfonated kerosene are mixed and then saponified with alkali solution; wherein the volume content of P507 is 10-30% and the saponification rate is 50-70%; The nickel-cobalt filtrate is extracted under the conditions of an extraction phase ratio O / A of 1:1-3, an extraction pH of 2-4, an extraction temperature of 25°C, and an extraction time of 1-5 min; The phase separation time is 2-4 minutes, and the extraction levels are 3-6.

6. The method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials according to claim 1, characterized in that: The method of using the cobalt acid to perform a cobalt-removal treatment on the cobalt-containing organic phase is specifically as follows: The trans-cobalt acid concentration is 1-2.5 mol / L sulfuric acid, the O / A ratio is 1-5:1, the temperature is 25°C, and the mixing time is 1-5 min; The phase separation time is 2-4 minutes, and the level is 3-8.

7. The method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials according to claim 1, characterized in that: The impurity-containing organic phase is treated with 3-5 mol / L sulfuric acid; wherein the O / A ratio is 2-5:1, the temperature is 25° C., and the mixing time is 1-5 min; After phase separation with a phase separation time of 2-4 minutes and a stage number of 4-8, a regenerated organic phase and a liquid containing impurities are obtained, and the regenerated organic phase can be reused.

8. The method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw materials according to claim 1, characterized in that: During the acid leaching process: The acid-ore ratio of nickel-cobalt hydroxide raw material and concentrated sulfuric acid is 800-1400kg / t. When mixing, stir for 2-5 minutes and then place for 1-2 hours, then add water to a liquid-solid ratio of 8-12:1 and stir for 0.5-2 hours. The added second reducing agent is selected from one of H2O2 and SO2 or a mixture of the two, the dosage of the second reducing agent / Mn content of the ore is 0.5-1.5 mol / mol, the reduction time is 0.3-1h, the temperature is 80-95°C, and the stirring speed is 300-800r / min.

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