Preparation method of cobalt extraction pre-solution

Abstract

This invention relates to the field of valuable metal recovery technology and discloses a method for preparing a cobalt extraction pre-liquid. The method includes: extracting a crude cobalt hydroxide leaching solution with a post-soap extractant Bp-α to obtain an iron-zinc-calcium-cobalt organic phase and a decalcified solution; and extracting the decalcified solution with a post-soap extractant Bp-β to obtain a calcium-copper-manganese-cobalt organic phase and a cobalt extraction pre-liquid. The post-soap extractant Bp-α comprises a P204 extractant with a volume concentration of 23%–27% and a saponification rate of 19%–21%. The post-soap extractant Bp-β comprises a P204 extractant with a volume concentration of 18%–22% and a saponification rate of 44%–46%, and an N910 extractant with a volume concentration of 4%–6%. This method significantly reduces production costs while still obtaining a qualified cobalt extraction pre-liquid.

Description

Technical Field

[0001] This invention relates to the field of valuable metal recycling technology, and more specifically, to a method for preparing cobalt extraction pre-extraction solution. Background Technology

[0002] In recent years, due to continuous breakthroughs in battery technology, the new energy industry has also flourished, which has led to a huge market demand for battery cathode materials.

[0003] The existing and well-established methods for preparing cobalt extraction pre-liquids involve using precipitation to separate impurities from crude cobalt hydroxide leachate. This method suffers from high acid and alkali losses and can lead to cobalt metal loss. Alternatively, the traditional extractant P204 is used for impurity removal. While technically mature, this method still has drawbacks, with high acid and alkali losses being its biggest weakness. However, P204's low price makes it widely used in various extraction fields, making technological improvements to the P204 extraction method a major future direction. When using P204 for extraction, the copper ion extraction rate only increases from 54% to 56% when the O / A ratio is between 1.0 and 2.0. Therefore, a larger phase ratio is often required, or the saponification rate needs to be increased to reduce the copper ion content in the aqueous phase to the appropriate range. This method not only suffers from high acid and alkali losses but also consumes a lot of energy. The P204 extraction method also suffers from the problem of calcium slag formation due to calcium ions, leading to production discontinuity, which urgently needs to be addressed.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing cobalt extraction pre-liquid, which aims to improve at least one of the problems mentioned in the background art.

[0006] This invention is implemented as follows:

[0007] In a first aspect, the present invention provides a method for preparing a cobalt extraction pre-extraction solution, comprising:

[0008] The crude cobalt hydroxide leachate was extracted using the post-soap extractant Bp-α to obtain an iron-zinc-calcium-cobalt organic phase and a decalcified liquid.

[0009] The calcium-removed liquid was extracted using the post-soap extractant Bp-β to obtain a calcium-copper-manganese-cobalt-loaded organic phase and a pre-cobalt extraction liquid;

[0010] The post-saponification extractant Bp-α includes P204 extractant with a volume concentration of 23%–27% and a saponification rate of 19%–21%;

[0011] The post-saponification extractant Bp-β includes P204 extractant with a volume concentration of 18%–22% and a saponification rate of 44%–46% and N910 extractant with a volume concentration of 4%–6%.

[0012] In optional embodiments, at least one of the following features (1) to (6) is also included:

[0013] (1) When the post-soap extractant Bp-α is used to extract crude cobalt hydroxide leachate, the ratio of O / A is 0.4 to 0.42;

[0014] (2) When the post-soap extractant Bp-β is used to extract the calcium-removed liquid, the ratio of O / A is 0.51 to 0.53.

[0015] (3) The extraction stages of the crude cobalt hydroxide leachate by the post-soap extractant Bp-α are 6 to 8.

[0016] (4) The extraction stage number of the post-soap extractant Bp-β when extracting the calcium-removed liquid is 8 to 9;

[0017] (5) The diluent in the post-soap extractant Bp-α is selected from at least one of sulfonated kerosene and cyclohexane;

[0018] (6) The diluent in the post-soap extractant Bp-β is selected from at least one of sulfonated kerosene and cyclohexane.

[0019] In an optional embodiment, the saponifying agent used for saponifying the P204 extractant in the post-saponification extractant Bp-α is ammonia.

[0020] And / or, the saponifying agent used for saponification of P204 extractant in post-saponification extractant Bp-β is ammonia.

[0021] In an optional embodiment, after obtaining the supported iron-zinc-calcium-cobalt organic phase, the method further includes:

[0022] The iron-zinc-calcium-cobalt organic phase was acid-washed with a first sulfuric acid solution to obtain the iron-zinc-calcium organic phase and the cobalt sulfate solution.

[0023] The iron-zinc-calcium-supported organic phase was back-extracted using a first hydrochloric acid solution to obtain a calcium chloride solution and an iron-zinc-supported organic phase.

[0024] The iron-zinc-loaded organic phase was deferrotreated using a second hydrochloric acid solution to obtain a first unloaded organic phase and a first deferrotreated liquid.

[0025] The first empty organic phase is washed with pure water to obtain the first regenerated extractant and the first washing chlorine water;

[0026] Optionally, the cobalt sulfate solution obtained by acid washing the iron-zinc-calcium-cobalt organic phase with the first sulfuric acid solution is refluxed and combined with the crude cobalt hydroxide leachate, and then extracted again by the soap extractant Bp-α.

[0027] Optionally, the first anti-iron solution and the first chlorine washing solution are reused to prepare the first hydrochloric acid solution;

[0028] Optionally, the first regenerated extractant, Bp-α, is used as a post-soap extractant to extract the crude cobalt hydroxide leachate.

[0029] In an optional implementation, at least one of the following features (7) to (12) is also included:

[0030] (7) The phase O / A ratio during acid washing of the supported iron-zinc-calcium-cobalt organic phase with the first sulfuric acid solution is 9.8 to 10.2;

[0031] (8) The phase O / A ratio during the back-extraction of the iron-zinc-calcium organic phase by the first hydrochloric acid solution is 37-38;

[0032] (9) The phase O / A ratio of the second hydrochloric acid solution during the antiferrore reaction of the supported iron-zinc organic phase was 26.8–27.2;

[0033] (10) The acid washing stage when the first sulfuric acid solution is used to acid wash the iron-zinc-calcium-cobalt organic phase is 3 to 5 stages;

[0034] (11) The number of back-extraction stages when the first hydrochloric acid solution back-extracts the iron-zinc-calcium organic phase is 6 to 8;

[0035] (12) The antiferrochemical reaction of the second hydrochloric acid solution on the iron-zinc organic phase is of the third order.

[0036] In an optional implementation, at least one of the following features (13) to (15) is also included:

[0037] (13) The equivalent concentration of the first sulfuric acid solution, expressed as hydrogen ions, is 0.29–0.31 N;

[0038] (14) The equivalent concentration of the first hydrochloric acid solution, expressed as hydrogen ions, is 4.2–4.7 N;

[0039] (15) The equivalent concentration of the second hydrochloric acid solution, expressed as hydrogen ions, is 5.5 to 6.5 N.

[0040] In an optional embodiment, after obtaining the supported calcium-copper-manganese-cobalt organic phase, the method further includes:

[0041] The calcium-copper-manganese-cobalt organic phase was acid-washed with a second sulfuric acid solution to obtain the calcium-copper-manganese organic phase and a cobalt sulfate solution.

[0042] The calcium-copper-manganese organic phase was back-extracted using a third hydrochloric acid solution to obtain an iron-zinc-loaded organic phase and a crude manganese chloride solution.

[0043] The iron-zinc-loaded organic phase was deferrotreated using a fourth hydrochloric acid solution to obtain a second unloaded organic phase and a second antiferrochemical solution.

[0044] The second empty organic phase was washed with pure water to obtain the second regenerated extractant and the second washing chlorine water;

[0045] Optionally, the cobalt sulfate solution obtained by acid washing the loaded calcium-copper-manganese-cobalt organic phase with a second sulfuric acid solution is refluxed and combined with the decalcified solution, and then extracted again by the soap extractant Bp-β.

[0046] Optionally, the second anti-iron solution and the second washing chlorine water are reused to prepare the third hydrochloric acid solution;

[0047] Optionally, the second regenerating extractant, Bp-β, is used as a post-soap extractant to extract the decalcified solution. In optional embodiments, at least one of the following features (16) to (21) is also included:

[0048] (16) The phase O / A ratio when the second sulfuric acid solution is used to acid wash the supported calcium, copper, manganese and cobalt organic phase is 14.6 to 15;

[0049] (17) The phase O / A ratio during back-extraction of the supported calcium-copper-manganese organic phase by the third hydrochloric acid solution is 22-22.5;

[0050] (18) The phase O / A ratio of the fourth hydrochloric acid solution during the antiferrore reaction of the supported iron-zinc organic phase is 36 to 36.3;

[0051] (19) The washing stage when the second sulfuric acid solution is used to acid wash the calcium-copper-manganese-cobalt organic phase is 6 to 8 stages;

[0052] (20) The number of back-extraction stages when the third hydrochloric acid solution back-extracts the calcium-copper-manganese organic phase is 6 to 8;

[0053] (21) The antiferrochemical order of the fourth hydrochloric acid solution on the iron-zinc organic phase is 3.

[0054] In an optional implementation, at least one of the following features (22) to (24) is also included:

[0055] (22) The equivalent concentration of the second sulfuric acid solution, expressed as hydrogen ions, is 0.9–1.1 N;

[0056] (23) The equivalent concentration of the third hydrochloric acid solution, expressed as hydrogen ions, is 4.2–4.7 N;

[0057] (24) The equivalent concentration of the fourth hydrochloric acid solution, expressed as hydrogen ions, is 5.5–6.5 N.

[0058] In an optional embodiment, after obtaining the crude manganese chloride solution, the process further includes:

[0059] The crude manganese chloride solution is mixed with manganese powder, and after the reaction is complete, manganese chloride solution and sponge copper are obtained.

[0060] Optionally, the particle size of the manganese powder is less than or equal to 0.074 mm;

[0061] Optionally, the molar amount of manganese powder added is 1.05 to 1.20 times the total molar amount of all metal elements other than manganese in the crude manganese chloride solution;

[0062] Optionally, the reaction temperature is 60–70°C and the reaction time is 1.5–2.5 h.

[0063] The present invention has the following beneficial effects:

[0064] The method for preparing cobalt extraction pre-liquid provided by this invention involves first performing a primary extraction using P204 pre-extracted calcium, followed by a secondary extraction using a P204+N910 compound extractant for deep impurity removal, resulting in a qualified cobalt extraction pre-liquid. During the secondary extraction, the use of a small amount of N910 effectively removes copper while having minimal impact on other impurities. Because copper is effectively removed, the subsequent acid washing process suffers from a low over-extraction rate of total impurities (copper, manganese, and calcium), reducing the risk of cobalt loss. In the secondary extraction, the P204+N910 compound extractant provides excellent copper extraction, allowing for a reduction in the original extraction stage, significantly reducing space costs, material filling costs, and equipment construction costs. This two-stage extraction method not only yields a qualified high-cobalt-concentration cobalt extraction pre-liquid, but the resulting calcium-copper-manganese-cobalt organic phase can also be used as a raw material for extracting manganese chloride solution. Compared to the existing P204 primary extraction method, this method does not produce calcium slag, and further processing of the extracted organic phase can significantly reduce subsequent acid loss. Attached Figure Description

[0065] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0066] Figure 1 A flowchart illustrating the preparation method of the cobalt extraction pre-liquid provided by this invention. Detailed Implementation

[0067] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0068] like Figure 1 As shown, this embodiment of the invention provides a method for preparing a pre-extraction solution for cobalt extraction, comprising:

[0069] The crude cobalt hydroxide leachate was extracted using the post-soap extractant Bp-α to obtain an iron-zinc-calcium-cobalt organic phase and a decalcified liquid.

[0070] The calcium-removed liquid was extracted using the post-soap extractant Bp-β to obtain a calcium-copper-manganese-cobalt-loaded organic phase and a pre-cobalt extraction liquid;

[0071] The post-saponification extractant Bp-α includes P204 extractant with a volume concentration of 23%–27% and a saponification rate of 19%–21%;

[0072] The post-saponification extractant Bp-β includes P204 extractant with a volume concentration of 18%–22% and a saponification rate of 44%–46% and N910 extractant with a volume concentration of 4%–6%.

[0073] The method for preparing cobalt extraction pre-liquid provided by this invention involves first performing a primary extraction using P204 pre-extracted calcium, followed by a secondary extraction using a P204+N910 compound extractant for deep impurity removal, resulting in a qualified cobalt extraction pre-liquid. During the secondary extraction, the use of a small amount of N910 effectively removes copper while having minimal impact on other impurities. Because copper is effectively removed, the subsequent acid washing process suffers from a low over-extraction rate of total impurities (copper, manganese, and calcium), reducing the risk of cobalt loss. Furthermore, the use of the P204+N910 compound extractant during the secondary extraction further mitigates the impact of the process. The N910 extractant eliminates the need for saponification, saving on saponifying agents. Furthermore, the N910 extractant provides excellent copper extraction, allowing for a reduction in the original extraction stages and significantly lowering space, material filling, and equipment construction costs. The two-stage extraction process not only yields a qualified high-cobalt-concentration cobalt extraction pre-liquid, but the resulting calcium-copper-manganese-cobalt organic phase can also be used as a raw material for extracting manganese chloride solution. Compared to the existing single-stage P204 extraction method, this method does not produce calcium slag, and further processing of the extracted organic phase can greatly reduce subsequent acid loss.

[0074] The crude cobalt hydroxide leaching solution involved in this invention can be obtained by oxidative acid leaching (leaching with sulfuric acid and hydrogen peroxide) of crude cobalt hydroxide solid (containing impurities such as manganese, nickel, iron, aluminum, copper, zinc, calcium, and magnesium). It should be noted that the crude cobalt hydroxide leaching solution involved in this invention, besides the crude cobalt hydroxide obtained by oxidative acid leaching mentioned above, can be any solution whose main metallic element is cobalt and contains small amounts of metallic impurities such as manganese, nickel, iron, aluminum, copper, zinc, calcium, and magnesium.

[0075] like Figure 1 As shown, specifically, the preparation method includes:

[0076] S1. The crude cobalt hydroxide leachate was extracted using the post-soap extractant Bp-α to obtain an iron-zinc-calcium-cobalt organic phase and a decalcified liquid.

[0077] The post-saponification extractant Bp-α includes a P204 extractant with a volume concentration of 23% to 27% (e.g., 23%, 25%, or 27%), and the P204 extractant has a saponification rate of 19% to 21% (e.g., 19%, 20%, or 21%).

[0078] A higher saponification rate results in a higher extraction rate, but an excessively high saponification rate can hinder phase separation. Furthermore, higher saponification also means more over-extraction, requiring an increase in the amount of acid used for washing, thus raising costs. When the saponification rate of the extractant in this step is within the aforementioned range, a high extraction rate and easy phase separation can be guaranteed.

[0079] Optionally, the P204 extractant in the post-soap extraction agent Bp-α is obtained by saponification with ammonia. It should be noted that while sodium hydroxide solution can be used for saponification alone, using sodium hydroxide solution results in sodium ions in the pre-extraction solution, leading to sodium sulfate as a byproduct in the subsequent processing. Using ammonia, however, results in magnesium ammonium sulfate, a more valuable byproduct, in the subsequent processing. Since the cobalt chloride solution obtained from the next step of cobalt extraction generally has sodium content requirements, ammonium soap is chosen.

[0080] Optionally, the diluent in the post-soap extractant Bp-α is selected from at least one of sulfonated kerosene and cyclohexane.

[0081] Optionally, the O / A ratio during extraction in this step is 0.4 to 0.42 (e.g., 0.4, 0.41, or 0.42).

[0082] Optionally, the extraction process in this step may involve 6 to 8 stages (e.g., 6, 7, or 8 stages).

[0083] S2. The iron-zinc-calcium-cobalt organic phase is acid-washed with the first sulfuric acid solution to obtain the iron-zinc-calcium organic phase and the cobalt sulfate solution.

[0084] Optionally, to ensure better pickling effect, the equivalent concentration of the first sulfuric acid solution, calculated as hydrogen ions, is 0.29 to 0.31N (e.g., 0.29N, 0.3N, or 0.31N).

[0085] Optionally, to ensure better pickling effect, the ratio O / A when the first sulfuric acid solution pickles the iron-zinc-calcium-cobalt organic phase is 9.8 to 10.2 (e.g., 9.8, 10, or 10.2).

[0086] Optionally, to ensure better pickling effect, the first sulfuric acid solution is used to pickle the iron-zinc-calcium-cobalt organic phase with 3 to 5 washing stages (e.g., 3, 4 or 5 stages).

[0087] Optionally, the cobalt sulfate solution obtained by acid washing the iron-zinc-calcium-cobalt organic phase with the first sulfuric acid solution is refluxed and combined with the crude cobalt hydroxide leachate, and then extracted again by the soap extractant Bp-α.

[0088] S3. The iron-zinc-calcium organic phase is back-extracted using a first hydrochloric acid solution to obtain a calcium chloride solution and an iron-zinc-calcium organic phase.

[0089] Optionally, to ensure better back-extraction, the equivalent concentration of the first hydrochloric acid solution, calculated as hydrogen ions, is 4.2–4.7N.

[0090] Optionally, to ensure better back-extraction, the ratio O / A during the back-extraction of the iron-zinc-calcium organic phase with the first hydrochloric acid solution is 37 to 38 (e.g., 37, 37.5, or 38).

[0091] Optionally, to ensure better back-extraction effect, the number of back-extraction stages when the first hydrochloric acid solution back-extracts the supported iron-zinc-calcium organic phase is 6 to 8 (e.g., 6, 7 or 8 stages).

[0092] S4. The iron-zinc organic phase loaded with a second hydrochloric acid solution is deferrotreated to obtain a first unloaded organic phase and a first deferrotreated liquid.

[0093] In some embodiments of the present invention, the reagent used for anti-iron extraction in this step can also be sulfuric acid solution. Compared with sulfuric acid solution, hydrochloric acid solution has a better effect on iron extraction and is also cheaper.

[0094] Optionally, to ensure better antiferroic effect, the equivalent concentration of the second hydrochloric acid solution, calculated as hydrogen ions, is 5.5 to 6.5N (e.g., 5.5N, 6.0N, or 6.5N).

[0095] Optionally, to ensure better antiferrolysis, the ratio O / A of the second hydrochloric acid solution during antiferrolysis of the supported iron-zinc organic phase is 26.8 to 27.2 (e.g., 26.8, 27, or 27.2).

[0096] Optionally, to ensure better antiferrolysis, the antiferrolysis order of the second hydrochloric acid solution on the iron-zinc-supported organic phase is 3.

[0097] S5. The first empty organic phase is washed with pure water to obtain the first regenerated extractant and the first chlorine washing water.

[0098] The first antiferroic solution from step S4 and the first chlorine washing solution from this step can be reused to prepare the first hydrochloric acid solution. The first regenerated extractant can be recycled as the post-soap extractant Bp-α to extract the crude cobalt hydroxide leachate.

[0099] S6. The calcium-removed liquid was extracted using the post-soap extraction agent Bp-β to obtain a calcium-copper-manganese-cobalt organic phase and a pre-cobalt extraction liquid.

[0100] The post-saponification extractant Bp-β includes a P204 extractant with a volume concentration of 18% to 22% (e.g., 18%, 20%, or 22%) and an N910 extractant with a volume concentration of 4% to 6% (e.g., 4%, 5%, or 6%), wherein the saponification rate of the P204 extractant is 44% to 46% (e.g., 44%, 45%, or 46%).

[0101] The post-saponification extractant Bp-β is a combination of P204 and N910 extractants, with both concentrations set within a suitable range to reduce extraction costs while ensuring good impurity removal. When the saponification rate of the extractants in this step is within the above-mentioned range, a high extraction rate and easy phase separation can be guaranteed.

[0102] Optionally, the P204 extractant in the post-saponification extractant Bp-β is obtained by saponification with ammonia. It should be noted that if only saponification is required, sodium hydroxide solution can also be used; however, using sodium hydroxide solution produces sodium sulfate as a byproduct, while using ammonia produces magnesium ammonium sulfate, which is of higher value.

[0103] Optionally, the diluent in the post-soap extractant Bp-β is selected from at least one of sulfonated kerosene and cyclohexane.

[0104] Optionally, the O / A ratio during extraction in this step is 0.51 to 0.53 (e.g., 0.51, 0.52, or 0.53).

[0105] Optionally, the extraction process in this step can be performed using 8 or 9 stages.

[0106] S7. The calcium-copper-manganese-cobalt organic phase is acid-washed with a second sulfuric acid solution to obtain the calcium-copper-manganese organic phase and the cobalt sulfate solution.

[0107] Optionally, to ensure better pickling effect, the equivalent concentration of the second sulfuric acid solution, calculated as hydrogen ions, is 0.9 to 1.1N (e.g., 0.9N, 1N, or 1.1N).

[0108] Optionally, to ensure better pickling effect, the ratio of O / A when the second sulfuric acid solution washes the supported calcium, copper, manganese, and cobalt organic phase is 14.6 to 15 (e.g., 14.6, 14.8, or 15).

[0109] Optionally, to ensure better pickling effect, the second sulfuric acid solution is used to wash the calcium, copper, manganese and cobalt organic phase with 6 to 8 washing stages (e.g., 6, 7 or 8 stages).

[0110] Optionally, the cobalt sulfate solution obtained by acid washing the loaded calcium-copper-manganese-cobalt organic phase with a second sulfuric acid solution is refluxed and combined with the decalcified solution, and then extracted again by the soap extractant Bp-β.

[0111] S8. The calcium-copper-manganese organic phase loaded with a third hydrochloric acid solution is back-extracted to obtain an iron-zinc-loaded organic phase and a crude manganese chloride solution.

[0112] The impurity elements loaded in the calcium-copper-manganese organic phase are mainly calcium, copper and manganese. In addition, a small amount of iron and zinc are also loaded. During back-extraction, calcium, copper and manganese elements enter the aqueous phase to obtain manganese chloride solution, while iron and zinc remain in the organic phase to obtain the iron-zinc loaded organic phase.

[0113] Optionally, to ensure better back-extraction, the equivalent concentration of the third hydrochloric acid solution, calculated as hydrogen ions, is 4.2 to 4.7N (e.g., 4.2N, 4.5N, or 4.7N).

[0114] Optionally, to ensure better back-extraction, the ratio O / A of the third hydrochloric acid solution for back-extracting the supported calcium, copper, and manganese organic phase is 22 to 22.5 (e.g., 22, 22.3, or 22.5).

[0115] Optionally, to ensure better back-extraction effect, the number of back-extraction stages when the third hydrochloric acid solution back-extracts the calcium-copper-manganese organic phase is 6 to 8 (e.g., 6, 7 or 8 stages).

[0116] S7. The iron-zinc organic phase loaded with the fourth hydrochloric acid solution is deferrotreated to obtain the second unloaded organic phase and the second deferrotreated liquid.

[0117] Optionally, to ensure better antiferroic effect, the equivalent concentration of the fourth hydrochloric acid solution, calculated as hydrogen ions, is 5.5–6.5N (e.g., 5.5N, 6N, or 6.5N).

[0118] Optionally, to ensure better antiferrolysis, the ratio O / A of the fourth hydrochloric acid solution during antiferrolysis of the iron-zinc organic phase is 36 to 36.3 (e.g., 36, 36.2 or 36.3).

[0119] Optionally, to ensure better antiferrolysis, the antiferrolysis order of the fourth hydrochloric acid solution on the supported iron-zinc organic phase is 3.

[0120] S8. The second empty organic phase is washed with pure water to obtain the second regenerated extractant and the second washing chlorine water.

[0121] The second antiferroic solution from step S7 and the second chlorine washing solution from this step can be reused to prepare the third hydrochloric acid solution. The second regenerated extractant can be recycled as the post-soap extractant Bp-β to extract the decalcified solution.

[0122] S9. Mix the crude manganese chloride solution with manganese powder, and after the reaction is complete, obtain manganese chloride solution and sponge copper.

[0123] Optionally, the particle size of the manganese powder is less than or equal to 0.074 mm (i.e., under a 200-mesh sieve);

[0124] Optionally, to ensure higher purity of the manganese chloride solution, the molar amount of manganese powder added is 1.05 to 1.20 times (e.g., 1.05, 1.1, or 1.2) of the total molar amount of all other metal elements besides manganese in the crude manganese chloride solution.

[0125] Optionally, to increase the reaction rate and ensure a complete reaction, the reaction temperature is 60–70°C (e.g., 60°C, 65°C, or 70°C), and the reaction time is 1.5–2.5 h (e.g., 1.5 h, 2 h, or 2.5 h).

[0126] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0127] The reagents used in the following examples and comparative examples are as follows:

[0128] N910 extractant was purchased from Zhengzhou Hecheng New Material Technology Co., Ltd., and is a β-diketone extractant. Solvent oil No. 260 was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd., also known as sulfonated kerosene, a colorless and transparent solvent oil produced by sulfonating kerosene. P204 (diisooctyl phosphate) extractant was purchased from Luoyang Sannuo Chemical Co., Ltd.

[0129] The elemental content and acidity / alkalinity of the crude cobalt hydroxide leachate from the following examples and comparative examples are shown in Table 1:

[0130] Table 1. Component content of crude cobalt hydroxide leachate

[0131]

[0132] Example 1

[0133] The organic phase (25% P204 extractant) of extractant Bp-α (containing 25% P204 extractant by volume, with the remainder being diluent, which is solvent oil No. 260) was saponified with ammonia water (wt=20%) until the saponification rate was 19%, thus obtaining saponified extractant Bp-α.

[0134] like Figure 1As shown, crude cobalt hydroxide leachate was extracted using the post-soap extractant Bp-α at an extraction ratio of O / A = 0.41 and an extraction stage of 8 stages, yielding an iron-zinc-calcium-cobalt organic phase and a decalcified liquid.

[0135] The iron-zinc-calcium-cobalt organic phase was acid-washed with 0.31N sulfuric acid (calculated as hydrogen ions, all of which are consistent below), with an acid washing rate of 21%, a washing ratio of O / A of 10.00, and a washing stage of 3. The resulting iron-zinc-calcium organic phase and cobalt sulfate solution were obtained. The obtained cobalt sulfate solution was refluxed and combined with the crude cobalt hydroxide leachate. After combination, it was extracted again with the soap extractant Bp-α.

[0136] The iron-zinc-calcium-supported organic phase was back-extracted using 4.50N hydrochloric acid with an O / A ratio of 37.50 and a back-extraction stage of 6, yielding a calcium chloride solution and an iron-zinc-supported organic phase.

[0137] Antiferrochemical treatment was performed on the iron-zinc-supported organic phase using 6.00N hydrochloric acid. The antiferrochemical ratio O / A = 27.09, and the antiferrochemical stage was 3, yielding a first unsupported organic phase and a first antiferrochemical solution. The obtained first antiferrochemical solution was prepared with acid and reused in the previous step for back-extraction of the iron-zinc-calcium-supported organic phase.

[0138] The first unloaded organic phase is washed with pure water to obtain a first regenerated extractant and a first washing chlorine water. The first regenerated extractant can be recycled and reused, and the first washing chlorine water is reused to prepare hydrochloric acid solution for back-extraction of the iron-zinc-calcium-loaded organic phase.

[0139] The P204 extractant in the extractant Bp-β (containing 20% ​​P204 extractant, 5% N910 extractant, and the remainder being diluent, which is solvent oil No. 260) was saponified with ammonia water (wt=20%) until the saponification rate was 46%, thus obtaining the saponified extractant Bp-β.

[0140] The calcium-removed liquid was extracted using the post-soap extraction agent Bp-β at an extraction ratio of O / A = 0.52 and an extraction stage of 8 stages to obtain the pre-cobalt extraction liquid and the calcium-copper-manganese-cobalt organic phase.

[0141] The calcium-copper-manganese-cobalt organic phase was acid-washed with 1.10N sulfuric acid. The acid washing rate was 26%, the washing ratio O / A was 14.81, and the washing stage was 6 stages. The calcium-copper-manganese organic phase and cobalt sulfate solution were obtained. The cobalt sulfate solution was refluxed and combined with the calcium-removed liquid. After merging, it was extracted again with the soap extractant Bp-β.

[0142] The calcium-copper-manganese organic phase was back-extracted using 4.50N hydrochloric acid. The back-extraction ratio O / A = 22.22, and the back-extraction stage was 6 stages, yielding a crude manganese chloride solution and an iron-zinc-supported organic phase.

[0143] The iron-zinc supported organic phase was deferrotreated using 6N hydrochloric acid. The deferrotreatment ratio O / A = 36.12, and the deferrotreatment stage was 3, yielding a second unloaded organic phase and a second deferrotreatment solution. The obtained second deferrotreatment solution was prepared with acid and reused in the previous step for back-extraction of the calcium-copper-manganese supported organic phase.

[0144] The second unloaded organic phase is washed with pure water to obtain a second regenerated extractant and a second washing chlorine water. The second regenerated extractant can be recycled and reused, and the second washing chlorine water is reused to prepare hydrochloric acid solution for back-extraction of the calcium, copper and manganese-loaded organic phase.

[0145] The crude manganese chloride solution was heated to 60.00℃, and manganese powder with a particle size of 1.20 times the theoretical impurities (the sum of all metal elements except manganese) was added. The reaction time was 1.5h to obtain a refined manganese chloride solution and sponge copper.

[0146] Example 2

[0147] The organic phase (25% P204 extractant) of extractant Bp-α (containing 25% P204 extractant by volume, with the remainder being diluent, which is solvent oil No. 260) was saponified with ammonia water (wt=20%) until the saponification rate was 20%, thus obtaining saponified extractant Bp-α.

[0148] like Figure 1 As shown, crude cobalt hydroxide leachate was extracted using the post-soap extractant Bp-α at an extraction ratio of O / A = 0.41 and an extraction stage of 7, yielding an iron-zinc-calcium-cobalt organic phase and a decalcified liquid.

[0149] The iron-zinc-calcium-cobalt-loaded organic phase was acid-washed with 0.30N sulfuric acid (calculated as hydrogen ions, all of which are consistent below), with an acid washing rate of 21%, a washing ratio of O / A of 10.00, and a washing stage of 3. The resulting iron-zinc-calcium-loaded organic phase and cobalt sulfate solution were obtained. The obtained cobalt sulfate solution was refluxed and combined with the crude cobalt hydroxide leachate. After combination, it was extracted again by the soap extractant Bp-α.

[0150] The iron-zinc-calcium-supported organic phase was back-extracted using 4.50N hydrochloric acid with an O / A ratio of 37.50 and a back-extraction stage of 6, yielding a calcium chloride solution and an iron-zinc-supported organic phase.

[0151] Antiferrochemical treatment was performed on the iron-zinc-supported organic phase using 6.00N hydrochloric acid. The antiferrochemical ratio O / A = 27.09, and the antiferrochemical stage was 3, yielding a first unsupported organic phase and a first antiferrochemical solution. The obtained first antiferrochemical solution was prepared with acid and reused in the previous step for back-extraction of the iron-zinc-calcium-supported organic phase.

[0152] The first unloaded organic phase is washed with pure water to obtain a first regenerated extractant and a first washing chlorine water. The first regenerated extractant can be recycled and reused, and the first washing chlorine water is reused to prepare hydrochloric acid solution for back-extraction of the iron-zinc-calcium-loaded organic phase.

[0153] The P204 extractant in the extractant Bp-β (containing 20% ​​P204 extractant, 5% N910 extractant, and the remainder being diluent, which is solvent oil No. 260) was saponified with ammonia water (wt=20%) until the saponification rate was 45%, thus obtaining the saponified extractant Bp-β.

[0154] The calcium-removed liquid was extracted using the post-soap extraction agent Bp-β at an extraction ratio of O / A = 0.52 and an extraction stage of 8 stages to obtain the pre-cobalt extraction liquid and the calcium-copper-manganese-cobalt organic phase.

[0155] The calcium-copper-manganese-cobalt organic phase was acid-washed with 1.10N sulfuric acid. The acid washing rate was 26%, the washing ratio O / A was 14.81, and the washing stage was 6 stages. The calcium-copper-manganese organic phase and cobalt sulfate solution were obtained. The cobalt sulfate solution was refluxed and combined with the calcium-removed liquid. After merging, it was extracted again with the soap extractant Bp-β.

[0156] The calcium-copper-manganese organic phase was back-extracted using 4.50N hydrochloric acid. The back-extraction ratio O / A = 22.22, and the back-extraction stage was 6 stages, yielding a crude manganese chloride solution and an iron-zinc-supported organic phase.

[0157] The iron-zinc supported organic phase was deferrotreated using 6N hydrochloric acid. The deferrotreatment ratio O / A = 36.12, and the deferrotreatment stage was 3, yielding a second unloaded organic phase and a second deferrotreatment solution. The obtained second deferrotreatment solution was prepared with acid and reused in the previous step for back-extraction of the calcium-copper-manganese supported organic phase.

[0158] The second unloaded organic phase is washed with pure water to obtain a second regenerated extractant and a second washing chlorine water. The second regenerated extractant can be recycled and reused, and the second washing chlorine water is reused to prepare hydrochloric acid solution for back-extraction of the calcium, copper and manganese-loaded organic phase.

[0159] The crude manganese chloride solution was heated to 65.00℃, and manganese powder with a particle size of 1.15 times the theoretical impurities (the sum of all metal elements other than manganese) was added. The reaction time was 2 hours to obtain a refined manganese chloride solution and sponge copper.

[0160] Example 3

[0161] The organic phase (25% P204 extractant) of extractant Bp-α (containing 25% P204 extractant by volume, with the remainder being diluent, which is solvent oil No. 260) was saponified with ammonia water (wt=20%) until the saponification rate was 21%, thus obtaining saponified extractant Bp-α.

[0162] like Figure 1 As shown, crude cobalt hydroxide leachate was extracted using the post-soap extractant Bp-α at an extraction ratio of O / A = 0.41 and an extraction stage of 6 stages, yielding an iron-zinc-calcium-cobalt loaded organic phase and a decalcified liquid.

[0163] The iron-zinc-calcium-cobalt-loaded organic phase was acid-washed with 0.29N sulfuric acid (calculated as hydrogen ions, all of which are consistent below), with an acid washing rate of 21%, a washing ratio of O / A of 10.00, and a washing stage of 3. The resulting iron-zinc-calcium-loaded organic phase and cobalt sulfate solution were obtained. The obtained cobalt sulfate solution was refluxed and combined with the crude cobalt hydroxide leachate. After combination, it was extracted again with the soap extractant Bp-α.

[0164] The iron-zinc-calcium-supported organic phase was back-extracted using 4.50N hydrochloric acid with an O / A ratio of 37.50 and a back-extraction stage of 6, yielding a calcium chloride solution and an iron-zinc-supported organic phase.

[0165] Antiferrochemical treatment was performed on the iron-zinc-supported organic phase using 6.00N hydrochloric acid. The antiferrochemical ratio O / A = 27.09, and the antiferrochemical stage was 3, yielding a first unsupported organic phase and a first antiferrochemical solution. The obtained first antiferrochemical solution was prepared with acid and reused in the previous step for back-extraction of the iron-zinc-calcium-supported organic phase.

[0166] The first unloaded organic phase is washed with pure water to obtain a first regenerated extractant and a first washing chlorine water. The first regenerated extractant can be recycled and reused, and the first washing chlorine water is reused to prepare hydrochloric acid solution for back-extraction of the iron-zinc-calcium-loaded organic phase.

[0167] The P204 extractant in the extractant Bp-β (containing 20% ​​P204 extractant, 5% N910 extractant, and the remainder being diluent, which is No. 260 solvent oil) was saponified with ammonia water (wt=20%) until the saponification rate was 44%, thus obtaining the saponified extractant Bp-β.

[0168] The calcium-removed liquid was extracted using the post-soap extraction agent Bp-β at an extraction ratio of O / A = 0.52 and an extraction stage of 8 stages to obtain the pre-cobalt extraction liquid and the calcium-copper-manganese-cobalt organic phase.

[0169] The calcium-copper-manganese-cobalt organic phase was acid-washed with 1.10N sulfuric acid. The acid washing rate was 26%, the washing ratio O / A was 14.81, and the washing stage was 6 stages. The calcium-copper-manganese organic phase and cobalt sulfate solution were obtained. The cobalt sulfate solution was refluxed and combined with the calcium-removed liquid. After merging, it was extracted again with the soap extractant Bp-β.

[0170] The calcium-copper-manganese organic phase was back-extracted using 4.50N hydrochloric acid. The back-extraction ratio O / A = 22.22, and the back-extraction stage was 6 stages, yielding a crude manganese chloride solution and an iron-zinc-supported organic phase.

[0171] The iron-zinc supported organic phase was deferrotreated using 6N hydrochloric acid. The deferrotreatment ratio O / A = 36.12, and the deferrotreatment stage was 3, yielding a second unloaded organic phase and a second deferrotreatment solution. The obtained second deferrotreatment solution was prepared with acid and reused in the previous step for back-extraction of the calcium-copper-manganese supported organic phase.

[0172] The second unloaded organic phase is washed with pure water to obtain a second regenerated extractant and a second washing chlorine water. The second regenerated extractant can be recycled and reused, and the second washing chlorine water is reused to prepare hydrochloric acid solution for back-extraction of the calcium, copper and manganese-loaded organic phase.

[0173] The crude manganese chloride solution was heated to 70.00℃, and manganese powder with a particle size of 1.05 times the theoretical impurities (the sum of all metal elements other than manganese) was added. The reaction time was 2.5h to obtain a refined manganese chloride solution and sponge copper.

[0174] Comparative Example 1

[0175] The difference between this comparative example and Example 1 is that a single-stage extraction method is used to remove impurities.

[0176] The content of this comparative example is as follows:

[0177] The organic phase (25% P204 extractant) of extractant Bp-α (containing 25% P204 extractant by volume, with the remainder being diluent, which is solvent oil No. 260) was saponified with ammonia water (wt=20%) until the saponification rate was 45%, thus obtaining saponified extractant Bp-α.

[0178] The crude cobalt hydroxide leachate was extracted using the post-soap extractant Bp-α at an extraction ratio of O / A = 0.76 and an extraction stage of 14 stages, yielding a calcium-manganese organic phase and a calcium-manganese residue.

[0179] The organic phase of the calcium-manganese extraction was acid-washed with 2.00N sulfuric acid (calculated as hydrogen ions, all subsequent steps are the same), with a washing ratio O / A = 14.81 and 8 washing stages, yielding the first organic phase and a cobalt sulfate solution. The obtained cobalt sulfate solution was refluxed and combined with the crude cobalt hydroxide leachate, and then extracted again with the post-soap extraction agent Bp-α. The resulting organic phase was back-extracted with 4.50N hydrochloric acid, with a back-extraction ratio O / A = 22.22 and 6 back-extraction stages, yielding a calcium-manganese chloride solution and a second organic phase. The second organic phase was then subjected to anti-iron treatment with 6.00N hydrochloric acid, with an anti-iron ratio O / A = 50.51 and 3 anti-iron stages.

[0180] Comparative Example 2

[0181] This comparative example is basically the same as Example 1, except that the extractant used in the two-stage extraction is different:

[0182] In Example 1, 20% P2O4 + 5% N910 was used to extract the decalcified solution after soaping, while in this comparative example, 25% P2O4 was used to extract the decalcified solution after soaping.

[0183] Specifically:

[0184] The organic phase (25% P204 extractant) of extractant Bp-α (containing 25% P204 extractant by volume, with the remainder being diluent, which is solvent oil No. 260) was saponified with ammonia water (wt=20%) until the saponification rate was 19%, thus obtaining saponified extractant Bp-α.

[0185] The crude cobalt hydroxide leachate was extracted using the post-soap extractant Bp-α at an extraction ratio of O / A = 0.41 and an extraction stage of 8 stages, yielding an iron-zinc-calcium-cobalt loaded organic phase and a decalcified liquid.

[0186] The iron-zinc-calcium-cobalt organic phase was acid-washed with 0.31N sulfuric acid (calculated as hydrogen ions, all of which are consistent below), with an acid washing rate of 21%, a washing ratio of O / A of 10.00, and a washing stage of 3. The resulting iron-zinc-calcium organic phase and cobalt sulfate solution were obtained. The obtained cobalt sulfate solution was refluxed and combined with the crude cobalt hydroxide leachate. After combination, it was extracted again with the soap extractant Bp-α.

[0187] The iron-zinc-calcium-supported organic phase was back-extracted using 4.50N hydrochloric acid with an O / A ratio of 37.50 and a back-extraction stage of 6, yielding a calcium chloride solution and an iron-zinc-supported organic phase.

[0188] Antiferrochemical treatment was performed on the iron-zinc-supported organic phase using 6.00N hydrochloric acid. The antiferrochemical ratio O / A = 27.09, and the antiferrochemical stage was 3, yielding a first unsupported organic phase and a first antiferrochemical solution. The obtained first antiferrochemical solution was acidic and was prepared for reuse in the previous step for back-extraction of the iron-zinc-calcium-supported organic phase.

[0189] The first empty organic phase is washed with pure water to obtain the first regenerated extractant, which can be recycled and reused.

[0190] The P204 extractant (containing 25% P204 extractant by volume and No. 260 solvent oil as diluent) in the extractant was saponified to a saponification rate of 55% using ammonia water (wt=20%) to obtain saponified P204 extractant.

[0191] The calcium-removed liquid was extracted using P204 extractant with an extraction ratio of O / A = 0.75 and 12 extraction stages to obtain the pre-cobalt extraction liquid and the calcium-copper-manganese-cobalt organic phase.

[0192] The organic phase loaded with calcium, copper, manganese and cobalt was acid-washed with 2.00N sulfuric acid. The washing ratio O / A = 14.81 and the washing stage was 8 stages. The resulting organic phase loaded with calcium, copper and manganese and cobalt sulfate solution were obtained. The cobalt sulfate solution was refluxed and combined with the decalcified solution. The combined solution was then extracted again with soap-treated P204 extractant.

[0193] The calcium-copper-manganese organic phase was back-extracted using 4.50N hydrochloric acid. The back-extraction ratio O / A = 31.68, and the back-extraction stage was 6 stages, yielding a crude manganese chloride solution and an iron-zinc-supported organic phase.

[0194] Antiferrochemical reaction was performed on the supported iron-zinc organic phase using 6N hydrochloric acid. The antiferrochemical ratio O / A = 51.88, and the antiferrochemical order was 3.

[0195] Experimental Example 1

[0196] The concentrations of each metal ion in the cobalt extraction pre-solutions prepared in each embodiment and comparative example were tested and recorded in Table 2.

[0197] Table 2. Metal ion content in the cobalt extraction pre-liquids prepared in each example and comparative example.

[0198]

[0199] As can be seen from Table 2, Comparative Example 1 uses a single-stage extraction method, resulting in the highest cobalt concentration. Comparative Example 2 uses a two-stage extraction method and has a high washing rate during the second stage. Due to the large amount of acid used during acid washing, the resulting cobalt sulfate solution has a large volume and low cobalt concentration. After combining the cobalt sulfate solution with the decalcification solution, the cobalt concentration is low, resulting in a low cobalt concentration in the pre-extraction solution. However, the two-stage extraction method used in the various embodiments provided by this invention does not affect the cobalt concentration in the pre-extraction solution. Furthermore, due to the extractant formulation, the copper concentration in the pre-extraction solution is the lowest, and the pass rate of the pre-extraction solution is high.

[0200] Experiment Example 2

[0201] Calculate the costs of Example 1 and the two comparative examples. Record the consumption and costs of Example 1 and Comparative Examples 1 and 2 in Table 3.

[0202] Table 3 Comparison of Consumption and Cost

[0203]

[0204] As can be seen from Table 3, the overall cost of Example 1 is significantly lower than that of Comparative Example 1 and Comparative Example 2. In particular, Example 1 consumes less hydrochloric acid than Comparative Example 1 and Comparative Example 2 because the antiferroic solution obtained after antiferroic acid treatment is reused and the chlorine washing water obtained after washing the organic phase with pure water is reused.

[0205] Experimental Example 3

[0206] The two-stage extraction stages of Example 1 and Comparative Example 2 were compared, that is, the extraction of the decalcified liquid was compared with different extractants, and the ion concentration in the residual liquid of each extraction stage was recorded, as shown in Table 4.

[0207] Table 4 Comparison of extraction stages for different extractants

[0208]

[0209] As shown in Table 4, in Comparative Example 2, 12 stages of extraction were required to reduce the copper ion concentration in the raffinate to below 1 mg / L. In contrast, in Example 1, using soap and 20% P2O4 + 5% N910 for extraction of the decalcified solution, only 8 stages of extraction were needed to reduce the copper ion concentration to below 1 mg / L. Compared to Comparative Example 2, Example 1 significantly reduces space requirements, material filling tanks, and equipment manufacturing costs.

[0210] Experiment Example 4

[0211] The amount of cobalt lost from the organic phase after each washing stage was determined when sulfuric acid was used to acid wash the supported calcium, copper, manganese and cobalt organic phase in Example 1.

[0212] The amount of cobalt lost from the organic phase after each washing stage was determined when sulfuric acid was used to acid wash the supported calcium, copper, manganese, and cobalt organic phase in Comparative Example 2.

[0213] The amount of cobalt ions lost in each organic phase after washing with sulfuric acid in Example 1 and Comparative Example 2 is recorded in Table 5.

[0214] Table 5 shows the loss of cobalt ions in each stage of the organic phase after acid washing in Example 1 and Comparative Example 2.

[0215]

[0216] As shown in Table 5, in Comparative Example 2, the cobalt content in the organic phase was reduced to below 1 mg / L only after 8 washes, while in Example 1, the cobalt content in the organic phase was reduced to below 1 mg / L only after 6 washes. Therefore, Example 1 of the present invention significantly reduces space requirements, material filling tanks, and equipment manufacturing costs compared to Comparative Example 2.

[0217] The preparation method provided in Comparative Example 1 can prepare the pre-extraction solution for cobalt extraction, but compared to Example 1, it suffers from the drawbacks of calcium slag and high acid-base consumption. Comparative Example 2 can also prepare the pre-extraction solution for cobalt extraction, but compared to Example 1, it has a higher number of extraction and washing stages and higher acid-base consumption.

[0218] In summary, the method provided by the embodiments of the present invention has the following characteristics:

[0219] 1. This invention uses a two-stage impurity removal method to obtain not only qualified high-cobalt-concentration cobalt extraction pre-liquid but also high-purity manganese chloride solution. This process not only improves the calcium slag problem of the traditional one-stage extraction impurity removal method but also reduces the acid and alkali loss of the P204 extraction impurity removal method by 20%. This invention uses a small amount of washing acid and generates a small amount of wastewater, reducing the pressure on downstream processes.

[0220] 2. In this invention, calcium is first pre-extracted using P204, and then a compound extractant of P204+N910 is used for deep impurity removal to obtain a qualified cobalt extraction pre-liquid. During the second-stage extraction and impurity removal, the risk of cobalt loss is small due to the low washing rate.

[0221] 3. Due to the good copper extraction effect during the two-stage extraction and impurity removal process, the present invention can reduce the original extraction stage of 12 stages to 8 stages and the washing stage of 8 stages to 6 stages, which greatly reduces space costs, material filling costs, and equipment construction costs.

[0222] 4. The method provided by this invention overcomes the problems of discontinuous production, large acid and alkali losses, and low value of by-products in existing processes. This method does not introduce new impurity ions and the entire process is carried out under normal pressure, which is conducive to industrial production.

[0223] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a cobalt extraction pretreatment solution, characterized in that, include: The crude cobalt hydroxide leachate was extracted using the post-soap extractant Bp-α to obtain an iron-zinc-calcium-cobalt organic phase and a decalcified liquid. The decalcification solution was extracted using the post-soap extractant Bp-β to obtain a calcium-copper-manganese-cobalt organic phase and a pre-cobalt extraction solution. The post-saponification extractant Bp-α includes a P204 extractant with a volume concentration of 23%~27% and a saponification rate of 19%~21%. The post-saponification extractant Bp-β includes a P204 extractant with a volume concentration of 18%~22% and a saponification rate of 44%~46% and an N910 extractant with a volume concentration of 4%~6%.

2. The preparation method according to claim 1, characterized in that, It also includes at least one of the following features (1) to (6): (1) When the post-soap extractant Bp-α is used to extract crude cobalt hydroxide leachate, the ratio of O / A is 0.4~0.42; (2) When the post-soap extractant Bp-β is used to extract the calcium-removed liquid, the ratio of O / A is 0.51 to 0.53; (3) The extraction stage number of the post-soap extractant Bp-α when extracting crude cobalt hydroxide leachate is 6 to 8; (4) The extraction stage number of the post-soap extraction agent Bp-β when extracting the calcium-removed liquid is 8 to 9; (5) The diluent in the post-soap extractant Bp-α is selected from at least one of sulfonated kerosene and cyclohexane; (6) The diluent in the post-soap extractant Bp-β is selected from at least one of sulfonated kerosene and cyclohexane.

3. The preparation method according to claim 1, characterized in that, The saponifying agent used for the saponification of the P204 extractant in the post-saponification extractant Bp-α is ammonia.

4. The preparation method according to claim 1, characterized in that, After obtaining the supported iron-zinc-calcium-cobalt organic phase, the process further includes: The supported iron-zinc-calcium-cobalt organic phase was acid-washed with a first sulfuric acid solution to obtain the supported iron-zinc-calcium organic phase and a cobalt sulfate solution. The iron-zinc-calcium-supported organic phase was back-extracted using a first hydrochloric acid solution to obtain a calcium chloride solution and an iron-zinc-supported organic phase. The iron-zinc-loaded organic phase was deferrotreated using a second hydrochloric acid solution to obtain a first unloaded organic phase and a first deferrotreated liquid. The first empty organic phase is washed with pure water to obtain the first regenerated extractant and the first washing chlorine water.

5. The preparation method according to claim 4, characterized in that, The cobalt sulfate solution obtained by acid washing the loaded iron-zinc-calcium-cobalt organic phase with the first sulfuric acid solution is refluxed and combined with the crude cobalt hydroxide leachate. After merging, it is extracted again by the soap extractant Bp-α.

6. The preparation method according to claim 4, characterized in that, The first anti-iron solution and the first chlorine washing solution are reused to prepare the first hydrochloric acid solution.

7. The preparation method according to claim 4, characterized in that, The first regenerated extractant, Bp-α, is used as the post-soap extractant to extract crude cobalt hydroxide leachate.

8. The preparation method according to claim 4, characterized in that, It also includes at least one of the following features (7) to (12): (7) The phase O / A ratio of the first sulfuric acid solution when acid washing the supported iron-zinc-calcium-cobalt organic phase is 9.8~10.2; (8) The phase O / A ratio of the first hydrochloric acid solution during back-extraction of the supported iron-zinc-calcium organic phase is 37~38; (9) The phase O / A ratio of the second hydrochloric acid solution during the antiferrore reaction of the supported iron-zinc organic phase is 26.8~27.2; (10) The acid washing grade of the first sulfuric acid solution when acid washing the supported iron-zinc-calcium-cobalt organic phase is 3 to 5; (11) The number of back-extraction stages when the first hydrochloric acid solution back-extracts the supported iron-zinc-calcium organic phase is 6 to 8; (12) The antiferroic order of the second hydrochloric acid solution when it antiferrolytes the supported iron-zinc organic phase is 3.

9. The preparation method according to claim 4, characterized in that, It also includes at least one of the following features (13) to (15): (13) The equivalent concentration of the first sulfuric acid solution, expressed as hydrogen ions, is 0.29~0.31N; (14) The equivalent concentration of the first hydrochloric acid solution, expressed as hydrogen ions, is 4.2~4.7N; (15) The equivalent concentration of the second hydrochloric acid solution, expressed as hydrogen ions, is 5.5~6.5N.

10. The preparation method according to claim 1, characterized in that, After obtaining the supported calcium-copper-manganese-cobalt organic phase, the process further includes: The loaded calcium-copper-manganese-cobalt organic phase was acid-washed with a second sulfuric acid solution to obtain the loaded calcium-copper-manganese organic phase and a cobalt sulfate solution. The loaded calcium-copper-manganese organic phase was back-extracted using a third hydrochloric acid solution to obtain a loaded iron-zinc organic phase and a crude manganese chloride solution. The loaded iron-zinc organic phase was deferrotreated with a fourth hydrochloric acid solution to obtain a second unloaded organic phase and a second antiferrochemical solution. The second empty organic phase is washed with pure water to obtain the second regenerated extractant and the second washing chlorine water.

11. The preparation method according to claim 10, characterized in that, The cobalt sulfate solution obtained by acid washing the loaded calcium-copper-manganese-cobalt organic phase with a second sulfuric acid solution is refluxed and combined with the decalcified solution. After merging, it is extracted again by the soap extractant Bp-β.

12. The preparation method according to claim 10, characterized in that, The second anti-iron solution and the second chlorine washing solution are reused to prepare the third hydrochloric acid solution.

13. The preparation method according to claim 10, characterized in that, The second regenerating extractant, Bp-β, is used as a post-soap extractant to extract the calcium-removed liquid.

14. The preparation method according to claim 10, characterized in that, It also includes at least one of the following features (16) to (21): (16) The phase O / A ratio when the second sulfuric acid solution is used to acid wash the supported calcium-copper-manganese-cobalt organic phase is 14.6~15; (17) The phase O / A ratio of the third hydrochloric acid solution during back-extraction of the supported calcium-copper-manganese organic phase is 22~22.5; (18) The phase O / A ratio of the fourth hydrochloric acid solution during the antiferrore reaction of the supported iron-zinc organic phase is 36~36.3; (19) The washing grade of the second sulfuric acid solution when acid washing the supported calcium-copper-manganese-cobalt organic phase is 6 to 8; (20) The number of back-extraction stages when the third hydrochloric acid solution back-extracts the supported calcium-copper-manganese organic phase is 6 to 8; (21) The antiferroic order of the fourth hydrochloric acid solution when it antiferrolytes the supported iron-zinc organic phase is 3.

15. The preparation method according to claim 10, characterized in that, It also includes at least one of the following features (22) to (24): (22) The equivalent concentration of the second sulfuric acid solution, expressed as hydrogen ions, is 0.9~1.1N; (23) The equivalent concentration of the third hydrochloric acid solution, expressed as hydrogen ions, is 4.2~4.7N; (24) The equivalent concentration of the fourth hydrochloric acid solution, expressed as hydrogen ions, is 5.5~6.5N.

16. The preparation method according to claim 10, characterized in that, After obtaining the crude manganese chloride solution, the process further includes: The crude manganese chloride solution is mixed with manganese powder, and after sufficient reaction, manganese chloride solution and sponge copper are obtained.

17. The preparation method according to claim 16, characterized in that, The particle size of the manganese powder is less than or equal to 0.074 mm.

18. The preparation method according to claim 16, characterized in that, The molar amount of manganese powder added is 1.05 to 1.20 times the total molar amount of all metal elements other than manganese in the crude manganese chloride solution.

19. The preparation method according to claim 16, characterized in that, The reaction temperature is 60~70℃, and the reaction time is 1.5~2.5 h.

Images