Preparation method of cobalt extraction precursor solution

Abstract

The invention relates to the technical field of valuable metal recovery, and discloses a preparation method of cobalt extraction pre-liquid, which comprises the following steps: extracting crude cobalt hydroxide leaching liquid by using a soaped extracting agent Bp-alpha to obtain an iron-zinc-calcium-cobalt loaded organic phase and calcium-removed liquid; a soaped extracting agent Bp-beta is adopted for extracting the calcium-removed liquid, and a calcium-loaded copper-manganese-cobalt organic phase and cobalt extraction pre-liquid are obtained; the soaped extraction agent Bp-alpha comprises a P204 extraction agent with the volume concentration of 23%-27% and the saponification rate of 19%-21%; the soaped extraction agent Bp-beta comprises a P204 extraction agent with the volume concentration of 18%-22% and the saponification rate of 44%-46% and an N910 extraction agent with the volume concentration of 4%-6%. According to the method, the production cost is remarkably reduced on the premise that the qualified cobalt extraction precursor solution can be obtained.

Description

Technical Field

[0001] The invention relates to the technical field of valuable metal recovery, and in particular to a method for preparing a cobalt extraction pre-liquid. Background Art

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

[0003] The existing and mature method for preparing the cobalt extraction pre-liquid is to use the precipitation method to precipitate and separate the impurities in the crude cobalt hydroxide leaching solution. This method has large acid and alkali losses and will cause cobalt metal loss, or use the traditional extractant P204 to remove impurities. Although this method is technically mature, it still has shortcomings. For example, large acid and alkali losses are the biggest pain point of this method, but it is also widely used in various extraction fields due to the low price of P204. Technical improvement of the P204 impurity extraction method is a major direction in the future. When using P204 for impurity extraction, because the extraction rate of copper ions is only increased from 54% to 56% between O / A=1.0~2.0, a larger relative ratio is often required, or the copper ion content in the aqueous phase is reduced to the corresponding index range by increasing the saponification rate. This method not only has large acid and alkali losses but also high energy consumption. The P204 method of impurity extraction also has the problem of calcium slag due to calcium ions, which leads to discontinuous production, which is also a problem that needs to be solved at present.

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

[0005] The object of the present invention is to provide a method for preparing a cobalt extraction pre-liquid, aiming to improve at least one of the problems mentioned in the background technology.

[0006] The present invention is achieved in that:

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

[0008] The crude cobalt hydroxide leaching solution is extracted with a post-soap extractant Bp-α to obtain an organic phase loaded with iron, zinc, calcium and cobalt and a decalcified solution;

[0009] The post-soap extractant Bp-β is used to extract the decalcified liquid to obtain an organic phase loaded with calcium, copper, manganese and cobalt and a pre-cobalt extraction liquid;

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

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

[0012] In an optional embodiment, the invention further comprises at least one of the following features (1) to (6):

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

[0014] (2) When the soap extractant Bp-β was used to extract the decalcified solution, the relative O / A ratio was 0.51 to 0.53;

[0015] (3) The extraction level of the crude cobalt hydroxide leaching solution extracted by the post-soap extractant Bp-α is 6 to 8;

[0016] (4) The extraction level of the post-soap extractant Bp-β when extracting the decalcified liquid is 8 to 9 levels;

[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 saponification of the P204 extractant in the post-soap extractant Bp-α is aqueous ammonia;

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

[0021] In an optional embodiment, after obtaining the iron, zinc, calcium and cobalt loaded organic phase, the method further comprises:

[0022] The iron, zinc, calcium and cobalt loaded organic phase is acid-washed with a first sulfuric acid solution to obtain an iron, zinc and calcium loaded organic phase and a cobalt sulfate solution;

[0023] The first hydrochloric acid solution is used to strip the iron, zinc and calcium loaded organic phase to obtain a calcium chloride solution and an iron, zinc loaded organic phase;

[0024] Using a second hydrochloric acid solution to perform anti-ferromagnetism on the iron-zinc loaded organic phase to obtain a first unloaded organic phase and a first anti-ferromagnetism solution;

[0025] Washing the first empty organic phase with pure water to obtain a first regenerated extractant and a first chlorine washing water;

[0026] Optionally, the cobalt sulfate solution obtained by pickling the organic phase loaded with iron, zinc, calcium and cobalt with the first sulfuric acid solution is refluxed to be combined with the crude cobalt hydroxide leaching solution, and then extracted again with the post-soap extractant Bp-α after the combination;

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

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

[0029] In an optional embodiment, the method further comprises at least one of the following features (7) to (12):

[0030] (7) when the first sulfuric acid solution is used to acid-wash the organic phase loaded with iron, zinc, calcium and cobalt, the relative O / A is 9.8 to 10.2;

[0031] (8) when the first hydrochloric acid solution is used to strip the organic phase loaded with iron, zinc and calcium, the relative O / A is 37 to 38;

[0032] (9) when the second hydrochloric acid solution is used to reverse the iron-zinc organic phase, the relative O / A is 26.8 to 27.2;

[0033] (10) the first sulfuric acid solution is used to pickle the organic phase loaded with iron, zinc, calcium and cobalt, and the pickling level is 3 to 5;

[0034] (11) the number of stripping stages when the first hydrochloric acid solution strips the organic phase loaded with iron, zinc and calcium is 6 to 8;

[0035] (12) When the second hydrochloric acid solution performs anti-ferromagnetism on the organic phase loaded with iron and zinc, the anti-ferromagnetism level is 3.

[0036] In an optional embodiment, the method further comprises at least one of the following features (13) to (15):

[0037] (13) the first sulfuric acid solution has an equivalent concentration of 0.29 to 0.31 N in terms of hydrogen ions;

[0038] (14) the first hydrochloric acid solution has an equivalent concentration of 4.2 to 4.7 N in terms of hydrogen ions;

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

[0040] In an optional embodiment, after obtaining the calcium, copper, manganese and cobalt loaded organic phase, the method further comprises:

[0041] The calcium-copper-manganese-cobalt loaded organic phase is acid-washed with a second sulfuric acid solution to obtain a calcium-copper-manganese loaded organic phase and a cobalt sulfate solution;

[0042] The calcium-copper-manganese loaded organic phase is stripped with a third hydrochloric acid solution to obtain an iron-zinc loaded organic phase and a crude manganese chloride solution;

[0043] Using a fourth hydrochloric acid solution to perform anti-ferromagnetism on the iron-zinc loaded organic phase to obtain a second unloaded organic phase and a second anti-ferromagnetic solution;

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

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

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

[0047] Optionally, the second regenerated extractant is used as a post-soap extractant Bp-β to extract the decalcified liquid. In an optional embodiment, it also includes at least one of the following features (16) to (21):

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

[0049] (17) when the third hydrochloric acid solution is used to strip the calcium, copper and manganese loaded organic phase, the phase O / A is 22 to 22.5;

[0050] (18) when the fourth hydrochloric acid solution is used to reverse the iron-zinc organic phase, the relative O / A is 36 to 36.3;

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

[0052] (20) The number of stripping stages when the third hydrochloric acid solution strips the calcium, copper and manganese loaded organic phase is 6 to 8;

[0053] (21) When the fourth hydrochloric acid solution performs anti-ferromagnetism on the organic phase loaded with iron and zinc, the anti-ferromagnetism order is 3.

[0054] In an optional embodiment, the method further includes at least one of the following features (22) to (24):

[0055] (22) the second sulfuric acid solution has an equivalent concentration of 0.9 to 1.1 N in terms of hydrogen ions;

[0056] (23) the third hydrochloric acid solution has an equivalent concentration of 4.2 to 4.7 N in terms of hydrogen ions;

[0057] (24) The fourth hydrochloric acid solution has an equivalent concentration of 5.5 to 6.5 N in terms of hydrogen ions.

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

[0059] The crude manganese chloride solution is mixed with manganese powder, and after sufficient reaction, a 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 except 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 invention provides a method for preparing a cobalt extraction pre-liquid. The method comprises the following steps: firstly using P204 to pre-extract calcium for one-stage extraction, and then using a P204+N910 compound extractant for two-stage extraction and deep impurity removal to obtain a qualified cobalt extraction pre-liquid. During the two-stage extraction and impurity removal, a small amount of N910 is used to well remove copper without causing much influence on other impurities. Since copper is well removed, the risk of cobalt loss can be reduced in the subsequent pickling process due to the low over-extraction rate of the total amount of impurities (copper, manganese and calcium) by pickling. During the two-stage extraction, since the P204+N910 compound extractant has a good extraction effect on copper, the original extraction level can be reduced, and the space cost, material tank filling cost and equipment construction cost can be greatly reduced. By using two-stage extraction and impurity removal, not only a qualified high-cobalt concentration cobalt extraction pre-liquid can be obtained, but also the obtained calcium, copper, manganese and cobalt loaded organic phase can be used as a raw material for extracting a manganese chloride solution. Compared with the existing P204 one-stage extraction method, the method does not generate calcium slag, and if the organic phase generated by the extraction is continuously processed, the subsequent acid loss can be greatly reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0066] Figure 1 The present invention provides a flow chart of a method for preparing a cobalt extraction pre-liquid. DETAILED DESCRIPTION

[0067] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

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

[0069] The crude cobalt hydroxide leaching solution is extracted with a post-soap extractant Bp-α to obtain an organic phase loaded with iron, zinc, calcium and cobalt and a decalcified solution;

[0070] The post-soap extractant Bp-β is used to extract the decalcified liquid to obtain an organic phase loaded with calcium, copper, manganese and cobalt and a pre-cobalt extraction liquid;

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

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

[0073] The preparation method of the cobalt extraction pre-liquid provided by the present invention comprises the following steps: firstly using P204 pre-extracted calcium for one-stage extraction, and then using P204+N910 compound extractant for two-stage extraction and deep impurity removal, so as to obtain a qualified cobalt extraction pre-liquid; during the two-stage extraction and impurity removal, a small amount of N910 is used to well remove copper, while other impurities are not greatly affected; since copper is well removed, the over-extraction rate of the total amount of impurities (copper, manganese and calcium) by pickling is small in the subsequent pickling treatment process, so that the risk of cobalt loss can be reduced; during the two-stage extraction, the P204+N910 compound extractant is used, The N910 extractant does not need to be saponified, which can save the use of saponifiers. The N910 extractant has a good copper extraction effect, which can reduce the original extraction stage, greatly reducing space costs, material filling costs, and equipment construction costs. The two-stage extraction and impurity removal can not only obtain a qualified high-cobalt concentration cobalt extraction pre-liquid, but also the obtained calcium-copper-manganese-cobalt loaded organic phase can be used as a raw material for extracting manganese chloride solution. Compared with the existing P204 one-stage extraction method, this method does not produce calcium slag, and if the organic phase produced by the extraction is further processed, the subsequent acid loss can be greatly reduced.

[0074] The crude cobalt hydroxide leachate involved in the present invention can be obtained by oxidative acid leaching (sulfuric acid and hydrogen peroxide leaching) of crude cobalt hydroxide solid (containing impurity elements such as manganese, nickel, iron, aluminum, copper, zinc, calcium and magnesium). It should be noted that the crude cobalt hydroxide leachate involved in the present invention, in addition to the crude cobalt hydroxide obtained by oxidative acid leaching mentioned above, can be used as the treatment object of the present invention as long as the main metal element is cobalt and contains a small amount of metal 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 leaching solution is extracted with a post-soap extractant Bp-α to obtain an organic phase loaded with iron, zinc, calcium and cobalt and a decalcified solution.

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

[0078] The higher the saponification rate, the higher the extraction rate. However, if the saponification rate is too high, it will be difficult to separate the phases. The higher the saponification rate, the more over-extraction will be. The amount of acid washing will also need to be increased, which will increase the cost. When the saponification rate of the extractant in this step is within the above range, a higher extraction rate can be guaranteed and phase separation is easy.

[0079] Optionally, the P204 extractant in the post-soap extractant Bp-α is obtained by saponification of ammonia water. It should be noted that if only saponification is achieved, sodium hydroxide solution can also be used, but if sodium hydroxide solution is used, the obtained cobalt extraction pre-liquid contains sodium ions, and the by-product obtained in the process of treating the cobalt extraction pre-liquid at the back end is sodium sulfate, while if ammonia water is used, the by-product in the process of treating the cobalt extraction pre-liquid at the back end is ammonium magnesium sulfate, which is more valuable. The cobalt chloride solution obtained by the next step of cobalt extraction of the cobalt extraction pre-liquid generally has an index requirement for the sodium element, so ammonium soap is selected.

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

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

[0082] Optionally, the extraction stage in this step is 6 to 8 stages (for example, 6, 7 or 8).

[0083] S2. A first sulfuric acid solution is used to acid-wash the organic phase loaded with iron, zinc, calcium and cobalt to obtain an organic phase loaded with iron, zinc and calcium and a cobalt sulfate solution.

[0084] Optionally, to ensure a better pickling effect, the equivalent concentration of the first sulfuric acid solution in terms of hydrogen ions is 0.29 to 0.31 N (for example, 0.29 N, 0.3 N or 0.31 N);

[0085] Optionally, to ensure a better pickling effect, the first sulfuric acid solution has a relative O / A ratio of 9.8 to 10.2 (eg, 9.8, 10 or 10.2) when pickling the organic phase loaded with iron, zinc, calcium and cobalt.

[0086] Optionally, to ensure a better pickling effect, the number of washing stages when the first sulfuric acid solution is used to pickle the organic phase loaded with iron, zinc, calcium and cobalt is 3 to 5 (for example, 3, 4 or 5).

[0087] Optionally, the cobalt sulfate solution obtained by acid-washing the organic phase loaded with iron, zinc, calcium and cobalt with the first sulfuric acid solution is refluxed to be combined with the crude cobalt hydroxide leaching solution, and after the combination, it is extracted again with the post-soap extractant Bp-α.

[0088] S3. Using the first hydrochloric acid solution to strip the iron, zinc and calcium loaded organic phase to obtain a calcium chloride solution and an iron, zinc loaded organic phase.

[0089] Optionally, to ensure a better stripping effect, the equivalent concentration of the first hydrochloric acid solution in terms of hydrogen ions is 4.2-4.7N.

[0090] Optionally, to ensure a better stripping effect, the O / A ratio of the first hydrochloric acid solution when stripping the organic phase loaded with iron, zinc and calcium is 37 to 38 (for example, 37, 37.5 or 38).

[0091] Optionally, to ensure a better stripping effect, the stripping level when the first hydrochloric acid solution strips the iron, zinc and calcium loaded organic phase is 6 to 8 (for example, 6, 7 or 8).

[0092] S4, using a second hydrochloric acid solution to perform anti-iron treatment on the iron-zinc loaded organic phase to obtain a first unloaded organic phase and a first anti-iron solution.

[0093] In some embodiments of the present invention, the reagent used for stripping iron in this step may also be a sulfuric acid solution. Compared with a sulfuric acid solution, a hydrochloric acid solution has a better effect of stripping iron, and the cost of a hydrochloric acid solution is lower.

[0094] Optionally, to ensure a better anti-ferroic effect, the equivalent concentration of the second hydrochloric acid solution in terms of hydrogen ions is 5.5-6.5N (eg, 5.5N, 6.0N or 6.5N).

[0095] Optionally, to ensure a better anti-ferromagnetic effect, the second hydrochloric acid solution has a relative O / A ratio of 26.8 to 27.2 (for example, 26.8, 27 or 27.2) when anti-ferromagneticating the iron-zinc organic phase;

[0096] Optionally, to ensure a better anti-ferromagnetic effect, the anti-ferromagnetic level when the second hydrochloric acid solution carries out anti-ferromagnetic treatment on the organic phase loaded with iron and zinc is 3 levels.

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

[0098] The first anti-iron solution in step S4 and the first chlorine washing water in this step can be reused to prepare the first hydrochloric acid solution. The first regenerated extractant can be circulated as the post-soap extractant Bp-α to extract the crude cobalt hydroxide leaching solution.

[0099] S6. Use post-soap extractant Bp-β to extract the decalcified liquid to obtain an organic phase loaded with calcium, copper, manganese and cobalt and a pre-cobalt extraction liquid.

[0100] Among them, the post-soap extractant Bp-β includes a P204 extractant with a volume concentration of 18% to 22% (for example, 18%, 20% or 22%) and a N910 extractant with a volume concentration of 4% to 6% (for example, 4%, 5% or 6%), and the saponification rate of the P204 extractant is 44% to 46% (for example, 44%, 45% or 46%).

[0101] The post-soap extractant Bp-β is a composite of P204 extractant and N910 extractant, and the two are set within a suitable concentration range to reduce the extraction cost while ensuring a better impurity removal effect. When the saponification rate of the extractant in this step is within the above range, a higher extraction rate can be guaranteed and phase separation is easy.

[0102] Optionally, the P204 extractant in the post-soap extractant Bp-β is obtained by saponification of ammonia water. It should be noted that if only saponification is achieved, sodium hydroxide solution can also be used, but the byproduct of using sodium hydroxide solution is sodium sulfate, while if ammonia water is used, the byproduct is magnesium ammonium sulfate, which is more valuable.

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

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

[0105] Optionally, the extraction stage in this step is 8 or 9.

[0106] S7. A second sulfuric acid solution is used to acid-wash the calcium, copper, manganese and cobalt loaded organic phase to obtain a calcium, copper and manganese loaded organic phase and a cobalt sulfate solution.

[0107] Optionally, to ensure a better pickling effect, the equivalent concentration of the second sulfuric acid solution in terms of hydrogen ions is 0.9 to 1.1 N (for example, 0.9 N, 1 N or 1.1 N);

[0108] Optionally, to ensure a better pickling effect, the relative O / A ratio when the second sulfuric acid solution is used to wash the calcium, copper, manganese and cobalt loaded organic phase is 14.6 to 15 (for example, 14.6, 14.8 or 15).

[0109] Optionally, to ensure a better pickling effect, the number of washing stages when the second sulfuric acid solution is used to wash the calcium, copper, manganese and cobalt loaded organic phase is 6 to 8 (for example, 6, 7 or 8).

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

[0111] S8. Use the third hydrochloric acid solution to strip the calcium, copper and manganese loaded organic phase to obtain an iron and zinc loaded organic phase and a crude manganese chloride solution.

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

[0113] Optionally, to ensure a better stripping effect, the equivalent concentration of the third hydrochloric acid solution in terms of hydrogen ions is 4.2-4.7N (eg, 4.2N, 4.5N or 4.7N).

[0114] Optionally, to ensure a better stripping effect, the phase ratio O / A when the third hydrochloric acid solution strips the calcium-copper-manganese loaded organic phase is 22 to 22.5 (eg, 22, 22.3 or 22.5).

[0115] Optionally, to ensure a better stripping effect, the stripping stage number when the third hydrochloric acid solution strips the calcium, copper and manganese loaded organic phase is 6 to 8 (eg 6, 7 or 8).

[0116] S7, using the fourth hydrochloric acid solution to perform anti-ferromagnetism on the iron-zinc loaded organic phase to obtain a second unloaded organic phase and a second anti-ferromagnetic solution.

[0117] Optionally, to ensure a better anti-ferroic effect, the fourth hydrochloric acid solution has an equivalent concentration of 5.5-6.5N (eg, 5.5N, 6N or 6.5N) in terms of hydrogen ions.

[0118] Optionally, to ensure a better anti-ferromagnetic effect, the fourth hydrochloric acid solution has a relative O / A ratio of 36 to 36.3 (for example, 36, 36.2 or 36.3) when anti-ferromagneticating the iron-zinc organic phase;

[0119] Optionally, to ensure a better anti-ferromagnetic effect, the anti-ferromagnetic level when the fourth hydrochloric acid solution performs anti-ferromagnetic treatment on the iron-zinc loaded organic phase is 3 levels.

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

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

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

[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 that the manganese chloride solution has a higher purity, the molar amount of manganese powder added is 1.05 to 1.20 times (for example, 1.05, 1.1 or 1.2) the total molar amount of all metal elements except manganese in the crude manganese chloride solution.

[0125] Optionally, to increase the reaction rate and ensure sufficient reaction, the reaction temperature is 60-70°C (eg, 60°C, 65°C or 70°C), and the reaction time is 1.5-2.5h (eg, 1.5h, 2h or 2.5h).

[0126] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0127] In the following examples and comparative examples, the reagents used are as follows:

[0128] N910 extractant was purchased from Zhengzhou Hecheng New Material Technology Co., Ltd., which is a β-diketone extractant. No. 260 solvent oil was purchased from Guangdong Hongjiang Chemical Reagent Co., Ltd., which is also known as sulfonated kerosene, a colorless and transparent solvent oil made by sulfonation of kerosene. P204 (di-2-octyl phosphate) extractant was purchased from Luoyang Sannuo Chemical Co., Ltd.

[0129] The content of each element and the acidity and alkalinity of the crude cobalt hydroxide leaching solution of the following embodiments and comparative examples are shown in Table 1:

[0130] Table 1 Component content of crude cobalt hydroxide leaching solution

[0131]

[0132] Example 1

[0133] The organic phase (25% of P204 extractant) of the extractant Bp-α (containing a P204 extractant with a volume concentration of 25%, the remainder being a diluent, and the diluent being No. 260 solvent oil) was saponified using aqueous ammonia (wt=20%) to a saponification rate of 19% to obtain the post-soap extractant Bp-α.

[0134] like Figure 1As shown, the crude cobalt hydroxide leaching solution was extracted using a post-soap extractant Bp-α according to an extraction phase ratio of O / A=0.41 and an extraction stage of 8 to obtain an organic phase loaded with iron, zinc, calcium and cobalt and a decalcified liquid.

[0135] The iron, zinc, calcium and cobalt loaded organic phase was pickled with 0.31N sulfuric acid (in terms of hydrogen ions, the same below), the pickling washing rate = 21%, the washing phase ratio O / A = 10.00, the washing stage number was 3, and the iron, zinc and calcium loaded organic phase and the cobalt sulfate solution were obtained. The obtained cobalt sulfate solution was refluxed to be combined with the crude cobalt hydroxide leachate, and after the combination, it was extracted again with the post-soap extractant Bp-α.

[0136] The iron, zinc and calcium loaded organic phase was back-extracted using 4.50N hydrochloric acid, the back-extraction phase ratio O / A was 37.50, the back-extraction stage was 6, and calcium chloride solution and iron, zinc and calcium loaded organic phase were obtained.

[0137] 6.00N hydrochloric acid was used to perform back extraction on the organic phase loaded with iron and zinc, and the back extraction ratio O / A was 27.09, and the back extraction level was 3, to obtain the first empty organic phase and the first back extraction liquid. The first back extraction liquid was prepared with acid solution and then used in the previous step to back extract the organic phase loaded with iron, zinc and calcium.

[0138] The first empty organic phase is washed with pure water to obtain a first regenerated extractant and a first chlorine washing water. The first regenerated extractant can be recovered and reused, and the first chlorine washing water is reused to prepare a hydrochloric acid solution for stripping the iron, zinc and calcium loaded organic phase.

[0139] The P204 extractant in the extractant Bp-β (containing a P204 extractant with a volume concentration of 20%, a N910 extractant with a volume concentration of 5%, and the remainder being a diluent, wherein the diluent is No. 260 solvent oil) is saponified using ammonia water (wt=20%) to a saponification rate of 46% to obtain the post-soap extractant Bp-β.

[0140] The decalcified liquid was extracted with a post-soap extractant Bp-β at an extraction phase ratio of O / A=0.52 and an extraction stage of 8 to obtain a cobalt extraction pre-liquid and an organic phase loaded with calcium, copper, manganese and cobalt.

[0141] The calcium, copper, manganese and cobalt loaded organic phase was pickled with 1.10N sulfuric acid, the pickling washing rate was 26%, the washing phase ratio O / A was 14.81, and the washing stage was 6 to obtain the calcium, copper and manganese loaded organic phase and cobalt sulfate solution. The cobalt sulfate solution was refluxed to be combined with the decalcified liquid, and then extracted again with the post-soap extractant Bp-β.

[0142] The calcium, copper and manganese loaded organic phase was stripped with 4.50N hydrochloric acid, the stripping phase ratio O / A was 22.22, the stripping stage was 6, and a crude manganese chloride solution and an iron and zinc loaded organic phase were obtained.

[0143] 6N hydrochloric acid was used to perform back extraction on the organic phase loaded with iron and zinc, and the back extraction ratio O / A was 36.12, and the back extraction level was 3, to obtain the second empty organic phase and the second back extraction liquid. The obtained second back extraction liquid was prepared with acid solution and then reused in the previous step to extract the organic phase loaded with calcium, copper and manganese.

[0144] The second empty organic phase is washed with pure water to obtain a second regenerated extractant and a second chlorine washing water. The second regenerated extractant can be recovered and reused, and the second chlorine washing water is reused to prepare a hydrochloric acid solution for stripping the calcium, copper and manganese loaded organic phase.

[0145] The crude manganese chloride solution was heated to 60.00°C, and 1.20 times the molar amount of theoretical impurities (the sum of all metal elements except manganese) of manganese powder was added, and the particle size of the manganese powder was under 300 mesh sieve. The reaction time was 1.5h to obtain a refined manganese chloride solution and sponge copper.

[0146] Example 2

[0147] The organic phase (25% of P204 extractant) of the extractant Bp-α (containing a P204 extractant with a volume concentration of 25%, the remainder being a diluent, and the diluent being No. 260 solvent oil) is saponified using ammonia water (wt=20%) to a saponification rate of 20% to obtain the post-soap extractant Bp-α.

[0148] like Figure 1 As shown, the crude cobalt hydroxide leaching solution was extracted using a post-soap extractant Bp-α according to an extraction phase ratio of O / A=0.41 and 7 extraction stages to obtain an organic phase loaded with iron, zinc, calcium and cobalt and a decalcified liquid.

[0149] The iron, zinc, calcium and cobalt loaded organic phase was pickled with 0.30N sulfuric acid (in terms of hydrogen ions, the same below), the pickling washing rate = 21%, the washing phase ratio O / A = 10.00, the washing stage number was 3, and the iron, zinc and calcium loaded organic phase and the cobalt sulfate solution were obtained. The obtained cobalt sulfate solution was refluxed to be combined with the crude cobalt hydroxide leachate, and after the combination, it was extracted again with the post-soap extractant Bp-α.

[0150] The iron, zinc and calcium loaded organic phase was back-extracted using 4.50N hydrochloric acid, the back-extraction phase ratio O / A was 37.50, the back-extraction stage was 6, and calcium chloride solution and iron, zinc and calcium loaded organic phase were obtained.

[0151] 6.00N hydrochloric acid was used to perform back extraction on the organic phase loaded with iron and zinc, and the back extraction ratio O / A was 27.09, and the back extraction level was 3, to obtain the first empty organic phase and the first back extraction liquid. The first back extraction liquid was prepared with acid solution and then used in the previous step to back extract the organic phase loaded with iron, zinc and calcium.

[0152] The first empty organic phase is washed with pure water to obtain a first regenerated extractant and a first chlorine washing water. The first regenerated extractant can be recovered and reused, and the first chlorine washing water is reused to prepare a hydrochloric acid solution for stripping the iron, zinc and calcium loaded organic phase.

[0153] The P204 extractant in the extractant Bp-β (containing a P204 extractant with a volume concentration of 20%, a N910 extractant with a volume concentration of 5%, and the remainder being a diluent, wherein the diluent is No. 260 solvent oil) is saponified using ammonia water (wt=20%) to a saponification rate of 45% to obtain the post-soap extractant Bp-β.

[0154] The decalcified liquid was extracted with a post-soap extractant Bp-β at an extraction phase ratio of O / A=0.52 and an extraction stage of 8 to obtain a cobalt extraction pre-liquid and an organic phase loaded with calcium, copper, manganese and cobalt.

[0155] The calcium, copper, manganese and cobalt loaded organic phase was pickled with 1.10N sulfuric acid, the pickling washing rate was 26%, the washing phase ratio O / A was 14.81, and the washing stage was 6 to obtain the calcium, copper and manganese loaded organic phase and cobalt sulfate solution. The cobalt sulfate solution was refluxed to be combined with the decalcified liquid, and then extracted again with the post-soap extractant Bp-β.

[0156] The calcium, copper and manganese loaded organic phase was stripped with 4.50N hydrochloric acid, the stripping phase ratio O / A was 22.22, the stripping stage was 6, and a crude manganese chloride solution and an iron and zinc loaded organic phase were obtained.

[0157] 6N hydrochloric acid was used to perform back extraction on the organic phase loaded with iron and zinc, and the back extraction ratio O / A was 36.12, and the back extraction level was 3, to obtain the second empty organic phase and the second back extraction liquid. The obtained second back extraction liquid was prepared with acid solution and then reused in the previous step to extract the organic phase loaded with calcium, copper and manganese.

[0158] The second empty organic phase is washed with pure water to obtain a second regenerated extractant and a second chlorine washing water. The second regenerated extractant can be recovered and reused, and the second chlorine washing water is reused to prepare a hydrochloric acid solution for stripping the calcium, copper and manganese loaded organic phase.

[0159] The crude manganese chloride solution was heated to 65.00°C, and 1.15 times the molar amount of theoretical impurities (the sum of all metal elements except manganese) of manganese powder was added, and the particle size of the manganese powder was under 300 mesh sieve. The reaction time was 2h to obtain a refined manganese chloride solution and sponge copper.

[0160] Example 3

[0161] The organic phase (25% of P204 extractant) of the extractant Bp-α (containing a P204 extractant with a volume concentration of 25%, the remainder being a diluent, and the diluent being No. 260 solvent oil) was saponified using ammonia water (wt=20%) to a saponification rate of 21% to obtain the post-soap extractant Bp-α.

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

[0163] The iron, zinc, calcium and cobalt loaded organic phase was pickled with 0.29N sulfuric acid (in terms of hydrogen ions, the same below), the pickling washing rate = 21%, the washing phase ratio O / A = 10.00, the washing stage number was 3, and the iron, zinc and calcium loaded organic phase and the cobalt sulfate solution were obtained. The obtained cobalt sulfate solution was refluxed to be combined with the crude cobalt hydroxide leachate, and after the combination, it was extracted again with the post-soap extractant Bp-α.

[0164] The iron, zinc and calcium loaded organic phase was back-extracted using 4.50N hydrochloric acid, the back-extraction phase ratio O / A was 37.50, the back-extraction stage was 6, and calcium chloride solution and iron, zinc and calcium loaded organic phase were obtained.

[0165] 6.00N hydrochloric acid was used to perform back extraction on the organic phase loaded with iron and zinc, and the back extraction ratio O / A was 27.09, and the back extraction level was 3, to obtain the first empty organic phase and the first back extraction liquid. The first back extraction liquid was prepared with acid solution and then used in the previous step to back extract the organic phase loaded with iron, zinc and calcium.

[0166] The first empty organic phase is washed with pure water to obtain a first regenerated extractant and a first chlorine washing water. The first regenerated extractant can be recovered and reused, and the first chlorine washing water is reused to prepare a hydrochloric acid solution for stripping the iron, zinc and calcium loaded organic phase.

[0167] The P204 extractant in the extractant Bp-β (containing a P204 extractant with a volume concentration of 20%, a N910 extractant with a volume concentration of 5%, and the remainder being a diluent, wherein the diluent is No. 260 solvent oil) is saponified using ammonia water (wt=20%) to a saponification rate of 44% to obtain the post-soap extractant Bp-β.

[0168] The decalcified liquid was extracted with a post-soap extractant Bp-β at an extraction phase ratio of O / A=0.52 and an extraction stage of 8 to obtain a cobalt extraction pre-liquid and an organic phase loaded with calcium, copper, manganese and cobalt.

[0169] The calcium, copper, manganese and cobalt loaded organic phase was pickled with 1.10N sulfuric acid, the pickling washing rate was 26%, the washing phase ratio O / A was 14.81, and the washing stage was 6 to obtain the calcium, copper and manganese loaded organic phase and cobalt sulfate solution. The cobalt sulfate solution was refluxed to be combined with the decalcified liquid, and then extracted again with the post-soap extractant Bp-β.

[0170] The calcium, copper and manganese loaded organic phase was stripped with 4.50N hydrochloric acid, the stripping phase ratio O / A was 22.22, the stripping stage was 6, and a crude manganese chloride solution and an iron and zinc loaded organic phase were obtained.

[0171] 6N hydrochloric acid was used to perform back extraction on the organic phase loaded with iron and zinc, and the back extraction ratio O / A was 36.12, and the back extraction level was 3, to obtain the second empty organic phase and the second back extraction liquid. The obtained second back extraction liquid was prepared with acid solution and then reused in the previous step to extract the organic phase loaded with calcium, copper and manganese.

[0172] The second empty organic phase is washed with pure water to obtain a second regenerated extractant and a second chlorine washing water. The second regenerated extractant can be recovered and reused, and the second chlorine washing water is reused to prepare a hydrochloric acid solution for stripping the calcium, copper and manganese loaded organic phase.

[0173] The crude manganese chloride solution was heated to 70.00°C, and 1.05 times the molar amount of theoretical impurities (the sum of all metal elements except manganese) of manganese powder was added, and the particle size of the manganese powder was under 300 mesh sieve. 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 one-stage extraction method is used to remove impurities.

[0176] The content of this comparative example is:

[0177] The organic phase (25% of P204 extractant) of the extractant Bp-α (containing a P204 extractant with a volume concentration of 25%, the remainder being a diluent, and the diluent being No. 260 solvent oil) is saponified using ammonia water (wt=20%) to a saponification rate of 45% to obtain the post-soap extractant Bp-α.

[0178] The crude cobalt hydroxide leaching solution was extracted with a post-soap extractant Bp-α at an extraction phase ratio of O / A=0.76 and 14 extraction stages to obtain a calcium-manganese extracted organic phase and a calcium-manganese extracted residual solution.

[0179] The calcium manganese organic phase was pickled with 2.00N sulfuric acid (in terms of hydrogen ions, all the same below), the pickling ratio O / A=14.81, the washing level was 8, and the first organic phase and cobalt sulfate solution were obtained, and the obtained cobalt sulfate solution was refluxed to be combined with the crude cobalt hydroxide leaching solution, and then extracted again with the soap extractant Bp-α after merging. The obtained organic phase was stripped with 4.50N hydrochloric acid, the stripping ratio O / A=22.22, the stripping level was 6, and the calcium manganese chloride solution and the second organic phase were obtained. The second organic phase was reversed with 6.00N hydrochloric acid, the reversed iron ratio O / A=50.51, and the reversed iron level was 3.

[0180] Comparative Example 2

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

[0182] In Example 1, 20% P204+5% N910 after soap was used to extract the decalcified liquid, while in this comparative example, 25% P204 after soap was used to extract the decalcified liquid.

[0183] Specifically:

[0184] The organic phase (25% of P204 extractant) of the extractant Bp-α (containing a P204 extractant with a volume concentration of 25%, the remainder being a diluent, and the diluent being No. 260 solvent oil) was saponified using aqueous ammonia (wt=20%) to a saponification rate of 19% to obtain the post-soap extractant Bp-α.

[0185] The crude cobalt hydroxide leaching solution was extracted with a post-soap extractant Bp-α at an extraction phase ratio of O / A=0.41 and an extraction stage of 8 to obtain an organic phase loaded with iron, zinc, calcium and cobalt and a decalcified liquid.

[0186] The iron, zinc, calcium and cobalt loaded organic phase was pickled with 0.31N sulfuric acid (in terms of hydrogen ions, the same below), the pickling washing rate = 21%, the washing phase ratio O / A = 10.00, the washing stage number was 3, and the iron, zinc and calcium loaded organic phase and the cobalt sulfate solution were obtained. The obtained cobalt sulfate solution was refluxed to be combined with the crude cobalt hydroxide leachate, and after the combination, it was extracted again with the post-soap extractant Bp-α.

[0187] The iron, zinc and calcium loaded organic phase was back-extracted using 4.50N hydrochloric acid, the back-extraction phase ratio O / A was 37.50, the back-extraction stage was 6, and calcium chloride solution and iron, zinc and calcium loaded organic phase were obtained.

[0188] 6.00N hydrochloric acid was used to perform back extraction on the organic phase loaded with iron and zinc, and the back extraction ratio O / A was 27.09, and the back extraction level was 3, to obtain the first empty organic phase and the first back extraction liquid. The first back extraction liquid was an acid solution, which was used in the previous step to back extract the organic phase loaded with iron, zinc and calcium after preparation.

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

[0190] The P204 extractant in the extractant (containing a P204 extractant with a volume concentration of 25%, and the diluent is No. 260 solvent oil) is saponified with ammonia water (wt=20%) to a saponification rate of 55% to obtain a soaped P204 extractant.

[0191] The decalcified liquid was extracted with soap P204 extractant at an extraction phase ratio of O / A=0.75 and 12 extraction stages to obtain a cobalt extraction pre-liquid and an organic phase loaded with calcium, copper, manganese and cobalt.

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

[0193] The calcium, copper and manganese loaded organic phase was stripped with 4.50N hydrochloric acid, the stripping phase ratio O / A was 31.68, the stripping stage was 6, and a crude manganese chloride solution and an iron and zinc loaded organic phase were obtained.

[0194] The iron-zinc loaded organic phase was subjected to anti-ferromagnetism using 6N hydrochloric acid. The anti-ferromagnetism phase ratio O / A was 51.88, and the anti-ferromagnetism order was 3.

[0195] Experimental Example 1

[0196] The concentrations of various metal ions in the cobalt extraction pre-solutions prepared in various embodiments and comparative examples were tested and recorded in Table 2.

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

[0198]

[0199] As can be seen from Table 2, Comparative Example 1 adopts a one-stage extraction method, so the cobalt concentration is the highest, and Comparative Example 2 uses a two-stage extraction method and has a high washing rate in the second-stage extraction. Since a large amount of acid is used during pickling, the volume of the obtained cobalt sulfate solution is large and the cobalt concentration is low. After the cobalt sulfate solution is combined with the decalcified solution, the cobalt concentration is low, so the cobalt concentration in the obtained cobalt extraction pre-liquid is low. The use of the two-stage extraction method in each embodiment provided by the present invention does not affect the cobalt concentration of the cobalt extraction pre-liquid, and due to the extractant formula, the concentration of copper element in the cobalt extraction pre-liquid is the lowest, and the qualified rate of the cobalt extraction pre-liquid is high.

[0200] Experimental Example 2

[0201] The cost of Example 1 and two comparative examples was calculated. The consumption and cost of Example 1 and Comparative Examples 1 and 2 were compared and recorded in Table 3.

[0202] Table 3 Consumption and cost comparison

[0203]

[0204] As can be seen from Table 3, the overall cost of Example 1 is greatly reduced compared with Comparative Examples 1 and 2. In Example 1, the anti-iron liquid obtained after hydrochloric acid anti-ironification is reused, and the chlorine washing water obtained after washing the organic phase with pure water is reused, so the hydrochloric acid consumption of Example 1 is less than that of Comparative Examples 1 and 2.

[0205] Experimental Example 3

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

[0207] Table 4 Comparison of extraction levels of different extractants

[0208]

[0209] As can be seen from Table 4, in Comparative Example 2, the copper ion in the raffinate can be reduced to less than 1 mg / l after 12 extractions, while in Example 1, the copper ion concentration can be reduced to less than 1 mg / l after only 8 extractions using 20% ​​P204 + 5% N910 after soap. Compared with Comparative Example 2, Example 1 can greatly reduce the space, material filling tank, and equipment manufacturing costs.

[0210] Experimental Example 4

[0211] When the organic phase loaded with calcium, copper, manganese and cobalt is acid-washed with sulfuric acid in Example 1, the loss of cobalt element in the organic phase after each level of washing is detected;

[0212] When the organic phase loaded with calcium, copper, manganese and cobalt was acid-washed with sulfuric acid in comparative example 2, the loss of cobalt element in the organic phase after each level of washing was detected.

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

[0214] Table 5 Loss of cobalt ions in each organic phase after pickling in Example 1 and Comparative Example 2

[0215]

[0216] As can be seen from Table 5, the cobalt in the organic phase of Comparative Example 2 can be reduced to less than 1 mg / l after 8 washings, while the cobalt content in the organic phase of Example 1 can be reduced to less than 1 mg / l after 6 washings. It can be seen that Example 1 of the present invention can greatly reduce the space, material filling tank, and equipment manufacturing costs compared to Comparative Example 2.

[0217] The preparation method provided in Comparative Example 1 can complete the preparation of the cobalt extraction pre-liquid, but it also has the problems of calcium slag and large acid and alkali consumption compared with Example 1. Comparative Example 2 can also complete the preparation of the cobalt extraction pre-liquid, but the extraction stage and washing stage are large compared with Example 1, and the acid and alkali consumption is large.

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

[0219] 1. The present invention uses a two-stage impurity removal method to obtain not only a qualified high-cobalt concentration cobalt extraction pre-liquid but also a 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%. The present invention uses a small amount of washing acid, generates a small amount of wastewater, and reduces the pressure of the back-end process;

[0220] 2. The present invention first uses P204 to pre-extract calcium, and then uses P204+N910 compound extractant to perform 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 because the washing rate is small.

[0221] 3. The present invention has a good copper extraction effect during the two-stage extraction and impurity removal, and can reduce the original 12-stage extraction to 8-stage extraction, and reduce the 8-stage washing to 6-stage washing, thereby greatly reducing space costs, material filling costs, and equipment construction costs.

[0222] 4. The method provided by the present invention overcomes the problems of discontinuous production, large acid and alkali loss, 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 only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

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

2. The preparation method according to claim 1, characterized in that: Also includes at least one of the following features (1) to (6): (1) When the post-soap extractant Bp-α is used to extract the crude cobalt hydroxide leaching solution, the ratio O / A is 0.4 to 0.42; (2) when the post-soap extractant Bp-β extracts the decalcified liquid, the relative O / A is 0.51 to 0.53; (3) The extraction level of the crude cobalt hydroxide leaching solution extracted by the post-soap extractant Bp-α is 6 to 8; (4) The extraction level of the post-soap extractant Bp-β when extracting the decalcified liquid is 8 to 9 levels; (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 saponification of the P204 extractant in the post-soap extractant Bp-α is ammonia water.

4. The preparation method according to claim 1, characterized in that: After obtaining the iron, zinc, calcium and cobalt loaded organic phase, the method further comprises: The iron, zinc, calcium and cobalt loaded organic phase is acid-washed with a first sulfuric acid solution to obtain an iron, zinc and calcium loaded organic phase and a cobalt sulfate solution; Using a first hydrochloric acid solution to strip the iron, zinc and calcium loaded organic phase to obtain a calcium chloride solution and an iron, zinc loaded organic phase; Using a second hydrochloric acid solution to perform anti-ferromagnetism on the iron-zinc loaded organic phase to obtain a first unloaded organic phase and a first anti-ferromagnetism solution; Washing the first empty organic phase with pure water to obtain a first regenerated extractant and a first chlorine washing water; Optionally, the cobalt sulfate solution obtained by pickling the organic phase loaded with iron, zinc, calcium and cobalt with a first sulfuric acid solution is refluxed to be combined with the crude cobalt hydroxide leaching solution, and after the combination, it is extracted again with the post-soap extractant Bp-α; Optionally, the first anti-iron solution and the first chlorine washing water are reused to prepare the first hydrochloric acid solution; Optionally, the first regenerated extractant is used as the post-soap extractant Bp-α to extract the crude cobalt hydroxide leachate.

5. The preparation method according to claim 4, characterized in that: Also includes at least one of the following features (7) to (12): (7) the first sulfuric acid solution is used to acid-wash the organic phase loaded with iron, zinc, calcium and cobalt, and the relative O / A is 9.8 to 10.2; (8) the O / A ratio of the first hydrochloric acid solution to the organic phase loaded with iron, zinc and calcium is 37 to 38; (9) the O / A ratio of the second hydrochloric acid solution to the iron-zinc organic phase is 26.8 to 27.2; (10) the first sulfuric acid solution is used to pickle the organic phase loaded with iron, zinc, calcium and cobalt, and the pickling level is 3 to 5; (11) The number of stripping stages when the first hydrochloric acid solution strips the organic phase loaded with iron, zinc and calcium is 6 to 8; (12) The second hydrochloric acid solution performs anti-ferromagnetism on the iron-zinc loaded organic phase, and the anti-ferromagnetism level is 3.

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

7. The preparation method according to claim 1, characterized in that: After obtaining the calcium, copper, manganese and cobalt loaded organic phase, the method further comprises: acid-washing the calcium-copper-manganese-cobalt loaded organic phase with a second sulfuric acid solution to obtain a calcium-copper-manganese loaded organic phase and a cobalt sulfate solution; Using a third hydrochloric acid solution to strip the calcium, copper and manganese loaded organic phase to obtain an iron and zinc loaded organic phase and a crude manganese chloride solution; Using a fourth hydrochloric acid solution to perform anti-ferromagnetism on the iron-zinc loaded organic phase to obtain a second unloaded organic phase and a second anti-ferromagnetic solution; Washing the second empty organic phase with pure water to obtain a second regenerated extractant and a second chlorine washing water; Optionally, the cobalt sulfate solution obtained by acid-washing the calcium, copper, manganese and cobalt loaded organic phase with a second sulfuric acid solution is refluxed to be combined with the decalcified solution, and then extracted again with the post-soap extractant Bp-β after the combination; Optionally, the second anti-iron solution and the second chlorine washing water are reused to prepare the third hydrochloric acid solution; Optionally, the second regenerated extractant is used as a post-soap extractant Bp-β to extract the decalcified liquid.

8. The preparation method according to claim 7, characterized in that: Also includes at least one of the following features (16) to (21): (16) the relative O / A when the second sulfuric acid solution is used to acid-wash the calcium, copper, manganese and cobalt loaded organic phase is 14.6 to 15; (17) the phase ratio O / A when the third hydrochloric acid solution is used to strip the calcium, copper and manganese loaded organic phase is 22 to 22.5; (18) the fourth hydrochloric acid solution reacts the iron-zinc organic phase with the organic phase to produce an O / A ratio of 36 to 36.3; (19) The washing stages when the second sulfuric acid solution is used to acid wash the calcium, copper, manganese and cobalt loaded organic phase are 6 to 8 stages; (20) The number of stripping stages when the third hydrochloric acid solution strips the calcium, copper and manganese loaded organic phase is 6 to 8; (21) The fourth hydrochloric acid solution performs anti-ferromagnetism on the iron-zinc loaded organic phase, and the anti-ferromagnetism level is 3.

9. The preparation method according to claim 7, characterized in that: Also includes at least one of the following features (22) to (24): (22) the equivalent concentration of the second sulfuric acid solution in terms of hydrogen ions is 0.9 to 1.1 N; (23) The third hydrochloric acid solution has an equivalent concentration of 4.2 to 4.7 N in terms of hydrogen ions; (24) The fourth hydrochloric acid solution has an equivalent concentration of 5.5 to 6.5 N in terms of hydrogen ions.

10. The preparation method according to claim 7, characterized in that: After obtaining the crude manganese chloride solution, the method further comprises: The crude manganese chloride solution is mixed with the manganese powder to obtain a manganese chloride solution and sponge copper after sufficient reaction; Optionally, the particle size of the manganese powder is less than or equal to 0.074 mm; Optionally, the added molar amount of the manganese powder is 1.05 to 1.20 times the total molar amount of all other metal elements in the crude manganese chloride solution except manganese; Optionally, the reaction temperature is 60-70° C. and the reaction time is 1.5-2.5 h.

Images