Method for recovering battery-grade manganese sulfate from manganese-containing feed liquid

Abstract

The invention provides a method for recycling battery-grade manganese sulfate from manganese-containing feed liquid. The method comprises the following steps: (1) carrying out resin adsorption on a manganese-containing feed liquid to obtain a nickel-cobalt adsorbate and an adsorbed feed liquid; (2) sequentially carrying out extraction treatment and reverse extraction treatment on the adsorbed feed liquid to obtain a solution containing manganese sulfate and an organic phase after reverse extraction; (3) carrying out evaporative crystallization on the solution containing manganese sulfate to obtain battery-grade manganese sulfate; positive ions in the manganese-containing feed liquid comprise manganese ions, nickel ions, cobalt ions, calcium ions and magnesium ions, and negative ions in the manganese-containing feed liquid comprise sulfate ions; an extraction agent adopted in the extraction treatment process comprises an HBL116 extraction agent. According to the method disclosed by the invention, metal oxidation hydrolysis cannot be caused to generate a third phase, the extraction process is stable, enrichment of a high-concentration manganese sulfate solution is realized, high-purity manganese sulfate crystals with qualified impurities are obtained, and efficient recovery of manganese in a high-calcium-magnesium feed liquid system can be realized; and a complicated recovery process is not needed, so that the cost is lower.

Description

Technical Field

[0001] The present invention belongs to the field of manganese sulfate recovery and relates to a method for recovering battery-grade manganese sulfate from a manganese-containing liquor. Background Art

[0002] In recent years, the number of lithium-ion batteries used has doubled, accompanied by a doubling of the demand for ternary precursor materials. At the same time, the demand for battery-grade manganese sulfate raw materials required for preparing ternary materials is also increasing synchronously. However, manganese-containing raw materials, such as manganese ore, laterite nickel ore, and other recycled raw materials, are doped with a large amount of other impurities, such as common metal impurities like nickel, cobalt, calcium, magnesium, iron, chromium, or aluminum. Therefore, impurity removal is necessary during the preparation process. The solvent extraction method is an effective purification method for preparing battery-grade high-purity manganese sulfate. Manganese can be selectively extracted from a manganese sulfate solution containing impurities, ultimately meeting the requirements of battery-grade manganese sulfate. However, the calcium and magnesium contents in the battery-grade manganese sulfate prepared by the existing process are relatively high. Even if the standard is met, the impurity removal agents used for impurity removal are fluorides or sulfides, which not only cause environmental pollution but also increase the difficulty of wastewater treatment. Moreover, it is difficult to enrich a high-concentration manganese sulfate solution through a single extraction to obtain manganese sulfate crystals with qualified impurities and high purity.

[0003] CN109704408A discloses a method for producing battery-grade high-purity manganese sulfate, which uses a fluoride salt to remove calcium and then a calcium salt to remove fluorine. New polluting elements are added during impurity removal, which not only makes the product impure but also increases the difficulty of wastewater treatment. During the production of cobalt salts or nickel salts, along with the recovery of manganese, the traditional treatment method is to use P204 or P507 for extraction to obtain a reverse manganese solution with high copper, zinc, and iron contents, and then use sulfides or extraction for recycling. The process is complex and high-purity manganese sulfate cannot be obtained; or only an extractant is used for impurity removal, and it is difficult to prepare high-purity manganese sulfate.

[0004] CN104445424A discloses a method for preparing high-purity manganese sulfate from a manganese-containing waste liquor, which uses a C272 extraction solution to extract manganese. However, the impurity content in the post-back extraction solution is relatively high, with impurities (Cu, Zn, Fe) ≤ 10 ppm and impurities (Ca, Mg) ≤ 50 ppm. Moreover, zinc needs to enter the system after back extraction, which easily causes zinc enrichment in the system and makes it difficult to control the zinc content in the reverse manganese solution during reverse manganese.

[0005] Therefore, how to recover battery-grade manganese sulfate from a manganese-containing liquor, improve the separation effect, simplify the process, and reduce costs are technical problems that need to be solved urgently. Summary of the Invention

[0006] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide a method for recovering battery-grade manganese sulfate from a manganese-containing liquor. The method provided by the present invention will not cause the formation of a third phase due to metal oxidation and hydrolysis, the extraction process is stable, the enrichment of a high-concentration manganese sulfate solution is realized, high-purity manganese sulfate crystals with qualified impurities are obtained, and the efficient recovery of manganese in a high-calcium and magnesium-containing liquor system can be achieved; moreover, no complex recovery process is required, and the cost is lower.

[0007] To achieve the purpose of this invention, the following technical solutions are adopted:

[0008] In the first aspect, the present invention provides a method for recovering battery-grade manganese sulfate from a manganese-containing liquor, and the method includes the following steps:

[0009] (1) Resin adsorption is carried out on the manganese-containing liquor to obtain nickel-cobalt adsorbate and the adsorbed liquor.

[0010] (2) The adsorbed liquor is successively subjected to extraction treatment and stripping treatment to obtain a solution containing manganese sulfate and the stripped organic phase.

[0011] (3) The solution containing manganese sulfate is subjected to evaporation crystallization to obtain battery-grade manganese sulfate.

[0012] Among them, the cations in the manganese-containing liquor include manganese ions, nickel ions, cobalt ions, calcium ions and magnesium ions, and the anions in the manganese-containing liquor include sulfate ions; the extractant used in the extraction treatment process includes HBL116 extractant.

[0013] It should be noted that the present invention does not make special restrictions on the source of the manganese-containing liquor. As long as the raw material that meets the above characteristic limitations can be used to recover manganese sulfate, the present invention is applicable; for example, the manganese-containing liquor can be selected from manganese ore liquor, the solution after high-pressure acid leaching and iron-aluminum removal of laterite nickel ore, etc.

[0014] In the present invention, nickel ions and cobalt ions in the manganese-containing liquor are adsorbed by resin to avoid the influence on the extraction of manganese sulfate in the subsequent extraction process; in cooperation with a specific HBL116 extractant, while effectively extracting manganese sulfate, this extractant will not cause the formation of a third phase due to metal oxidation and hydrolysis, and the extraction process is stable; through extraction treatment and stripping treatment, the enrichment of a high-concentration manganese sulfate solution is realized, and further through evaporation crystallization, high-purity battery-grade manganese sulfate crystals with qualified impurities are obtained; at the same time, the method for recovering battery-grade manganese sulfate provided by the present invention can realize the recovery of manganese sulfate in a manganese-containing liquor with high calcium and magnesium contents, and there is no need for an additional calcium and magnesium removal process; the recovery process is simple, the recovery efficiency is high and the cost is lower.

[0015] In the present invention, resin adsorption and subsequent specific HBL116 extractant cooperate with each other and are indispensable. Without resin adsorption or by using other extractants, such as P204 extractant, P507 extractant or C272 extractant, etc., the recovery of high-purity battery-grade manganese sulfate cannot be achieved.

[0016] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the technical objectives and beneficial effects of the present invention can be better achieved.

[0017] Preferably, the pH value of the manganese-containing feed liquid in step (1) is 4-6, such as 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9 or 6, etc.

[0018] In the present invention, adjusting the pH value of the manganese-containing feed liquid to 4-6 is not only more conducive to the resin to adsorb nickel ions and cobalt ions in the manganese-containing feed liquid, but also can improve the extraction stability during the subsequent extraction process, ensure the extraction equilibrium of the extractant (the equilibrium pH of the HBL116 extractant is 3.5-4.0), and avoid the formation of a third phase due to metal oxidation and hydrolysis, thereby effectively extracting manganese sulfate in the adsorbed feed liquid.

[0019] Preferably, the manganese-containing feed liquid in step (1) further includes other impurity ions, and the other impurity ions include any one or a combination of at least two of iron ions, chromium ions or aluminum ions.

[0020] In the manganese-containing feed liquid provided by the present invention, other impurity ions may also be included. The above impurity ions do not affect the extraction effect and the impurity content is relatively low.

[0021] Preferably, in the manganese-containing feed liquid in step (1), the content of manganese ions is 2-2.5 g / L, the content of nickel ions is 8-10 mg / L, the content of cobalt ions is 5-10 mg / L, the content of calcium ions is ≥0.4 g / L, and the content of magnesium ions is 4.5-5 g / L.

[0022] For example, the content of the manganese ions can be 2 g / L, 2.1 g / L, 2.2 g / L, 2.3 g / L, 2.4 g / L, 2.5 g / L, etc.; the content of the nickel ions can be 8 mg / L, 8.5 mg / L, 9 mg / L, 9.5 mg / L, 10 mg / L, etc.; the content of the cobalt ions can be 5 mg / L, 5.5 mg / L, 6 mg / L, 6.5 mg / L, 7 mg / L, 7.5 mg / L, 8 mg / L, 8.5 mg / L, 9 mg / L, 9.5 mg / L, 10 mg / L, etc.; the content of the calcium ions can be 0.4 g / L, 0.43 g / L, 0.45 g / L, 0.48 g / L, 0.5 g / L, etc.; the content of the magnesium ions can be 4.5 g / L, 4.6 g / L, 4.7 g / L, 4.8 g / L, 4.9 g / L, 5 g / L, etc.

[0023] The method for recovering battery-grade manganese sulfate provided by the present invention can realize the recovery of manganese-containing feed liquid with high calcium content and high magnesium content, and there is no need for additional calcium removal and magnesium removal processes. Through resin adsorption and extraction with a specific extractant, the efficient enrichment of manganese sulfate can be achieved.

[0024] Preferably, in the manganese-containing feed liquid in step (1), the content of each ion among other impurity ions is independently ≥ 1 mg / L, such as 1 mg / L, 1.1 mg / L, 1.2 mg / L, 1.3 mg / L, 1.4 mg / L, 1.5 mg / L, 1.6 mg / L, 1.7 mg / L, 1.8 mg / L, 1.9 mg / L, 2 mg / L, etc.

[0025] Preferably, the resin used in the resin adsorption process in step (1) includes an ion exchange resin, and the ion exchange resin includes resin LSC-930.

[0026] In the present invention, an ion exchange resin is selected for the adsorption of nickel and cobalt, which is more conducive to the removal of nickel and cobalt metals in the feed liquid and realizes the separation of manganese from nickel and cobalt.

[0027] Further preferably, the resin is soaked in sodium hydroxide with a mass fraction of 3-5% (such as 3%, 3.5%, 4%, 4.5%, 5%, etc.) for 1-5 h (1 h, 2 h, 3 h, 4 h, 5 h, etc.) for activation, and then the resin is rinsed with pure water until the pH of the rinsing water is 7.

[0028] In the present invention, the resin is first subjected to an activation treatment, and the purpose is to remove the impurities therein. For example, a new ion exchange resin often contains reaction solvents, unreacted substances, a small amount of low molecular weight polymers, impurities such as iron, lead, and copper. Therefore, after the activation treatment, the adsorption effect can be further improved.

[0029] When the ion exchange resin has been used for a period of time and the adsorbed impurities are close to the saturation state, activation treatment can also be carried out. Sodium hydroxide with a mass fraction of 3-5% can still be used to elute the ions and other impurities adsorbed by the resin, so that it can be restored to its original composition and performance, so as to achieve the purpose of its reuse and cost reduction.

[0030] Preferably, in the resin adsorption process of step (1), the adsorption rate of the manganese-containing feed liquid is 3-4 BV / h, such as 3 BV / h, 3.1 BV / h, 3.2 BV / h, 3.3 BV / h, 3.4 BV / h, 3.5 BV / h, 3.6 BV / h, 3.7 BV / h, 3.8 BV / h, 3.9 BV / h or 4 BV / h, etc.

[0031] In the present invention, during the regulation of the resin adsorption process, the adsorption rate of the manganese-containing feed liquid is preferably selected from 3-4 BV / h (i.e., the flow rate of the manganese-containing feed liquid through the resin adsorption column), so as to further effectively reduce the nickel and cobalt contents in the manganese-containing feed liquid and achieve the efficient separation of nickel and cobalt from manganese.

[0032] Preferably, in the feed liquid after adsorption in step (1), the contents of nickel ions and cobalt ions are both <0.1 mg / L.

[0033] In the resin adsorption process of the present invention, the feed liquid after adsorption is detected every 2-3 hours until the contents of nickel ions and cobalt ions in the feed liquid after adsorption both meet the target of <0.1 mg / L, and then the adsorption can be stopped.

[0034] Preferably, in step (2), the volume ratio of the feed liquid after adsorption to the extraction phase is (3-4):1, such as 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1 or 4:1, etc., and the extraction phase includes the HBL116 extractant.

[0035] In step (2) of the present invention, by regulating the volume ratio of the feed liquid after adsorption to the extraction phase to be (3-4):1, the extraction rate of manganese in the feed liquid can be better improved, and the manganese content in the raffinate will be reduced to the lowest.

[0036] Preferably, the extraction phase further includes an auxiliary agent, and the auxiliary agent includes a diluent and / or a saponifying agent.

[0037] More preferably, in the extraction treatment process of the present invention, in addition to the HBL116 extractant, a diluent and a saponifying agent can also be added to the extraction phase; the diluent includes kerosene, and the saponifying agent includes liquid caustic soda.

[0038] More preferably, the dilution rate of the diluent is 40% - 50%, such as 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49% or 50%, etc., and the saponification rate of the saponifying agent is 50% - 60%, such as 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59% or 60%, etc.

[0039] Preferably, the extraction stage of the extraction treatment in step (2) is 8 - 9 stages, such as 8 stages or 9 stages.

[0040] Preferably, in step (2), after the extraction treatment, a first loaded organic phase and a raffinate are obtained.

[0041] Preferably, the first loaded organic phase is subjected to a washing treatment to obtain a second loaded organic phase and wash water, and the second loaded organic phase is subjected to a stripping treatment.

[0042] More preferably, the detergent used in the washing treatment includes an acid solution, and the concentration of the acid solution is selected from 0.015 - 0.5 mol / L, such as 0.015 mol / L, 0.02 mol / L, 0.05 mol / L, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L or 0.5 mol / L, etc.

[0043] In the present invention, an acid solution is selected for the washing treatment of the first loaded organic phase, further removing other impurities in the first loaded organic phase except for the main element of manganese removal. The target element manganese in the washing solution will return to the extraction section for continuous extraction and recovery; it should also be noted that the acid solution in the present invention includes but is not limited to at least one of hydrochloric acid solution, sulfuric acid solution or nitric acid solution.

[0044] More preferably, the volume ratio of the first loaded organic phase to the washing solution used in the washing treatment is 1:(0.1 - 0.2), such as 1:0.1, 1:0.11, 1:0.12, 1:0.13, 1:0.14, 1:0.15, 1:0.16, 1:0.17, 1:0.18, 1:0.19 or 1:0.2, etc.

[0045] More preferably, the washing stage of the washing treatment is 7 - 8 stages, such as 7 stages or 8 stages.

[0046] Preferably, the stripping solution in the stripping treatment process of step (2) includes an acid solution; the concentration of the acid solution is 1-5 mol / L, such as 1 mol / L, 1.1 mol / L, 1.2 mol / L, 1.3 mol / L, 1.4 mol / L, 1.5 mol / L, 1.6 mol / L, 1.7 mol / L, 1.8 mol / L, 1.9 mol / L, 2 mol / L, 2.1 mol / L, 2.2 mol / L, 2.3 mol / L, 2.4 mol / L, 2.5 mol / L, 3 mol / L, 3.5 mol / L, 4 mol / L, 4.5 mol / L or 5 mol / L, etc.

[0047] Furthermore:

[0048] In the stripping treatment process of step (2), when the acid in the acid solution is selected from dibasic acids, such as sulfuric acid, the concentration of the acid solution is 1-2.5 mol / L.

[0049] In the stripping treatment process of step (2), when the acid in the acid solution is selected from monobasic acids, such as hydrochloric acid or nitric acid, the concentration of the acid solution is 2-5 mol / L.

[0050] In the present invention, using an acid solution for stripping treatment is more conducive to effectively stripping the metal in the second loaded organic phase into the aqueous phase; and further limiting the concentration of the acid solution to 1-5 mol / L is a selection based on the acid resistance of the extractant, which can better exert the stripping effect.

[0051] Preferably, in the stripping treatment process of step (2), the volume ratio of the second loaded organic phase to the stripping solution is 1:(0.05-0.1), such as 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09 or 1:0.1, etc.

[0052] Preferably, in the stripping treatment process of step (2), the number of stripping stages is 10-13 stages, such as 10 stages, 11 stages, 12 stages or 13 stages, etc.

[0053] Preferably, the temperature of the evaporation crystallization in step (3) is 95-110 °C, such as 95 °C, 96 °C, 97 °C, 98 °C, 99 °C, 100 °C, 101 °C, 102 °C, 103 °C, 104 °C, 105 °C, 106 °C, 107 °C, 108 °C, 109 °C or 110 °C, etc.

[0054] Preferably, the time of evaporation crystallization is 50-60 min, such as 50 min, 51 min, 52 min, 53 min, 54 min, 55 min, 56 min, 57 min, 58 min, 59 min or 60 min, etc.

[0055] Preferably, after the evaporation crystallization in step (3), solid-liquid separation and drying are sequentially performed on the evaporation crystallization slurry to obtain battery-grade manganese sulfate.

[0056] It can be understood that the present invention does not specifically limit the specific method of solid-liquid separation, and any method that can separate the crystallization product of evaporation crystallization from the solvent in the slurry is applicable to the present invention; for example, filtration treatment or centrifugation treatment, etc.

[0057] For example, centrifugation can be used for solid-liquid separation. During the centrifugation process, the centrifugal speed can be selected from 1000 to 3000 rpm, such as 1000 rpm, 1500 rpm, 2000 rpm, 2500 rpm or 3000 rpm, etc., and the centrifugation time can be 20 to 40 min, such as 20 min, 25 min, 30 min, 35 min or 40 min, etc.

[0058] As a preferred technical solution, the method includes the following steps:

[0059] (1) Adsorb a manganese-containing feed liquid with a pH value of 4 to 6 using an ion exchange resin to obtain a nickel-cobalt adsorbate and an adsorbed feed liquid. In the adsorbed feed liquid, the contents of nickel ions and cobalt ions are both < 0.1 mg / L;

[0060] (2) Perform 8 to 9 stages of extraction treatment on the adsorbed feed liquid using an extraction liquid containing HBL116 extractant. The volume ratio of the adsorbed feed liquid to the extraction liquid is (3 to 4):1 to obtain a first loaded organic phase and a raffinate;

[0061] Wash the first loaded organic phase to obtain a second loaded organic phase and wash water;

[0062] Perform 10 to 13 stages of stripping treatment on the second loaded organic phase using an acid solution stripping liquid with a concentration of 1 to 5 mol / L. The volume ratio of the second loaded organic phase to the stripping liquid is 1:(0.05 to 0.1) to obtain a solution containing manganese sulfate and a stripped organic phase;

[0063] (3) Evaporate and crystallize the solution containing manganese sulfate at a temperature of 95 to 110 °C, and sequentially perform solid-liquid separation and drying on the evaporation crystallization slurry to obtain battery-grade manganese sulfate;

[0064] Among them, in the manganese-containing feed liquid described in step (1), the content of manganese ions is 2-2.5 g / L, the content of nickel ions is 8-10 mg / L, the content of cobalt ions is 5-10 mg / L, the content of calcium ions is ≥ 0.4 g / L, the content of magnesium ions is 4.5-5 g / L, and the content of each ion among other impurity ions is independently ≥ 1 mg / L; the other impurity ions include any one or a combination of at least two of iron ions, chromium ions or aluminum ions; the anions in the manganese-containing feed liquid include sulfate ions.

[0065] The numerical ranges described in the present invention not only include the point values exemplified above, but also include any point values between the above numerical ranges not exemplified. Due to space limitations and for the sake of brevity, the specific point values included in the ranges of the present invention are not exhaustively listed herein.

[0066] Compared with the prior art, the present invention has the following beneficial effects:

[0067] In the present invention, the nickel ions and cobalt ions in the manganese-containing feed liquid are adsorbed by the resin to avoid the influence on the extraction of manganese sulfate in the subsequent extraction process; a specific HBL116 extractant is used in a coordinated manner. This extractant can effectively extract manganese sulfate without causing the formation of a third phase due to metal oxidation and hydrolysis, and the extraction process is stable; through extraction treatment and stripping treatment, the enrichment of a high-concentration manganese sulfate solution is achieved, and further through evaporation and crystallization, battery-grade manganese sulfate crystals with qualified impurities and high purity are obtained; at the same time, the method for recovering battery-grade manganese sulfate provided by the present invention can realize the recovery of manganese sulfate from a manganese-containing feed liquid with high calcium and magnesium contents without the need for additional calcium and magnesium removal processes; the recovery process is simple, the recovery efficiency is high and the cost is lower. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] Figure 1 It is a process flow diagram of the method for recovering battery-grade manganese sulfate from a manganese-containing feed liquid provided in Example 1. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0069] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0070] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in this application are intended to cover non-exclusive inclusion.

[0071] In the description of this application, technical terms such as "first" and "second" are only used to distinguish different objects, and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity, specific order or primary-secondary relationship of the indicated technical features. In the description of the embodiments of this application, the meaning of "a plurality" is more than two, unless otherwise clearly and specifically defined.

[0072] In a specific embodiment, the present invention provides a manganese-containing feed liquid for battery-grade manganese sulfate to be recycled, and the specific components of the manganese-containing feed liquid are shown in Table 1.

[0073] Table 1

[0074]

[0075] The anions in the manganese-containing feed liquid include sulfate ions.

[0076] The following examples and comparative examples all use the manganese-containing feed liquid provided in the above specific embodiment to carry out the recovery treatment of manganese sulfate.

[0077] Example 1

[0078] This example provides a method for recovering battery-grade manganese sulfate from a manganese-containing feed liquid, as Figure 1 shown, the method is as follows:

[0079] (1) Adjust the pH value of the manganese-containing feed liquid to 4.8 - 5.0, and then use commercial resin LSC-930 (the resin is soaked in 4% sodium hydroxide for 2 h for activation, and then the resin is rinsed with pure water until the pH of the rinsing water is 7) to adsorb the manganese-containing feed liquid at a column passing rate of 3 BV / h. During the adsorption treatment, the metal concentration of the adsorbed feed liquid is detected every 2 h until the adsorption is stopped when the nickel and cobalt in the adsorbed feed liquid are < 0.1 mg / L. The composition of the adsorbed tail liquid is shown in Table 2, and nickel-cobalt adsorbate and the adsorbed feed liquid are obtained;

[0080] (2) First, prepare the extraction phase: Use HBL116 extractant, the diluent is kerosene, and the saponifying agent is liquid alkali to obtain an extraction liquid with a dilution rate of 40% and a saponification rate of 50%;

[0081] The extraction phase and the loaded liquor after adsorption are mixed at a volume ratio of 1:3 for extraction treatment. The number of extraction stages is 9 to obtain a first loaded organic phase and a raffinate. The first loaded organic phase is washed with a 0.13 mol / L sulfuric acid solution at a volume ratio of the first loaded organic phase to the sulfuric acid solution of 1:0.1 to elute other cation impurities except manganese in the first loaded organic phase. The number of washing stages is 8 to obtain a second loaded organic phase and wash water (the wash water can be recycled). The metal in the washed second loaded organic phase is stripped with 1.25 mol / L sulfuric acid. The volume ratio of the second loaded organic phase to the sulfuric acid solution is 1:0.1, and the number of stripping stages is 13 to obtain a solution containing manganese sulfate (the composition is shown in Table 3 below) and the stripped organic phase (the stripped organic phase can be recycled after being washed with water and regenerated).

[0082] (3) The solution containing manganese sulfate is added to a water bath for evaporation crystallization at a temperature of 95 °C and an evaporation time of 60 min. Then, it is filtered to obtain a solid product, which is dried in an oven at 100 °C to obtain a battery-grade manganese sulfate product, and the sample is sent for element detection. The results are shown in Table 4.

[0083] Example 2

[0084] The difference between this example and Example 1 is that in step (2) of this example, an extraction phase with a dilution rate of 50% and a saponification rate of 60% is prepared.

[0085] The remaining recovery methods and parameters are the same as those in Example 1.

[0086] Example 3

[0087] The difference between this example and Example 1 is that in step (2) of this example, the concentration of sulfuric acid is 0.5 mol / L during the washing of the first loaded organic phase.

[0088] The remaining recovery methods and parameters are the same as those in Example 1.

[0089] Example 4

[0090] This example provides a method for recovering battery-grade manganese sulfate from a manganese-containing liquor, and the method is as follows:

[0091] (1) The pH value of the manganese-containing liquor is adjusted to 4 - 4.1, and then the manganese-containing liquor is adsorbed with commercial resin LSC-930 (the resin is activated by soaking it in 3% sodium hydroxide for 2 h and then rinsing the resin with pure water until the pH of the wash water is 7) at a column passing rate of 4 BV / h. During the adsorption process, the metal concentration of the loaded liquor is detected every 2 h until the adsorption is stopped when the nickel and cobalt in the loaded liquor are <0.1 mg / L. The composition of the tail liquor after adsorption is shown in Table 2 to obtain a nickel-cobalt adsorbent and the loaded liquor after adsorption.

[0092] (2) First, prepare the extraction phase: Use HBL116 extractant, kerosene as the diluent, and liquid alkali as the saponifier to obtain an extraction phase with a dilution rate of 40% and a saponification rate of 50%.

[0093] Mix the extraction phase with the adsorbed feed liquid in a volume ratio of 1:4 for extraction treatment. The number of extraction stages is 8 to obtain the first loaded organic phase and the raffinate. Wash the first loaded organic phase with a 0.13 mol / L sulfuric acid solution in a volume ratio of the first loaded organic phase to the sulfuric acid solution of 1:0.2 to elute other cation impurities except manganese in the first loaded organic phase. The number of washing stages is 7 to obtain the second loaded organic phase. Use 2.5 mol / L sulfuric acid to strip the metals in the washed second loaded organic phase. The volume ratio of the second loaded organic phase to the sulfuric acid solution is 1:0.05, and the number of stripping stages is 10 to obtain a solution containing manganese sulfate (the composition is shown in Table 3 below) and the stripped organic phase.

[0094] (3) Add the solution containing manganese sulfate to a water bath for evaporation crystallization at a temperature of 110 °C for an evaporation time of 50 min. Then filter to obtain a solid product, and dry it in an oven at 100 °C to obtain a battery-grade manganese sulfate product, and send a sample for element detection. The results are shown in Table 4.

[0095] Example 5

[0096] This example provides a method for recovering battery-grade manganese sulfate from a manganese-containing feed liquid. The method is as follows:

[0097] (1) Adjust the pH value of the manganese-containing feed liquid to 5.8 - 6, and then use commercial resin LSC-930 (soak the resin in 5% sodium hydroxide for 2 h for activation, and then rinse the resin with pure water until the pH of the washing water is 7) to adsorb the manganese-containing feed liquid at a column passing rate of 3.5 BV / h. During the adsorption process, take the adsorbed feed liquid to detect the metal concentration every 2 h until the adsorption is stopped when the nickel and cobalt in the adsorbed feed liquid are <0.1 mg / L. The composition of the adsorbed tail liquid is shown in Table 2 to obtain nickel-cobalt adsorbate and the adsorbed feed liquid.

[0098] (2) First, prepare the extraction phase: Use HBL116 extractant, kerosene as the diluent, and liquid alkali as the saponifier to obtain an extraction phase with a dilution rate of 40% and a saponification rate of 50%.

[0099] The extraction phase and the leaching solution after adsorption are mixed at a volume ratio of 1:3.5 for extraction treatment. The number of extraction stages is 9 to obtain the first loaded organic phase and the raffinate. The first loaded organic phase is washed with a 0.3 mol / L sulfuric acid solution at a volume ratio of the first loaded organic phase to the sulfuric acid solution of 1:0.15 to elute other cation impurities except manganese in the first loaded organic phase. The number of washing stages is 8 to obtain the second loaded organic phase. The metals in the washed second loaded organic phase are stripped with 1.25 mol / L sulfuric acid at a volume ratio of the second loaded organic phase to the sulfuric acid solution of 1:0.08. The number of stripping stages is 11 to obtain a solution containing manganese sulfate (the composition is shown in Table 3 below) and the stripped organic phase.

[0100] (3) The solution containing manganese sulfate is added to a water bath for evaporation crystallization at a temperature of 105 °C and an evaporation time of 55 min. Then, it is filtered to obtain a solid product, which is dried in an oven at 100 °C to obtain a battery-grade manganese sulfate product, and the sample is sent for elemental detection. The results are shown in Table 4.

[0101] Example 6

[0102] The difference between this example and Example 1 is that in step (1) of this example, the pH value of the manganese-containing leaching solution is 3.5.

[0103] The remaining recovery methods and parameters are the same as those in Example 1.

[0104] Example 7

[0105] The difference between this example and Example 1 is that in step (1) of this example, the pH value of the manganese-containing leaching solution is 6.5.

[0106] The remaining recovery methods and parameters are the same as those in Example 1.

[0107] Example 8

[0108] The difference between this example and Example 1 is that in step (1) of this example, the manganese-containing leaching solution is subjected to adsorption treatment at a column passing rate of 2 BV / h.

[0109] The remaining recovery methods and parameters are the same as those in Example 1.

[0110] Example 9

[0111] The difference between this example and Example 1 is that in step (1) of this example, the manganese-containing leaching solution is subjected to adsorption treatment at a column passing rate of 5 BV / h.

[0112] The remaining recovery methods and parameters are the same as those in Example 1.

[0113] Example 10

[0114] The difference between this embodiment and Embodiment 1 is that in step (2) of this embodiment, the extraction phase and the material liquid after adsorption are mixed at a volume ratio of 1:2 for extraction treatment.

[0115] The remaining recovery methods and parameters are the same as those in Embodiment 1.

[0116] Embodiment 11

[0117] The difference between this embodiment and Embodiment 1 is that in step (2) of this embodiment, the extraction phase and the material liquid after adsorption are mixed at a volume ratio of 1:5 for extraction treatment.

[0118] The remaining recovery methods and parameters are the same as those in Embodiment 1.

[0119] Embodiment 12

[0120] The difference between this embodiment and Embodiment 1 is that in step (2) of this embodiment, after the extraction treatment, the washing treatment is not carried out, that is, the first loaded organic phase is directly subjected to stripping treatment.

[0121] The remaining recovery methods and parameters are the same as those in Embodiment 1.

[0122] Embodiment 13

[0123] The difference between this embodiment and Embodiment 1 is that in step (2) of this embodiment, the number of extraction stages is 7.

[0124] The remaining recovery methods and parameters are the same as those in Embodiment 1.

[0125] Embodiment 14

[0126] The difference between this embodiment and Embodiment 1 is that in step (2) of this embodiment, the number of extraction stages is 10.

[0127] The remaining recovery methods and parameters are the same as those in Embodiment 1.

[0128] Comparative Example 1

[0129] The difference between this comparative example and Embodiment 1 is that in this comparative example, step (1) is not carried out, and the manganese-containing material liquid is directly subjected to step (2).

[0130] The remaining preparation methods and parameters are the same as those in Embodiment 1.

[0131] Comparative Example 2

[0132] The difference between this comparative example and Embodiment 1 is that the extractant in step (2) of this comparative example is P204 extractant.

[0133] The remaining preparation methods and parameters are the same as those in Embodiment 1.

[0134] Table 2 shows the composition table (unit: mg / L) of the liquid after adsorption in Examples 1-14 and Comparative Examples 1-2 after step (1).

[0135] Table 2

[0136]

[0137]

[0138] Table 3 shows the composition table (unit: mg / L) of the manganese sulfate-containing solution in Examples 1-14 and Comparative Examples 1-2 after step (2).

[0139] Table 3

[0140]

[0141]

[0142]

[0143] Table 4 shows the composition table (unit: mass percentage %) of the battery-grade manganese sulfate recovered in Examples 1-14 and Comparative Examples 1-2.

[0144] Table 4

[0145]

[0146]

[0147] Note: HG / T 4823-2015 in Table 4 is the standard value of battery-grade manganese sulfate in the chemical industry standard.

[0148] In summary, in the present invention, the nickel ions and cobalt ions in the manganese-containing liquid are adsorbed by the resin to avoid the influence on the extraction of manganese sulfate in the subsequent extraction process; the specific HBL116 extractant is synergistically used, which can effectively extract manganese sulfate and will not cause the formation of a third phase due to metal oxidation and hydrolysis, and the extraction process is stable; through extraction treatment and stripping treatment, the enrichment of a high-concentration manganese sulfate solution is achieved, and further through evaporation and crystallization, battery-grade manganese sulfate crystals with qualified impurities and high purity are obtained; at the same time, the method for recovering battery-grade manganese sulfate provided by the present invention can realize the recovery of manganese sulfate in the manganese-containing liquid with high calcium and magnesium contents, and there is no need for an additional calcium and magnesium removal process; the recovery process is simple, the recovery efficiency is high and the cost is lower.

[0149] The applicant declares that the above description is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A method for recovering battery-grade manganese sulfate from a manganese-containing liquid, characterized in that: The method comprises the following steps: (1) subjecting a manganese-containing feed liquid to resin adsorption to obtain a nickel-cobalt adsorbate and a feed liquid after adsorption; (2) subjecting the adsorbed feed liquid to extraction treatment and stripping treatment in sequence to obtain a solution containing manganese sulfate and an organic phase after stripping; (3) evaporating and crystallizing the solution containing manganese sulfate to obtain battery-grade manganese sulfate; Among them, the cations in the manganese-containing solution include manganese ions, nickel ions, cobalt ions, calcium ions and magnesium ions, and the anions in the manganese-containing solution include sulfate ions; the extractant used in the extraction process includes HBL116 extractant.

2. The method for recovering battery-grade manganese sulfate from a manganese-containing liquid according to claim 1, characterized in that: The pH value of the manganese-containing solution in step (1) is 4-6.

3. The method for recovering battery-grade manganese sulfate from a manganese-containing liquid according to claim 1, characterized in that: The manganese-containing liquid in step (1) further comprises other impurity ions, wherein the other impurity ions comprise any one of iron ions, chromium ions or aluminum ions, or a combination of at least two thereof; Preferably, in the manganese-containing solution of step (1), the content of manganese ions is 2 to 2.5 g / L, the content of nickel ions is 8 to 10 mg / L, the content of cobalt ions is 5 to 10 mg / L, the content of calcium ions is ≥0.4 g / L, and the content of magnesium ions is 4.5 to 5 g / L; Preferably, in the manganese-containing solution of step (1), the content of each of the other impurity ions is independently ≥ 1 mg / L.

4. The method for recovering battery-grade manganese sulfate from a manganese-containing liquid according to claim 1, characterized in that: The resin used in the resin adsorption process of step (1) includes an ion exchange resin, and the ion exchange resin includes resin LSC-930; Preferably, during the resin adsorption process in step (1), the adsorption rate of the manganese-containing liquid is 3 to 4 BV / h; Preferably, in the slurry after the adsorption in step (1), the contents of nickel ions and cobalt ions are both less than 0.1 mg / L.

5. The method for recovering battery-grade manganese sulfate from a manganese-containing liquid according to claim 1 or 2, characterized in that: In step (2), the volume ratio of the adsorbed feed liquid to the extraction phase is (3-4):1, and the extraction phase includes HBL116 extraction agent; Preferably, the extraction phase further comprises an auxiliary agent, and the auxiliary agent comprises a diluent and / or a saponifier; Preferably, the extraction stage number of the extraction treatment in step (2) is 8 to 9.

6. The method for recovering battery-grade manganese sulfate from a manganese-containing liquid according to claim 1, characterized in that: In step (2), after the extraction treatment, a first loaded organic phase and a raffinate are obtained; Preferably, the first loaded organic phase is subjected to a washing treatment to obtain a second loaded organic phase and washing water, and the second loaded organic phase is subjected to a stripping treatment.

7. The method for recovering battery-grade manganese sulfate from a manganese-containing liquid according to claim 6, characterized in that: The stripping solution in the stripping process of step (2) comprises an acid solution; the concentration of the acid solution is 1 to 5 mol / L; Preferably, during the stripping treatment in step (2), the volume ratio of the second loaded organic phase to the stripping liquid is 1:(0.05-0.1); Preferably, in the stripping treatment process of step (2), the stripping stage number is 10 to 13.

8. The method for recovering battery-grade manganese sulfate from a manganese-containing liquid according to claim 1, characterized in that: The temperature of the evaporation crystallization in step (3) is 95-110° C., and the time of the evaporation crystallization is 50-60 min.

9. The method for recovering battery-grade manganese sulfate from a manganese-containing liquid according to claim 1, characterized in that: After the evaporation and crystallization in step (3), the evaporated crystal slurry is sequentially subjected to solid-liquid separation and drying to obtain battery-grade manganese sulfate.

10. The method for recovering battery-grade manganese sulfate from a manganese-containing liquid according to claim 1, characterized in that: The method comprises the following steps: (1) subjecting a manganese-containing feed liquid having a pH value of 4 to 6 to ion exchange resin adsorption to obtain a nickel-cobalt adsorbate and a feed liquid after adsorption, wherein the contents of nickel ions and cobalt ions in the feed liquid after adsorption are both less than 0.1 mg / L; (2) subjecting the adsorbed feed liquid to 8-9 levels of extraction treatment using an extraction phase containing an HBL116 extractant, wherein the extraction phase also includes a diluent and a saponifier, and the volume ratio of the adsorbed feed liquid to the extraction phase is (3-4):1, to obtain a first loaded organic phase and a raffinate; Washing the first loaded organic phase to obtain a second loaded organic phase and washing water; The second loaded organic phase is subjected to 10 to 13 levels of stripping treatment using an acid solution stripping solution with a concentration of 1 to 5 mol / L, and the volume ratio of the second loaded organic phase to the stripping solution is 1:(0.05 to 0.1), to obtain a solution containing manganese sulfate and an organic phase after stripping; (3) evaporating and crystallizing the manganese sulfate-containing solution at a temperature of 95 to 110° C., and sequentially performing solid-liquid separation and drying on the evaporated crystal slurry to obtain battery-grade manganese sulfate; In the manganese-containing solution of step (1), the content of manganese ions is 2-2.5 g / L, the content of nickel ions is 8-10 mg / L, the content of cobalt ions is 5-10 mg / L, the content of calcium ions is ≥0.4 g / L, the content of magnesium ions is 4.5-5 g / L, and the content of each ion in other impurity ions is independently ≥1 mg / L; the other impurity ions include any one of iron ions, chromium ions or aluminum ions or a combination of at least two thereof; and the anions in the manganese-containing solution include sulfate ions.

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