WO2011065682A2 - Method for producing cmb catalyst recycled with lithium ion battery and ternary cathode materials - Google Patents

Abstract

The present invention relates to recovery of cobalt and manganese from waste battery materials, and a method for making liquid catalysts from recovered Co-Mn-Br (CMB). More specifically, lithium-ion powder and ternary cathode materials are produced by leaching scrap battery materials with sulfate reduction, and sequential application of the following three process steps: neutralization titration, solid-liquid separation and solvent extraction, leads to recovery of cobalt and manganese as a liquid extract comprised of a Co-Mn-Br catalyst. According to the present invention, a CMB liquid phase catalyst that is useful for application in various manufacturing processes is provided by recovery of cobalt and manganese from waste ternary cathode and lithium-ion battery materials, enhancing the removal of other impurities, and recovering high purity cobalt and manganese.

Description

[Name of invention given by ISA under Rule 37.2] Method for producing CMC catalyst from lithium ion battery and ternary cathode active material

The present invention relates to a method for recovering cobalt and manganese from waste battery materials, and to a method for producing a Co-Mn-Br liquid catalyst using the same, more specifically, in the process of manufacturing waste lithium ion battery powder and ternary cathode active material. Cobalt and manganese recovery method characterized by recovering cobalt and manganese by sequentially applying a sulfuric acid reduction leaching, neutralization titration, solid-liquid separation, solvent extraction and water washing process to the generated scrap, and the cobalt and It relates to a method for preparing a Co-Mn-Br liquid catalyst using an extract containing manganese.

Lithium secondary batteries, which have recently increased in usage among lithium batteries, are composed of a cathode, an anode, an organic electrolyte, and an organic separator. In addition, lithium cobalt oxide, which has excellent reversibility, low self discharge rate, high capacity and high energy density, and is easily synthesized, is commercially available as a positive electrode active material.

In particular, lithium-ion batteries are widely used as a power source for small portable devices due to their light weight, and in recent years, demand for them has increased in proportion to the explosion of mobile communication terminals. In addition, as the demand for lithium ion batteries increases, the amount of generated lithium ion batteries is also rapidly increasing.

This waste lithium ion battery is simple in appearance and contains a large amount of valuable metals such as lithium and cobalt, which are relatively expensive as a cathode active material, and thus, it is recognized as an economically valuable waste resource and requires recycling. However, in the case of a lithium ion battery employing lithium cobalt oxide as a cathode active material, valuable metals such as cobalt and lithium should be recycled, and for efficient recycling of lithium ion batteries, not only efficient recovery of valuable metals but also recycling of waste lithium batteries Hazardous wastes generated should be properly disposed of.

In particular, during the mechanical treatment of waste lithium ion batteries, metal lithium is oxidized while reacting violently with water, which can be very dangerous. Therefore, in order to efficiently recover cobalt from waste lithium ion batteries, it is necessary to provide stable mechanical treatment and minimize harmful components. It is important.

Currently, the commercialization trend of positive electrode active materials in lithium ion batteries is moving from LiCoO ₂ to ternary positive electrode active materials. In particular, as the use of lithium ion batteries increases and diversifies (hybrid cars, electric cars, robots, energy storage, etc.) As the demand for lithium ion batteries using ternary cathode active materials is expected to increase exponentially, development of corresponding recycling technologies is required.

CMB liquid catalyst is a catalyst composed of Co-Mn-Br, and is used as a catalyst for producing TPA (Terephthalic Acid) by oxidizing para-xylene, one of petrochemical products. In addition, TPA becomes a raw material for polyester fiber, PET (Polyethylene Terephthalate) bottles, films, paints, and tire cords that are closely related to our lives. Korea is a major producer of TPA. In 2006, domestic TPA production amounted to 5.5 million tons. The market for CMB catalysts is huge. Therefore, by recovering Co and Mn from the waste containing Co and Mn discarded in the process, it is possible to economically produce a CMB catalyst.

Accordingly, the present inventors have made diligent efforts to develop an efficient cobalt and manganese recovery method from scrap generated during the production of waste lithium ion batteries and ternary cathode active materials. When the separation) and solvent extraction and water washing processes were sequentially applied, it was confirmed that the high-purity cobalt and manganese from which impurities were removed were recovered, and that the CMB liquid catalyst could be prepared using the same, thereby completing the present invention. It became.

It is an object of the present invention to provide a method for recovering cobalt and manganese from scrap generated during the production of waste lithium ion batteries and ternary cathode active materials, and a Co-Mn-Br liquid phase using an extract containing cobalt and manganese obtained by the above method. It is to provide a method for producing a catalyst.

In order to achieve the above object, the present invention comprises the steps of: (a) leaching with respect to the spent battery material using sulfuric acid and a reducing agent; (b) neutralizing the leaching solution obtained in step (a) to remove impurities; (c) solid-liquid separation of the leaching solution obtained in step (b) into a solution and a residue; (d) extracting by adding a solvent to the solution liquid-separated in step (c); And (e) provides a method for recovering cobalt and manganese comprising the step of washing the extract obtained in step (d).

The present invention also comprises the steps of: (f) adding a HBr solution to the extract obtained in the recovery method of cobalt and manganese, back extraction to obtain a Co-Mn-Br stripping solution; And (g) adding a cobalt salt and a manganese salt to the Co-Mn-Br stripping solution to adjust an appropriate concentration to prepare a Co-Mn-Br liquid catalyst using cobalt and manganese recovered from a waste battery material. Provide a method.

1 is a process chart for the preparation of Co-Mn-Br-based liquid catalyst.

FIG. 2 is a schematic diagram of a recovery simulation test of major elements using 40% saponification solvent of 0.7M Cyanex 272. FIG.

3 is a schematic diagram of the recovery simulation test of the main elements using 45% saponification solvent of 0.85M Cyanex 272.

The present invention in one aspect, (a) leaching with respect to the spent battery material using sulfuric acid and a reducing agent; (b) neutralizing the leaching solution obtained in step (a) to remove impurities; (c) solid-liquid separation of the leaching solution obtained in step (b) into a solution and a residue; (d) extracting by adding a solvent to the solution liquid-separated in step (c); And (e) relates to a method for recovering cobalt and manganese comprising the step of washing the extract obtained in step (d).

In the present invention, the waste battery material may be scrap generated in the process of manufacturing the waste lithium ion battery and the ternary cathode active material.

In the present invention, the waste lithium ion battery may be in a powder state, it is preferable to use a powder of 8 mesh or less in the method of the present invention.

The waste lithium ion battery powder may be obtained by a physical treatment method of Korean Patent No. 860972, which is a prior patent of the present inventors.

In the present invention, the waste battery material may be a cathode material rejected material or a cathode active material scrap generated in the process of manufacturing a lithium ion battery cathode material, and ternary cathode by separating into a powder form through simple crushing and heat treatment. It may be recovered as an active material powder.

The waste battery material contains a large amount of impurities in addition to valuable metals such as cobalt and lithium. Therefore, in order to remove impurities from the solution obtained after leaching the waste battery material using sulfuric acid and a reducing agent in step (a), neutralization titration is performed.

The reducing agent may be H ₂ , H ₂ S, SO ₂ , FeSO ₄ , coal (pyal) or pyrite (Pyrite), preferably H ₂ O ₂ may be used.

In the present invention, the neutralization titration of step (b) is a calcium compound selected from the group consisting of CaO, Ca (OH) ₂ and CaCO ₃ ; Alkaline solution which is NaOH or NH ₄ OH; And it can be adjusted to pH 5.5 ~ 6.5 by a material selected from the group consisting of a mixture thereof, preferably CaCO ₃ can be used.

Impurities that can be removed from the leaching solution by neutralization titration may be selected from the group consisting of Fe, Cu, Al and mixtures thereof, but is limited to impurities other than recyclable valuable metals such as Co and Mn. It doesn't happen.

In the present invention, the solid-liquid separation of step (c) can be separated into a solution and a residue using a filter press or filter paper, and the solid-liquid separation means can be easily selected by those skilled in the art.

In the present invention, the solvent used in the step (d) is di-2-ethyl hexyl phosporic acid, 2-ethyl hexyl phosphonic acid, mono-2-ethyl hexyl ester, di-2,4,4- trimethyl penthyl phosphonic acid, di-2-ethyl hexyl phosphinic acid, di-2,4,4-trimethyl penthyl dithiophosphinic acid and di-2,4,4-trimethyl penthyl monothiophosphinic acid The di-2-ethyl hexyl phosporic acid solvent may be used.

The solvent is preferably saponified by an alkaline solution, and in this case, 30 to 60% saponified solvent may be used, and preferably 40 to 50% saponified solvent may be used to increase the recovery rate of cobalt and manganese and to remove impurities. Occurrence can be minimized. In addition, saponifying the solvent used during the solvent extraction can prevent the pH change during solvent extraction to increase the efficiency of solvent extraction.

For example, cobalt and manganese extraction scheme (1) using bis (2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272, Cytec Inc., USA) as a solvent is shown below. Wherein X is Co or Mn and R is C ₁₆ H ₃₄ PO ₂ ^— .

X ²⁺ + 2HR ↔ XR ₂ + 2H ⁺ (1)

In this case, the Cyanex 272 has a molecular weight of 290, viscosity 142cp (25 ℃), specific gravity 0.92gm / cc (24 ℃) and purity of 85%, the molecular formula is C ₁₆ H ₃₄ PO ₂ H, has the same structure as formula (I).

(I)

(I)

As the reaction of Scheme (1) proceeds, the pH of the solid-liquid separated solution of step (c) decreases, so that the solvent used for extracting the solvent using an alkaline solution such as NaOH, NH ₄ OH, etc. to suppress the pH decrease. After saponification (Scheme (2)), it was used for solvent extraction (Scheme (3)).

HR + NaOH (or NH ₄ OH) ↔ NaR (or NH ₄ R) + H ₂ O (2)

X ²⁺ + NaR (or NH ₄ R) ↔ XR ₂ + 2Na ⁺ (or 2NH ₄ ⁺ ) (3)

Scheme (2) is a reaction formulating the saponification process of the solvent, and the H ⁺ ions of the solvent is replaced with Na ⁺ or NH ₄ ⁺ ions, and thus when cobalt or manganese ions are extracted by the solvent as in Scheme (3) In addition, since the Na ⁺ or NH ₄ ⁺ ions substituted in the reaction scheme (2) are discharged into the solution phase, it is possible to prevent the pH change of the solution.

The water washing step of step (e) of the present invention is a ratio of O / A (Organic / Aqueous) to the solvent extracted using a distilled water of 50 ℃ to 70 ℃ in a condition of 10: 1 to 1:10 It can be washed within minutes, and preferably, using distilled water at 60 ° C. under O / A (Organic / Aqueous) condition of 2: 1.

In another aspect, (f) adding a HBr solution to the extract obtained in the recovery method of cobalt and manganese, back extraction to obtain a Co-Mn-Br stripping solution; And (g) adding a cobalt salt and a manganese salt to the Co-Mn-Br stripping solution to adjust an appropriate concentration to prepare a Co-Mn-Br liquid catalyst using cobalt and manganese recovered from a spent battery material. It is about.

In the present invention, the 'extraction solution' may be mixed with 'extraction solvent' or 'extraction solvent' extracted by Cyanex 272, and the extraction solvent used in the Co-Mn-Br liquid catalyst preparation method is cobalt and manganese. The extract obtained in step (d) or step (e) of the recovery method can be used as the starting solvent.

In the present invention, the waste battery material may be scrap generated in the process of manufacturing the waste lithium ion battery and the ternary cathode active material.

In the present invention, the waste lithium ion battery may be in a powder state, it is preferable to use a powder of 8 mesh or less in the method of the present invention.

The Co-Mn-Br stripping solution obtained by the reverse extraction (removal) step of the present invention may be used as a Co-Mn-Br liquid catalyst, and thus the content of each component may not reach an appropriate amount. Thus, a stripping solution may be obtained using an HBr solution. Thereafter, an appropriate concentration of cobalt salt and manganese salt may be further mixed with the stripping solution to achieve a proper content ratio of the Co-Mn-Br liquid catalyst.

In the step (g), the cobalt salt and manganese salt may be CoBr ₂ (Cobalt bromide), MnBr ₂ (Maganese Bromide) and Mn (OAc) ₂ (maganese acetate), to prepare a Co-Mn-Br liquid catalyst. The amount of cobalt, manganese, and bromine in the first Co-Mn-Br stripping solution was added so that the amount of Co, Mn, and Br, which are the CMB liquid catalyst components, was 0.51 M, 1.09 M, and 1.91 M, respectively. Can be determined.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention. .

Example 1: Preparation of Solvent Extraction Feed Solution

Regarding the scrap generated during the production of waste lithium ion battery powder and ternary cathode active material, using a mixed solution of 2 M H ₂ SO ₄ solution and reducing agent 5 ~ 6 vol% H ₂ O ₂ as a leaching solution, Reducing sulfuric acid leaching of the scrap generated during the production of 8 mesh waste lithium ion battery powder and ternary cathode active material at a reaction temperature of 60 ° C., a reaction rate of 200 to 250 rpm, a solid solution ratio of 1:10 and a reaction time of 1 hr. .

In this case, the waste lithium ion battery powder was obtained by physical treatment as disclosed in Korean Patent No. 860972, and the scrap generated in the process of manufacturing the ternary positive electrode active material is formed in the form of powder through simple crushing and heat treatment. Separated and used in powder form.

In order to prepare the sulfuric acid leaching solution as a solvent extraction feed solution, 150 mL of 50% CaCO ₃ solution and 25 mL of 4M NaOH solution were added to 500 mL of the leaching solution, neutralized and titrated with stirring at 400 rpm at room temperature, and then the pH was adjusted to 5.5-6. Then, the solid-liquid separation was carried out by a filter press to remove residues containing impurities and to prepare a solvent extraction feed solution. Finally, as a result of component analysis of the solvent extraction feed solution obtained by adjusting the pH of the leaching solution, Cu, It was confirmed that Fe and Al were completely removed (Table 1).

Table 1 Composition of components with controlled impurities by adjusting pH of leachate (mg / L) Raw material Co Ni Li Mn Cu Fe Al pH Waste Lithium Ion Battery 19850 45.75 6120 212 3.532 0.768 0.248 7.01 Pulmonary Ternary Bipolar Active Material 8890 12620 6060 12950 - - - 6.08

Example 2: Solvent Extraction of Co and Mn from Waste Lithium Ion Battery

* For the solvent extraction feed solution obtained from the leachate of the waste lithium ion battery powder of Example 1, using Cyanex 272 solvent, the following experiment to select the optimal Co and Mn selective extraction conditions including the degree of saponification and the number of washes Was performed.

2-1. Co and Mn extraction with 40% and 50% saponified solvents of 0.7M Cyanex 272

For the solvent extraction feed solution derived from the waste lithium ion battery obtained in Example 1, 0.7 M bis (2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272, Cytec Inc., saponified to 40% and 50% using NaOH). , USA) was mixed with an organic phase of 0 / A (Organic / Aqueous) = 2: 1 (40 ml: 20 ml) and subjected to one extraction with stirring at 25 ° C. for 5 min.

TABLE 2 Composition of Solvent Extraction Feed Solution (mg / L) Raw material Co Ni Li Mn Cu Fe Al pH Waste Lithium Ion Battery 19850 45.75 6120 212 3.532 0.768 0.248 7.01

As a result, for the components of the initial solvent extraction feed solution of [Table 2], according to the degree of saponification, Co, Ni, Li, Mn, Cu components were extracted with Raffinate as shown in [Table 3]. As a result, the extraction rates of Co and Mn according to the degree of saponification of 0.7M Cyanex 272 were 68.7% and 93.2% at 40% saponification conditions, and 80.7% and 94.5% at 50% saponification conditions (Table 4). In addition to the impurities Cu and Al showed a very high extraction rate, but because the content in the solution is about 1-2 ppm is not significant.

TABLE 3 Composition of Raffinate after Solvent Extraction (mg / L) Saponification degree Co Ni Li Mn Cu Fe Al pH 40% 6220 49.87 6180 14.43 0.72 1.041 0 4.28 50% 3835 49.79 5970 11.56 0.591 1.022 0.142 4.48

Table 4 Extraction rate of valuable metals according to degree of saponification (%) Saponification degree Co Ni Li Mn Cu Fe Al 40% 68.7 -9.0 -1.0 93.2 79.6 -35.5 100.0 50% 80.7 -8.8 2.5 94.5 83.3 -33.1 42.7

With respect to the solvent extracted in the above process, by further washing, it was observed how much the extraction rate is improved. Washing conditions of the extracted solvent was stirred for 1 minute using distilled water at 60 ℃ under conditions of O / A = 2: 1 (40ml: 20ml) and repeated three times.

As a result, it was confirmed that residual Ni and Li were completely removed through three washes for both the extraction solvent using 40% and 50% saponified solvent (Tables 5 and 6).

Table 5 Residual Valuable Metal Concentration (40 mg / L) with 40% Saponified Solvent Extraction 40% saponification Co Ni Li Mn Cu Fe Al pH 1 time wash 220 One 356 One 0 0 0 4.78 2 washes 90 0 5 0 0 0 0 4.9 3 washes 70 0 0 0 0 0 0 4.97

Table 6 Residual valuable metal concentration (mg / L) according to the number of washing after 50% saponified solvent extraction 50% saponification Co Ni Li Mn Cu Fe Al pH 1 time wash 487 2 190 One 0 0 0 4.97 2 washes 105 0 9 0 0 0 0 4.88 3 washes 56 0 One 0 0 0 0 5.12

2-2. Preparation of Stripping Solution Using HBr Solution

With respect to the extraction solvent extracted by 0.7M Cyanex 272 saponified in Example 2-1, 2M HBr solution to have a mixing ratio of O / A = 4: 1, and then stripped once with stirring for 5 minutes. As a result, the removal efficiencies of Co and Mn from the extraction solvents obtained at 40% saponification conditions were 79.3% and 85.3%, respectively. The removal efficiencies of Co and Mn of the extraction solvents obtained at 50% saponification conditions were 85.2% and 79.4%. It was confirmed (Tables 7 and 8).

TABLE 7 Component Composition (mg / L) of Stripping Solution Using 2M HBr Solution from Extraction Solvent Saponification degree Co Ni Li Mn Cu Fe Al Na Ca Sum of impurities 40% 21630 0.126 0 337.2 1.387 0.556 0.554 8.42 3.29 14.333 50% 27290 0.046 0.107 318.3 1.246 0.544 0.432 2.15 2.621 7.146

Table 8 % Removal using 2M HBr solution from extractant Saponification degree Co Ni Li Mn Cu Fe Al 40% 79.3 -1.5 0.0 85.3 24.7 -101.8 111.7 50% 85.2 -0.6 0.0 79.4 21.2 -107.1 203.8

Example 3: Solvent Extraction of Co and Mn from Waste Ternary Cathode Active Material Leachate

For the solvent extraction feed solution obtained from the waste ternary cathode active material leaching solution of Example 1, the following experiment was performed to select the optimal Co and Mn selective extraction conditions including the degree of saponification and the number of washings using a Cyanex 272 solvent. It was.

3-1. Co and Mn extraction with 40%, 45% and 50% saponified solvents of 0.85M Cyanex 272

For the solvent extraction feed solution derived from the waste ternary positive electrode active material leaching solution obtained in Example 1, 0.85 M bis (2,4,4-trimethyl pentyl) phosphinic acid saponified to 40%, 45% and 50% using NaOH. Cyanex 272, Cytec Inc., USA) was mixed with organic phase at a ratio of 0 / A (Organic / Aqueous) = 2: 1 (40ml: 20ml) and extracted once with stirring at 25 ° C for 5 min. Was implemented.

Table 9 Composition of Feed Solution (mg / L) origin Co Ni Li Mn pH Pulmonary Ternary Bipolar Active Material 8890 12620 6060 12950 6.08

As a result, Co, Ni, Li, Mn, Cu components were extracted with Raffinate as shown in [Table 10] for the components of the initial solvent extraction feed solution of [Table 9] according to different degree of saponification. As a result, the extraction rates of Co and Mn according to the saponification degree of 0.85M Cyanex 272 were 56.7%, 78.8% at 40% saponification condition, 62.1% at 8% saponification condition, 84.6%, and 77.4% at 50% saponification condition. The extraction rate of Co and Mn was found to increase with the increase of saponification. However, Li, which is an impurity, was extracted with 4% under 40% saponification, 3.5% under 45% saponification, and 11.7% under 50% saponification (Table 11).

Table 10 Composition of Raffinate after Solvent Extraction (mg / L) Saponification degree Co Ni Li Mn pH 40% 3845 13260 5820 2741 4.18 45% 3371 12630 5850 1995 4.19 50% 2010 16970 5350 705 4.77

Table 11 Extraction rate of valuable metals according to degree of saponification (%) Saponification degree Co Ni Li Mn 40% 56.7 -5.1 4.0 78.8 45% 62.1 -0.1 3.5 84.6 50% 77.4 -34.5 11.7 94.6

For the solvent extracted by the above process, by further washing, it was observed how much the extraction rate is improved. Washing conditions of the extracted solvent was stirred for 1 minute using distilled water at 60 ℃ under conditions of O / A = 2: 1 (40ml: 20ml), it was repeated three times.

As a result, it was confirmed that residual Ni and Li were relatively completely removed by three washings with respect to the extraction solvent using 40% saponified solvent, and three washing with the extraction solvent using 45% and 50% saponification solvent. It was confirmed that impurities were removed (Tables 12, 13 and 14).

Table 12 Residual Valuable Metal Concentration (40 mg / L) with 40% Saponified Solvent Extraction 40% saponification Co Ni Li Mn pH 1 time wash 255 341 183 131 4.56 2 washes 91 22 11 43 4.61 3 washes 64 One 0 32 4.63

Table 13 Residual valuable metal concentration (mg / L) according to the number of washes after extracting 45% saponified solvent (mg / L) 45% saponification Co Ni Li Mn pH 1 time wash 279 410 39 102 4.51 2 washes 98 32 3 38 4.85 3 washes 70 2 0 26 4.86

Table 14 Residual valuable metal concentration (mg / L) according to the number of washing after 50% saponified solvent extraction 50% saponification Co Ni Li Mn pH 1 time wash 140 355 175 57 4.99 2 washes 75 24 11 24 4.97 3 washes 56 3 One 18 4.96

3-2. Preparation of Stripping Solution Using HBr Solution

For the extraction solvent extracted with 0.85M Cyanex 272 saponified in Example 3-1, 2M HBr solution was allowed to have a mixing ratio of O / A = 4: 1, and then stripped once with stirring for 5 minutes. As a result, the stripping efficiency of Co and Mn at 40% saponification condition was 97% and 84.4%, respectively, 86.9% and 100.7% at 45% saponification condition, and one stage at stripping reaction at 50% saponification condition. In the stripping, complete stripping was not carried out, and stripping liquid was obtained by performing two-stage stripping, and the stripping efficiency of Co and Mn in two-stage stripping was confirmed to be 100% and 92.2% (Tables 15 and 16).

Table 15 Extraction Components (mg / L) Using 2M HBr Solution from Extraction Solvent Saponification degree Co Ni Li Mn Na pH Sum of impurities 40% 9789 0.089 0.047 17230 1.79 -0.51 1.926 45% 9587 1.908 0.138 22070 2.42 -0.03 4.466 50% 13834.2 4.003 0.153 22578 8.07 -0.17 12.226

Table 16 % Removal using 2M HBr solution from extractant Saponification degree Co Ni Li Mn 40% 97.0 0.0 0.0 84.4 45% 86.9 0.0 0.0 100.7 50% 100.5 0.0 0.0 92.2

Example 3 Preparation of CMB Liquid Catalyst from Stripping Solution

To prepare a CMB liquid catalyst from the stripping solution (Co-Mn-Br stripping solution) prepared in Examples 2-2 and 3-2, the components of the CMB liquid catalyst (CMB spec.) And the stripping solution of the prepared stripping solution were prepared. It was measured using ion chromatography and ICP (Table 17).

Table 17 Component analysis of the prepared stripping solution (mg / L) Co Mn Br Li Ni CMB spec. 30 g / L 60 g / L 153 g / L <10 mg / L <10 mg / L 0.7M 40% 21630 337.2 66400 0 0.126 0.7M 50% 27290 318.3 68300 0.107 0.046 0.85M 40% 9789 17230 66500 0.047 0.089 0.85M 45% 9587 22070 60100 0.138 1.908

As a result, the cobalt bromide, manganese bromide and manganese acetate were added to prepare the CMB liquid catalyst from the stripping solution, which is an intermediate product of the CMB liquid catalyst, because each component contained in the stripping solution was insufficient in forming the CMB liquid catalyst. It was prepared by. The amount required to prepare the CMB liquid catalyst is different depending on the extraction conditions, and according to the component analysis was added to the concentration of Co-Mn-Br in the concentration of [Table 18] to the same as the CMB spec.

Table 18 Cobalt and Manganese Salts Used in the Preparation of CMB Catalysts (mol) mol Number of moles of metal in solution Confiscation of necessary cobalt and manganese salts Co Mn Br CoBr ₂ MnBr ₂ Mn (OAc) ₂ CMB spec. 0.51 1.09 1.91 - - - 0.7M 40% 0.37 0.006 0.83 0.14 0.69 0.40 0.7M 50% 0.46 0.006 0.85 0.05 0.60 0.48 0.85M 40% 0.17 0.31 0.83 0.34 0.58 0.19 0.85M 45% 0.16 0.40 0.75 0.35 0.46 0.23

Experimental Example 1: Co and Mn extraction efficiency simulation test according to the degree of saponification of the solvent

1 -1. Simulation of Co and Mn Extraction Efficiency from Waste Lithium-ion Battery

For the solvent extraction feed solution obtained from the leachate of the waste lithium ion battery powder of Example 1, Co and Mn extraction efficiency simulation tests were performed according to the saponification degree of the 0.7 M Cyanex 272 (Cytec Inc., USA) solvent. All solvent extraction and stripping process was carried out under O / A = 2: 1 (40ml: 20ml), 25 ℃ stirring conditions of 5 minutes.

As a result of 2 step count-current extraction simulation extraction using 40% saponified solvent of 0.7M cyanex 272, Co extraction rate was 99.6% and Mn was 93.3%. In the case of one-stage extraction, Co was 6.9%, Mn was 79.9%, and both Li and Ni showed negative extraction ratios. Finally, the amounts of Co and Mn exiting raffinate were 89.3 mg / L and 0.542 mg / L, respectively (Tables 19 and 20, Fig. 2).

Table 19 2 step count-current simulation extraction with 40% saponified solvent (mg / L) Loading Co Ni Li Mn Cu Fe Al pH 1-stage Raffinate 18480 55.12 6180 42.55 0.991 0.881 0.456 3.93 2-stage Raffinate 89.3 108 6580 0.542 0.235 1.03 0.088 5.43

Table 20 2 step count-current simulation extraction using 40% saponified solvent Loading Co Ni Li Mn Cu Fe Al 1st stage extraction rate 6.9 -20.5 -1.0 79.9 71.9 -14.7 -83.9 2-stage extraction rate 99.6 -136.1 -7.5 99.7 93.3 -34.1 64.5

1-2. Simulation of Co and Mn Extraction Efficiency from Waste Ternary Cathode Active Material Leachate

The solvent extraction feed solution obtained from the waste ternary positive electrode active material leaching solution of Example 1 was subjected to a simulation test of Co and Mn extraction efficiency according to the saponification degree of the solvent of 0.85M Cyanex 272 (Cytec Inc., USA). All solvent extraction and stripping process was carried out under O / A = 2: 1 (40ml: 20ml), 25 ℃ stirring conditions of 5 minutes.

Two-step count-current extraction simulation extraction using 45% saponified solvent of 0.85M cyanex 272 showed that the extraction rate of Co was 99.8% and Mn was extracted 100%. In the case of one-stage extraction, Co was -14.1%, Mn was 55.2%, and in the case of impurity Ni, it was confirmed that it was not extracted at all because it showed negative extraction rate, but Li was extracted 0.3%. there was. The amounts of Co and Mn exiting the final Raffinate were 17.48 mg / L and 1.179 mg / L, respectively, and the total amount of Li extracted was found to be 18 mg / L (Tables 21 and 22, FIG. 3).

Table 21 Results of 2 step count-current simulation extraction experiment using 45% saponified solvent (mg / L) Loading Co Ni Li Mn pH 1-stage Raffinate 10146 16958 6157 5795 3.89 2-stage Raffinate 17.48 15783 6042 1.179 5.8

Table 22 2 step count-current simulation extraction using 45% saponified solvent (%) Loading Co Ni Li Mn 1st stage extraction rate -14.1 -34.4 -1.6 55.2 2-stage extraction rate 99.8 -25.1 0.3 100.0

In conclusion, in the case of the pH control solution of the lithium ion battery leachate, it was possible to selectively extract Co and Mn under 0.7M Cyanex 272 40% saponified condition, and the extraction rate was 99.6% for Co and 93.3% for Mn. Could confirm. In addition, Co and Mn were extracted under the saponified conditions of 0.85M Cyanex 272 45% of waste ternary cathode active material leachate. The extraction rates were 99.8% and 100%, respectively.

Having described the specific parts of the present invention in detail, it is apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, thereby not limiting the scope of the present invention. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

According to the present invention, while recovering cobalt and manganese from scrap generated during the production of waste lithium ion batteries and ternary cathode active materials, by increasing the removal rate and recovery of impurities, high-purity cobalt and manganese can be recovered, the recovery solution Is useful as a raw material for the production of CMB liquid catalysts.

Claims (10)

A method for recovering cobalt and manganese from spent battery materials, comprising the following steps: (a) leaching sulfuric acid with a reducing agent to the spent battery material; (b) neutralizing the leaching solution obtained in step (a) to remove impurities; (c) solid-liquid separation of the leaching solution obtained in step (b) into a solution and a residue; (d) extracting by adding a solvent to the solution separated from the solid-liquid separated in step (c); And (e) washing the extract obtained in step (d). The method of claim 1, wherein the waste battery material is scrap lithium ion battery powder or a method of producing a scrap generated during the ternary cathode active material. The method of claim 1, wherein the neutralization titration of step (b) is selected from the group consisting of CaO, Ca (OH) ₂ and CaCO ₃ ; Alkaline solution which is NaOH or NH ₄ OH; And it is adjusted to pH 5.5-6.5 by the substance chosen from the group which consists of these mixtures. The method of claim 1, wherein the impurity of step (b) comprises selecting from the group consisting of Fe, Cu, Al, and mixtures thereof. The method of claim 1, wherein the solvent used in the solvent extraction of step (d) is di-2-ethyl hexyl phosporic acid solvent, 2-ethyl hexyl phosphonic acid solvent, mono-2-ethyl hexyl ester solvent, di -2,4,4-trimethyl penthyl phosphinic acid solvent, di-2-ethyl hexyl phosphinic acid solvent, di-2,4,4-trimethyl penthyl dithiophosphinic acid solvent, di-2,4,4-trimethyl penthyl monothiophosphinic acid solvents and mixtures thereof. The method of claim 5, wherein the solvent is saponified by an alkaline solution. 6. The method of claim 5, wherein the solvent is a 30-50% saponified solvent. A process for preparing a Co-Mn-Br liquid catalyst using cobalt and manganese recovered from a spent battery material, comprising the following steps: (f) adding an HBr solution to the extract obtained in claim 1 and back extracting to obtain a Co-Mn-Br stripping solution; And (g) adding cobalt salt and manganese salt to the Co-Mn-Br stripping solution to adjust an appropriate concentration. The method of claim 8, wherein the waste battery material is a waste lithium ion battery powder or a method for producing a Co-Mn-Br liquid catalyst, characterized in that the scrap generated in the process of manufacturing a ternary cathode active material. The method of claim 8, wherein the extract obtained in step 1 of step (f) is obtained in step (d) or step (e) of claim 1.

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