Manufacturing method for waste sagger peeling material, waste sagger peeling material and method for recovering lithium by using same

Abstract

The present invention relates to a manufacturing method for waste sagger peeling material, comprising the steps of: separating, from waste sagger, a lithium-containing layer that includes a degraded layer and an attached layer; crushing the lithium-containing layer; and sorting a crushed lithium-containing layer powder, wherein, in the step of sorting a lithium-containing layer powder, a powder having a D90 particle diameter of 100 μm or less is selected or a powder having a whiteness of 83 or less is selected.

Description

Method for producing a wastewater treatment product, wastewater treatment product, and method for recovering lithium using the same

[0001] The present invention relates to a method for producing a wastewater treatment product, a wastewater treatment product, and a method for recovering lithium using the same.

[0002] The cathode active material for secondary batteries is manufactured by mixing lithium hydroxide (LiOH·H2O) with NCM or NCMA-based metal oxides and then conducting a sintering reaction at a high temperature of approximately 1,000°C. The reaction vessel containing the mixed material is a ceramic box, commonly referred to as a box sagger.

[0003] Lithium hydroxide is used in somewhat excessive quantities in the production of cathode active materials. Continuous and repeated high-temperature calcination reactions degrade physical resistance and cause diffusion and erosion of lithium, a raw material for cathode active materials, into the refractory material. Consequently, the lifespan of the refractory material is shortened, and periodic replacement of the refractory material is required at intervals of approximately 30 to 60 days.

[0004] Waste box saggers, which are inevitably generated after use, are currently being disposed of due to a lack of recycling technology. The rapid demand for secondary batteries is expected to lead to a sharp increase in the amount of waste box saggers generated. Therefore, the development of a method for recycling waste box saggers is urgently needed.

[0005] The present invention aims to provide a method for producing a waste endocardium peel material capable of recycling waste endocardium by utilizing a lithium source of waste endocardium.

[0006] In addition, the present invention seeks to provide a waste slag stripping material capable of recovering lithium, including a lithium source from waste slag, and in particular, recovering lithium by replacing a portion of lithium ore.

[0007] In addition, the present invention aims to provide a method for recovering lithium by using the aforementioned endocardial desquamation material.

[0008] The present invention provides a method for producing a waste endocarp peel, comprising the steps of: separating a lithium-containing layer including an altered layer and an adhesion layer from a waste endocarp; crushing the lithium-containing layer; and selecting a powder of the crushed lithium-containing layer; wherein the step of selecting the lithium-containing layer powder selects a powder having a D90 particle size of 100 ㎛ or less, or a powder having a whiteness of 83 or less.

[0009] In addition, the present invention provides a pulmonary cyst exfoliation product comprising a powder of a modified layer of a pulmonary cyst and an adhesion layer of a pulmonary cyst, and having a D90 particle size of 100 μm or less.

[0010] In addition, the present invention provides a pulmonary cyst exfoliation product comprising a powder of a modified layer of a pulmonary cyst and an adhesion layer of a pulmonary cyst, and having a whiteness of 83 or less.

[0011] In addition, the present invention provides a method for recovering lithium, comprising the steps of: preparing a waste slag peel having a D90 particle size of 100 ㎛ or less or a whiteness of 83 or less; calcining the waste slag peel; roasting the calcined waste slag peel with sulfuric acid; leaching lithium from the roasted waste slag peel to obtain a leaching slurry; and separating the leaching slurry into solid and liquid; wherein the waste slag peel includes an altered layer of the waste slag and a powder of an attached layer of the waste slag.

[0012] In addition, the present invention provides a method for recovering lithium, comprising the steps of: preparing a waste slag strip having a D90 particle size of 100 ㎛ or less or a whiteness of 83 or less; preparing an ore containing lithium; mixing the lithium-containing ore and the waste slag strip to obtain a mixture; calcining the mixture; roasting the calcined mixture with sulfuric acid; leaching lithium from the sulfuric acid-roasted mixture to obtain a leach slurry; and separating the leach slurry into solid and liquid; wherein the waste slag strip includes an altered layer of the waste slag and an attached layer powder of the waste slag.

[0013] The method for manufacturing a waste endocardium slag peeling material according to the present invention has excellent environmental advantages because it can recover the lithium-containing layer of waste endocardium slag that was previously discarded.

[0014] Furthermore, the spodumene concentrate according to the present invention contains lithium, making it advantageous in terms of lithium recovery. Furthermore, it can replace existing spodumene concentrates, offering significant advantages in both price and environmental aspects.

[0015] In addition, the method for recovering lithium according to the present invention can recover lithium using the waste spodumene peel recovered from the waste spodumene, and in particular, can replace the existing spodumene concentrate, so it has excellent advantages in both price and environmental aspects.

[0016] Figure 1 is an image showing the external appearance of the layers of the pulmonary artery.

[0017] FIG. 2 is a diagram showing the results of XRD analysis of a pulmonary fibrosis exfoliation material according to some embodiments of the present invention.

[0018] FIG. 3 is a diagram showing the particle size distribution of the crushed adhesion layer, the deteriorated layer, and the original layer according to some embodiments of the present invention.

[0019] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention. The present invention is defined solely by the scope of the claims set forth below.

[0020] In the present invention, when it is said that a member is located “on” another member, this includes not only cases where a member is in direct contact with another member, but also cases where another member is interposed between the two members.

[0021] When a part of the present invention is said to "include" a certain component, this does not mean that other components are excluded, but rather that other components may be included, unless otherwise specifically stated.

[0022]

[0023] <Method for producing a lung cancer exfoliant>

[0024] One aspect of the present invention relates to a method for producing a waste endocarp peel, comprising the steps of: separating a lithium-containing layer including an altered layer and an adhered layer from a waste endocarp; crushing the lithium-containing layer; and selecting a powder of the crushed lithium-containing layer, wherein the step of selecting the lithium-containing layer powder selects a powder having a D90 particle size of 100 ㎛ or less, or a powder having a whiteness of 83 or less.

[0025]

[0026] During the manufacturing process of the positive electrode active material, the affected layer of the slag crucible, which is formed by surface erosion / reaction, contains a large amount of lithium, which is the main raw material of the positive electrode active material. It mainly exists in the form of LiAlO2 or Li4SiO4 due to the reaction between the slag crucible and lithium compounds. This affected layer causes cracks on the surface of the crucible, which reduces the recovery rate of the positive electrode active material after its manufacture, or causes problems such as a decrease in quality due to the mixing of slag refractory components caused by the affected layer during the manufacturing of the positive electrode active material. Therefore, the slag crucible must be discarded periodically.

[0027] However, since the discarded refractory is a high-grade lithium-containing raw material containing a large amount of lithium, the present invention devised a method for separating only the lithium-containing layer from the discarded refractory, and recovering lithium more effectively therefrom, and utilizing it as a substitute for spodumene raw material in a lithium process using ore.

[0028]

[0029] A method for manufacturing a lithium-containing layer including a deteriorated layer and an adhesion layer according to the present invention comprises a step of separating a lithium-containing layer including a deteriorated layer and an adhesion layer from a lithium-containing layer.

[0030] In one embodiment of the present invention, the step of separating the lithium-containing layer including the altered layer and the attached layer from the closed endocarp may be a step of separating the lithium-containing layer including the altered layer and the attached layer from the original layer of the closed endocarp.

[0031] The step of separating the lithium-containing layer including the altered layer and the attached layer from the original layer of the above-mentioned lung cancer can be performed by applying a physical force.

[0032] For example, the above-mentioned waste enamel can be crushed with a crusher or shearer, tapped with a tapping machine, or any general equipment that can selectively obtain a desired layer on the surface of the waste enamel, such as a high-speed surface grinder or polisher, can be used, and after obtaining the crushed material, the lithium-containing layer including the altered layer and the adhesion layer can be separated from the original layer of the waste enamel.

[0033] At this time, when crushing the above-mentioned closed-cell slurry, the size of the crushed material is not particularly limited. Specifically, if it is a size that can easily and directly separate the lithium-containing layer including the altered layer and the attached layer from the original layer of the closed-cell slurry, there is no particular limitation.

[0034] Since the composition of the components contained in the above-mentioned altered layer and the above-mentioned original layer are somewhat different, they can be easily separated by applying an appropriate physical force.

[0035]

[0036] Figure 1 is an image showing the appearance of the layers of the endolithic sulphate. Specifically, the endolithic sulphate can be divided into a primary layer, a deteriorated layer in which substances such as lithium have diffused or penetrated into the endolithic sulphate and deteriorated, and an adhesion layer formed on top of the deteriorated layer.

[0037] As can be seen in Figure 1, the original layer, the altered layer, and the attached layer can be visually confirmed, but specifically, the original layer can be classified as a layer that does not contain lithium because lithium is not substantially introduced, and the altered layer and the attached layer can be classified as layers that contain lithium.

[0038] The above-mentioned adhesion layer refers to the residual layer remaining after securing the positive electrode active material including lithium in the refractory saggar after firing. The above-mentioned altered layer is generated by the continuous diffusion of lithium into the refractory saggar and the high-temperature chemical reaction due to the repeated high-temperature firing of the positive electrode active material contained in the refractory saggar. The diffused lithium reacts with the refractory saggar raw materials to exist as LiAlO2 or Li4SiO4, and shows physicochemical differences from the original layer and the adhesion layer. Since the diffusion of lithium depends on various factors such as time and temperature, the content (wt%) of lithium present in the altered layer cannot but be relatively less than the lithium, which is the positive electrode active material source remaining in the adhesion layer. However, since the thickness of the altered layer is relatively thicker than that of the adhesion layer, the total amount of lithium may depend on the absolute amounts of the altered layer and the adhesion layer.

[0039] In short, in the present invention, the lithium-containing layer is a general term for the altered layer and the attached layer containing lithium.

[0040]

[0041] In another embodiment of the present invention, the modified layer may include at least one selected from the group consisting of LiAlO2 and Li4SiO4.

[0042] In another embodiment of the present invention, the attachment layer may include a transition metal compound containing lithium.

[0043]

[0044] The method for manufacturing a pulmonary fibrosis exfoliation material according to the present invention includes a step of crushing the lithium-containing layer.

[0045] The above shredding can be performed using a crusher or a shredder.

[0046]

[0047] The method for manufacturing a pulmonary fibrosis exfoliation material according to the present invention includes a step of selecting the crushed lithium-containing layer powder.

[0048] At this time, the step of selecting the lithium layer powder may be a step of selecting a powder having a D90 particle size of 100㎛ or less, or a step of selecting a powder having a whiteness of 83 or less.

[0049] In the present invention, the “Whiteness Index” can be calculated from the following equation 1 using Lab color coordinates.

[0050]

[0051] [Formula 1]

[0052] Whiteness [WI] = 100-[(100-L*) 2 +(a*) 2 +(b*) 2 ] 0.5

[0053]

[0054] In short, the method for manufacturing a pulmonary fibrosis exfoliation material according to the present invention may include a step of selecting a lithium-containing layer powder having a D90 particle size of 100 ㎛ or less.

[0055] Specifically, the crushed lithium-containing layer powder may contain a certain amount of the original layer powder. Since the inclusion of the original layer powder that does not contain lithium is equivalent to an impurity, it is desirable to minimize the inclusion of the original layer.

[0056] Since the above-mentioned original layer, altered layer, and adhesion layer have different stable phases within each layer, the degree of crushing will be different when crushed with the same crushing strength.

[0057] Specifically, the above-mentioned raw material layer powder has a relatively large particle size compared to the above-mentioned lithium layer powder.

[0058] Therefore, in the present invention, by selecting powder having a D90 particle size of 100㎛ or less, mixing of the raw material powder is minimized.

[0059] At this time, D90 can be defined as the particle diameter corresponding to 90% of the volume accumulation amount in the particle diameter distribution curve. The D90 can be measured using, for example, the laser diffraction method.

[0060]

[0061] The step of selecting the above lithium-containing layer powder can be performed using a vibrating screen, etc. For example, meshes having various types of particle size distributions can be used, and by using an appropriate screen of 200 mesh or more capable of selecting powders of 100 μm or less and applying vibration, lithium-containing layer powder having a D90 of 100 μm or less can be selected, but is not limited thereto.

[0062]

[0063] Alternatively, the method for manufacturing a pulmonary fibrosis exfoliation product according to the present invention may include a step of selecting a powder having a whiteness of 83 or less.

[0064] As can be seen in Figure 1, the original layer, the altered layer, and the adhesion layer can be easily distinguished with the naked eye.

[0065] Specifically, the above-mentioned altered layer and the above-mentioned adhesion layer have lower whiteness than the above-mentioned original layer, and specifically, when selecting powder having a whiteness of 83 or less, the lithium-containing layer powder can be easily selected.

[0066]

[0067] In another embodiment of the present invention, the modified layer may have a whiteness of 83 or less.

[0068] In another embodiment of the present invention, the adhesive layer may have a whiteness of 50 or less.

[0069]

[0070] The method for manufacturing a pulmonary fibrosis exfoliation product according to the present invention may include both a step of selecting a powder having a whiteness of 83 or less and a step of selecting a powder having a D90 particle size of 100 μm or less.

[0071] For example, after selecting a powder having a whiteness of 83 or less, a powder having a D90 particle size of 100㎛ or less can be selected from the powder.

[0072]

[0073] The method for manufacturing a wastewater treatment product according to the present invention has the advantage of being able to obtain a wastewater treatment product having a lower content of impurities and a higher content of lithium than when the entire wastewater treatment product is used, since the wastewater treatment product is manufactured by appropriately separating the lithium-containing layer.

[0074]

[0075] <Pulmonary spleen peeling material>

[0076] Another aspect of the present invention relates to a pulmonary cyst exfoliation product comprising a pulmonary cyst layer and an adhesion layer powder of the pulmonary cyst, and having a D90 particle size of 100 μm or less.

[0077] Specifically, another aspect of the present invention relates to a waste endocarp peel having a D90 particle size of 100 ㎛ or less, produced by a method for producing a waste endocarp peel, comprising the steps of: separating a lithium-containing layer including an altered layer and an adhesion layer from a waste endocarp; crushing the lithium-containing layer; and selecting a powder of the crushed lithium-containing layer, wherein the step of selecting the lithium-containing layer powder selects a powder having a D90 particle size of 100 ㎛ or less.

[0078] Another aspect of the present invention relates to a pulmonary cyst exfoliation product comprising a pulmonary cyst layer and an adhesion layer powder of the pulmonary cyst, and having a whiteness of 83 or less.

[0079] Specifically, another aspect of the present invention includes a step of separating a lithium-containing layer including an altered layer and an adhesion layer from a waste slag; a step of crushing the lithium-containing layer; and a step of sorting the crushed lithium-containing layer powder; wherein the step of sorting the lithium-containing layer powder relates to a waste slag peel having a whiteness of 83 or less, manufactured by a method for producing a waste slag peel having a whiteness of 83 or less.

[0080]

[0081] In short, the pulmonary fibrous tissue peeling material according to the present invention may have a D90 particle size of 100 ㎛ or less and a whiteness of 83 or less. Specifically, the pulmonary fibrous tissue peeling material according to the present invention has a D90 particle size of 100 ㎛ or less and a whiteness of 83 or less.

[0082]

[0083] The waste slag exfoliation material according to the present invention has the advantage of a high lithium content because it includes a powder of an altered layer of waste slag and an attached layer of waste slag, and therefore can be usefully used to replace and reduce the amount of spodumene, which is a major lithium raw material in an ore lithium process.

[0084]

[0085] In another embodiment of the present invention, the modified layer powder may include at least one selected from the group consisting of LiAlO2 and Li4SiO4.

[0086] In another embodiment of the present invention, the attachment layer powder may include a transition metal compound containing lithium.

[0087] In short, the pulmonary fibrosis exfoliation material according to the present invention may include a compound containing lithium.

[0088]

[0089] In another embodiment of the present invention, the pulmonary fibrosis exfoliation material may have a D50 particle size of 35 μm or less.

[0090] The above-mentioned pulmonary fibrosis exfoliation material may have a D10 particle size of 3.5㎛ or less.

[0091] At this time, D50 can be defined as a particle size corresponding to 50% of the volume accumulation amount in the particle size distribution curve, and D10 can be defined as a particle size corresponding to 10% of the volume accumulation amount.

[0092]

[0093] In another embodiment of the present invention, the modified layer may have a whiteness of 83 or less.

[0094] In another embodiment of the present invention, the adhesive layer may have a whiteness of 50 or less.

[0095]

[0096] <Method of recovering lithium>

[0097] Another aspect of the present invention relates to a method for recovering lithium, comprising the steps of: preparing a waste slag strip having a D90 particle size of 100 ㎛ or less or a whiteness of 83 or less; calcining the waste slag strip; roasting the calcined waste slag strip with sulfuric acid; leaching lithium from the roasted waste slag strip to obtain a leaching slurry; and separating the leaching slurry from solid and liquid; wherein the waste slag strip includes an altered layer of the waste slag and an attached layer powder of the waste slag.

[0098] In addition, another aspect of the present invention relates to a method for recovering lithium, comprising the steps of: preparing a waste slag strip having a D90 particle size of 100 ㎛ or less or a whiteness of 83 or less; preparing an ore containing lithium; mixing the lithium-containing ore and the waste slag strip to obtain a mixture; calcining the mixture; roasting the calcined mixture with sulfuric acid; leaching lithium from the sulfuric acid-roasted mixture to obtain a leach slurry; and separating the leach slurry into solid and liquid; wherein the waste slag strip includes an altered layer of the waste slag and an attached layer powder of the waste slag.

[0099] The method for recovering lithium according to the present invention utilizes the aforementioned waste endocarp strip, specifically, the waste endocarp strip manufactured by the aforementioned method for producing the waste endocarp strip, so that the waste endocarp can be recycled, which is desirable from an economical and environmental perspective, and has the advantage of efficiently recovering lithium.

[0100] In short, the method for recovering lithium according to the present invention may recover lithium from the aforementioned waste slag stripping material, or may recover lithium from the above-mentioned waste slag stripping material by mixing it with an ore containing lithium.

[0101] The above-mentioned contents can be applied to the above-mentioned pulmonary fibrosis.

[0102] The step of preparing the above-mentioned pulmonary cyst peeling material can apply the above-mentioned method for manufacturing the pulmonary cyst peeling material.

[0103]

[0104] In another embodiment of the present invention, the lithium-containing ore may include at least one selected from the group consisting of spodumene, petalite, lepidolite, hectorite, eucryptite, jadarite, zinnwaldite, and amblygonite.

[0105] In another embodiment of the present invention, the lithium-containing ore may be spodumene.

[0106] There is an advantage in that the above spodumene can be mixed with the high lithium content of the exfoliated spores of the lung, thereby securing an excellent lithium leaching rate and reducing costs.

[0107]

[0108] The step of obtaining a mixture by mixing the above lithium-containing ore and the above waste carbide stripping material can be obtained by mixing the above waste carbide stripping material and the above lithium-containing ore using a mixer, but is not limited thereto.

[0109] The step of preparing the above lithium-containing ore may include the step of crushing the above lithium-containing ore.

[0110] Specifically, the above lithium-containing ore can be crushed using a crusher so that the average particle size of the ore is 150 ㎛ or less, preferably 100 ㎛ or less, and more preferably 50 to 100 ㎛, but is not limited thereto.

[0111] When the average particle size of the above lithium-containing ore is crushed to satisfy the above range, mixing with the waste slag is easy, and it is more preferable in the calcination process and sulfuric acid roasting process described later.

[0112] In another embodiment of the present invention, in the step of obtaining the mixture, the endolithic slag may be mixed in an amount of 5 wt% or less based on the weight of the ore containing lithium.

[0113] In another embodiment of the present invention, in the step of obtaining the mixture, the endolithic slag may be mixed in an amount of 1.4 to 5 wt% based on the weight of the ore containing lithium.

[0114] It is preferable that the above-mentioned endothelium-containing exfoliated material be mixed within the above range because it is easy to remove impurities during the purification process.

[0115]

[0116] A step of calcining the above-mentioned waste metal or a mixture of the above-mentioned waste metal and the above-mentioned lithium-containing ore is carried out.

[0117] In the step of calcining the above-mentioned endothelium-containing material, the calcination time may be performed for 5 minutes to 5 hours, preferably 10 minutes to 3 hours.

[0118] When the above calcination time satisfies the above range, the phase transition from the α phase to the β phase of the lithium-containing ore is sufficient, and the phenomenon of the lithium leaching rate being lowered due to micro-calcination or under-calcination can be suppressed, which is preferable.

[0119]

[0120] Thereafter, a step of calcining the calcined endothelium-containing exfoliated material or mixture with sulfuric acid is included.

[0121] By calcining the calcined waste nitrate or mixture with sulfuric acid, the waste nitrate and lithium in the lithium-containing ore can be transformed into a form of a water-soluble substance.

[0122] The above sulfuric acid oxidation can be performed at a temperature range of 175 to 250°C, preferably 200 to 250°C, for 30 minutes to 2 hours, preferably 30 minutes to 1 hour.

[0123] When the sulfuric acid oxidation is performed within the above-mentioned time range at the above-mentioned temperature range, it is preferable because the oxidation time and energy consumption can be minimized.

[0124]

[0125]

[0126] Lithium is leached from the above-mentioned sulfuric acid-decomposed waste or mixture to obtain a leaching slurry.

[0127] Specifically, the above-mentioned sulfuric acid-decomposed waste or mixture can be mixed with a solvent and subjected to water leaching to obtain a leaching slurry.

[0128] The above solvent may be pure water or distilled water, but is not limited thereto.

[0129] The solvent preferably does not contain acid substances such as sulfuric acid, but this is not limited to this. A solvent free of acid substances such as sulfuric acid is preferable because it is environmentally friendly. Furthermore, even if the solvent contains a small amount of acid within a complex process, recycling it without compromising the overall production process can be economically and environmentally beneficial.

[0130]

[0131] In the step of obtaining the above-mentioned leaching slurry, the slurry may be prepared by adding an additive, but is not limited thereto.

[0132] The additive may be, for example, at least one selected from alkali metal compounds or alkaline earth metal compounds, and specifically, at least one selected from alkali metal oxides, alkali metal hydroxides, alkali metal salts, alkaline earth metal oxides, alkaline earth metal hydroxides, or alkaline earth metal salts. More specifically, the additive may be at least one selected from NaOH, Na2CO3, NaHCO3, NaCl, Na2SO4, KOH, K2CO3, KHCO3, KCl, K2SO4, Ca(OH)2, CaO, Ca(NO3)2, CaSO4, Mg(OH)2, MgO, Mg(NO3)2, MgSO4, or CaCO3.

[0133] For the above-described exfoliated lung cancer cell or mixture, the additive may be mixed in an amount ranging from 10 to 60 wt% based on weight, and specifically, may be mixed in an amount ranging from 30 to 60 wt%, but is not limited thereto.

[0134] When the above additive is mixed within the above range, it is preferable to efficiently recover lithium while minimizing the generation of subsequent pollutants.

[0135] In addition to the above additives, auxiliary additives may be additionally mixed, but are not limited thereto.

[0136] The above auxiliary additive may be a compound containing one or more metal elements selected from, for example, Al or Ca.

[0137] Specifically, the auxiliary additive may be at least one selected from among Al(OH)3, Al(NO3)3, Al2(SO4)3, AlCl3, Ca(OH)2, Ca(NO3)2, CaSO4 and its hydrates or CaCl2, but is not limited thereto.

[0138] The above auxiliary additive may be mixed in an amount of 5 to 40 wt% based on the weight of the above-described ore, but is not limited thereto.

[0139]

[0140] The solvent may be added in an amount of 1 to 4 times, preferably 1.5 to 3 times, and more preferably 2 to 3 times, by weight, relative to the amount of the exfoliated pulmonary artery spur or mixture.

[0141] When the solvent is added to satisfy the above content, it is preferable to minimize the content of the solvent while improving lithium leaching efficiency, thereby reducing the process cost.

[0142] The above lithium leaching time can be performed for 30 minutes to 5 hours, preferably 30 minutes to 4 hours, and more preferably 1 to 3 hours.

[0143] When the time for leaching the lithium satisfies the above range, it is preferable because the lithium leaching efficiency is excellent while reducing energy consumption.

[0144] At this time, the leaching of the lithium can be carried out at room temperature, and can be carried out while stirring at 50 to 500 RPM, preferably 100 to 400 RPM, and more preferably 200 to 300 RPM.

[0145] When the above lithium leaching is performed while stirring at the above stirring speed, it is preferable to maximize the lithium leaching efficiency while minimizing the lithium leaching time.

[0146]

[0147] The above leaching slurry may contain lithium and one or more impurities selected from the group consisting of Al, Si, Fe, Mg, Ca, Na, K, Ni, Co and Mn.

[0148] In short, the above-mentioned leaching slurry may contain some raw materials for lithium and cathode active materials derived from the exfoliated waste of the slag.

[0149]

[0150] Thereafter, a step of separating the solid and liquid from the above-mentioned leaching slurry is included.

[0151] The step of separating the solid and liquid of the above-mentioned leaching slurry may be a step of separating the leaching slurry into a leaching residue and a leachate in which the lithium is dissolved.

[0152] By separating the solid and liquid of the above-mentioned leachate, it can be separated into a solid leachate residue containing impurities such as Al and Si and a leachate containing lithium and Mg, Ca, Fe, Co, Mn, Ni, Na, K, etc. dissolved therein.

[0153] The present invention is not limited to the above high-liquid separation method.

[0154] For example, the solid-liquid separation may be performed using a microfilter, but is not limited thereto, and may be performed using a conventional method performed in the art.

[0155]

[0156] The method for recovering lithium from ore according to the present invention may further include a step of purifying the leachate.

[0157] The above purification may be performed two or more times, but is not limited thereto. Specifically, the purification step may include a first purification step and a second purification step.

[0158] The above purification can be performed by a method commonly performed in the art using a purification raw material, and the present invention is not limited to the above purification method.

[0159]

[0160] The method for recovering lithium according to the present invention may further include, but is not limited to, a step of concentrating the leachate.

[0161]

[0162] Hereinafter, preferred embodiments and comparative examples of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

[0163]

[0164] Analysis of the components of spodumene and lungwort

[0165] Spodumene was used as the lithium-containing ore, and N65 type (Ni content of 65% among NCM type cathode active materials) was used as the waste metal oxide.

[0166] At this time, since the phase and composition of each layer of the pulmonary rhizome differed, the differences between layers were identified through basic chemical analysis. Figure 1 shows the appearance of each layer of the pulmonary rhizome. Based on the appearance evaluation of Figure 1, the layers of the pulmonary rhizome were classified and named as the adherent layer, the altered layer, and the original layer.

[0167]

[0168] The composition (wt%) of the raw materials used in each layer is shown in Table 1 below through ICP-OES analysis. Except for the original layer of the closed-cell sphagnum moss, all the raw materials contained lithium. Furthermore, it is noteworthy that the lithium content is higher than that of spodumene ore.

[0169]

[0170] Raw material classification LiAlSiMgCaFeCoMnNiNaKSpodumene-2.4912.329.50.670.781.22---0.651.05 Waste refractory layer attached layer 6.791.050.060.55-0.028.239.9435.5--Deteriorated layer 3.0022.98.153.94-0.200.090.070.22--Original layer-34.610.67.31-0.330.090.010.004--

[0171] Referring to Fig. 1, in the case of the attached layer, it can be seen that the lithium content is relatively high, and the impurities Co, Mn, and Ni are also high, at around 8 to 35 wt%. However, since the layer is very thin, the absolute amount is estimated to be very small. In contrast, the altered layer has a relatively low lithium content compared to the attached layer, but has low positive electrode active material impurities such as Fe, Co, Ni, and Mn, excluding Mg. Therefore, the altered layer is expected to be the main lithium source of the waste metallurgy, and the influence of the impurities of the positive electrode active material is expected to be somewhat small. However, due to the high Mg content (3.94 wt%) of the altered layer, the Mg content (g / L) in the leachate is expected to be somewhat high.

[0172]

[0173] The stability of the endocardial detachment (adhesion layer and altered layer) was identified through XRD analysis, and this is shown in Figure 2.

[0174] Referring to Figure 2, for the attachment layer, the anode material mixture (LiNi 0.33 Mn 0.33 Co 0.133 [Mn,Mg] 0.1 In the case of the degenerate layer, two types of stable phases, LiAlO2 and Li4SiO4, were confirmed. It can be clearly confirmed that both phases contain lithium.

[0175]

[0176] Color and particle size analysis of lung cancer cells

[0177] The spodumene concentrate used was finely ground with an average particle size of 75 μm. For the closed spores, the layers were physically separated based on the apparent boundaries of the adherent, altered, and original layers. The separated layers were crushed using a crusher to obtain fine powder.

[0178] The colorimetric coefficient values ​​for each layer were obtained through the colorimetric analysis of the separated powder layers. The colorimetric analysis was performed using a MINOLTA Spectrophotometer (CM-3500d model). Before measuring the sample, the blackness (reference dark) and standard whiteness (reference white) of the cylinder were measured. The sample was analyzed based on the (reference) value of this reference material, and L * (Lightness), a * (Greenness to redness spectrum), b * (Blueness to yellowness spectrum) values ​​were obtained. Among the obtained coefficients, L * Since the value is the main brightness indicator of chromaticity, L * The stratification was primarily evaluated through values. In addition, the L*, a*, and b* values ​​were converted into a whiteness index (WI) using Equation 1 below, and the results are shown in Table 2 below.

[0179]

[0180] [Formula 1]

[0181] [WI] = 100-[(100-L*) 2 +(a*) 2 +(b*) 2 ] 0.5

[0182]

[0183] Category L * a * b * c * h * Whiteness Index (WI) Reference 96.82-0.16-0.25 0.30 236.71 96.81 Attached layer 42.74 0.35 3.06 3.08 83.42 42.66 Alteration layer 82.86-0.25 155.15 92.20 82.10 Original layer 84.94-0.47 5.41 5.43 94.98 83.99

[0184] L *The higher the value, the closer it is to white, L * The lower the value, the closer it is to black. According to the color analysis, the adhesion layer and the altered layer to be used should be L compared to the original layer. * It can be seen that the value is effectively low. In addition, it can be seen through the WI value that the fine particles below the level of about WI=83 are layers containing lithium. In other words, L at the level of the original layer * A value lower than the value (approximately 84) or the WI value (approximately 83) can be judged as a layer containing effective lithium.

[0185]

[0186] In addition, the particle size distribution of each layer was evaluated through particle size analysis. The particle size analysis was performed using a Malvern Mastersizer 3000. After mixing appropriately with water and injecting it in the form of a slurry, the analysis values ​​were obtained, and the results are shown in Figure 3, and the volume density (%) D10, D50, and D90 by major particle sizes are shown in Table 3.

[0187]

[0188] Classification particle size (㎛) D10 D50 D90 Adhesive layer 2.3 1 10.13 9.4 Alteration layer 2.9 9 3 2.8 125 Original layer 3.3 3 2 8.7 4 40

[0189] From the results in Figure 3 and Table 3, it can be seen that the original layer has a form of finely divided raw material with a relatively high particle size compared to the attached layer and altered layer.

[0190]

[0191] Example

[0192] The secured spore-bearing slag (adhered layer + altered layer) and spodumene raw material were uniformly mixed under specific mixing conditions. Afterwards, the homogeneously mixed samples underwent the unit processes of calcination-sulfuric acid roasting-water leaching-solid / liquid separation for lithium extraction according to the ore lithium process standard. In detail, the mixed sample was calcined using a box furnace at a heating rate of 5 K / min, maintained at a temperature of 1,000°C for 1 hour, and then cooled in the furnace to obtain a sample. The secured sample was homogeneously mixed with 98% pure sulfuric acid at a mass ratio of 30% of the amount of the calcined mixed sample. Homogenization was performed using a glass rod at least 200 times. The mixed sample was roasted in a box furnace. The temperature was increased at a rate of 5 K / min, maintained at a temperature of 250°C for 1 hour, and then cooled in the furnace to obtain a sample. Double the mass of the secured sample was used, and deionized water (DI water) was used for water leaching. Leaching was performed at room temperature for 1 hour, and continuous stirring was performed at 250 rpm using a magnetic bar during leaching. Afterwards, the leaching slurry was separated into solid and liquid using a micro filter to secure the leachate and leaching residue.

[0193]

[0194] Experimental example

[0195] Based on a mixed sample of spodumene ore and waste slag stripping, for three conditions in which spodumene was replaced with 0 wt%, 1.4 wt%, and 5 wt% of waste slag stripping in weight ratio in the entire sample, the main components (g / L) in the final lithium-containing leachate extracted were obtained through ICP-OES analysis, and the results are shown in Table 4 below.

[0196]

[0197] Conditions (replacement rate of slag sheath) LiAlSiMgCaFeCoMnNiNaKS0% Slag sheath 10.141.480.130.100.510.83---1.100.4030.61.4% Slag sheath 10.500.980.080.100.580.37-0.090.0030.930.3330.95% Slag sheath 11.541.700.050.280.580.330.0040.10.020.770.2331.6

[0198] Referring to Table 4 above, it was confirmed that the lithium (Li) content in the leachate increased from 10.14 g / L to 11.54 g / L depending on the replacement rate of the exfoliated slag. Subsequently, the content of Ni, a cathode material, increased from 0 g / L to 0.02 g / L, Mn from 0 g / L to 0.1 g / L, and Co from 0 to 0.004 g / L, but Fe decreased from 0.83 g / L to 0.33 g / L.

[0199] Al and Si, which are impurities in the ore lithium process, are expected to be preferably removed in the first purification by adjusting the pH even if the amount of waste slag stripping increases to 5 wt%. However, if the Mg content in the leachate is somewhat high, it may be difficult to remove it preferably in the second purification. In the leachate produced by the lithium recovery method according to the present invention, Mg increased from 0.1 g / L to 0.28 g / L, but it is expected that the level of Mg removal is sufficient even at 0.28 g / L with a 5 wt% waste slag stripping replacement rate. In the case of Ca, it increased from 0.51 g / L to 0.58 g / L, but it is not considered to be a noticeable increase.

[0200] Additionally, the Na and K contents affecting the crystallization process were confirmed to decrease from 1.10 g / L to 0.77 g / L and from 0.40 g / L to 0.23 g / L, respectively. This is expected to also reduce the Na and K removed to produce battery-grade lithium hydroxide.

[0201]

[0202] Through the above experimental example, it was found that when the waste spodumene concentrate is used as a substitute lithium raw material, lithium recovery is possible and the content of specific impurities is reduced.

[0203] In addition, it was possible to secure an appropriate replacement content range for the use of the exfoliated material of the lung cancer and an appropriate utilization methodology necessary for securing an effective lithium source within the lung cancer.

[0204]

[0205] The present invention is not limited to the above-described embodiments, but can be manufactured in a variety of different forms. Those skilled in the art will appreciate that the present invention can be implemented in other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. A step of separating a lithium-containing layer including a deteriorated layer and an adhesion layer from a closed cell; A step of crushing the above lithium layer; and A step of selecting the crushed lithium layer powder; Including, The step of selecting the lithium layer powder is; Select powders with a D90 particle size of 100㎛ or less, or Selecting powders with a whiteness of 83 or less, A method for producing a pulmonary fibrosis exfoliative material.

2. In paragraph 1, The step of separating the lithium layer including the deteriorated layer and the adhesion layer from the above-mentioned closed cell is as follows: A method for producing a lung cancer peeled product, the method comprising the step of separating a lithium-containing layer including the altered layer and the adhesion layer from the original layer of the lung cancer peeled product.

3. In paragraph 1, A method for manufacturing a lung cancer exfoliation product, wherein the above-mentioned modified layer comprises at least one selected from the group consisting of LiAlO2 and Li4SiO4.

4. In paragraph 1, A method for producing a pulmonary fibrosis exfoliation agent, wherein the above-mentioned adhesive layer comprises a transition metal compound containing lithium.

5. In paragraph 1, A method for manufacturing a lung cancer peeling material, wherein the above-mentioned altered layer has a whiteness of 83 or less.

6. In paragraph 1, A method for manufacturing a lung cancer peeling material, wherein the above-mentioned adhesive layer has a whiteness of 50 or less.

7. Contains powder of the modified layer of the pulmonary endocardium and the adhesion layer of the pulmonary endocardium, D90 Pulmonary cystic fibrous material with a particle size of 100㎛ or less.

8. In paragraph 7, A lung cancer exfoliation product wherein the above-mentioned modified layer powder comprises at least one selected from the group consisting of LiAlO2 and Li4SiO4.

9. In paragraph 7, A pulmonary fibrosis exfoliative agent, wherein the above-mentioned adhesive layer powder comprises a transition metal compound containing lithium.

10. In paragraph 7, D50 Pulmonary cystic fibrosis with a particle size of 35㎛ or less.

11. Contains powder of the modified layer of the pulmonary endocardium and the adhesion layer of the pulmonary endocardium, A pulmonary fibrous tissue with a whiteness of 83 or less.

12. In paragraph 11, A lung cancer exfoliation product wherein the above-mentioned modified layer powder comprises at least one selected from the group consisting of LiAlO2 and Li4SiO4.

13. In paragraph 11, A pulmonary fibrosis exfoliative agent, wherein the above-mentioned adhesive layer powder comprises a transition metal compound containing lithium.

14. In paragraph 11, The above-mentioned desquamated layer is a lung endocardium peeling material having a whiteness of 83 or less.

15. In paragraph 11, The above-mentioned adhesive layer is a lung cancer detachment material having a whiteness of 50 or less. 16.D90 Step for preparing a lung endocardial detachment having a particle size of 100㎛ or less or a whiteness of 83 or less; A step of calcining the above-mentioned endothelium-containing exfoliated material; A step of extinguishing the calcined pulmonary fibrosis exfoliation material with sulfuric acid; A step of obtaining a leaching slurry by leaching lithium from the above-described pulmonary fibrosis exfoliation material; and A step of separating the solid and liquid of the above-mentioned leaching slurry; Including, The above-mentioned pulmonary cyst detachment material includes a pulmonary cyst deterioration layer and a pulmonary cyst adhesion layer powder. Method for recovering lithium. 17.D90 Step for preparing a lung endocardial detachment having a particle size of 100㎛ or less or a whiteness of 83 or less; A step of preparing an ore containing lithium; A step of obtaining a mixture by mixing the above lithium-containing ore and the above waste slag; A step of calcining the above mixture; A step of calcining the above-mentioned mixture with sulfuric acid; A step of leaching lithium from the mixture subjected to sulfuric acid oxidation to obtain a leaching slurry; and A step of separating the solid and liquid of the above-mentioned leaching slurry; Including, The above-mentioned pulmonary cyst detachment material includes a pulmonary cyst deterioration layer and a pulmonary cyst adhesion layer powder. Method for recovering lithium.

18. In paragraph 17, A method for recovering lithium, wherein in the step of obtaining the mixture, the endolithic sequestered matter is mixed in an amount of 5 wt% or less with respect to the weight of the ore containing lithium.

19. In Article 18, A method for recovering lithium, wherein in the step of obtaining the mixture, the lithium-containing ore is mixed in an amount of 1.4 to 5 wt% based on the weight of the lithium-containing ore.

20. In paragraph 17, A method for recovering lithium, wherein the lithium-containing ore comprises at least one selected from the group consisting of spodumene, petalite, lepidolite, hectorite, eucryptite, jadarite, zinnwaldite, and amblygonite.

21. In paragraph 20, A method for recovering lithium, wherein the lithium-containing ore is spodumene.

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