A method for recycling lithium-containing waste materials

Abstract

The present application relates to a kind of resource utilization methods of lithium-containing waste, the resource utilization method includes the following steps: using hydrochloric acid to carry out acid leaching of lithium-containing waste, obtain acid leaching residue and acid leaching liquid;Using extractant extracts the obtained acid leaching liquid, obtain extract liquid and raffinate;The obtained raffinate carries out at least two times adjustment pH value, realizes the recovery of aluminum and nickel cobalt manganese element;The obtained extract liquid is back extracted, obtains lithium-rich liquid;Lithium-rich liquid is used for the preparation of lithium product after impurity removal.The resource utilization method provided by the present application can efficiently recover valuable metal elements in lithium-containing waste, avoid the generation of hazardous waste, and the acid leaching residue can be used as raw material for building materials and cement, which has high economic and environmental value;Furthermore, the use of specific extractant can also achieve efficient separation of Li and Al.

Description

Technical Field

[0001] This invention belongs to the field of battery resource recycling technology, and relates to a method for the resource utilization of battery waste, particularly a method for the resource utilization of lithium-containing waste. Background Technology

[0002] The production and use of lithium-ion batteries generate lithium-containing waste containing elements such as lithium, nickel, cobalt, and manganese. If this lithium-containing waste is not recycled, it will not only waste valuable metals but also cause environmental pollution.

[0003] Taking a crucible as an example, lithium-ion battery cathode materials commonly use crucibles as the sintering solution. During the sintering process, lithium sources such as lithium carbonate or lithium hydroxide react fully with precursors containing elements such as nickel, cobalt, and manganese to prepare the cathode material. However, in this process, the lithium source also reacts with the crucible. Due to the occurrence of side reactions, the crucible is scrapped after a certain number of uses. However, the scrapped crucible contains valuable metals such as lithium, nickel, cobalt, and manganese of high grade. Directly scrapping it would waste resources and also generate high hazardous waste disposal costs.

[0004] CN109911909A discloses a method for recycling and processing waste crucibles during the preparation of lithium cobalt oxide cathode materials, comprising: mixing waste crucibles, acid, and additives, performing a leaching reaction, and separating to obtain purified crucibles and leachate; adjusting the pH of the leachate to 2-4, and performing solid-liquid separation to obtain solid slag and separation liquid; adjusting the pH of the separation liquid to 4.5-5.5, and performing solid-liquid separation to obtain solid slag and aluminum removal liquid; adjusting the pH of the aluminum removal liquid, and performing solid-liquid separation to obtain cobalt-containing substances and cobalt precipitation liquid; adjusting the pH of the cobalt precipitation liquid, and performing solid-liquid separation to obtain solid slag and magnesium removal liquid; adding a precipitant to the magnesium removal liquid, and performing solid-liquid separation to obtain lithium-containing substances and lithium precipitation liquid.

[0005] CN109911946A discloses a method for recycling and processing waste crucibles during the preparation of lithium cobalt oxide battery materials, comprising: mixing waste crucibles, acid solution, and additives, performing a leaching reaction, separating the mixture after the reaction to obtain purified crucibles and leachate; adjusting the pH value of the leachate to separate solid slag and separation liquid; adding an aluminum removal agent to the separation liquid, crystallizing, and then separating to obtain solid slag and aluminum removal liquid; adjusting the pH value of the aluminum removal liquid to separate cobalt-containing substances and cobalt precipitation liquid; adding a magnesium removal agent to the cobalt precipitation liquid to separate solid slag and magnesium removal liquid; and adding a precipitant to the magnesium removal liquid to react and separate lithium-containing substances and lithium precipitation liquid.

[0006] The existing methods for recycling waste crucibles are cumbersome and cannot effectively recover other valuable elements besides lithium. Therefore, there is a need for a resource utilization method for lithium-containing waste that can fully recover and utilize valuable metals from lithium-containing waste. Summary of the Invention

[0007] The purpose of this invention is to provide a method for the resource utilization of lithium-containing waste. This method can efficiently recover valuable metal elements from lithium-containing waste, avoiding the generation of hazardous waste. At the same time, the acid leaching residue can be used as a raw material for building materials and cement, which has extremely high economic and environmental value. Moreover, the use of a specific extractant in this invention can also achieve efficient separation of Li and Al.

[0008] To achieve this objective, the present invention employs the following technical solution:

[0009] This invention provides a method for the resource utilization of lithium-containing waste, the method comprising the following steps:

[0010] (1) Use hydrochloric acid to leach lithium-containing waste to obtain leaching residue and leaching solution;

[0011] (2) Extract the acid leaching solution obtained in step (1) using an extractant to obtain an extract and a raffinate;

[0012] (3) The pH value of the raffinate obtained in step (2) is adjusted at least twice to achieve the recovery of aluminum, nickel, cobalt and manganese elements;

[0013] (4) The extract obtained in step (2) is back-extracted to obtain lithium-rich solution; after impurity removal, the lithium-rich solution is used for the preparation of lithium products.

[0014] Steps (3) and (4) are not in any particular order;

[0015] The extractant in step (2) includes a first component, a second component, a third component, and a diluent; the first component includes TBP (tributyl phosphate) and / or a TBP derivative; the second component includes FeCl3; and the third component includes P507 (2-ethylhexyl phosphate mono-2-ethylhexyl ester) and / or a P507 derivative.

[0016] The lithium-containing waste mentioned in this invention refers to solid waste containing lithium, nickel, cobalt, manganese and aluminum elements generated during the production and use of lithium-ion batteries. The resource utilization method provided by this invention can efficiently recover valuable metal elements from lithium-containing waste, avoiding the generation of hazardous waste. At the same time, the acid leaching residue can be used as a raw material for building materials and cement, which has extremely high economic and environmental value.

[0017] Moreover, the extractant used in the resource utilization method provided by this invention has a very good separation effect on Li and Al; by acid leaching with hydrochloric acid, good leaching effect on lithium, nickel, cobalt and manganese can be achieved under low pH conditions, and the leaching residue can be used as raw material for building materials and cement, thus realizing the efficient separation of lithium and aluminum.

[0018] Preferably, the concentration of hydrochloric acid used in step (1) is 30-35 wt%, for example, it can be 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt% or 35 wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0019] When using hydrochloric acid within a certain concentration range, this invention can achieve good leaching effects for lithium, nickel, cobalt, and manganese.

[0020] Preferably, the lithium-containing waste in step (1) includes waste crucibles.

[0021] The main materials of the sagger include cordierite, mullite, and alumina. During the preparation of lithium-ion cathode materials using saggers, lithium sources such as aluminum hydroxide and lithium carbonate react with the sagger, resulting in the presence of valuable metals such as nickel, cobalt, manganese, lithium, and aluminum in the waste saggers. Therefore, recycling the valuable metals from waste saggers can achieve sustainable resource utilization and reduce the environmental harm caused by solid waste.

[0022] Preferably, the waste crucible contains 1.8-2.2 wt% Li, 0.15-0.2 wt% Ni, 0.15-0.2 wt% Co, and 0.15-0.2 wt% Mn by mass percentage.

[0023] The content of Li element in the waste crucible is 1.8-2.2 wt% by mass, for example, it can be 1.8 wt%, 1.9 wt%, 2 wt%, 2.1 wt% or 2.2 wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0024] The content of Ni element in the waste crucible is 0.15-0.2wt% by mass, for example, it can be 0.15wt%, 0.16wt%, 0.18wt%, 0.19wt% or 0.2wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0025] The content of Co in the waste crucible is 0.15-0.2 wt% by mass, for example, it can be 0.15 wt%, 0.16 wt%, 0.18 wt%, 0.19 wt% or 0.2 wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0026] The content of Mn element in the waste crucible is 0.15-0.2wt% by mass, for example, it can be 0.15wt%, 0.16wt%, 0.18wt%, 0.19wt% or 0.2wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0027] Preferably, the acid leaching temperature in step (1) is 60-90℃, for example, it can be 60℃, 65℃, 70℃, 75℃, 80℃, 85℃ or 90℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0028] Preferably, the acid leaching time in step (1) is 1-5 hours, for example, it can be 1 hour, 2 hours, 3 hours, 4 hours or 5 hours, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0029] Preferably, during acid leaching, the liquid-to-solid ratio of lithium-containing waste to water is (2-10) mL:1g; for example, it can be 2 mL:1g, 4 mL:1g, 5 mL:1g, 6 mL:1g, 8 mL:1g or 10 mL:1g, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0030] Preferably, the extractant in step (2) comprises 30-50 wt% of a first component, 1-4 wt% of a second component, 20-40 wt% of a third component, and the remainder being a diluent, by mass percentage.

[0031] With the total mass percentage of the first component, second component, third component and diluent being 100 wt%, the mass percentage of the first component in the extractant is 30-50 wt%, for example, it can be 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0032] With the total mass percentage of the first component, second component, third component and diluent being 100 wt%, the mass percentage of the second component in the extractant is 1-4 wt%, for example, it can be 1 wt%, 2 wt%, 3 wt% or 4 wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0033] With the total mass percentage of the first component, second component, third component and diluent being 100 wt%, the mass percentage of the third component in the extractant is 20-40 wt%, for example, it can be 20 wt%, 25 wt%, 30 wt%, 35 wt% or 40 wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0034] Preferably, the diluent comprises kerosene.

[0035] Preferably, before the extraction in step (2), the pH value and chloride ion concentration of the acid leaching solution are adjusted.

[0036] The extractant used in this invention has a stronger extraction effect on hydrogen ions than on lithium ions. Therefore, it is necessary to adjust the pH value of the acid leaching solution. However, while adjusting the pH value, it is necessary to ensure that the chloride ion concentration in the acid leaching solution is within a suitable range.

[0037] Preferably, before the extraction in step (2), the pH value of the acid leaching solution is adjusted to 1.5-2.5, for example, it can be 1.5, 1.8, 2, 2.2 or 2.5, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0038] Preferably, before the extraction in step (2), the chloride ion concentration of the acid leaching solution is adjusted to 4.95-7.61 mol / L, for example, it can be 4.95 mol / L, 5 mol / L, 6 mol / L, 7 mol / L or 7.61 mol / L, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0039] Preferably, before the extraction in step (2), the pH value and chloride ion concentration of the acid leaching solution are adjusted using hydrochloric acid and / or aluminum hydroxide. The present invention does not further limit the hydrochloric acid concentration here, as long as the pH value of the acid leaching solution is 1.5-2.5 and the chloride ion concentration is 4.95-7.61 mol / L.

[0040] More preferably, the aluminum hydroxide is derived from at least two pH adjustments of the extract.

[0041] Preferably, the pH value of the raffinate obtained in step (2) is adjusted twice to achieve the recovery of aluminum, nickel, cobalt, and manganese elements:

[0042] The raffinate obtained in step (2) is subjected to a first-stage adjustment and a second-stage adjustment. The first-stage adjustment realizes the recovery of aluminum hydroxide, and the second-stage adjustment realizes the recovery of nickel, cobalt and manganese hydroxide.

[0043] Preferably, sodium hydroxide is used for the adjustment of the voltage level.

[0044] Preferably, the pH value of the adjustment range is 4-6, for example, it can be 4, 5 or 6, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0045] Preferably, the temperature range of the set value is 60-90℃, for example, it can be 60℃, 70℃, 80℃ or 90℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0046] Preferably, the duration of the adjustment is 1-5 hours, for example, it can be 1 hour, 2 hours, 3 hours, 4 hours or 5 hours, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0047] Under the pH adjustment conditions provided by this invention, aluminum hydroxide can be recovered. As a further preferred embodiment, the recovered aluminum hydroxide can be used to adjust the pH of the acid leaching solution.

[0048] Preferably, sodium hydroxide is used for the two-stage adjustment.

[0049] Preferably, the pH value of the two-stage adjustment is 9-11, for example, it can be 9, 10 or 11, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0050] Preferably, the temperature range for the two-stage adjustment is 60-90℃, for example, it can be 60℃, 70℃, 80℃ or 90℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0051] Preferably, the duration of the two-stage adjustment is 1-5 hours, for example, it can be 1 hour, 2 hours, 3 hours, 4 hours or 5 hours, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0052] Under the two-stage adjustment conditions provided by this invention, the recovery of nickel-cobalt-manganese hydroxide can be achieved.

[0053] The sodium hydroxide used in the first and second stage adjustment stages of this invention includes solid sodium hydroxide or sodium hydroxide solution. To avoid excessive solvent introduction from the sodium hydroxide solution, the sodium hydroxide used in the first and second stage adjustment stages is solid sodium hydroxide.

[0054] Preferably, the stripping agent used in step (4) includes water or dilute hydrochloric acid;

[0055] The concentration of hydrogen ions in the dilute hydrochloric acid is below 0.5 mol / L, for example, it can be 0.1 mol / L, 0.2 mol / L, 0.3 mol / L or 0.4 mol / L, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0056] In the resource utilization method provided by the present invention, the extraction is carried out under acidic conditions. The back-extraction agent provided by the present invention can ensure that P507 and / or P507 derivatives are not saponified. Therefore, the extraction system does not have a significant extraction effect on nickel, cobalt and manganese, thereby realizing the separation of Li from Ni, Co and Mn.

[0057] As a preferred embodiment of the resource utilization method provided by the present invention, the resource utilization method includes the following steps:

[0058] (1) The waste sagger is crushed and ground to a particle size of less than 80 mesh, and then acid leaching is carried out at 60-90℃ for 1-5 hours with hydrochloric acid of 30-35wt% to obtain acid leaching residue and acid leaching solution.

[0059] The waste crucible contains 1.8-2.2 wt% Li, 0.15-0.2 wt% Ni, 0.15-0.2 wt% Co, and 0.15-0.2 wt% Mn by mass percentage.

[0060] During the acid leaching process, the liquid-to-solid ratio of the waste crucible to water is (2-10) mL:1g;

[0061] (2) Adjust the pH of the acid leaching solution to 1.5-2.5 using hydrochloric acid and / or aluminum hydroxide, and adjust the chloride ion concentration to 4.95-7.61 mol / L. Then extract the acid leaching solution obtained in step (1) using an extractant to obtain the extract and raffinate.

[0062] The extractant in step (2) comprises 30-50 wt% of a first component, 1-4 wt% of a second component, 20-40 wt% of a third component, and the remainder being a diluent, by mass percentage.

[0063] The first component includes TBP and / or TBP derivatives; the second component includes FeCl3; the third component includes P507 and / or P507 derivatives.

[0064] (3) Sodium hydroxide is used to adjust the raffinate obtained in step (2) in two stages. The first stage adjustment realizes the recovery of aluminum hydroxide, and the second stage adjustment realizes the recovery of nickel, cobalt and manganese hydroxide.

[0065] The pH value of the aforementioned adjustment is 4-6, the temperature is 60-90℃, and the time is 1-5h;

[0066] The two-stage pH adjustment is performed at a value of 9-11, a temperature of 60-90℃, and a time of 1-5 hours.

[0067] (4) The extract obtained in step (2) is back-extracted to obtain a lithium-rich solution; after removing impurities from the lithium-rich solution, sodium carbonate is added to prepare lithium carbonate.

[0068] The stripping agent used in the stripping process includes water or dilute hydrochloric acid with a hydrogen ion concentration of less than 0.5 mol / L;

[0069] Steps (3) and (4) are not in any particular order.

[0070] The crushing and grinding to a particle size of less than 80 mesh refers to taking the portion that passes through an 80-mesh sieve after crushing and grinding the waste sagger.

[0071] As a preferred technical solution, if the acid leaching solution obtained in step (1) simultaneously meets the requirements of pH value of 1.5-2.5 and chloride ion concentration of 4.95-7.61 mol / L, then hydrochloric acid and / or aluminum hydroxide can be omitted for adjustment.

[0072] Compared with the prior art, the present invention has the following beneficial effects:

[0073] The resource utilization method provided by this invention can efficiently recover valuable metal elements from lithium-containing waste, avoiding the generation of hazardous waste. At the same time, the acid leaching residue can be used as a raw material for building materials and cement, which has extremely high economic and environmental value. Moreover, the extractant used in the resource utilization method provided by this invention has a very good separation effect on Li and Al. Acid leaching with hydrochloric acid can achieve good leaching effect on lithium, nickel, cobalt and manganese under low pH conditions. The leaching residue can be used as a raw material for building materials and cement, realizing the efficient separation of lithium and aluminum. Attached Figure Description

[0074] Figure 1 This is a flowchart illustrating the resource utilization method provided by the present invention. Detailed Implementation

[0075] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0076] In this specific embodiment of the invention, the lithium-containing waste material is a crushed and ground waste crucible that has passed through an 80-mesh sieve. By mass percentage, the waste crucible contains 2 wt% Li, 0.2 wt% Ni, 0.15 wt% Co, and 0.15 wt% Mn, primarily in the form of LiAlO2 and ternary cathode materials. The above limitation on the lithium-containing waste material is merely for clearly illustrating the technical solution of the invention and is not considered a further limitation on the resource utilization method of the lithium-containing waste material of the invention.

[0077] Example 1

[0078] This embodiment provides a method such as Figure 1 The method for resource utilization of lithium-containing waste shown includes the following steps:

[0079] (1) 1000g of lithium-containing waste was acid-leached at 75°C for 3h using 31wt% hydrochloric acid to obtain acid-leaching residue and acid-leaching solution with pH value of 6.2;

[0080] During the acid leaching process, the liquid-to-solid ratio of the waste crucible to water is 2 mL: 1 g.

[0081] The resulting acid leaching residue is aluminum slag, which, after simple post-treatment, can be used as building materials and cement raw materials.

[0082] (2) The pH of the acid leaching solution was adjusted to 2 using hydrochloric acid, and the chloride ion concentration after adjustment was 7.13 mol / L. Then the acid leaching solution obtained in step (1) was extracted with an extractant to obtain the extract and the raffinate.

[0083] The extractant in step (2) comprises 40 wt% TBP, 30 wt% P507 and 2 wt% FeCl3, and the diluent is kerosene.

[0084] (3) Sodium hydroxide is used to adjust the raffinate obtained in step (2) in a first stage and a second stage. After the first stage adjustment, solid-liquid separation is performed to recover aluminum hydroxide. After the second stage adjustment, solid-liquid separation is performed to recover nickel, cobalt and manganese hydroxide.

[0085] The pH value of the adjustment was 4, the temperature was 60℃, and the time was 1 hour.

[0086] The pH value of the two-stage adjustment was 9, the temperature was 60℃, and the time was 1 hour;

[0087] (4) The extract obtained in step (2) is washed with pure water and back-extracted to obtain lithium-rich solution; after removing impurities from the lithium-rich solution, sodium carbonate is added to prepare lithium carbonate.

[0088] Steps (3) and (4) are not in any particular order.

[0089] Example 2

[0090] This embodiment provides a method such as Figure 1 The method for resource utilization of lithium-containing waste shown includes the following steps:

[0091] (1) 1000g of lithium-containing waste was acid-leached at 75°C for 3h using 31wt% hydrochloric acid to obtain acid-leaching residue and acid-leaching solution with pH value of 4.4.

[0092] During the acid leaching process, the liquid-to-solid ratio of the waste crucible to water is 2 mL: 1 g.

[0093] The resulting acid leaching residue is aluminum slag, which, after simple post-treatment, can be used as building materials and cement raw materials.

[0094] (2) Use hydrochloric acid to adjust the pH of the acid leaching solution to 2, and the chloride ion concentration after adjustment is 7.15 mol / L. Then use an extractant to extract the acid leaching solution obtained in step (1) to obtain the extract and the raffinate.

[0095] The extractant in step (2) comprises 40 wt% TBP, 30 wt% P507 and 2 wt% FeCl3, and the diluent is kerosene.

[0096] (3) Sodium hydroxide is used to adjust the raffinate obtained in step (2) in a first stage and a second stage. After the first stage adjustment, solid-liquid separation is performed to recover aluminum hydroxide. After the second stage adjustment, solid-liquid separation is performed to recover nickel, cobalt and manganese hydroxide.

[0097] The pH value of the adjustment was 4, the temperature was 60℃, and the time was 1 hour.

[0098] The pH value of the two-stage adjustment was 9, the temperature was 60℃, and the time was 1 hour;

[0099] (4) The extract obtained in step (2) is washed with pure water and back-extracted to obtain lithium-rich solution; after removing impurities from the lithium-rich solution, sodium carbonate is added to prepare lithium carbonate.

[0100] Steps (3) and (4) are not in any particular order.

[0101] Example 3

[0102] This embodiment provides a method such as Figure 1 The method for resource utilization of lithium-containing waste shown includes the following steps:

[0103] (1) 1000g of lithium-containing waste was acid-leached at 75°C for 3h using 31wt% hydrochloric acid to obtain acid-leaching residue and acid-leaching solution with pH value of 2.5.

[0104] During the acid leaching process, the liquid-to-solid ratio of the waste crucible to water is 2 mL: 1 g.

[0105] The resulting acid leaching residue is aluminum slag, which, after simple post-treatment, can be used as building materials and cement raw materials.

[0106] (2) The pH value of the acid leaching solution is 2.5 and the chloride ion concentration is 7.02 mol / L. The acid leaching solution obtained in step (1) is extracted with an extractant to obtain an extract and a raffinate.

[0107] The extractant in step (2) comprises 40 wt% TBP, 30 wt% P507 and 2 wt% FeCl3, and the diluent is kerosene.

[0108] (3) Sodium hydroxide is used to adjust the raffinate obtained in step (2) in a first stage and a second stage. After the first stage adjustment, solid-liquid separation is performed to recover aluminum hydroxide. After the second stage adjustment, solid-liquid separation is performed to recover nickel, cobalt and manganese hydroxide.

[0109] The pH value of the adjustment was 4, the temperature was 60℃, and the time was 1 hour.

[0110] The pH value of the two-stage adjustment was 9, the temperature was 60℃, and the time was 1 hour;

[0111] (4) The extract obtained in step (2) is washed with pure water and back-extracted to obtain lithium-rich solution; after removing impurities from the lithium-rich solution, sodium carbonate is added to prepare lithium carbonate.

[0112] Steps (3) and (4) are not in any particular order.

[0113] Example 4

[0114] This embodiment provides a method such as Figure 1 The method for resource utilization of lithium-containing waste shown includes the following steps:

[0115] (1) 1000g of lithium-containing waste was acid-leached at 75°C for 3h using 31wt% hydrochloric acid to obtain acid-leaching residue and acid-leaching solution with pH value of 0.5.

[0116] During the acid leaching process, the liquid-to-solid ratio of the waste crucible to water is 2 mL: 1 g.

[0117] The resulting acid leaching residue is aluminum slag, which, after simple post-treatment, can be used as building materials and cement raw materials.

[0118] (2) The pH of the acid leaching solution was adjusted to 2 using aluminum hydroxide obtained from the first-stage adjustment and recovery. The chloride ion concentration after adjustment was 7.61 mol / L. The acid leaching solution obtained in step (1) was extracted with an extractant to obtain extract and raffinate.

[0119] The extractant in step (2) comprises 40 wt% TBP, 30 wt% P507 and 2 wt% FeCl3, and the diluent is kerosene.

[0120] (3) Sodium hydroxide is used to adjust the raffinate obtained in step (2) in a first stage and a second stage. After the first stage adjustment, solid-liquid separation is performed to recover aluminum hydroxide. After the second stage adjustment, solid-liquid separation is performed to recover nickel, cobalt and manganese hydroxide.

[0121] The pH value of the adjustment was 4, the temperature was 60℃, and the time was 1 hour.

[0122] The pH value of the two-stage adjustment was 9, the temperature was 60℃, and the time was 1 hour;

[0123] (4) The extract obtained in step (2) is washed with pure water and back-extracted to obtain lithium-rich solution; after removing impurities from the lithium-rich solution, sodium carbonate is added to prepare lithium carbonate.

[0124] Steps (3) and (4) are not in any particular order.

[0125] Example 5

[0126] This embodiment provides a method such as Figure 1 The method for resource utilization of lithium-containing waste shown includes the following steps:

[0127] (1) 1000g of lithium-containing waste was acid-leached at 60℃ for 5h using 31wt% hydrochloric acid to obtain acid leaching residue and acid leaching solution with pH value of 6.8.

[0128] During the acid leaching process, the liquid-to-solid ratio of the waste crucible to water is 5 mL: 1 g.

[0129] The resulting acid leaching residue is aluminum slag, which, after simple post-treatment, can be used as building materials and cement raw materials.

[0130] (2) The pH of the acid leaching solution was adjusted to 1.5 using hydrochloric acid, and the chloride ion concentration after adjustment was 4.95 mol / L. Then the acid leaching solution obtained in step (1) was extracted with an extractant to obtain the extract and the raffinate.

[0131] The extractant in step (2) comprises 30 wt% TBP, 40 wt% P507 and 1 wt% FeCl3, and the diluent is kerosene.

[0132] (3) Sodium hydroxide is used to adjust the raffinate obtained in step (2) in two stages. The first stage adjustment realizes the recovery of aluminum hydroxide, and the second stage adjustment realizes the recovery of nickel, cobalt and manganese hydroxide.

[0133] The pH value of the adjustment was 5, the temperature was 75℃, and the time was 3 hours.

[0134] The pH value of the two-stage adjustment was 10, the temperature was 75℃, and the time was 3 hours.

[0135] (4) The extract obtained in step (2) is washed with pure water and back-extracted to obtain lithium-rich solution; after removing impurities from the lithium-rich solution, sodium carbonate is added to prepare lithium carbonate.

[0136] Steps (3) and (4) are not in any particular order.

[0137] Example 6

[0138] This embodiment provides a method such as Figure 1 The method for resource utilization of lithium-containing waste shown includes the following steps:

[0139] (1) 1000g of lithium-containing waste was acid-leached at 90℃ for 1h using 31wt% hydrochloric acid to obtain acid-leaching residue and acid-leaching solution with pH value of 7.1;

[0140] During the acid leaching process, the liquid-to-solid ratio of the waste crucible to water is 10 mL: 1 g.

[0141] The resulting acid leaching residue is aluminum slag, which, after simple post-treatment, can be used as building materials and cement raw materials.

[0142] (2) The pH of the acid leaching solution was adjusted to 2.5 using hydrochloric acid, and the chloride ion concentration after adjustment was 7.57 mol / L. Then the acid leaching solution obtained in step (1) was extracted with an extractant to obtain the extract and the raffinate.

[0143] The extractant in step (2) comprises 50 wt% TBP, 20 wt% P507 and 4 wt% FeCl3, and the diluent is kerosene.

[0144] (3) Sodium hydroxide is used to adjust the raffinate obtained in step (2) in a first stage and a second stage. After the first stage adjustment, solid-liquid separation is performed to recover aluminum hydroxide. After the second stage adjustment, solid-liquid separation is performed to recover nickel, cobalt and manganese hydroxide.

[0145] The pH value of the adjustment was 6, the temperature was 90℃, and the time was 5h.

[0146] The pH value for the two-stage adjustment was 11, the temperature was 90℃, and the time was 5h.

[0147] (4) The extract obtained in step (2) is washed with pure water and back-extracted to obtain lithium-rich solution; after removing impurities from the lithium-rich solution, sodium carbonate is added to prepare lithium carbonate.

[0148] Steps (3) and (4) are not in any particular order.

[0149] Example 7

[0150] This embodiment provides a method for the resource utilization of lithium-containing waste. Except that in step (2), the mass percentage of the first component in the extractant is 20 wt%, and the amount of diluent is appropriately adjusted to ensure that the mass percentage of the second and third components remains unchanged, the rest is the same as in Example 1.

[0151] Example 8

[0152] This embodiment provides a method for the resource utilization of lithium-containing waste. Except that in step (2), the mass percentage of the first component in the extractant is 60 wt%, and the amount of diluent is appropriately adjusted to ensure that the mass percentage of the second and third components remains unchanged, the rest is the same as in Example 1.

[0153] Example 9

[0154] This embodiment provides a method for the resource utilization of lithium-containing waste. Except that in step (2), the mass percentage of the third component in the extractant is 10 wt%, and the amount of diluent is appropriately adjusted to ensure that the mass percentage of the first and second components remains unchanged, the rest is the same as in Example 1.

[0155] Example 10

[0156] This embodiment provides a method for the resource utilization of lithium-containing waste. Except that in the extractant described in step (2), the mass percentage of the third component is 50 wt%, and the amount of diluent is appropriately adjusted to ensure that the mass percentage of the first component and the second component remains unchanged, the rest is the same as in Example 1.

[0157] Comparative Example 1

[0158] This comparative example provides a method for the resource utilization of lithium-containing waste. Except for the third component in the extractant being replaced by the first component by the same mass, the rest is the same as in Example 1.

[0159] Comparative Example 2

[0160] This comparative example provides a method for the resource utilization of lithium-containing waste. Except for replacing P507 with P204, the method is the same as in Example 1.

[0161] Effects characterization

[0162] In the resource utilization methods provided in Examples 1-6, the concentrations of Li ions, NCM (nickel, cobalt and manganese ions), Al ions, and lithium leaching rate of the acid leaching solution were measured. The concentrations of each metal ion were measured using ICP-OES, and the results are shown in Table 1.

[0163] Table 1

[0164] Li (g / L) NCM (g / L) Al(g / L) Lithium leaching rate (%) Example 1 9.0 2.25 34.99 90 Example 2 9.2 2.30 35.77 92 Example 3 9.5 2.38 36.93 95 Example 4 9.6 2.40 37.32 96 Example 5 3.4 0.86 13.37 86 Example 6 1.8 0.46 7.15 92

[0165] The recovery rates of nickel, cobalt, manganese and lithium in the resource utilization methods provided in the examples and comparative examples were measured, and the results are shown in Table 2.

[0166] Table 2

[0167]

[0168]

[0169] In summary, the resource utilization method provided by this invention can efficiently recover valuable metal elements from lithium-containing waste, avoiding the generation of hazardous waste. Simultaneously, the acid leaching residue can be used as a raw material for building materials and cement, possessing extremely high economic and environmental value. Furthermore, the extractant used in the resource utilization method provided by this invention has excellent separation effects on Li and Al. Acid leaching with hydrochloric acid can achieve good leaching effects on lithium, nickel, cobalt, and manganese under relatively low pH conditions, and the leaching residue can be used as a raw material for building materials and cement, achieving efficient separation of lithium and aluminum.

[0170] The above description is only a specific embodiment 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 conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for resource utilization of lithium-containing waste material, characterized by, The resource utilization method comprises the following steps: (1) using hydrochloric acid to perform acid leaching on the lithium-containing waste material to obtain acid leaching residue and acid leaching solution; (2) using an extractant to extract the acid leaching solution obtained in step (1) to obtain extraction solution and raffinate; (3) performing at least two times of pH adjustment on the raffinate obtained in step (2) to realize recovery of aluminum and elements of nickel, cobalt and manganese; (4) performing stripping on the extraction solution obtained in step (2) to obtain lithium-rich solution; after impurity removal, the lithium-rich solution is used for preparation of lithium product; Step (3) and step (4) are not in a specific order; The extractant in step (2) comprises a first component, a second component, a third component and a diluent; the first component comprises TBP and / or TBP derivative; the second component comprises FeCl3; the third component comprises P507 and / or P507 derivative; Before the extraction in step (2), the pH value of the acid leaching solution is adjusted to 1.5-2.5; Before the extraction in step (2), the chloride ion concentration of the acid leaching solution is adjusted to 4.95-7.61 mol / L.

2. The method of claim 1, wherein, The lithium-containing waste material in step (1) comprises waste kiln furniture.

3. The method of claim 2, wherein, The lithium-containing waste material in step (1) comprises waste kiln furniture.

4. The method of claim 1, wherein, The lithium-containing waste material in step (1) comprises waste kiln furniture.

5. The method of claim 1, wherein, The temperature of the acid leaching in step (1) is 60-90℃.

6. The method of claim 1, wherein, The time of the acid leaching in step (1) is 1-5h.

7. The method of claim 6, wherein, The extractant in step (2) comprises 30-50wt% of the first component, 1-4wt% of the second component, 20-40wt% of the third component and the balance of the diluent.

8. The method of resource utilization of claim 1, wherein, The diluent comprises kerosene. The raffinate obtained in step (2) is subjected to two times of pH adjustment to realize recovery of aluminum and elements of nickel, cobalt and manganese:

9. The method of claim 8, wherein, The raffinate obtained in step (2) is subjected to one-stage adjustment and two-stage adjustment in sequence; the one-stage adjustment realizes recovery of aluminum hydroxide, and the two-stage adjustment realizes recovery of nickel cobalt manganese hydroxide.

10. The method of claim 8, wherein, The pH value of the one-stage adjustment is 4-6.

11. The method of claim 8, wherein, The temperature of the one-stage adjustment is 60-90℃.

12. The resource utilization method of claim 8, wherein, The time of the one-stage adjustment is 1-5h.

13. The method of claim 8, wherein, The pH value of the two-stage adjustment is 9-11.

14. The method of claim 8, wherein, The temperature of the two-stage adjustment is 60-90℃.

15. The resource utilization method according to any one of claims 1 to 14, wherein, The time of the two-stage adjustment is 1-5h. The stripping agent used in step (4) comprises water or dilute hydrochloric acid; 16. The method of resourceful utilization of claim 1, wherein, The concentration of hydrogen ions in the dilute hydrochloric acid is 0.5 mol / L or less. The resource utilization method comprises the following steps: (1) crushing and grinding the waste kiln furniture to a particle size of 80 mesh or less, and then using hydrochloric acid with a concentration of 30-35wt% to perform acid leaching at 60-90℃ for 1-5h to obtain acid leaching residue and acid leaching solution; The lithium-containing waste material in step (1) comprises waste kiln furniture. The liquid-solid ratio of the waste kiln furniture to water during the acid leaching is (2-10) mL:1g; (2) using hydrochloric acid and / or aluminum hydroxide to adjust the pH value of the acid leaching solution to 1.5-2.5 and the chloride ion concentration to 4.95-7.61 mol / L, and then using an extractant to extract the acid leaching solution obtained in step (1) to obtain an extract and a raffinate; the extractant in step (2) comprises 30-50 wt% of a first component, 1-4 wt% of a second component, 20-40 wt% of a third component, and the balance of a diluent, all by mass percentage; the first component comprises TBP and / or a TBP derivative; the second component comprises FeCl3; the third component comprises P507 and / or a P507 derivative; and the diluent comprises kerosene; (3) using sodium hydroxide to sequentially perform one-stage adjustment and two-stage adjustment on the raffinate obtained in step (2), the one-stage adjustment achieving recovery of aluminum hydroxide, and the two-stage adjustment achieving recovery of nickel-cobalt-manganese hydroxide; the one-stage adjustment has a pH value of 4-6, a temperature of 60-90℃, and a time of 1-5 h; the two-stage adjustment has a pH value of 9-11, a temperature of 60-90℃, and a time of 1-5 h; (4) the extract obtained in step (2) is subjected to stripping to obtain a lithium-rich solution; after the lithium-rich solution is subjected to impurity removal, sodium carbonate is added to prepare lithium carbonate; the stripping agent used in the stripping comprises water or dilute hydrochloric acid with a hydrogen ion concentration of 0.5 mol / L or less; steps (3) and (4) are not in a specific order.

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