A method for separating and extracting valuable metals from an acidic leaching solution of ternary materials of waste batteries by using a chromatographic separation system

Abstract

The application provides a method for separating and extracting valuable metals from waste battery ternary material acidic leaching solution by using a chromatographic separation system, and belongs to the technical field of valuable metal recovery from waste batteries. The application obtains lithium-containing mixed solution, nickel-containing mixed solution, cobalt-containing mixed solution and manganese-containing mixed solution by filtering waste lithium battery positive electrode material acidic leaching solution and then processing the filtered solution through a first chromatographic separation system, a second chromatographic separation system and a third chromatographic separation system. Lithium hydroxide, nickel hydroxide, cobalt hydroxide, manganese hydroxide and acid are obtained by processing the collected lithium-containing mixed solution, nickel-containing mixed solution, cobalt-containing mixed solution and manganese-containing mixed solution through a bipolar membrane electrodialysis, respectively. The application adopts a series connection mode of a simulated moving bed to continuously separate lithium, cobalt, nickel and manganese in countercurrent flow, is suitable for waste lithium battery positive electrode ternary active material acidic leaching solution, has a simple separation process, and has high purity, large processing capacity and high yield of the separated lithium / cobalt / nickel / manganese resources, and is suitable for large-scale production.

Description

Technical Field

[0001] This invention relates to the field of valuable metal recycling technology from waste batteries, and in particular to a method for separating and extracting valuable metals from acidic leachate of ternary materials from waste batteries using a chromatographic separation system. Background Technology

[0002] The cathode materials of spent lithium-ion batteries include lithium nickel cobalt manganese oxide, lithium cobalt oxide, and lithium iron phosphate, which are key materials for recycling from spent batteries. The main recycling methods for spent batteries include pyrometallurgy and hydrometallurgy. Pyrometallurgy directly extracts metals or metal oxides from the electrodes using high-temperature treatment. While simple, pyrometallurgical processes result in low purity of recycled materials. The electrolyte, binders, and other organic matter in the battery can produce harmful gases due to high-temperature reactions, requiring secondary waste gas treatment facilities. This process is not conducive to achieving closed-loop recycling of spent lithium-ion batteries. A major drawback of direct pyrometallurgical smelting is the loss of lithium in the high-temperature furnace. Therefore, hydrometallurgy is currently the mainstream technology for spent battery recycling. Hydrometallurgy involves first disassembling the battery casing, crushing and screening it to obtain the electrode materials. Valuable metals in the electrode materials are leached in acid or biological solutions, and then separated to obtain the corresponding salts or oxides of each metal. The hydrometallurgical process mainly includes cathode pretreatment, valuable metal leaching, and valuable metal separation and recovery. The separation and recovery of valuable metals is crucial to the entire recycling process and represents a significant technical challenge for its large-scale production. The separation and extraction of valuable metals from leachates primarily involves extraction and precipitation methods. Extraction generally requires multiple organic solvents as extractants, offering low energy consumption, simple equipment operation, good separation efficiency, and high metal purity. However, the extractants are often toxic organic solvents, resulting in higher costs and a complex separation process. Precipitation methods are simple, low-cost, and have a short process flow, leading to high metal ion recovery efficiency. However, Ni, Co, and Mn are all transition metals with similar chemical properties, making them prone to co-precipitation and resulting in lower product purity. Ternary cathode active materials for lithium-ion batteries contain large amounts of valuable metals such as cobalt, nickel, manganese, and lithium. Leaching methods for valuable metals in ternary materials are largely uniform, mainly acid leaching. However, methods for achieving efficient recovery of valuable metals from acid leaching solutions are limited. Therefore, developing a highly efficient method for separating and extracting valuable metals from acidic lithium battery leachates is a pressing technical problem that needs to be solved. Summary of the Invention

[0003] The purpose of this invention is to provide a simple, efficient, and large-scale production process for separating and recovering valuable metals such as lithium, nickel, cobalt, and manganese from the leachate of ternary cathode materials from waste lithium batteries.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0005] This invention provides a method for separating and extracting valuable metals from acidic leachate of ternary materials from waste batteries using a chromatographic separation system. The chromatographic separation system includes a packed column and comprises the following steps:

[0006] The acidic leachate of waste lithium battery cathode material was filtered and then processed by the first chromatographic separation system to obtain a lithium-containing mixed solution and a nickel-cobalt-manganese mixed solution.

[0007] The nickel-cobalt-manganese mixture was processed by a second chromatographic separation system to obtain a nickel-containing mixture and a cobalt-manganese mixture.

[0008] The cobalt-manganese mixture was processed by a third chromatographic separation system to obtain a cobalt-containing mixture and a manganese-containing mixture.

[0009] The collected lithium-containing, nickel-containing, cobalt-containing, and manganese-containing mixtures were treated by bipolar membrane electrodialysis to obtain lithium hydroxide, nickel hydroxide, cobalt hydroxide, manganese hydroxide, and acid, respectively.

[0010] Furthermore, the first chromatographic separation system, the second chromatographic separation system, and the third chromatographic separation system each contain N packed columns, the packed columns being carboxylate cationic silica gel packing, wherein N is 5 to 8.

[0011] Furthermore, the lithium-containing mixture contains LiCl and HCl, the nickel-containing mixture contains NiCl2 and HCl, the cobalt-containing mixture contains CoCl2 and HCl, and the manganese-containing mixture contains MnCl2 and HCl.

[0012] Furthermore, the feed temperature of the acidic leachate of the waste lithium battery cathode material is 30~60℃, and the feed flow rate is 20~30ml / min.

[0013] Furthermore, the bipolar membrane electrodialysis treatment includes:

[0014] The collected mixture is then subjected to an electric current, causing anions to pass through an anion exchange membrane into an HCl cell to react with H+ generated by the bipolar membrane. + The reaction produces an HCl solution; cations pass through the cation exchange membrane into the MOH cell and react with OH- generated by the bipolar membrane. - The corresponding MOH products are obtained through this process;

[0015] M is one of Li, Ni, Co, and Mn.

[0016] Furthermore, the bipolar membrane used in the bipolar membrane electrodialysis treatment includes a BPM-Aquivion-Durion composite bipolar membrane.

[0017] Furthermore, the working voltage of the bipolar membrane electrodialysis treatment is 20~40V, and the working current is 20~300A.

[0018] The beneficial effects of this invention are:

[0019] The bipolar membrane of this invention is a novel composite ion exchange membrane, consisting of anion and cation exchange layers and an intermediate interface layer forming a sandwich-like structure. Under the action of a DC electric field, the intermediate layer splits water, yielding H+ on both sides of the membrane. + and OH - This technology, combined with anion and cation exchange membranes, forms a bipolar membrane electrodialysis system that converts salts in solution into acids and bases without introducing new components. The inventors used this technology to treat simulated moving bed effluents (such as MCl and HCl (M represents lithium, magnesium, nickel, and cobalt)) to generate MOH products and reuse HCl.

[0020] This invention couples a series countercurrent simulated moving bed and a bipolar membrane electrodialysis system. It utilizes the simulated moving bed to separate valuable metals on a large scale, and uses electrodialysis to purify the separated valuable metal solution to obtain a high-purity metal alkali product. At the same time, the by-product acid (such as HCl) can be refluxed to the simulated moving bed and used as the mobile phase, saving resources. Attached Figure Description

[0021] Figure 1 This is a process flow diagram for separating and extracting valuable metals according to the present invention;

[0022] Figure 2 This is a schematic diagram of the chromatographic separation system of the present invention;

[0023] Figure 3 This is a schematic diagram of the bipolar membrane electrodialysis system of the present invention. Detailed Implementation

[0024] This invention provides a method for separating and extracting valuable metals from acidic leachate of ternary materials from waste batteries using a chromatographic separation system. The chromatographic separation system includes a packed column and comprises the following steps:

[0025] The acidic leachate of waste lithium battery cathode material was filtered and then processed by the first chromatographic separation system to obtain a lithium-containing mixed solution and a nickel-cobalt-manganese mixed solution.

[0026] The nickel-cobalt-manganese mixture was processed by a second chromatographic separation system to obtain a nickel-containing mixture and a cobalt-manganese mixture.

[0027] The cobalt-manganese mixture was processed by a third chromatographic separation system to obtain a cobalt-containing mixture and a manganese-containing mixture.

[0028] The collected lithium-containing, nickel-containing, cobalt-containing, and manganese-containing mixtures were treated by bipolar membrane electrodialysis to obtain lithium hydroxide, nickel hydroxide, cobalt hydroxide, manganese hydroxide, and acid, respectively.

[0029] In this invention, the first chromatographic separation system, the second chromatographic separation system, and the third chromatographic separation system each contain N packed columns, the packed columns being carboxylate cationic silica gel packing, wherein N is 5 to 8, preferably 8.

[0030] In this invention, the packed column is preferably a glass column with a diameter of 20-40 mm and a height of 500-700 mm; more preferably, the diameter of the packed column is 25-35 mm and the height is 600-700 mm; even more preferably, the diameter of the packed column is 30 mm and the height is 650 mm.

[0031] In this invention, the preferred method for processing by the chromatographic separation system is as follows: 1) The filtered acidic leachate of waste lithium battery cathode material is stored in a feed tank, and the HCl solution or H2SO4 solution is stored in a mobile phase tank. The feed and mobile phase are fed into the Mth packed column of the first chromatographic separation system by a transfer pump. Under the action of the mobile phase, the feed is separated in the packed column. The slow component nickel-cobalt-manganese mixture is collected from the bottom of the Ath column (counting forward from the Mth column along the counter-current phase direction) through a slow component collection line. The fast component lithium mixture is collected from the bottom of the Bth column (counting backward from the Mth column along the current phase direction) through a fast component collection line, completing one cycle. The collected mixture is fed into the packed column of the second chromatographic separation system. After completing the same operation as in the first separation system, nickel-containing mixture and cobalt-manganese mixture are obtained respectively. The collected cobalt-manganese mixture is fed into the packed column of the third separation system. After completing the same operation as in the second separation system, cobalt-containing mixture and manganese mixture are obtained respectively.

[0032] In this invention, the independence of M, A, and B is preferably <N.

[0033] In this invention, the chromatographic separation system adopts the principle of a simulated moving bed.

[0034] In this invention, the feed rate of the mobile phase is 30-50 ml / min, preferably 35-45 ml / min, and more preferably 40 ml / min.

[0035] In this invention, the lithium-containing mixture preferably contains LiCl and HCl, the nickel-containing mixture preferably contains NiCl2 and HCl, the cobalt-containing mixture preferably contains CoCl2 and HCl, and the manganese-containing mixture preferably contains MnCl2 and HCl.

[0036] In this invention, the feed temperature of the acidic leachate of the waste lithium battery cathode material is 30~60℃, and the feed flow rate is 20~30ml / min; preferably, the feed temperature of the acidic leachate of the waste lithium battery cathode material is 35~55℃, and the feed flow rate is 22~28ml / min; more preferably, the feed temperature of the acidic leachate of the waste lithium battery cathode material is 40~50℃, and the feed flow rate is 25ml / min.

[0037] In this invention, the bipolar membrane electrodialysis treatment includes:

[0038] The collected mixture is then subjected to an electric current, causing anions to pass through an anion exchange membrane into an HCl cell to react with H+ generated by the bipolar membrane. + The reaction produces an HCl solution; cations pass through the cation exchange membrane into the MOH cell and react with OH- generated by the bipolar membrane. - The corresponding MOH products are obtained through this process;

[0039] M is one of Li, Ni, Co, and Mn, preferably one of Li, Co, and Mn.

[0040] In this invention, the bipolar membrane used in the bipolar membrane electrodialysis treatment is preferably a BPM-Aquivion-Durion composite bipolar membrane.

[0041] In this invention, the working voltage of the bipolar membrane electrodialysis treatment is 20~40V and the working current is 20~300A; preferably, the working voltage is 25~35V and the working current is 50~200A; more preferably, the working voltage is 30V and the working current is 100A.

[0042] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0043] Example 1

[0044] A filtered acidic leachate of waste lithium battery cathode material was added to the liquid storage device at a flow rate of 25 ml / min and a temperature of 50°C. A 1.0 M hydrochloric acid solution was added to the mobile phase storage device at a circulation flow rate of 40 ml / min.

[0045] The continuous countercurrent chromatography separation system requires 18 sub-steps to complete one cycle. The first step is a dual-in, dual-out process. The acidic leachate of waste lithium battery cathode materials and the hydrochloric acid solution enter the system from the top of the 4th and 1st packed columns of the first chromatography separation system, respectively. Driven by the mobile phase, the acidic leachate of waste lithium battery cathode materials undergoes ion separation through the packed columns at a separation temperature of 55℃. The slow component (containing nickel, cobalt, and manganese mixture) and the fast component (LiCl hydrochloric acid solution) are collected at the bottom of columns 1 and 5, respectively. This process lasts for 200 seconds. The second step is circulation. During this stage, the acidic leachate of waste lithium battery cathode materials circulates within the system, neither entering nor leaving the system. The circulation time is approximately 600 seconds. The third step is a single-in, single-out process. The mobile phase enters from the top of column 2, and the fast component is collected at the bottom of column 6. This process lasts for 10 seconds. The mobile phase is then switched to column 2, and all feed and discharge ports are moved down one column. The collected nickel-cobalt-manganese mixture is sent to the second chromatographic separation system. After the same operation as the first chromatographic separation system, the slow component (cobalt-manganese mixture) and the fast component (nickel mixture) are collected. The collected cobalt-manganese mixture is then sent to the third chromatographic separation system. After the same operation as the second chromatographic separation system, the slow component (manganese mixture) and the fast component (cobalt mixture) are collected. This process is repeated to achieve efficient and continuous separation of lithium-nickel-cobalt-manganese solutions.

[0046] The collected high-purity fast fractions were pumped into a bipolar membrane electrodialysis system. Under the influence of current (30V, 150A), the Cl- in the LiCl hydrochloric acid solution... - It enters the HCl reaction cell through the anion exchange membrane and reacts with H+ generated by the bipolar membrane. + The reaction yielded an HCl solution, which was adjusted to pH and then recycled back to the mobile phase via a circulating pump; Li + It enters the LiOH reaction cell through the cation exchange membrane and reacts with the OH generated by the bipolar membrane. - The reaction yielded LiOH product with a purity of 98%.

[0047] Nickel-containing, cobalt-containing, and manganese-containing mixed solutions were fed into a bipolar membrane electrodialysis system. After ion exchange, the purity of Ni(OH)2 obtained was 97%, the purity of Co(OH)2 was 98%, and the purity of Mn(OH)2 was 98%.

[0048] Example 2

[0049] A filtered acidic leachate of waste lithium battery cathode material was added to the liquid storage device at a flow rate of 45 ml / min and a temperature of 35°C. A 1.0 M hydrochloric acid solution was added to the mobile phase storage device at a circulation flow rate of 45 ml / min.

[0050] The continuous countercurrent chromatography separation system requires 18 sub-steps to complete one cycle. The first step is a dual-in, dual-out process. The acidic leachate of waste lithium battery cathode materials and the hydrochloric acid solution enter the system from the top of the 4th and 1st packed columns of the first chromatography separation system, respectively. Driven by the mobile phase, the acidic leachate of waste lithium battery cathode materials undergoes ion separation through the packed columns at a separation temperature of 40℃. The slow component (containing nickel, cobalt, and manganese mixture) and the fast component (LiCl hydrochloric acid solution) are collected at the bottom of columns 1 and 5, respectively. This process lasts for 200 seconds. The second step is circulation. During this stage, the acidic leachate of waste lithium battery cathode materials circulates within the system, neither entering nor leaving the system. The circulation time is approximately 600 seconds. The third step is a single-in, single-out process. The mobile phase enters from the top of column 2, and the fast component is collected at the bottom of column 6. This process lasts for 10 seconds. The mobile phase is then switched to column 2, and all feed and discharge ports are moved down one column. The collected nickel-cobalt-manganese mixture is sent to the second chromatographic separation system. After the same operation as the first chromatographic separation system, the slow component (cobalt-manganese mixture) and the fast component (nickel mixture) are collected. The collected cobalt-manganese mixture is then sent to the third chromatographic separation system. After the same operation as the second chromatographic separation system, the slow component (manganese mixture) and the fast component (cobalt mixture) are collected. This process is repeated to achieve efficient and continuous separation of lithium-nickel-cobalt-manganese solutions.

[0051] The collected high-purity fast fractions were pumped into a bipolar membrane electrodialysis system. Under the influence of current (20V, 100A), the Cl- in the LiCl hydrochloric acid solution was... - It enters the HCl reaction cell through the anion exchange membrane and reacts with H+ generated by the bipolar membrane. + The reaction yielded an HCl solution, which was adjusted to pH and then recycled back to the mobile phase via a circulating pump; Li + It enters the LiOH reaction cell through the cation exchange membrane and reacts with the OH generated by the bipolar membrane. - The reaction yielded LiOH product with a purity of 95.7%.

[0052] Nickel-containing, cobalt-containing, and manganese-containing mixed solutions were fed into a bipolar membrane electrodialysis system. After ion exchange, the purity of Ni(OH)2 obtained was 98%, the purity of Co(OH)2 was 96%, and the purity of Mn(OH)2 was 96.5%.

[0053] Example 3

[0054] A filtered acidic leachate of waste lithium battery cathode material was added to the liquid storage device at a flow rate of 30 ml / min and a temperature of 55°C. A 1.0 M hydrochloric acid solution was added to the mobile phase storage device at a circulation flow rate of 45 ml / min.

[0055] A single cycle of continuous countercurrent chromatography requires 18 sub-steps. The first step is a dual-in, dual-out process. The acidic leachate of waste lithium-ion battery cathode materials and the hydrochloric acid solution enter the system from the top of the 4th and 1st packed columns, respectively. Driven by the mobile phase, the acidic leachate of waste lithium-ion battery cathode materials undergoes ion separation through the packed columns at a separation temperature of 60°C. The slow component (containing a nickel-cobalt-manganese mixture) and the fast component (LiCl hydrochloric acid solution) are collected at the bottom of columns 1 and 5, respectively. This process lasts for 200 seconds. The second step is circulation. During this stage, the acidic leachate of waste lithium-ion battery cathode materials circulates within the system, neither entering nor leaving the system. The circulation time is approximately 600 seconds. The third step is a single-in, single-out process. The mobile phase enters from the top of column 2, and the fast component is collected at the bottom of column 6. This process lasts for 10 seconds. The mobile phase is then switched to column 2, and all feed and discharge ports are moved down one column. The collected nickel-cobalt-manganese mixture is sent to the second chromatographic separation system. After the same operation as the first chromatographic separation system, the slow component (cobalt-manganese mixture) and the fast component (nickel mixture) are collected. The collected cobalt-manganese mixture is then sent to the third chromatographic separation system. After the same operation as the second chromatographic separation system, the slow component (manganese mixture) and the fast component (cobalt mixture) are collected. This process is repeated to achieve efficient and continuous separation of lithium-nickel-cobalt-manganese solutions.

[0056] The collected high-purity fast fractions were pumped into a bipolar membrane electrodialysis system. Under the influence of current (40V, 300A), the Cl- in the LiCl hydrochloric acid solution was... - It enters the HCl reaction cell through the anion exchange membrane and reacts with H+ generated by the bipolar membrane. + The reaction yielded an HCl solution, which was adjusted to pH and then recycled back to the mobile phase via a circulating pump; Li + It enters the LiOH reaction cell through the cation exchange membrane and reacts with the OH generated by the bipolar membrane. - The reaction yielded LiOH product with a purity of 96%.

[0057] Nickel-containing, cobalt-containing, and manganese-containing mixed solutions were fed into a bipolar membrane electrodialysis system. After ion exchange, the purity of Ni(OH)2 was 97%, the purity of Co(OH)2 was 96%, and the purity of Mn(OH)2 was 98%.

[0058] As can be seen from the above embodiments, the present invention provides a method for separating and extracting valuable metals from acidic leachate of ternary materials from waste batteries using a chromatographic separation system. The present invention couples a valuable metal separation system with a bipolar membrane electrodialysis system, utilizing the principle of a simulated moving bed in the valuable metal separation system to separate lithium, nickel, cobalt, and manganese on a large scale. The obtained lithium, nickel, cobalt, and manganese solutions are then purified using electrodialysis to obtain high-purity lithium alkali, nickel alkali, cobalt alkali, and manganese alkali products with a purity ≥95%. Simultaneously, the byproduct acid (HCl or H2SO4 solution) can be refluxed to the simulated moving bed as the mobile phase, saving resources.

Claims

1. A method for separating and extracting valuable metals from acidic leachate of ternary lithium materials from waste batteries using a chromatographic separation system, wherein the chromatographic separation system comprises a packed column, characterized in that... Includes the following steps: The acidic leachate of waste lithium battery cathode material was filtered and then processed by the first chromatographic separation system to obtain a lithium-containing mixed solution and a nickel-cobalt-manganese mixed solution. The nickel-cobalt-manganese mixture was processed by a second chromatographic separation system to obtain a nickel-containing mixture and a cobalt-manganese mixture. The cobalt-manganese mixture was processed by a third chromatographic separation system to obtain a cobalt-containing mixture and a manganese-containing mixture. The collected lithium-containing, nickel-containing, cobalt-containing, and manganese-containing mixtures were treated by bipolar membrane electrodialysis to obtain lithium hydroxide, nickel hydroxide, cobalt hydroxide, manganese hydroxide, and acid, respectively. The first chromatographic separation system, the second chromatographic separation system, and the third chromatographic separation system each contain N packed columns, the packed columns being carboxylate cationic silica gel packing, where N is 5 to 8; The working voltage of the bipolar membrane electrodialysis treatment is 20~40V, and the working current is 20~300A; The chromatographic separation system adopts the principle of simulating a moving bed; The mobile phase in the chromatographic separation system is hydrochloric acid solution, and the feed rate of the mobile phase is 30-50 ml / min; The lithium-containing mixture contains LiCl and HCl, the nickel-containing mixture contains NiCl2 and HCl, the cobalt-containing mixture contains CoCl2 and HCl, and the manganese-containing mixture contains MnCl2 and HCl; The feed temperature of the acidic leachate of the waste lithium battery cathode material is 30~60℃, and the feed flow rate is 20~30ml / min.

2. The method for separating and extracting valuable metals according to claim 1, characterized in that, The bipolar membrane electrodialysis treatment includes: The collected mixture is then subjected to an electric current, causing anions to pass through an anion exchange membrane into the HCl cell, where they react with H+ generated by the bipolar membrane. + The reaction produces an HCl solution; cations pass through the cation exchange membrane into the MOH cell, where they react with OH- produced by the bipolar membrane. - The corresponding MOH products are obtained through this process; M is one of Li, Ni, Co, and Mn.

3. The method for separating and extracting valuable metals according to claim 1 or 2, characterized in that, The bipolar membrane used in the bipolar membrane electrodialysis treatment includes a BPM-Aquivion-Durion composite bipolar membrane.

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