A heavy metal recovery system for waste lithium batteries

Abstract

The utility model relates to the technical field of high -efficient recovery heavy metal of waste lithium battery, specifically disclose a heavy metal recovery system of waste lithium battery, reduction leaching subsystem: obtain the reduction leaching solution of waste battery basic raw material and strong reducing agent formation, form liquid phase, strong reduction gas generation subsystem: obtain gas phase, multiple gas -liquid two -phase reaction subsystem: by multiple absorption tower and and circulating tank are composed, solid -liquid separation subsystem: separate liquid and solid in multiple gas -liquid two -phase reaction subsystem, tail gas treatment subsystem: handle liquid in multiple gas -liquid two -phase reaction subsystem, impurity removal subsystem: handle solid in multiple gas -liquid two -phase reaction subsystem, three times hydrothermal crystallization subsystem: including impurity removal filter press tank and primary hydrothermal solid -liquid separation tank and three times hydrothermal crystallization tank, filtrate enters primary hydrothermal solid -liquid separation tank and three times hydrothermal crystallization tank, the device solves the problem that the heavy metal recovery of traditional waste lithium battery is difficult.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of efficient recovery of heavy metals from waste lithium batteries, and specifically discloses a heavy metal recovery system for waste lithium batteries. BACKGROUND

[0002] In the face of the increasingly rapid development of the new energy automobile industry, power batteries, as an important part supporting the development of the new energy automobile industry, have a service life of generally only 5-8 years, and according to this service life, China will face a peak of power battery retirement of new energy vehicles around 2025, and a large number of batteries will face recycling and processing, and the existing waste battery recycling is also an important way of battery material source at present.

[0003] Waste lithium batteries contain heavy metal elements such as cobalt, nickel, manganese and lithium, and there are many methods for recovering metal elements at present, and generally, the positive electrode material obtained after battery disassembly is leached, and then solvent extraction, chemical precipitation or electrochemical deposition is used to obtain heavy metal elements such as cobalt, nickel, manganese and lithium. The extraction method has the disadvantages of high cost of extractant, easy volatilization of reagent and incomplete extraction; the chemical deposition method has a relatively simple operation process, but it is necessary to select a suitable precipitant and precipitation condition to improve the recovery rate, and the leaching solution contains various metal ions, and metal ion encapsulation inevitably occurs in the precipitation process, resulting in that the final obtained precipitate contains impurities and has low purity; the electrochemical deposition method has the advantage of high product purity, but for ions with similar reduction potentials, the electrochemical deposition method is prone to co-precipitation, and a large amount of electric power is consumed.

[0004] In view of the existing recovery method, the purpose of the present application is to provide a heavy metal recovery system for waste lithium batteries. CONTENT OF THE UTILITY MODEL

[0005] The utility model discloses a heavy metal recovery system for waste lithium batteries.

[0006] In order to achieve the above-mentioned purpose, the utility model provides the following basic scheme:

[0007] A heavy metal recovery system for waste lithium batteries is formed by the following subsystems:

[0008] Reduction leaching subsystem: obtaining a reduction leaching solution formed by a waste battery basic raw material and a strong reducing agent, and forming a liquid phase;

[0009] Strong reduction gas generation subsystem: obtaining a gas phase;

[0010] Multiple gas-liquid two-phase reaction subsystem: composed of multiple absorption towers and circulating tanks, the gas phase and the liquid phase circulate and react in the absorption towers and the circulating tanks.

[0011] Solid-liquid separation subsystem: separate the liquid and solid in the multiple gas-liquid two-phase reaction subsystem;

[0012] Tail gas treatment subsystem: treat the liquid in the multiple gas-liquid two-phase reaction subsystem;

[0013] Impurity removal subsystem: treat the solid in the multiple gas-liquid two-phase reaction subsystem, and remove impurities from the solid; three times hydrothermal crystallization subsystem: comprising a dewatering filter tank, a first hydrothermal solid-liquid separation tank and a third hydrothermal crystallization tank, the dewatering filter tank separates the filtrate and the filter cake, and the filtrate enters the first hydrothermal solid-liquid separation tank and the third hydrothermal crystallization tank;

[0014] Solid carbon synthesis subsystem: used for treating the liquid in the first hydrothermal solid-liquid separation tank.

[0015] The principle and effect of the present basic scheme are that:

[0016] 1. Compared with the prior art, the device is simple in structure and ingenious in design, and the purpose of the present application is to provide a new recycling system, which recycles heavy metal elements therein through a series of processes such as reduction leaching and hydrothermal crystallization, and obtains a positive electrode material, while the generated sodium sulfate waste liquid is treated to obtain a sodium carbonate solution which is recycled in the system, thereby reducing operating costs and increasing economic benefits of enterprises.

[0017] 2. Compared with the prior art, the system is relatively perfect in use and achieves the effect of efficient recovery of cobalt, nickel, manganese and lithium heavy metal elements in waste lithium batteries, which makes up for the defect that the process of recovering cobalt, nickel, manganese and lithium heavy metal elements in waste lithium batteries is basically uniform in China.

[0018] Further, the waste battery basic raw material is formed into a powder, the strong reducing agent is concentrated sulfuric acid, the concentrated sulfuric acid and the powder are mixed to form a reduction leaching solution, the strong reducing gas generation subsystem comprises a preparation tank and an air tank, the raw material in the preparation tank is sulfur powder, an air generator is arranged in the air tank, sulfur dioxide gas is prepared by the sulfur powder and air, and the reduction leaching solution and the sulfur dioxide gas both enter the multiple gas-liquid two-phase reaction subsystem.

[0019] Further, the multiple gas-liquid two-phase reaction subsystem further comprises a condenser, the condenser is used for condensing the remaining gas and liquid after the gas-liquid two-phase reaction, the gas is condensed into liquid and then enters the tail gas treatment subsystem, and the number of the absorption tower and the circulation tank is at least five groups.

[0020] Further, the solid-liquid separation subsystem includes a separator and a beater, the separator and the beater are connected, the separator separates the liquid and the solid in the multiple gas-liquid two-phase reaction subsystem, the beater beats the solid to re-enter the separator, and the liquid and the solid are separated again, and the separated liquid enters the tail gas treatment subsystem.

[0021] Further, the impurity removal subsystem includes a first impurity removal tank and a second impurity removal tank, the first impurity removal tank and the second impurity removal tank are communicated, the first impurity removal tank is provided with hydrogen peroxide, and the second impurity removal tank is provided with liquid caustic soda.

[0022] Further, the solid-liquid mixture after impurity removal enters a three-time hydrothermal crystallization subsystem, the impurity removal filter tank removes the impurity from the solid-liquid mixture, the solid forms a filter cake, and the liquid enters a first-time hydrothermal solid-liquid separation tank and then enters a three-time hydrothermal crystallization tank.

[0023] Further, the solid carbonization synthesis subsystem includes a collection barrel, a microcavity reactor, and a washing barrel, and the microcavity reactor processes the liquid in the first-time hydrothermal solid-liquid separation tank. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0025] Figure 1 The whole operation flow diagram of the heavy metal recovery system of the waste lithium battery according to the embodiment of the present application is shown.

[0026] Figure 2 The operation diagram of the heavy metal recovery system of the waste lithium battery according to the embodiment of the present application is shown. DETAILED DESCRIPTION

[0027] In order to further illustrate the technical means and effects adopted by the present application to achieve the predetermined utility model purposes, the specific embodiments, structures, features and effects according to the present application will be described in detail below in combination with the drawings and preferred embodiments.

[0028] The reference signs in the drawings of the specification include: reduction leaching subsystem 1, strong reduction gas generation subsystem 2, tail gas treatment subsystem 3, multiple gas-liquid two-phase reaction subsystem 4, solid-liquid separation subsystem 5, impurity removal subsystem 6, three-time hydrothermal crystallization subsystem 7, three-time hydrothermal solid-liquid separation 8, airflow drying 9, and solid carbonization synthesis subsystem 10.

[0029] The embodiments include: Figure 1 andFigure 2 as shown in the following table:

[0030] A heavy metal recovery system for waste lithium batteries is formed by the following subsystems:

[0031] Reduction leaching subsystem 1: obtain waste battery base raw materials and strong reducing agent to form a reduction leaching solution, forming a liquid phase;

[0032] Strong reduction gas generation subsystem 2: obtain a gas phase;

[0033] Specifically:

[0034] The waste battery base raw materials form a powder, the strong reducing agent is concentrated sulfuric acid, the concentrated sulfuric acid and the powder are mixed to form a reduction leaching solution, the strong reduction gas generation subsystem 2 includes a preparation tank and an air tank, the raw material in the preparation tank is sulfur powder, an air generator is arranged in the air tank, sulfur dioxide gas is prepared by sulfur powder and air, and the reduction leaching solution and the sulfur dioxide gas both enter the multiple gas-liquid two-phase reaction subsystem 4.

[0035] Multiple gas-liquid two-phase reaction subsystem 4: composed of multiple absorption towers and circulation tanks, the gas phase and the liquid phase circulate in the absorption towers and circulation tanks to occur gas-liquid two-phase reaction;

[0036] The multiple gas-liquid two-phase reaction subsystem 4 further includes a condenser for condensing the gas and liquid remaining after the gas-liquid two-phase reaction, the gas condensed into liquid enters the tail gas treatment subsystem 3, and the number of absorption towers and circulation tanks is at least five groups.

[0037] Solid-liquid separation subsystem 5: separates the liquid and solid in the multiple gas-liquid two-phase reaction subsystem 4;

[0038] The solid-liquid separation subsystem 5 includes a separator and a beater, the separator and the beater are connected, the separator separates the liquid and solid in the multiple gas-liquid two-phase reaction subsystem 4, the beater beats the solid to enter the separator again, the liquid and solid are separated again, and the separated liquid enters the tail gas treatment subsystem 3.

[0039] Tail gas treatment subsystem 3: treats the liquid in the multiple gas-liquid two-phase reaction subsystem 4;

[0040] Impurity removal subsystem 6: treats the solid in the multiple gas-liquid two-phase reaction subsystem 4 to remove impurities from the solid;

[0041] The impurity removal subsystem 6 includes a first impurity removal tank and a second impurity removal tank, the first impurity removal tank and the second impurity removal tank are communicated, hydrogen peroxide is placed in the first impurity removal tank, and liquid caustic is placed in the second impurity removal tank.

[0042] The solid-liquid mixture after impurity removal enters the third hydrothermal crystallization subsystem 7, the impurity removal pressure filter tank removes impurities from the solid-liquid mixture after impurity removal, the solid forms a filter cake, and the liquid first enters the first hydrothermal solid-liquid separation tank and then enters the third hydrothermal crystallization tank.

[0043] The third hydrothermal crystallization subsystem 7 includes an impurity removal pressure filter tank and a first hydrothermal solid-liquid separation tank and a third hydrothermal crystallization tank, the impurity removal pressure filter tank separates the filtrate and the filter cake, the filtrate enters the first hydrothermal solid-liquid separation tank and the third hydrothermal crystallization tank; the solid carbon synthesis subsystem 10 is used for processing the liquid in the first hydrothermal solid-liquid separation tank, and the solid carbon synthesis subsystem 10 includes a collection barrel, a microcavity reactor and a washing barrel, and the microcavity reactor processes the liquid in the first hydrothermal solid-liquid separation tank.

[0044] For details Figure 1

[0045] The embodiment is combined with the accompanying Figure 1 , which is shown in detail as follows:

[0046] 1. Concentrated sulfuric acid and material black powder are mixed to obtain a reduction leaching solution, the reduction leaching solution enters an absorption tower and a circulation tower, sulfur powder and air are used to prepare sulfur dioxide gas, and the sulfur dioxide gas also enters the absorption tower and the circulation tower, and a gas-liquid two-phase reaction is carried out in the absorption tower and the circulation tower;

[0047] 2. After the reaction, the waste liquid enters a condenser, and then enters a tail gas environmental protection tower, tail gas treatment is carried out to be discharged, and then lithium precipitation synthesis is carried out, specifically, sodium carbonate is added, the lithium precipitation synthesis is pressure filtered to obtain a pressure filter filtrate, and then a lithium carbonate removal process of the filter cake and a sodium carbonate removal process of the filtrate are carried out;

[0048] 3. Back to the absorption tower and the circulation tower, the reduction leaching is completed, and then the leaching is carried out, and the filter cake is formed by pressure filtration, the filter cake is secondly reacted and pulped, mainly by the action of hydrogen peroxide and concentrated sulfuric acid, then the second reaction is pressure filtered, the solid is transported out, and the liquid enters the absorption tower and the circulation tower for absorption and circulation again;

[0049] 4. Back to the mother liquor, first carry out the impurity removal reaction, about the impurity removal reaction, hydrogen peroxide and liquid caustic are added, the liquid caustic is liquid sodium hydroxide, after the reaction, the impurity removal pressure filtration is carried out, the solid and the liquid are separated, the solid is iron and aluminum impurities, forms a filter cake, is collected and treated, and then the filtrate after the impurity removal pressure filtration after the impurity removal reaction is returned;

[0050] ​5. After the impurity removal pressure filtration of the filtrate after the impurity removal reaction, first, the first hydrothermal crystallization, then the first hydrothermal solid separation, after the separation, the first hydrothermal mother liquor is formed, into the microcavity reactor, add 40% liquid alkali, pressure filtration, into the washing tank, add low-temperature condensed water, add carbon dioxide, synthesize lithium carbonate, pressure filtration, filtrate into the tail gas environmental protection tower, gas into the upper tail gas environmental protection tower and waste liquid lithium sink synthesis into lithium carbonate process and filtrate decarburization process, then for the solid, gas flow drying 9, gas is discharged, finished product packaging, the finished product is cobalt nickel carbonate.

[0051] 6. Back to the first hydrothermal solid separation, for the solid, add one water sulfuric acid solid, then two hydrothermal crystallization dissolution, then two hydrothermal crystallization, two hydrothermal solid-liquid separation, recrystallization, add pure water, three hydrothermal crystallization dissolution, form three hydrothermal crystallization, then three hydrothermal solid-liquid separation 8, three hydrothermal mother liquor is recycled to two hydrothermal crystallization dissolution, and then three hydrothermal solid-liquid separation 8, gas flow drying 9, dry tail gas is discharged, finished product packaging, obtain high-purity manganese sulfate.

[0052] The system solves the problem of difficulty in recycling heavy metals in traditional waste lithium batteries.

[0053] The above is only a preferred embodiment of the present application, and does not limit the present application in any form. Although the present application has been disclosed as above with a preferred embodiment, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications to the above disclosed technical content without departing from the scope of the present application, and any equivalent embodiments with equivalent changes are still within the scope of the present application.

Claims

1. A heavy metal recycling system for waste lithium batteries, characterized in that: It is formed by combining the following subsystems; Reduction Leaching Subsystem: Obtains basic raw materials from waste batteries and forms a reduction leaching solution with a strong reducing agent, resulting in a liquid phase; Strong reducing gas generation subsystem: Obtain gas phase; Multiple gas-liquid two-phase reaction subsystem: composed of multiple absorption towers and circulation tanks, wherein the gas phase and the liquid phase circulate in the absorption towers and circulation tanks to undergo gas-liquid two-phase reactions; Solid-liquid separation subsystem: Separates liquids and solids in a multi-phase gas-liquid reaction subsystem; Exhaust gas treatment subsystem: Treats the liquid in the multiple gas-liquid two-phase reaction subsystem; Impurity Removal Subsystem: This subsystem processes solids in a multi-phase gas-liquid reaction system to remove impurities from the solids. The three-stage hydrothermal crystallization subsystem includes a filter press for impurity removal, a primary hydrothermal solid-liquid separation tank, and a tertiary hydrothermal crystallization tank. The filter press for impurity removal separates the filtrate and the filter cake. The filtrate enters the primary hydrothermal solid-liquid separation tank and the tertiary hydrothermal crystallization tank. Solid carbonization synthesis subsystem: used to process liquids in a primary hydrothermal solid-liquid separation tank.

2. The heavy metal recycling system for waste lithium batteries according to claim 1, characterized in that, The strong reducing gas generation subsystem includes a preparation tank and an air tank. The raw material in the preparation tank is sulfur powder, and the air tank is equipped with an air generator. Sulfur dioxide gas is prepared by using sulfur powder and air. Both the reducing leaching solution and the sulfur dioxide gas enter the multiple gas-liquid two-phase reaction subsystem.

3. The heavy metal recycling system for waste lithium batteries according to claim 2, characterized in that, The multiple gas-liquid two-phase reaction subsystem also includes a condenser, which is used to condense the gas and liquid remaining after the gas-liquid two-phase reaction. The gas is condensed into liquid and then enters the tail gas treatment subsystem. The number of absorption towers and circulation tanks is at least five.

4. The heavy metal recycling system for waste lithium batteries according to claim 3, characterized in that, The solid-liquid separation subsystem includes a separator and a slurry mixer connected together. The separator separates the liquid and solid in the multiple gas-liquid two-phase reaction subsystem. The slurry mixer slurries the solid and sends it back into the separator, where the liquid and solid are separated again. The liquid is then separated again and sent to the tail gas treatment subsystem.

5. A heavy metal recycling system for waste lithium batteries according to claim 4, characterized in that, The impurity removal subsystem includes a first impurity removal tank and a second impurity removal tank, which are connected. The first impurity removal tank contains hydrogen peroxide, and the second impurity removal tank contains liquid alkali.

6. The heavy metal recycling system for waste lithium batteries according to claim 1, characterized in that, The impurity-removed solid-liquid mixture enters the three-stage hydrothermal crystallization subsystem. The impurity-removed solid-liquid mixture is filtered in the impurity-removing filter tank. The solid forms a filter cake, and the liquid first enters the primary hydrothermal solid-liquid separation tank, and then enters the tertiary hydrothermal crystallization tank.

7. A heavy metal recycling system for waste lithium batteries according to claim 1, characterized in that, The solid carbonization synthesis subsystem includes a collection tank, a microcavity reactor, and a washing tank. The microcavity reactor processes the liquid in the primary hydrothermal solid-liquid separation tank.

Images