A nickel-cobalt sulfide slag collaborative ternary battery black powder recovery system

Abstract

The nickel cobalt sulfide slag and ternary battery black powder recovery system described in the utility model comprises a microwave device, a leaching device, an impurity removal reaction device, an extraction device, a weight removal reaction device and a precipitation reaction device which are arranged in sequence; the microwave device is connected to the leaching device, and a nickel cobalt sulfide slag inlet is arranged on the microwave device, and a ternary battery black powder inlet is arranged on the leaching device; a first solid-liquid separation device is arranged between the leaching device and the impurity removal reaction device, a second solid-liquid separation device is arranged between the impurity removal device and the extraction device, a third solid-liquid separation device is arranged between the weight removal reaction device and the precipitation reaction device, and the precipitation reaction device is connected to a fourth solid-liquid separation device, and the slag outlet of the fourth solid-liquid separation device is a lithium product outlet. The utility model activates the nickel cobalt sulfide slag through a microwave device, and then uses the oxidizability of the ternary battery black powder to fully cause an oxidation-reduction reaction between the two raw materials, thereby realizing high-value recovery of the valuable metals of the two raw materials.

Description

Technical Field

[0001] The utility model relates to the technical field of battery recycling devices, in particular to a nickel-cobalt sulfide slag cooperative ternary battery black powder recovery system. Background Art

[0002] The black mixture obtained after the waste nickel-cobalt-manganese ternary lithium battery is discharged, disassembled, crushed, sorted and separated is called ternary battery black powder. Ternary battery black powder contains a large amount of valuable metals such as nickel, cobalt, manganese and lithium. In the prior art, the valuable metals in the ternary battery black powder are usually recovered by hydrometallurgical process. The hydrometallurgical process includes an acid leaching process, that is, the battery powder reacts with water and sulfuric acid to obtain a leachate containing nickel, cobalt, manganese and lithium. However, due to the low solubility of high-priced nickel, cobalt and manganese in water, and how to fully reduce nickel, cobalt and manganese into more soluble +2-valent metal ions is the difficulty in research and development. In the prior art, the large amount of reducing agent added during the acid leaching process has a poor reduction effect and introduces impurities, affecting the quality of subsequent products.

[0003] Nickel-cobalt sulfide slag is the tailings produced by sulfide removal in the production process of metallurgy, battery materials, etc. Nickel-cobalt sulfide slag contains a large amount of valuable metals such as nickel, cobalt, manganese and lithium. Most of the slag exists in the form of nickel sulfide, cobalt sulfide and manganese sulfide, and has important recovery value.

[0004] In the prior art, the recycling of nickel cobalt sulfide slag mostly adopts the method of continuously introducing oxygen as an oxidant, which has high production cost and low recycling efficiency. In the recycling of waste nickel cobalt manganese ternary lithium batteries, acid is added for leaching reaction. During the acid leaching process, the high-priced nickel, cobalt and manganese have low solubility in water and cannot be fully reduced. So far, there is no system for comprehensive recycling of nickel cobalt sulfide slag and waste nickel cobalt manganese ternary lithium batteries, so it is urgent to develop. Utility Model Content

[0005] The technical problem solved by the utility model is to provide a nickel-cobalt sulfide slag cooperative ternary battery black powder recovery system to solve the shortcomings of the above-mentioned background technology.

[0006] The technical problem solved by the utility model is achieved by the following technical solutions:

[0007] A nickel-cobalt sulfide slag and ternary battery black powder recovery system, comprising a microwave device, a leaching device, an impurity removal reaction device, an extraction device, a weight removal reaction device and a precipitation reaction device which are arranged in sequence; the microwave device is connected to the leaching device, and a nickel-cobalt sulfide slag inlet is provided on the microwave device, and a ternary battery black powder inlet is provided on the leaching device; a first solid-liquid separation device is provided between the leaching device and the impurity removal reaction device, and a liquid outlet of the first solid-liquid separation device is connected to the impurity removal reaction device; a second solid-liquid separation device is provided between the impurity removal device and the extraction device, and a liquid outlet of the second solid-liquid separation device is connected to the extraction device; a raffinate outlet of the extraction device is connected to a weight removal reaction device; a third solid-liquid separation device is provided between the weight removal reaction device and the precipitation reaction device, and a liquid outlet of the third solid-liquid separation device is connected to the precipitation reaction device; the precipitation reaction device is connected to a fourth solid-liquid separation device, and a slag outlet of the fourth solid-liquid separation device is an outlet for lithium products.

[0008] In the utility model, the leaching device, the impurity removal reaction device, the weight removal reaction device and the precipitation reaction device are respectively a leaching tank, an impurity removal reaction tank, a weight removal reaction tank and a precipitation reaction tank.

[0009] In the utility model, the leaching device is connected to the first auxiliary material tank, and the first auxiliary material tank is a sulfuric acid storage tank.

[0010] In the utility model, the impurity removal reaction device is connected to the second auxiliary material tank, and the second auxiliary material tank is a neutralizer storage tank.

[0011] In the utility model, the weight removal reaction device is connected to the third auxiliary material tank, and the third auxiliary material tank is a precipitant storage tank.

[0012] In the utility model, the precipitation reaction device is connected to the fourth auxiliary material storage tank, and the fourth auxiliary material storage tank is a lithium precipitation agent storage tank.

[0013] In the utility model, the extraction device comprises an extraction tank and a stripping tank, the feed port of the extraction tank is connected to the liquid outlet of the second solid-liquid separation device, and the raffinate outlet of the extraction device is connected to a weight removal reaction device; the extract of the extraction tank is connected to the stripping tank, and the upper part of the stripping tank is connected to a nickel-cobalt-manganese solution storage tank.

[0014] In the utility model, the first solid-liquid separation device, the second solid-liquid separation device, the third solid-liquid separation device, and the fourth solid-liquid separation device are all filter press devices.

[0015] Beneficial effects: The nickel-cobalt sulfide slag and ternary battery black powder recovery system described in the utility model can simultaneously recover nickel-cobalt sulfide slag and ternary battery black powder. The nickel-cobalt sulfide slag is activated by a microwave device, and subsequent treatment can utilize the oxidizing property of the ternary battery black powder to fully cause the nickel-cobalt sulfide slag and the ternary battery black powder to undergo redox reaction, thereby achieving efficient recovery of the valuable metals in the two raw materials.

[0016] By adopting the system of the utility model, the comprehensive recovery rate of nickel can be ≥98.45%, the recovery rate of cobalt can be ≥99.9%, the recovery rate of manganese can be ≥98.45%, and the recovery rate of lithium can be ≥98.64%. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a schematic diagram of a preferred embodiment of the utility model.

[0018] Wherein: 1. microwave device; 2. leaching device; 3. impurity removal reaction device; 4. extraction device; 41. extraction tank; 42. stripping tank; 5. nickel-cobalt-manganese solution storage tank; 6. weight removal reaction device; 7. precipitation reaction device; 8. first auxiliary material tank; 9. second auxiliary material tank; 10. third auxiliary material tank; 11. fourth auxiliary material tank; 12. first solid-liquid separation device; 13. second solid-liquid separation device; 14. third solid-liquid separation device; 15. fourth solid-liquid separation device. DETAILED DESCRIPTION

[0019] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further described below with reference to specific illustrations.

[0020] See also Figure 1 As shown, a nickel-cobalt sulfide slag coordinated ternary battery black powder recovery system includes a microwave device 1, a leaching device 2, an impurity removal reaction device 4, an extraction device 5, a weight removal reaction device 6 and a precipitation reaction device 7 which are arranged in sequence.

[0021] In this embodiment, the leaching device 2, the impurity removal reaction device 3, the weight removal reaction device 6, and the precipitation reaction device 7 are respectively a leaching tank, an impurity removal reaction tank, a weight removal reaction tank, and a precipitation reaction tank. In other embodiments, the leaching device 2, the impurity removal reaction device 3, the weight removal reaction device 6, and the precipitation reaction device 7 can also be a reaction tank, a reaction barrel, and other devices as needed.

[0022] The microwave device 1 is connected to the leaching device 2, wherein the microwave device 1 is provided with an inlet for nickel cobalt sulfide slag, and the nickel cobalt sulfide slag is subjected to microwave heating treatment in the microwave device 1 to be activated; the leaching device 2 is provided with an inlet for ternary battery black powder; the leaching device 2 is connected to the first auxiliary material tank 8, which is a sulfuric acid storage tank; the ternary battery black powder and the activated nickel cobalt sulfide slag undergo leaching reaction in the leaching device 2, and the first auxiliary material tank 8 is used to provide sulfuric acid to the leaching device 2.

[0023] The leaching device 2 is connected to the first solid-liquid separation device 12, and the leachate in the leaching device 2 enters the first solid-liquid separation device 12. The first solid-liquid separation device 12 is preferably a filter press, and the liquid outlet of the first solid-liquid separation device 12 is connected to the impurity removal reaction device 3. The impurity removal reaction device 3 is connected to the second auxiliary material tank 9, which is a neutralizer storage tank. The impurity removal reaction device 3 is connected to the second solid-liquid separation device. The second auxiliary material tank 9 provides a neutralizer in the impurity removal reaction device 3. The neutralizer is one or more of an alkaline metal oxide, a hydroxide, ammonia water, hydrogen peroxide, or an alkaline salt. After the neutralizer reacts with the leachate, it enters the second solid-liquid separation device 13 for solid-liquid separation.

[0024] The liquid outlet of the second solid-liquid separation device 13 is connected to the extraction device 4; specifically, the extraction device 4 includes an extraction tank 41 and a stripping tank 42, the feed port of the extraction tank 41 is connected to the liquid outlet of the second solid-liquid separation device 13, the extract of the extraction tank 41 is connected to the stripping tank 42, and the upper part of the stripping tank 42 is connected to the nickel-cobalt-manganese solution storage tank 5, and a nickel-cobalt-manganese solution is obtained after stripping, and the nickel-cobalt-manganese solution can be used as a raw material for a nickel-cobalt-manganese ternary precursor.

[0025] The raffinate outlet of the extraction device 4 is connected to the weight removal reaction device 6; the weight removal reaction device 6 is connected to the third auxiliary material tank 10, which is a precipitant storage tank, and the precipitant is a sulfide salt or an alkaline pH regulator. A third solid-liquid separation device 14 is arranged between the weight removal reaction device 6 and the precipitation reaction device 7, and the liquid outlet of the third solid-liquid separation device 14 is connected to the precipitation reaction device 7. The raffinate reacts in the weight removal reaction device 6 to remove heavy metals, and is treated by the third solid-liquid separation device 14 to obtain a lithium-containing solution.

[0026] The lithium-containing solution enters the precipitation reaction device 7, and the precipitation reaction device 7 is connected to the fourth auxiliary material storage tank 11, which is a lithium precipitation agent storage tank. The lithium precipitation agent storage tank is used to provide a lithium precipitation agent to the precipitation reaction device 7. The lithium precipitation agent is a soluble salt of phosphate, fluoride or carbonate. The precipitation reaction device 7 is connected to the fourth solid-liquid separation device 15, and the slag outlet of the fourth solid-liquid separation device 15 is the lithium product outlet.

[0027] In a preferred embodiment, the first solid-liquid separation device 12, the second solid-liquid separation device 13, the third solid-liquid separation device 14, and the fourth solid-liquid separation device 15 are all filter press devices.

[0028] The ternary battery black powder described in the utility model is a solid powder obtained by crushing, pulverizing and roasting the ternary battery, and the nickel cobalt sulfide slag is the nickel and cobalt slag removed in the production process of battery-grade manganese sulfate, and the main components of the nickel cobalt sulfide slag are nickel sulfide, cobalt sulfide and manganese sulfide. The system described in the utility model can realize the comprehensive recovery and treatment of the ternary battery black powder and the nickel cobalt sulfide slag, and after being processed by the system described in the utility model, the comprehensive recovery rate of nickel can be ≥98.45%, the recovery rate of cobalt can be ≥99.9%, the recovery rate of manganese can be ≥98.45%, and the recovery rate of lithium can be ≥98.64%.

[0029] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present invention.

[0030] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. In the description of the present utility model, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.

[0031] In the present utility model, unless otherwise clearly stipulated and limited, the terms such as "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, or it can be the internal connection of two elements.

[0032] The above contents are further detailed descriptions of the present invention in combination with specific implementation methods, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions. For ordinary technicians in the technical field to which the present invention belongs, several simple deductions or substitutions can be made without departing from the concept of the present invention.

Claims

1. A nickel-cobalt sulfide slag and ternary battery black powder recovery system, characterized in that: It comprises a microwave device, a leaching device, an impurity removal reaction device, an extraction device, a weight removal reaction device and a precipitation reaction device which are arranged in sequence; the microwave device is connected to the leaching device, a nickel-cobalt sulfide slag inlet is arranged on the microwave device, and a ternary battery black powder inlet is arranged on the leaching device; a first solid-liquid separation device is arranged between the leaching device and the impurity removal reaction device, and a liquid outlet of the first solid-liquid separation device is connected to the impurity removal reaction device; a second solid-liquid separation device is arranged between the impurity removal reaction device and the extraction device, and a liquid outlet of the second solid-liquid separation device is connected to the extraction device; a raffinate outlet of the extraction device is connected to the weight removal reaction device; a third solid-liquid separation device is arranged between the weight removal reaction device and the precipitation reaction device, and a liquid outlet of the third solid-liquid separation device is connected to the precipitation reaction device; the precipitation reaction device is connected to a fourth solid-liquid separation device, and a slag outlet of the fourth solid-liquid separation device is an outlet for lithium products.

2. The nickel-cobalt sulfide slag cooperative ternary battery black powder recovery system according to claim 1 is characterized in that: The leaching device, impurity removal reaction device, weight removal reaction device and precipitation reaction device are respectively a leaching tank, an impurity removal reaction tank, a weight removal reaction tank and a precipitation reaction tank.

3. The nickel-cobalt sulfide slag cooperative ternary battery black powder recovery system according to claim 1 is characterized in that: The leaching device is connected to a first auxiliary material tank, which is a sulfuric acid storage tank.

4. The nickel-cobalt sulfide slag cooperative ternary battery black powder recovery system according to claim 1, characterized in that: The impurity removal reaction device is connected to a second auxiliary material tank, and the second auxiliary material tank is a neutralizer storage tank.

5. The nickel-cobalt sulfide slag cooperative ternary battery black powder recovery system according to claim 1, characterized in that: The weight removal reaction device is connected to a third auxiliary material tank, and the third auxiliary material tank is a precipitant storage tank.

6. The nickel-cobalt sulfide slag cooperative ternary battery black powder recovery system according to claim 1, characterized in that: The precipitation reaction device is connected to a fourth auxiliary material storage tank, and the fourth auxiliary material storage tank is a lithium precipitation agent storage tank.

7. The nickel-cobalt sulfide slag cooperative ternary battery black powder recovery system according to claim 1, characterized in that: The extraction device comprises an extraction tank and a stripping tank, the feed port of the extraction tank is connected to the liquid outlet of the second solid-liquid separation device, and the raffinate outlet of the extraction device is connected to a weight removal reaction device; the extract of the extraction tank is connected to the stripping tank, and the upper part of the stripping tank is connected to a nickel-cobalt-manganese solution storage tank.

8. The nickel-cobalt sulfide slag cooperative ternary battery black powder recovery system according to claim 1, characterized in that: The first solid-liquid separation device, the second solid-liquid separation device, the third solid-liquid separation device, and the fourth solid-liquid separation device are all filter press devices.

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