A method and apparatus for acidification and calcination of ternary lithium battery black powder

Abstract

This disclosure provides a method and apparatus for acid roasting of ternary lithium battery black powder. The acid roasting method includes: after the ternary lithium battery black powder is metered by a loss-in-weight stabilizing device, it is fed into the front of a rotary drum by a first feeding device and mixed with the return material at the return outlet for the first time; sulfuric acid is sprayed into the rotary drum through a flue pipe, so that the sulfuric acid is mixed with the mixture after the first mixing for the second time to form a mixed acid material; the mixed acid material enters the interior of the rotary drum for acidification reaction to form acidified tailings, part of which is sent from the return inlet through the outer return screw to the return outlet at the front of the rotary drum for discharge, completing the return cycle, and the remaining acidified tailings are discharged from the outlet of the rotary drum; the acidified material is fed into the roasting kiln for reaction; the roasted material from the roasting kiln is sent into the cooling kiln for cooling; and dust is removed from the acidified flue gas discharged from the acidification kiln and the roasting flue gas discharged from the roasting kiln by a dust removal component.

Description

Technical Field

[0001] The present disclosure relates to the technical field of material recycling, and in particular, to a method and device for acidifying and roasting black powder of ternary batteries. Background Art

[0002] With the continuous development of society, new energy vehicles have entered thousands of households. After a period of rapid development, the power batteries supporting new energy vehicles have also started to be retired in large quantities. A large number of retired power batteries contain toxic and harmful substances, and at the same time contain raw materials such as nickel, cobalt, and lithium required for the production of power batteries. The toxic and harmful substances in power batteries will cause serious pollution to the environment, and the nickel, cobalt, and lithium elements contained therein can be recycled industrially to form a circular utilization.

[0003] Therefore, how to deal with retired power batteries has become an urgent problem to be solved.

[0004] It should be noted that the information disclosed in the above background art section is only used to enhance the understanding of the background of the present disclosure, and therefore may include information that does not constitute the prior art known to those of ordinary skill in the art. Summary of the Invention

[0005] The purpose of the embodiments of the present disclosure is to provide a method and device for acidifying and roasting black powder of ternary batteries, which can regenerate the black powder of ternary batteries.

[0006] According to one aspect of the embodiments of the present disclosure, a method for acidifying and roasting black powder of ternary batteries is provided. The method for acidifying and roasting black powder of ternary batteries includes:

[0007] A ternary lithium battery black powder acidification and roasting apparatus is provided, comprising a loss-in-weight stabilization device, an acidification kiln, an acid addition and exhaust device, a roasting kiln, a cooling kiln, and a dust removal assembly. The loss-in-weight stabilization device is used to fill the ternary lithium battery black powder through an inlet and to meter the ternary lithium battery black powder. The acidification kiln includes a rotary drum, a first heating assembly, and a first feeding device. The first feeding device is used to transport the ternary lithium battery black powder from the loss-in-weight stabilization device to the rotary drum. Along the axial direction of the rotary drum, a forward spiral and a reverse spiral are provided on the inner wall of the rotary drum near the inlet to form a homogenization and dispersion structure. A positive tail spiral is provided on the inner wall of the rotary cylinder near the discharge port; the first heating assembly includes a heating sleeve, which is sleeved on the rotary cylinder; an external return spiral is provided on the outer wall of the rotary cylinder along its axial direction; a return inlet is provided at one end of the rotary cylinder near the discharge port, and a return outlet is provided at one end of the rotary cylinder near the feed inlet; the external return spiral is located in the channel between the rotary cylinder and the heating sleeve, and is used to transport the return material from the return inlet to the return outlet, so that the return material enters the rotary cylinder through the return outlet; along the rotary cylinder... Along the axial direction, a crushing component is provided on the middle part of the inner wall of the rotary cylinder. The crushing component cooperates with the inner wall of the rotary cylinder to crush the agglomerated acidified material. The acid adding and exhaust equipment includes an exhaust pipe and an acid adding component. The exhaust pipe is connected to the interior of the acidification kiln, and the acid adding component is connected to the exhaust pipe. The acid adding component can add acid to the interior of the acidification kiln through the exhaust pipe, and the acidification flue gas of the acidification kiln is discharged through the exhaust pipe. The roasting kiln includes a roasting kiln cylinder, a second heating component, a roasting kiln discharge box, and a second feeding device. The second feeding device is used to feed the acidified material discharged from the acidification kiln. The material is conveyed into the roasting kiln body; the second heating component is disposed on the roasting kiln body for heating the roasting kiln body; the cooling kiln includes a cooling kiln body, a cooling kiln discharge box, and a third feeding device; the third feeding device is used to convey the roasted material discharged from the roasting kiln to the cooling kiln body, where the roasted material is cooled and discharged; the dust removal component includes a dry dust removal component and a wet dust removal component, which are connected to the flue gas pipe of the acidification kiln and the flue gas pipe of the roasting kiln, and are used to remove dust from the acidification flue gas discharged from the acidification kiln and the roasting flue gas discharged from the roasting kiln.

[0008] The ternary battery black powder is fed into the weight loss stabilization device, and after being metered by the weight loss stabilization device, it is fed into the first feeding device of the acidification kiln. The first feeding device pushes the ternary battery black powder into the front of the rotary cylinder and mixes it with the return material at the return outlet for the first time.

[0009] Sulfuric acid is sprayed into the rotary drum through the exhaust pipe using an acid addition and exhaust equipment, so that the sulfuric acid is mixed with the mixture after the first mixing to form a mixed acid material; the rotary drum is heated by the first heating component;

[0010] The mixed acid material in the rotary drum enters the interior of the rotary drum for acidification reaction. It is then dispersed by the homogenizing and dispersing device composed of the front reverse spiral and the front forward spiral. The crushing component, in cooperation with the inner wall of the rotary drum, crushes the acidified material that has agglomerated after the acidification reaction. After the acidification reaction, acidification tailings are formed. Part of the acidification tailings are sent from the return material inlet to the return material outlet at the front end of the rotary drum through the outer return material spiral and discharged to complete the return material cycle. The remaining acidification tailings are discharged from the discharge box of the rotary drum.

[0011] The acidified material discharged from the discharge box of the acidification kiln is fed into the roasting kiln cylinder of the roasting kiln through the second feeding device for reaction; the roasting kiln cylinder is heated by the second heating component.

[0012] The roasted material from the roasting kiln is fed into the cooling kiln cylinder of the cooling kiln through the third feeding device for cooling.

[0013] The roasting flue gas drawn from the exhaust pipe of the roasting kiln and the acidification flue gas drawn from the exhaust pipe of the acidification kiln are dusted by the dry dust removal component. The dust removal component then removes dust from the acidification flue gas discharged from the acidification kiln and the roasting flue gas discharged from the roasting kiln.

[0014] In one embodiment of this disclosure, the sulfuric acid concentration is 95% to 100%, and the ratio of ternary battery black powder and concentrated sulfuric acid when they are mixed and acidified in an acidification kiln is 1:1.1 to 1:1.5.

[0015] In one embodiment of this disclosure, the acidified material enters the roasting kiln and roasts for 120 min to 180 min at a roasting temperature of 600°C to 750°C. The acidified material continues to react in the roasting kiln, and the temperature fluctuation of the entire heating section is within ±5°C. The temperature of the roasted material discharged from the roasting kiln after cooling in the cooling kiln is ≤60°C.

[0016] In one embodiment of this disclosure, the wet dust collection assembly includes: a Venturi dust collector, a spray scrubbing tower, a Venturi circulation tank, a Venturi circulation pump, and a heat exchanger. The inlet of the Venturi dust collector is connected to the outlet of the dry dust collection assembly, and the Venturi dust collector is used for wet dust removal of the acidified flue gas and calcination flue gas discharged from the dry dust collection assembly. The inlet of the spray scrubbing tower is connected to the outlet of the Venturi dust collector, and the spray scrubbing tower is used for wet dust removal of the acidified flue gas and calcination flue gas discharged from the Venturi dust collector. The outlet of the scrubbing tower is used to discharge the flue gas after wet dust removal; the Venturi circulation tank is used to contain the spray liquid, and the Venturi circulation tank is connected to the bottom of the spray scrubbing tower; the Venturi circulation pump is connected to the Venturi circulation tank and is used to draw the spray liquid; the heat exchanger is connected to the outlet of the Venturi circulation pump and is used to cool the spray liquid drawn by the Venturi circulation pump; the outlet of the heat exchanger is connected to the Venturi dust collector, and the cooled spray liquid is transported to the Venturi dust collector for wet dust removal.

[0017] The dust removal assembly removes dust from the acidification flue gas discharged from the acidification kiln and the roasting flue gas discharged from the roasting kiln, including:

[0018] The acidification flue gas drawn from the flue pipe of the acidification kiln is dusted by a cyclone dust collector, then dusted by liquid cooled by a heat exchanger from the Venturi tube circulation tank in the Venturi dust collector, and then dusted by raw water and liquid from the washing pump in the spray scrubbing tower to form the dust-removed acidification flue gas.

[0019] The roasting flue gas drawn from the exhaust pipe of the roasting kiln is dusted by a cyclone dust collector, then by liquid dust removal from the Venturi tube circulation tank after being cooled by a heat exchanger, and finally by dust removal in a spray scrubbing tower using raw water and liquid from a scrubbing pump, thus forming the dust-removed roasting flue gas.

[0020] According to another aspect of the present disclosure, a ternary lithium battery black powder acidification and calcination apparatus is provided, the ternary lithium battery black powder acidification and calcination apparatus comprising:

[0021] A loss-in-weight stabilizing device is used to fill ternary battery black powder through an inlet and to meter the ternary battery black powder.

[0022] An acidification kiln includes a rotary cylinder, a first heating assembly, and a first feeding device. The first feeding device is used to convey ternary battery black powder from the loss-in-weight stabilization device into the rotary cylinder. Along the axial direction of the rotary cylinder, a forward spiral and a reverse spiral are provided on the inner wall near the feed inlet to form a homogenization and dispersion structure. A tail-forward spiral is provided on the inner wall near the discharge outlet. The first heating assembly includes a heating sleeve fitted onto the rotary cylinder. Along the axial direction of the rotary cylinder, the outer... An external return screw is provided on the wall; a return inlet is provided at one end of the rotary drum near the discharge port, and a return outlet is provided at one end of the rotary drum near the feed port. The external return screw is located in the channel between the rotary drum and the heating sleeve, and is used to transport the return material from the return inlet to the return outlet, so that the return material enters the rotary drum through the return outlet; along the axial direction of the rotary drum, a crushing component is provided in the middle part of the inner wall of the rotary drum, and the crushing component cooperates with the inner wall of the rotary drum to crush the agglomerated acidified material;

[0023] An acid-adding flue gas device is provided, comprising a flue gas pipe and an acid-adding component. The flue gas pipe is connected to the interior of the acidification kiln, and the acid-adding component is connected to the flue gas pipe. The acid-adding component can add acid to the interior of the acidification kiln through the flue gas pipe, and the acidification flue gas of the acidification kiln is discharged through the flue gas pipe.

[0024] The roasting kiln includes a roasting kiln body, a second heating component, a roasting kiln discharge box, and a second feeding device. The second feeding device is used to transport the acidified material discharged from the acidification kiln to the roasting kiln body. The second heating component is disposed on the roasting kiln body and is used to heat the roasting kiln body.

[0025] A cooling kiln, comprising a cooling kiln cylinder, a cooling kiln discharge box, and a third feeding device, wherein the third feeding device is used to transport the roasted material discharged from the roasting kiln to the cooling kiln cylinder, thereby cooling and discharging the roasted material through the cooling kiln;

[0026] A dust removal component is connected to the exhaust pipe of the acidification kiln and the exhaust pipe of the roasting kiln, and is used to remove dust from the acidification flue gas discharged from the acidification kiln and the roasting flue gas discharged from the roasting kiln.

[0027] In one embodiment of this disclosure, a plurality of lifting plates are provided inside the discharge port of the rotary cylinder. The lifting plates are arranged radially along the rotary cylinder, and the plurality of lifting plates are distributed axially along the rotary cylinder.

[0028] In one embodiment of this disclosure, the dust removal assembly includes a dry dust removal assembly and a wet dust removal assembly. The dry dust removal assembly is connected to the exhaust pipe of the acidification kiln and the exhaust pipe of the roasting kiln, and is used to perform dry dust removal on the acidification flue gas discharged from the acidification kiln and the roasting flue gas discharged from the roasting kiln. The wet dust removal assembly is connected to the dry dust removal assembly and is used to perform wet dust removal on the acidification flue gas and the roasting flue gas discharged from the dry dust removal assembly.

[0029] In one embodiment of this disclosure, the dry dust collection assembly includes:

[0030] The first cyclone dust collector is connected to the flue gas pipe of the acidification kiln. The first cyclone dust collector is used to remove dust from the acidification flue gas entering through the flue gas pipe. The bottom of the first cyclone dust collector is connected to the second feeding device, through which the settled material is conveyed to the kiln body.

[0031] The second cyclone dust collector is connected to the interior of the roasting kiln body through a flue gas pipeline and is used to remove dust from the roasting flue gas discharged from the roasting kiln body; the bottom of the second cyclone dust collector is connected to the second feeding device, through which the settled material is transported to the roasting kiln body.

[0032] In one embodiment of this disclosure, the wet dust collection assembly includes:

[0033] The Venturi dust collector has its inlet connected to the outlets of the first cyclone dust collector and the second cyclone dust collector. The Venturi dust collector is used to perform wet dust removal on the acidified flue gas and roasting flue gas discharged from the first cyclone dust collector and the second cyclone dust collector.

[0034] A spray scrubbing tower is provided, the inlet of which is connected to the outlet of the Venturi dust collector. The spray scrubbing tower is used for wet dust removal of the acidified flue gas and roasting flue gas discharged from the Venturi dust collector. The outlet of the spray scrubbing tower is used to discharge the flue gas after wet dust removal.

[0035] A Venturi circulation tank is used to contain the spray liquid and is connected to the bottom of the spray scrubbing tower.

[0036] A Venturi circulation pump, which is connected to the Venturi circulation tank, is used to extract the spray liquid;

[0037] A heat exchanger is connected to the outlet of the Venturi circulating pump to cool the spray liquid drawn by the Venturi circulating pump; the outlet of the heat exchanger is connected to the Venturi dust collector to transport the cooled spray liquid to the Venturi dust collector for wet dust removal.

[0038] In one embodiment of this disclosure, the top of the spray scrubbing tower is provided with a raw water inlet, and the wet dust removal assembly further includes:

[0039] A washing pump, which is connected to the bottom of the spray scrubbing tower, is used to transport the washing liquid at the bottom of the spray scrubbing tower to the top of the spray scrubbing tower for wet dust removal.

[0040] The ternary lithium battery black powder acidification and roasting method disclosed herein uses a loss-in-weight stabilization device to meter the ternary lithium battery black powder. A first feeding device conveys the ternary lithium battery black powder from the loss-in-weight stabilization device to a rotary drum. The acid addition and exhaust device includes an exhaust pipe and an acid addition component. The acid addition component adds acid to the interior of the acidification kiln through the exhaust pipe, and the acidification flue gas from the acidification kiln is discharged through the exhaust pipe. A first heating component heats the rotary drum, thereby heating the acidified material and increasing the reaction rate. A self-returning structure consisting of a tail forward spiral and an external return spiral returns the high-temperature acidified material to the feed end of the rotary drum. The moist material falls directly onto the return material, without contacting the drum wall, reducing corrosion to the drum. At the same time, the large amount of return material effectively disperses the reactants that easily form a viscous state, making the reactants loose and preventing sticking. The homogenizing and dispersing structure and crushing components, consisting of a front-reverse spiral and a front-forward spiral, can break down and crush lumpy materials, making them loose and preventing the acidified material from forming scale on the cylinder wall. Simultaneously, the material does not adhere into particles during acidification, resulting in a high acidification rate and improved recovery rates of elements such as nickel, cobalt, and lithium, increasing the company's economic benefits and avoiding waste of industrial raw materials. Furthermore, the dust removal components effectively remove dust from the acidification flue gas discharged from the acidification kiln and the roasting flue gas discharged from the roasting kiln, preventing the leakage of large amounts of flue gas and dust during acidification production, thus avoiding environmental pollution and protecting the health of employees. The large amounts of flue gas, water vapor, and dust generated after acidification are discharged through the dust removal components without clogging the exhaust pipe, ensuring normal production and reducing equipment maintenance and worker workload.

[0041] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and are not intended to limit this disclosure. Attached Figure Description

[0042] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this disclosure and, together with the description, serve to explain the principles of this disclosure. It is obvious that the drawings described below are merely some embodiments of this disclosure, and those skilled in the art can obtain other drawings based on these drawings without any inventive effort. In the drawings:

[0043] Figure 1 A schematic diagram of a ternary lithium battery black powder acidification and calcination apparatus provided for one embodiment of the present disclosure;

[0044] Figure 2 This is a schematic diagram of the structure of an acidification kiln provided in one embodiment of the present disclosure;

[0045] Figure 3 for Figure 2 Cross-sectional view at point AA;

[0046] Figure 4 A schematic diagram of the structure of the first feeding device and the acid addition and exhaust device provided in one embodiment of this disclosure;

[0047] Figure 5 This is a schematic diagram of the structure of a roasting kiln provided in one embodiment of the present disclosure;

[0048] Figure 6 This is a schematic diagram of the structure of a cooling kiln provided in one embodiment of the present disclosure.

[0049] Explanation of reference numerals in the attached figures:

[0050] 10. Loss-in-weight stabilization equipment;

[0051] 20. Acidification kiln; 210. Rotary cylinder; 211. Front forward spiral; 212. Front reverse spiral; 213. Tail forward spiral; 214. External return spiral; 215. Return material inlet; 216. Return material outlet; 22. First feeding device; 221. First feeding spiral; 222. Front stationary ring seat; 223. Front stationary ring; 224. Spiral connecting short pipe; 225. Expansion joint connecting flange; 226. Expansion joint rear flange; 227. 228. Expansion joint front flange; 229. Spiral connection flange; 230. Heating sleeve; 241. Front moving ring bracket; 242. Front short section; 243. Front end plate; 244. Front moving ring; 251. Rear moving ring; 252. Rear short section; 253. Rear end plate; 254. Rear moving ring bracket; 260. Lifting plate; 271. Roller ring bracket; 272. Roller ring; 281. Crushing assembly; 282. Front partition plate; 283. Rear partition plate;

[0052] 30. Acid addition and exhaust equipment; 310. Exhaust pipe; 321. Sulfuric acid storage tank; 322. Sulfuric acid pump; 323. Acid inlet pipe;

[0053] 40. Firing kiln; 410. Firing kiln cylinder; 420. Second heating component; 430. Firing kiln discharge box; 440. Second feeding device;

[0054] 50. Cooling kiln; 510. Cooling kiln shell; 520. Cooling kiln discharge box; 530. Third feeding equipment;

[0055] 61. First cyclone dust collector; 62. Second cyclone dust collector; 63. Venturi dust collector; 631. Venturi circulation tank; 632. Venturi circulation pump; 64. Spray scrubbing tower; 641. Scrubber pump; 65. Heat exchanger. Detailed Implementation

[0056] Exemplary embodiments will now be described more fully with reference to the accompanying drawings. However, these exemplary embodiments can be implemented in many forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided so that this disclosure will be more thorough and complete, and will fully convey the concept of the exemplary embodiments to those skilled in the art.

[0057] Furthermore, the described features, structures, or characteristics can be combined in any suitable manner in one or more embodiments. Numerous specific details are provided in the following description to give a thorough understanding of embodiments of this disclosure. However, those skilled in the art will recognize that the technical solutions of this disclosure can be practiced without one or more of the specific details, or other methods, components, apparatuses, steps, etc., can be employed. In other instances, well-known methods, apparatuses, implementations, or operations are not shown or described in detail to avoid obscuring aspects of this disclosure. The block diagrams shown in the accompanying drawings are merely functional entities and do not necessarily correspond to physically independent entities. That is, these functional entities can be implemented in software, or in one or more hardware modules or integrated circuits, or in different network and / or processor devices and / or microcontroller devices.

[0058] Although relative terms such as "up" and "down" are used in this specification to describe the relative relationship of one component of an icon to another, these terms are used only for convenience, such as according to the orientation of the examples shown in the accompanying drawings. It is understood that if the device of the icon is flipped upside down, the component described as "up" will become the component described as "down." When a structure is "up" of another structure, it may mean that the structure is integrally formed on the other structure, or that the structure is "directly" mounted on the other structure, or that the structure is "indirectly" mounted on the other structure through another structure.

[0059] The terms “a,” “one,” “the,” and “at least one” are used to indicate the existence of one or more elements / components / etc.; the terms “including” and “having” are used to indicate an open-ended inclusion and to mean that there may be other elements / components / etc. in addition to the listed elements / components / etc.; the terms “first,” “second,” etc. are used only as markers and are not a limitation on the number of objects.

[0060] Currently, there are two main methods for the industrial processing of retired power batteries. One method is to directly reuse power batteries with a certain amount of spare power to build energy storage power stations. The other method is to dismantle power batteries without spare power, and then pre-treat the dismantled power batteries by sorting and crushing them into ternary lithium battery powder. The ternary lithium battery powder is then acidified, roasted, cooled, and slurryed to extract useful raw materials such as nickel, cobalt, and lithium, thus achieving industrial recycling.

[0061] However, the industrial acidification process for ternary battery black powder mainly involves mixing concentrated sulfuric acid and ternary battery black powder in a certain proportion in a stirring device. This acidification process generates a large amount of fumes and dust leaks, polluting the environment and harming the health of employees. The large amounts of fumes, water vapor, and dust produced after acidification can clog exhaust pipes, affecting normal production and increasing equipment maintenance and worker workload. Furthermore, material scaling and clumping adhere to equipment surfaces during acidification, causing corrosion, shortening equipment lifespan, and increasing production costs. The material also tends to clump together during acidification, resulting in a low acidification rate and affecting the recovery rate of elements such as nickel, cobalt, and lithium, reducing the company's economic benefits and wasting industrial raw materials.

[0062] To address the aforementioned technical problems, this disclosure provides a ternary lithium battery black powder acidification and calcination apparatus, such as... Figures 1-6As shown, the ternary battery black powder acidification and roasting device includes: a weight loss stabilization device 10, an acidification kiln 20, an acid addition and exhaust device 30, a roasting kiln 40, a cooling kiln 50, and a dust removal component. The loss-in-weight stabilization device 10 is used to fill ternary battery black powder through the inlet and to meter the ternary battery black powder; the acidification kiln 20 includes a rotary cylinder 210, a first heating component, and a first feeding device 22. The first feeding device 22 is used to transport the ternary battery black powder in the loss-in-weight stabilization device 10 to the rotary cylinder 210; the first heating component is located on the rotary cylinder 210 and is used to heat the rotary cylinder 210; the acid addition and exhaust device 30 includes an exhaust pipe 310 and an acid addition component. The exhaust pipe 310 is connected to the interior of the acidification kiln 20, and the acid addition component is connected to the exhaust pipe 310. The acid addition component can add acid to the interior of the acidification kiln 20 through the exhaust pipe 310, and the acidification flue gas of the acidification kiln 20 is discharged through the exhaust pipe 310; the roasting kiln 40 includes a roasting kiln cylinder 410, a second The furnace includes a heating assembly 420, a roasting kiln discharge box 430, and a second feeding device 440. The second feeding device 440 is used to transport the acidified material discharged from the acidification kiln 20 to the roasting kiln cylinder 410. The second heating assembly 420 is installed on the roasting kiln cylinder 410 and is used to heat the roasting kiln cylinder 410. The cooling kiln 50 includes a cooling kiln cylinder 510, a cooling kiln discharge box 520, and a third feeding device 530. The third feeding device 530 is used to transport the roasted material discharged from the roasting kiln 40 to the cooling kiln cylinder 510, whereby the roasted material is cooled and discharged through the cooling kiln 50. The dust removal assembly is connected to the exhaust pipe 310 of the acidification kiln 20 and the exhaust pipe of the roasting kiln 40 and is used to remove dust from the acidification flue gas discharged from the acidification kiln 20 and the roasting flue gas discharged from the roasting kiln 40.

[0063] The ternary lithium battery black powder acidification and roasting apparatus disclosed herein uses a loss-in-weight stabilization device 10 to meter the ternary lithium battery black powder. A first feeding device 22 conveys the ternary lithium battery black powder from the loss-in-weight stabilization device 10 to a rotary drum 210. An acid addition and exhaust device 30 includes an exhaust pipe 310 and an acid addition component. The acid addition component adds acid to the interior of the acidification kiln 20 through the exhaust pipe 310, and the acidification flue gas from the acidification kiln 20 is discharged through the exhaust pipe 310. A first heating component heats the rotary drum 210, thereby heating the acidified material and increasing the reaction rate. A self-returning structure consisting of a tail forward spiral 213 and an external return spiral 214 returns the high-temperature acidified material to the feed end of the rotary drum 210. Moist materials fall directly onto the return material, avoiding contact with the drum wall, reducing corrosion of the drum. Simultaneously, the large amount of return material effectively disperses the reaction materials that easily form a viscous state, allowing the reaction to proceed more smoothly. The material is kept in a loose state to prevent it from sticking to the wall and forming rings. The homogenizing and dispersing structure and crushing component 281, composed of the forward and reverse spirals 212 and the forward spiral 211, can break up and crush the lumpy material, making it loose and preventing the acidified material from forming scale on the cylinder wall. At the same time, the material will not stick together into particles during the acidification process, resulting in a high acidification rate, which in turn improves the recovery rate of elements such as nickel, cobalt, and lithium, increases the economic benefits of the enterprise, and avoids the waste of industrial raw materials. In addition, the dust removal component removes dust from the acidification flue gas discharged from the acidification kiln 20 and the roasting flue gas discharged from the roasting kiln 40, which can prevent the generation of a large amount of flue gas and dust during the acidification process from leaking and polluting the environment, and avoid harming the health of the employees. The large amount of flue gas, water vapor, and dust generated after acidification will not block the exhaust pipe when discharged from the exhaust pipe after passing through the dust removal component, so that the production can proceed normally and reduce the amount of equipment maintenance and the labor intensity of the workers.

[0064] Specifically, such as Figure 2 As shown, the first heating component includes a heating sleeve 230, which is sleeved on the rotating cylinder 210. A heat transfer medium or heating element is provided in the heating sleeve 230 to achieve the heating function.

[0065] Along the axial direction of the rotary cylinder 210, an external return spiral 214 is provided on the outer wall of the rotary cylinder 210; a return inlet 215 is provided at one end of the rotary cylinder 210 near the discharge port, and a return outlet 216 is provided at one end of the rotary cylinder 210 near the feed port. The external return spiral 214 is located in the channel between the rotary cylinder 210 and the heating sleeve 230, and is used to transport the return material from the return inlet 215 to the return outlet 216 so that the return material enters the rotary cylinder 210 through the return outlet 216.

[0066] Among them, such as Figure 2As shown, the acidification kiln 20 includes a rotary cylinder 210, a first heating assembly, and a first feeding device 22. Along the axial direction of the rotary cylinder 210, a forward spiral 211 and a reverse spiral 212 are provided on the inner wall of the rotary cylinder 210 near the feed inlet to form a homogenizing and dispersing structure. A tail spiral 213 is provided on the inner wall of the rotary cylinder 210 near the discharge outlet. The homogenizing and dispersing structure is formed by the forward spiral 211 and the reverse spiral 212 on the inner wall of the rotary cylinder near the feed inlet. The first feeding device 22 pushes the ternary battery black powder into the front of the rotary cylinder 210, where it is mixed for the first time with the return material from the return outlet 216, thus homogenizing and dispersing the ternary battery black powder entering from the feed inlet of the rotary cylinder 210.

[0067] Among them, such as Figure 2 As shown, a crushing component 281 is installed on the middle part of the inner wall of the rotary drum 210 along its axial direction. The crushing component 281 works in conjunction with the inner wall of the rotary drum 210 to crush agglomerated acidified material, preventing material from forming scale on the drum wall during acidification. This avoids agglomerated material adhering to the equipment surface and causing acid corrosion, thus improving the service life of the device and reducing production costs. The crushing component 281 can be a free spiral, chain, steel bar, or steel rod installed on the rotary drum 210. The rotation of the free spiral, chain, steel bar, or steel rod crushes the agglomerated acidified material adhering to the drum wall.

[0068] Among them, such as Figure 2 As shown, the crushing assembly 281 has a front baffle 282 at its front end and a rear baffle 283 at its rear end. The front baffle 282 and the rear baffle 283 are provided with through holes to allow the acidified material to move toward the tail of the rotary drum 210. The front baffle 282 and the rear baffle 283 can prevent the crushing assembly 281 from moving back and forth.

[0069] Among them, such as Figure 2 and Figure 3 As shown, multiple lifting plates 260 are installed inside the discharge port of the rotary drum 210. The lifting plates 260 are arranged radially along the rotary drum 210, and the multiple lifting plates 260 are distributed axially along the rotary drum 210. The mixed acid material enters the rotary drum 210 and undergoes an acidification reaction. After passing through the homogenization and dispersing structure composed of the front reverse spiral 212 and the front forward spiral 211, the exothermic chemical reaction proceeds rapidly. The resulting agglomerates are crushed by the crushing component 281. After the agglomerated acid material has fully reacted, it forms acidification tailings. A portion of the acidification tailings is sent from the return inlet 215 through the outer return spiral 214 to the return outlet 216 at the front end of the rotary drum 210 for discharge, completing the return cycle. The remaining acidification tailings are discharged from the tail end of the rotary drum 210 by the lifting plates 260 and sent to the subsequent process.

[0070] Among them, such as Figure 2and Figure 3 As shown, the acidified tailings, fed to the front end of the rotary drum 210 via the return material circulation, and discharged from the return material outlet 216, form an accumulation layer on the inner wall of the rotary drum 210, which protects the rotary drum 210. The wet material formed by the concentrated sulfuric acid flowing in from the acid addition and exhaust equipment 30 and the black powder fed in by the first feeding equipment 22 does not fall directly onto the drum wall of the rotary drum 210, but rather onto this accumulation layer. Since this accumulation layer is composed of fully reacted acidified tailings, it reduces the corrosion of the rotary drum 210.

[0071] Among them, such as Figure 2 and Figure 3 As shown, the front end of the rotary drum 210 is provided with a front moving ring bracket 241, a front short section 242, a front end plate 243, and a front moving ring 244, with the front moving ring 244 forming the feed inlet of the rotary drum 210; as Figure 4 As shown, the first feeding device 22 includes a first feeding screw 221, a front stationary ring seat 222, a front stationary ring 223, a spiral connecting short pipe 224, an expansion joint connecting flange 225, an expansion joint rear flange 226, an expansion joint 227, an expansion joint front flange 228, and a spiral connecting flange 229. The first feeding screw 221 includes a feeding screw shell and a screw shaft. The front end of the feeding screw shell is provided with a feed inlet, and the front end of the screw is provided with a driving device. The screw shaft can be driven to rotate by the driving device. The front stationary ring 223 is sleeved on the tail end of the feeding screw cylinder. The spiral connecting short pipe 224, the expansion joint connecting flange 225, the expansion joint rear flange 226, the expansion joint 227, the expansion joint front flange 228, and the spiral connecting flange 229 are also sequentially sleeved on the tail end of the feeding screw cylinder and are located on the side of the front stationary ring 223 near the front end of the feeding screw cylinder. The front stationary ring 223 of the first feeding device 22 contacts the front moving ring 244 on the rotary drum 210 so that the discharge port of the first feeding screw 221 is connected to the inlet of the rotary drum 210; the expansion joint 227 can compensate for the axial expansion of the feeding screw drum relative to the rotary drum 210.

[0072] Among them, such as Figure 1 and Figure 2 As shown, the rear end of the rotary drum 210 is provided with a rear moving ring 251, a rear short section 252, a rear end plate 253, and a rear moving ring bracket 254. A feeding device can also be provided at the rear end of the rotary drum 210 to transport the acidified material discharged from the rotary drum 210 to the calcining kiln 40. The feeding device at the rear end of the rotary drum 210 and the connection method between the feeding device and the rotary drum 210 can be the same as the connection method between the first feeding device 22 and the front end of the rotary drum 210 described above.

[0073] Among them, such as Figure 2As shown, the rotating cylinder 210 is provided with a rolling ring 272 and a rolling ring bracket 271. The rolling ring 272 is connected to the rotating cylinder 210 through the rolling ring bracket 271 to form rolling support for the rotating cylinder 210. The rolling ring 272 and the rolling ring bracket 271 can be set at positions near the front and rear ends of the rotating cylinder 210 respectively to improve the stability of the support.

[0074] Specifically, such as Figure 1 and Figure 4 As shown, the acid addition and exhaust device 30 includes an exhaust pipe 310, a sulfuric acid storage tank 321, a sulfuric acid pump 322, and an acid inlet pipe 323. The concentrated sulfuric acid in the sulfuric acid storage tank 321 is added to the acid inlet pipe 323 through the sulfuric acid pump 322. The acid inlet pipe 323 is connected to the exhaust pipe 310, thereby adding the concentrated sulfuric acid to the rotary cylinder 210.

[0075] Specifically, such as Figure 1 and Figure 5 As shown, the roasting kiln 40 includes a roasting kiln body 410, a second heating component 420, a roasting kiln discharge box 430, and a second feeding device 440. The acidified material discharged from the acidification kiln 20 enters the second feeding device 440, which transports the acidified material to the roasting kiln body 410. The second heating component 420 is fitted on the roasting kiln body 410 to heat and roast the acidified material. After roasting, the roasted material in the roasting kiln body 410 enters the roasting kiln discharge box 430.

[0076] The second heating component 420 can be an electric heating component or a flue gas heating component.

[0077] The roasting kiln cylinder 410 can rotate to discharge the roasting material from the discharge port into the roasting kiln discharge box 430.

[0078] The connection between the second feeding device 440 and the calcining kiln cylinder 410 can be the same as the connection between the first feeding device 22 and the front end of the rotary cylinder 210.

[0079] Specifically, such as Figure 1 and Figure 6 As shown, the cooling kiln 50 includes a cooling kiln shell 510, a cooling kiln discharge box 520, and a third feeding device 530. The inlet of the third feeding device 530 is connected to the outlet of the calcining kiln discharge box 430, and the third feeding device 530 transports the calcined material to the cooling kiln shell 510 for cooling. The cooling kiln shell 510 can be cooled by circulating liquid in the circulation pipeline, i.e., circulating water supply and circulating water return; after cooling, it is discharged through the cooling kiln discharge box 520 for use in subsequent processes.

[0080] Specifically, the dust removal components include dry dust removal components and wet dust removal components. The dry dust removal components are connected to the exhaust pipe 310 of the acidification kiln 20 and the exhaust pipe of the roasting kiln 40, and are used to perform dry dust removal on the acidification flue gas discharged from the acidification kiln 20 and the roasting flue gas discharged from the roasting kiln 40. The wet dust removal components are connected to the dry dust removal components and are used to perform wet dust removal on the acidification flue gas and the roasting flue gas discharged from the dry dust removal components.

[0081] Among them, such as Figure 1 As shown, the dry dust removal assembly includes a first cyclone dust collector 61 and a second cyclone dust collector 62. The first cyclone dust collector 61 is connected to the exhaust pipe 310 of the acidification kiln 20 and is used to remove dust from the acidification flue gas entering through the exhaust pipe 310. The bottom of the first cyclone dust collector 61 is connected to the second feeding device 440, through which the settled material is conveyed to the roasting kiln shell 410. The second cyclone dust collector 62 is connected to the interior of the roasting kiln shell 410 through a flue gas pipeline and is used to remove dust from the roasting flue gas discharged from the roasting kiln shell 410. The bottom of the second cyclone dust collector 62 is connected to the second feeding device 440, through which the settled material is conveyed to the roasting kiln shell 410.

[0082] Among them, such as Figure 1 As shown, the wet dust collection assembly includes a Venturi scrubber 63 and a spray scrubbing tower 64. The inlet of the Venturi scrubber 63 is connected to the outlets of the first cyclone scrubber 61 and the second cyclone scrubber 62, and the Venturi scrubber 63 is used to perform wet dust removal on the acidified flue gas and roasting flue gas discharged from the first cyclone scrubber 61 and the second cyclone scrubber 62; the inlet of the spray scrubbing tower 64 is connected to the outlet of the Venturi scrubber 63, and the spray scrubbing tower 64 is used to perform wet dust removal on the acidified flue gas and roasting flue gas discharged from the Venturi scrubber 63; the outlet of the spray scrubbing tower 64 is used to discharge the flue gas after wet dust removal.

[0083] Among them, such as Figure 1 As shown, the wet dust collection assembly also includes: a Venturi circulation tank 631, a Venturi circulation pump 632, and a heat exchanger 65. The Venturi circulation tank 631 contains the spray liquid and is connected to the bottom of the spray scrubbing tower 64; the Venturi circulation pump 632 is connected to the Venturi circulation tank 631 and is used to extract the spray liquid; the heat exchanger 65 is connected to the outlet of the Venturi circulation pump 632 and is used to cool the spray liquid extracted by the Venturi circulation pump 632; the outlet of the heat exchanger 65 is connected to the Venturi dust collector 63, transporting the cooled spray liquid to the Venturi dust collector 63 for wet dust removal. The heat exchanger 65 achieves liquid heat exchange through circulating water intake and exhaust.

[0084] Among them, such as Figure 1As shown, the top of the spray scrubbing tower 64 is provided with a raw water inlet. The wet dust removal assembly also includes a scrubbing pump 641, which is connected to the bottom of the spray scrubbing tower 64 and is used to transport the scrubbing liquid at the bottom of the spray scrubbing tower 64 to the top of the spray scrubbing tower 64 for wet dust removal.

[0085] The Venturi circulation tank 631 is equipped with a drain outlet to discharge excess washing liquid flowing from the spray washing tower 64.

[0086] The embodiments of this disclosure also provide a method for acidifying and calcining ternary lithium battery black powder, the method comprising:

[0087] Step S100: Provide a ternary battery black powder acidification and calcination apparatus, which can be the ternary battery black powder acidification and calcination apparatus provided in the above embodiment.

[0088] Step S200: The ternary battery black powder is fed into the loss-in-weight stabilization equipment. After being metered by the loss-in-weight stabilization equipment, it is fed into the first feeding equipment of the acidification kiln. The first feeding equipment pushes the ternary battery black powder to the front of the rotary cylinder and mixes it with the return material at the return outlet for the first time.

[0089] Step S300: Using an acid addition and fume extraction device, sulfuric acid is sprayed into the rotary drum through the fume extraction pipe, so that the sulfuric acid is mixed with the mixture after the first mixing to form a mixed acid material; the rotary drum is heated by the first heating component.

[0090] Step S400: The mixed acid material in the rotary drum enters the interior of the rotary drum for acidification reaction. It is then dispersed by a homogenizing and dispersing device composed of a front reverse spiral and a front forward spiral. The acidified material that has agglomerated due to acidification reaction is crushed by the crushing component in cooperation with the inner wall of the rotary drum. After the acidification reaction, acidification tailings are formed. Part of the acidification tailings are sent from the return material inlet to the return material outlet at the front end of the rotary drum through the outer return material spiral to complete the return material cycle. The remaining acidification tailings are discharged from the discharge port of the rotary drum.

[0091] Step S500: The acidified material discharged from the outlet of the acidification kiln is fed into the roasting kiln cylinder of the roasting kiln through the second feeding device for reaction; the roasting kiln cylinder is heated by the second heating component.

[0092] Step S600: The roasted material from the roasting kiln is fed into the cooling kiln cylinder of the cooling kiln through the third feeding device for cooling.

[0093] Step S700: After the calcining flue gas drawn from the flue gas pipe of the calcining kiln and the acidification flue gas drawn from the flue gas pipe of the acidification kiln are dusted by the dry dust removal component, the acidification flue gas discharged from the acidification kiln and the calcining flue gas discharged from the calcining kiln are dusted by the dust removal component and sent to the subsequent process of acid production.

[0094] Specifically, the specific process of the acid roasting apparatus provided in this disclosure is as follows:

[0095] 1) The ternary lithium battery black powder is fed into the loss-in-weight stabilization system, and after metering, it is fed into the feed screw of the acidification kiln 20. The first feeding screw 221 pushes the ternary lithium battery black powder into the front of the rotary cylinder 210, where it is mixed with the return material from the return outlet 216 for the first time. The return material brings a large amount of heat, which rapidly raises the temperature of the mixture and increases the reaction rate. For the conveying equipment, belt conveyors, bucket elevators, chain bucket conveyors, and other methods well known to those skilled in the art can be selected. Preferably, a bucket elevator is used.

[0096] 2) The acid inlet pipe 323 is obliquely inserted into the exhaust pipe 310. The acidified flue gas after the reaction is discharged from the front exhaust pipe 310. The concentrated sulfuric acid is sprayed into the rotary drum 210 through the exhaust pipe 310, and it is mixed with the above-mentioned primary mixture to form a mixed acid material. For the equipment material, a corrosion-resistant material is selected. The concentration of concentrated sulfuric acid can be 95% to 100%, such as 95%, 96%, 97%, 98%, 99%, and 100%. The ternary battery black powder and concentrated sulfuric acid are respectively introduced into the acidification kiln 20 for mixing and acidification. The material-acid ratio is 1:1.1 to 1:1.5, such as 1:1.1, 1:1.2, 1:1.25, 1:1.3, 1:1.35, 1:1.4, and 1:1.5. When the ratio of material to acid is 1:1.1, the particle size of the ternary battery black powder is 200 mesh, the feeding rate is 100 kg / h, the acid mixing time is 30 min, the acidified material particle size is less than 0.5 mm, accounting for 95%, less than 1 mm, accounting for 100%, and the acidification rate of the ternary battery black powder is 98%. When the material-to-acid ratio is 1:1.2, the particle size of the ternary lithium battery black powder is 200 mesh, the feeding rate is 120 kg / h, the acid mixing time is 40 min, the acidified material particles with a size less than 0.5 mm account for 96%, and those less than 1 mm account for 100%, resulting in an acidification rate of 98.5% for the ternary lithium battery black powder. When the material-to-acid ratio is 1:1.3, the particle size of the ternary lithium battery black powder is 200 mesh, the feeding rate is 120 kg / h, the acid mixing time is 50 min, the acidified material particles with a size less than 0.5 mm account for 96.5%, and those less than 1 mm account for 100%, resulting in an acidification rate of 99% for the ternary lithium battery black powder.

[0097] 3) The mixed acid material enters the rotary drum 210 and undergoes an acidification reaction. After passing through the homogenization and dispersing structure composed of the front reverse spiral 212 and the front forward spiral 211, the exothermic chemical reaction proceeds rapidly. The resulting clumps are crushed by the crushing device. After the clumps of acidified material have fully reacted, they form acidified tailings. A portion of the acidified tailings is sent from the return material inlet 215 through the external return material spiral 214 to the return material outlet 216 at the front end of the rotary drum 210 and discharged, completing the return material cycle. The remaining acidified tailings are discharged from the tail end of the rotary drum 210 by the lifting plate and sent to the subsequent process. The return material ratio can be (1~6):1, for example, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1. For the heating method of acidification kiln 20, methods well-known to those skilled in the art, such as hot flue gas heating or electric heating, can be selected; one or more forward and reverse homogenizing and dispersing spirals can be arranged; one or more free spirals, chains, steel bars, or steel rods can be arranged; one or more external or internal return spirals can be arranged for return material circulation. The acidification mixing time is 30-60 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, etc.; the acidification material reaction temperature is 250℃-300℃, 250℃, 260℃, 270℃, 28℃, 290℃, 300℃, etc.

[0098] 4) The acidified material discharged from the tail end of the acidification kiln 20 is fed into the roasting kiln 40 for reaction. The roasted material exiting the roasting kiln 40 enters the cooling kiln 50 for cooling before being sent to subsequent processes. This disclosure does not impose any particular restrictions on the heating method of the roasting kiln 40; methods well-known to those skilled in the art, such as hot flue gas heating or electric heating, can be used. Similarly, this disclosure does not impose any particular restrictions on the rotary cooling kiln 50; methods well-known to those skilled in the art, such as a tubular rotary cooling kiln 50 or a water-jacketed rotary cooling kiln 50, can be used. Preferably, a tubular rotary cooling kiln 50 is used. The acidified material discharged from the acidification kiln 20 enters the roasting kiln 40 via a second feeding device. The roasting time is 120-180 minutes, for example, 120, 130, 140, 150, 160, 170, and 180 minutes, with roasting temperatures of 600℃-750℃, 600℃, 650℃, 700℃, and 750℃. The acidified material continues to react within the roasting kiln 40, and the temperature fluctuation throughout the heating section is controlled within ±5℃. The roasted material discharged from the roasting kiln 40 is cooled indirectly by heat exchange with cooling circulating water in the cooling kiln 50, and the temperature of the cooled material is ≤60℃.

[0099] 5) The acidification flue gas drawn from the exhaust of the acidification kiln 20 is dedusted by a cyclone dust collector, then further dedusted in a Venturi dust collector 63 using liquid cooled by a heat exchanger 65 from a Venturi tube circulation tank 631. It is then further dedusted in a spray scrubbing tower 64 using raw water and liquid from a scrubbing pump 641. The dedusted exhaust gas is then sent to the subsequent acid production process. The dedusting liquid in the Venturi dust collector is cooled by the heat exchanger 65, which reduces the exhaust gas temperature and removes some of the dust. The dust collected by the cyclone dust collector is then reintroduced into the roasting kiln 40 for reaction. This disclosure does not impose any particular limitations on the equipment used for exhaust gas absorption; preferably, a tower-type equipment is used, and more preferably, a packed tower made of corrosion-resistant material is used.

[0100] 6) The roasting flue gas drawn from the kiln head of the roasting kiln 40 is dedusted by a cyclone dust collector, then further dedusted by liquid cooled by a heat exchanger from a Venturi tube circulation tank in a Venturi dust collector. Finally, it is dedusted by raw water and liquid from a scrubbing pump in a spray scrubbing tower. The dedusted flue gas is then sent to the subsequent acid production process. The dedusting liquid in the Venturi dust collector is cooled by a heat exchanger, which reduces the exhaust gas temperature and improves the dust removal efficiency. The dust collected by the cyclone dust collector re-enters the roasting kiln 40 for reaction. This disclosure does not impose any particular limitations on the exhaust gas absorption equipment; preferably, a tower-type equipment is used, and more preferably, a packed tower made of corrosion-resistant material is used.

[0101] Example 1

[0102] 1) After being metered by the loss-of-gravity stabilization system, the ternary battery black powder with a particle size of 200 mesh enters the feeding screw of the acidification kiln. The feeding screw pushes the ternary battery black powder to the front of the rotating cylinder and mixes it with a large amount of high-temperature return material returned by the return screw for the first time.

[0103] 2) The acid inlet pipe is inserted obliquely into the exhaust pipe, and the acidified flue gas after the reaction is discharged from the front exhaust pipe. 98% concentrated sulfuric acid is sprayed into the rotary drum through the exhaust pipe to complete the secondary mixing with the above primary mixture to form a mixed acid material. The mass ratio of ternary battery black powder to sulfuric acid is 1:1.4.

[0104] 3) The acidification reaction is carried out under a slight positive and negative pressure of ±500Pa, with an acidification temperature of 290℃ (electrically heated), a feed rate of 100kg / h, and a mixing time of 50 minutes. The acidified material has a particle size of <0.5mm (95%) and a particle size of <1mm (100%). The acidification kiln is equipped with two forward and reverse homogenizing and dispersing spirals, two steel rods, and one external return spiral. The conversion rate of the acidification reaction is 98%, and there is no scaling within the acidification kiln.

[0105] 4) The acidified material from the tail of the acidification kiln enters the roasting kiln (electrically heated) for reaction. The roasted material from the roasting kiln enters the tubular cooling kiln for cooling before entering the subsequent processes. The roasting temperature is 650℃ and the roasting time is 140min.

[0106] 5) The acidification flue gas and roasting flue gas drawn from the kiln head ducts of the acidification kiln and roasting kiln mainly consist of volatile water vapor, sulfuric acid vapor, some sulfur dioxide produced by the reaction, sulfur trioxide produced by the partial decomposition of sulfuric acid, a small amount of dust, and trace amounts of air leaking into the system. After dust removal by a cyclone dust collector, a Venturi dust collector, and a spray tower, they are sent to the subsequent acid production process. The dust content of the acid production tail gas is 11%.

[0107] Example 2

[0108] 1) After being metered by the loss-of-gravity stabilization system, the ternary battery black powder with a particle size of 200 mesh enters the feeding screw of the acidification kiln. The feeding screw pushes the ternary battery black powder to the front of the rotating cylinder and mixes it with a large amount of high-temperature return material returned by the return screw for the first time.

[0109] 2) The acid inlet pipe is inserted obliquely into the exhaust pipe, and the acidified flue gas after the reaction is discharged from the front exhaust pipe. 98% concentrated sulfuric acid is sprayed into the rotary drum through the exhaust pipe to complete the secondary mixing with the above primary mixture to form a mixed acid material. The mass ratio of ternary battery black powder to sulfuric acid is 1:1.3.

[0110] 3) The acidification reaction is carried out under a slight positive and negative pressure of ±500 Pa, with an acidification temperature of 280℃ (heated by hot flue gas), a feed rate of 100 kg / h, and a mixing time of 40 minutes. The acidified material has a particle size of <0.5 mm, accounting for 96%, and a particle size of <1 mm, accounting for 100%. The acidification kiln is equipped with one forward and reverse homogenizing and dispersing spiral, one free spiral, and one external return spiral. The conversion rate of the acidification reaction is 98%, and there is no scaling phenomenon in the acidification kiln.

[0111] 4) The acidified material from the tail of the acidification kiln enters the roasting kiln for reaction. The roasted material from the roasting kiln enters the water-jacketed cooling kiln for cooling before entering the subsequent processes. The roasting temperature is 660℃ (heated by hot flue gas), and the roasting time is 150 minutes.

[0112] 5) The acidification flue gas and roasting flue gas drawn from the kiln head ducts of the acidification kiln and roasting kiln mainly consist of volatile water vapor, sulfuric acid vapor, some sulfur dioxide produced by the reaction, sulfur trioxide produced by the partial decomposition of sulfuric acid, a small amount of dust, and trace amounts of air leaking into the system. After dust removal by a cyclone dust collector, a Venturi dust collector, and a spray tower, they are sent to the subsequent acid production process. The dust content of the acid production tail gas is 12%.

[0113] Example 3

[0114] 1) After being metered by the loss-of-gravity stabilization system, the ternary battery black powder with a particle size of 200 mesh enters the feeding screw of the acidification kiln. The feeding screw pushes the ternary battery black powder to the front of the rotating cylinder and mixes it with a large amount of high-temperature return material returned by the return screw for the first time.

[0115] 2) The acid inlet pipe is inserted obliquely into the exhaust pipe, and the acidified flue gas after the reaction is discharged from the front exhaust pipe. 98% concentrated sulfuric acid is sprayed into the rotary drum through the exhaust pipe to complete the secondary mixing with the above primary mixture to form a mixed acid material. The mass ratio of ternary battery black powder to sulfuric acid is 1:1.4.

[0116] 3) The acidification reaction is carried out under a slight positive and negative pressure of ±500Pa, with an acidification temperature of 290℃ (heated by hot flue gas), a feed rate of 100kg / h, a mixing time of 60 minutes, and acidified material with a particle size of <0.5mm accounting for 96% and a particle size of <1mm accounting for 100%. The acidification kiln is equipped with two forward and reverse homogenizing and dispersing spirals, two chains, and two external return spirals. The conversion rate of the acidification reaction is 99%, and there is no scaling phenomenon in the acidification kiln.

[0117] 4) The acidified material from the tail of the acidification kiln enters the roasting kiln for reaction. The roasted material from the roasting kiln enters the tubular cooling kiln for cooling before entering the subsequent processes. The roasting temperature is 700℃ (electrically heated), and the roasting time is 160 minutes.

[0118] 5) The acidification flue gas and roasting flue gas drawn from the kiln head ducts of the acidification kiln and roasting kiln mainly consist of volatile water vapor, sulfuric acid vapor, some sulfur dioxide produced by the reaction, sulfur trioxide produced by the partial decomposition of sulfuric acid, a small amount of dust, and trace amounts of air leaking into the system. After dust removal by a cyclone dust collector, a Venturi dust collector, and a spray tower, they are sent to the subsequent acid production process. The dust content of the acid production tail gas is 12%.

[0119] Example 4

[0120] 1) After being metered by the loss-of-gravity stabilization system, the ternary battery black powder with a particle size of 200 mesh enters the feeding screw of the acidification kiln. The feeding screw pushes the ternary battery black powder to the front of the rotating cylinder and mixes it with a large amount of high-temperature return material returned by the return screw for the first time.

[0121] 2) The acid inlet pipe is inserted obliquely into the exhaust pipe, and the acidified flue gas after the reaction is discharged from the front exhaust pipe. 99% concentrated sulfuric acid is sprayed into the rotary drum through the exhaust pipe to complete the secondary mixing with the above primary mixture to form a mixed acid material. The mass ratio of ternary battery black powder to sulfuric acid is 1:1.2.

[0122] 3) The acidification reaction is carried out under a slight positive and negative pressure of ±500Pa, with an acidification temperature of 280℃ (electrically heated), a feed rate of 120kg / h, and a mixing time of 50 minutes. The acidified material has a particle size of <0.5mm (97%) and a particle size of <1mm (100%). The acidification kiln is equipped with two forward and reverse homogenizing and dispersing spirals, one steel bar, and two external return spirals. The conversion rate of the acidification reaction is 98%, and there is no scaling within the acidification kiln.

[0123] 4) The acidified material from the tail of the acidification kiln enters the roasting kiln for reaction. The roasted material from the roasting kiln enters the water-jacketed cooling kiln for cooling before entering the subsequent processes. The roasting temperature is 680℃ (heated by hot flue gas), and the roasting time is 130 minutes.

[0124] 5) The acidification flue gas and roasting flue gas drawn from the kiln head ducts of the acidification kiln and roasting kiln mainly consist of volatile water vapor, sulfuric acid vapor, some sulfur dioxide produced by the reaction, sulfur trioxide produced by the partial decomposition of sulfuric acid, a small amount of dust, and trace amounts of air leaking into the system. After dust removal by a cyclone dust collector, a Venturi dust collector, and a spray tower, they are sent to the subsequent acid production process. The dust content of the acid production tail gas is 13%.

[0125] Example 5

[0126] 1) After being metered by the loss-of-gravity stabilization system, the ternary battery black powder with a particle size of 200 mesh enters the feeding screw of the acidification kiln. The feeding screw pushes the ternary battery black powder to the front of the rotating cylinder and mixes it with a large amount of high-temperature return material returned by the return screw for the first time.

[0127] 2) The acid inlet pipe is inserted obliquely into the exhaust pipe, and the acidified flue gas after the reaction is discharged from the front exhaust pipe. 99% concentrated sulfuric acid is sprayed into the rotary drum through the exhaust pipe to complete the secondary mixing with the above-mentioned primary mixture, forming a mixed acid material. The mass ratio of ternary battery black powder to sulfuric acid is 1:1.4.

[0128] 3) The acidification reaction is carried out under a slight positive and negative pressure of ±500 Pa, with an acidification temperature of 290℃ (electrically heated), a feed rate of 120 kg / h, and a mixing time of 60 minutes. The acidified material has a particle size of <0.5 mm (97%) and a particle size of <1 mm (100%). The acidification kiln is equipped with two forward and reverse homogenizing and dispersing spirals, two free spirals, and two external return spirals. The conversion rate of the acidification reaction is 99%, and there is no scaling within the acidification kiln.

[0129] 4) The acidified material from the tail of the acidification kiln enters the roasting kiln for reaction. The roasted material from the roasting kiln enters the tubular cooling kiln for cooling before entering the subsequent processes. The roasting temperature is 700℃ (electrically heated), and the roasting time is 160 minutes.

[0130] 5) The acidification flue gas and roasting flue gas drawn from the kiln head ducts of the acidification kiln and roasting kiln mainly consist of volatile water vapor, sulfuric acid vapor, some sulfur dioxide produced by the reaction, sulfur trioxide produced by the partial decomposition of sulfuric acid, a small amount of dust, and trace amounts of air leaking into the system. After dust removal by a cyclone dust collector, a Venturi dust collector, and a spray tower, they are sent to the subsequent acid production process. The dust content of the acid production tail gas is 13%.

[0131] The beneficial effects of the ternary lithium battery black powder acidification and calcination apparatus disclosed herein are as follows:

[0132] 1) The dynamic and static ring mechanical seals at the head and tail of the acidification kiln can effectively prevent the pollution of the environment by toxic and harmful dust and exhaust gas.

[0133] 2) The acid addition and exhaust equipment can remove some of the dust in the acidification flue gas, prevent dust from clogging the exhaust pipe, solve the problem of scaling on the pipe wall, and at the same time increase the temperature of concentrated sulfuric acid, thereby increasing the acidification reaction rate.

[0134] 3) The homogenization and dispersing structure can fully mix ternary battery black powder with concentrated sulfuric acid, effectively disperse the specific surface area of ​​the material, make the material loose, and improve the acidification rate of the material.

[0135] 4) The crushing component can break up the agglomerates of rapidly reacting mixed acid materials and the acidified materials adhering to the cylinder wall, making the chemical reaction more thorough and solving the problems of wall adhesion and scaling in the acidification kiln.

[0136] 5) The return material structure effectively solves the corrosion problem of the equipment body. The presence of the return material ensures that the newly added mixed acid material falls directly onto the return material, preventing the strong acid medium from directly contacting the cylinder wall, thus solving the problems of wall adhesion and scaling in the acidification kiln. At the same time, the return material brings a large amount of heat, causing the mixed material to heat up rapidly and increasing the reaction rate.

[0137] 6) After the acidification flue gas and roasting flue gas are removed by cyclone dust collector, venturi dust collector and spray scrubbing tower, they are sent to the subsequent acid production process, which reduces environmental pollution and equipment investment, increases material utilization, and saves energy and protects the environment.

[0138] This device significantly reduces the amount of smoke and dust emissions during the acidification process, effectively achieving environmental protection; it solves the problems of equipment corrosion, scaling on the walls of exhaust pipes, and scaling on the walls of the acidification kiln, thus improving the service life of the equipment; the equipment has a scientific and reasonable structure, allowing for more complete material reaction and improving the lithium recovery rate.

[0139] Other embodiments of this disclosure will readily occur to those skilled in the art upon consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of this disclosure that follow the general principles of this disclosure and include common knowledge or customary techniques in the art not disclosed herein. The specification and examples are to be considered exemplary only, and the true scope and spirit of this disclosure are indicated by the following claims.

[0140] It should be understood that this disclosure is not limited to the precise structures described above and shown in the accompanying drawings, and various modifications and changes can be made without departing from its scope. The scope of this disclosure is limited only by the appended claims.

Claims

1. A method for the acid roasting of ternary battery black powder, characterized by, The application relates to a ternary battery black powder acidification roasting device, which comprises a weight-loss stabilizing equipment, an acidification kiln, an acid adding and smoke discharging equipment, a roasting kiln, a cooling kiln and a dust removal assembly. The weight-loss stabilizing equipment is used for filling ternary battery black powder through an inlet and metering the ternary battery black powder; the acidification kiln comprises a rotary cylinder, a first heating assembly and a first feeding equipment; the first feeding equipment is used for conveying the ternary battery black powder in the weight-loss stabilizing equipment into the rotary cylinder; along the axial direction of the rotary cylinder, a front forward screw and a front reverse screw are arranged on the inner wall of the rotary cylinder close to the feeding inlet to form a homogenizing and dispersing structure, and a tail forward screw is arranged on the inner wall of the rotary cylinder close to the discharging outlet; the first heating assembly comprises a heating sleeve, and the heating sleeve is sleeved on the rotary cylinder; along the axial direction of the rotary cylinder, an outer return screw is arranged on the outer wall of the rotary cylinder; one end of the rotary cylinder close to the discharging outlet is provided with a return inlet, and one end of the rotary cylinder close to the feeding inlet is provided with a return outlet; the outer return screw is located in the channel between the rotary cylinder and the heating sleeve, is used for conveying the return material of the return inlet to the return outlet, so that the return material enters the rotary cylinder through the return outlet; along the axial direction of the rotary cylinder, a crushing assembly is arranged on the middle part of the inner wall of the rotary cylinder, and the crushing assembly is matched with the inner wall of the rotary cylinder and is used for crushing the caked acidification material; the acid adding and smoke discharging equipment comprises a smoke discharging pipe and an acid adding assembly; the smoke discharging pipe is communicated with the inside of the acidification kiln; the acid adding assembly is communicated with the smoke discharging pipe; the acid adding assembly can add acid into the inside of the acidification kiln through the smoke discharging pipe; the acidification flue gas of the acidification kiln is discharged through the smoke discharging pipe; the roasting kiln comprises a roasting kiln cylinder, a second heating assembly, a roasting kiln discharging box and a second feeding equipment; the second feeding equipment is used for conveying the acidification material discharged from the acidification kiln into the roasting kiln cylinder; the second heating assembly is arranged on the roasting kiln cylinder and is used for heating the roasting kiln cylinder; the cooling kiln comprises a cooling kiln cylinder, a cooling kiln discharging box and a third feeding equipment; the third feeding equipment is used for conveying the roasting material discharged from the roasting kiln into the cooling kiln cylinder, cooling the roasting material through the cooling kiln and discharging the roasting material; the dust removal assembly comprises a dry dust removal assembly and a wet dust removal assembly; the dust removal assembly is communicated with the smoke discharging pipes of the acidification kiln and the roasting kiln and is used for removing dust from the acidification flue gas discharged from the acidification kiln and the roasting flue gas discharged from the roasting kiln; ternary battery black powder is sent into the weight-loss stabilizing equipment, is metered through the weight-loss stabilizing equipment, is sent into the first feeding equipment of the acidification kiln, and the first feeding equipment pushes the ternary battery black powder into the first mixing of the return material of the front part of the rotary cylinder and the return outlet; The acid smoke exhaust equipment is used to spray sulfuric acid into the rotary cylinder through the smoke exhaust pipe, so that the sulfuric acid is mixed with the mixed material after the first mixing to form mixed acid material; the first heating assembly is used to heat the rotary cylinder; The mixed acid material in the rotary cylinder is subjected to acidification reaction in the interior of the rotary cylinder, is dispersed by the homogenizing and dispersing device composed of the front reverse screw and the front forward screw, is crushed by the crushing assembly in cooperation with the inner wall of the rotary cylinder, and is discharged from the return material outlet at the front end of the rotary cylinder through the outer return material screw after the acidification reaction, so that the return material circulation is completed; the remaining acidification tail material is discharged from the discharge box of the rotary cylinder; The acidification material discharged from the discharge box of the acidification kiln is sent into the roasting kiln cylinder of the roasting kiln through the second feeding equipment to be reacted; the second heating assembly is used to heat the roasting kiln cylinder; The roasting material from the roasting kiln is sent into the cooling kiln cylinder of the cooling kiln through the third feeding equipment to be cooled; After the roasting flue gas from the smoke exhaust pipe of the roasting kiln and the acidification flue gas from the smoke exhaust pipe of the acidification kiln are subjected to dust removal by the dry dust removal assembly, the acidification flue gas and the roasting flue gas discharged from the acidification kiln and the roasting kiln are subjected to dust removal by the dust removal assembly.

2. The method of trinary battery black acid roasting according to claim 1, characterized in that, The concentration of the sulfuric acid is 95% to 100%, and the ratio of the ternary battery black powder to the sulfuric acid is 1:1.1 to 1:1.5 when the ternary battery black powder and the sulfuric acid are respectively mixed and acidified in the acidification kiln.

3. The method of trinary battery black acid roasting according to claim 1, characterized in that, The roasting time of the acidification material in the roasting kiln is 120 min to 180 min, the roasting temperature is 600°C to 750°C, the acidification material continues to react in the roasting kiln, the temperature fluctuation in the heating section is within ±5°C, and the temperature of the roasting material cooled in the cooling kiln is ≤60°C.

4. The method of trinary battery black acid roasting according to claim 1, characterized in that, The wet dust removal assembly comprises a Venturi dust remover, a spray washing tower, a Venturi circulating tank, a Venturi circulating pump and a heat exchanger, the inlet of the Venturi dust remover is communicated with the outlet of the dry dust removal assembly, the Venturi dust remover is used to remove dust from the acidification flue gas and the roasting flue gas discharged from the dry dust removal assembly by a wet method, the inlet of the spray washing tower is communicated with the outlet of the Venturi dust remover, the spray washing tower is used to remove dust from the acidification flue gas and the roasting flue gas discharged from the Venturi dust remover by a wet method, the outlet of the spray washing tower is used to discharge the flue gas after the wet dust removal, the Venturi circulating tank is used to contain spray liquid, the Venturi circulating tank is communicated with the bottom of the spray washing tower, the Venturi circulating pump is communicated with the Venturi circulating tank and is used to extract the spray liquid, the heat exchanger is connected with the outlet of the Venturi circulating pump and is used to cool the spray liquid extracted by the Venturi circulating pump, and the outlet of the heat exchanger is connected with the Venturi dust remover and is used to deliver the cooled spray liquid into the Venturi dust remover for wet dust removal. The acidification kiln and the calcination kiln are connected in series, and the acidification kiln and the calcination kiln are connected in series. The acidification kiln and the calcination kiln are connected in series, and the acidification kiln and the calcination kiln are connected in series. The acidification kiln and the calcination kiln are connected in series, and the acidification kiln and the calcination kiln are connected in series.

5. A ternary battery black powder acid roasting device, characterized in that, It comprises: The weight loss stabilizing device is used to fill the ternary battery black powder through the inlet and measure the ternary battery black powder; The acidification kiln comprises a rotary cylinder, a first heating assembly and a first feeding device, the first feeding device is used to convey the ternary battery black powder in the weight loss stabilizing device into the rotary cylinder; along the axial direction of the rotary cylinder, a front forward spiral and a front reverse spiral are arranged on the inner wall of the rotary cylinder close to the inlet to form a homogenizing and dispersing structure, and a tail forward spiral is arranged on the inner wall of the rotary cylinder close to the outlet; the first heating assembly comprises a heating sleeve, and the heating sleeve is sleeved on the rotary cylinder; along the axial direction of the rotary cylinder, an outer return material spiral is arranged on the outer wall of the rotary cylinder; a return material inlet is arranged at one end of the rotary cylinder close to the outlet, and a return material outlet is arranged at one end of the rotary cylinder close to the inlet, and the outer return material spiral is located in the channel between the rotary cylinder and the heating sleeve, used to convey the return material of the return material inlet to the return material outlet, so that the return material enters the rotary cylinder through the return material outlet; along the axial direction of the rotary cylinder, a crushing assembly is arranged on the middle part of the inner wall of the rotary cylinder, and the crushing assembly is matched with the inner wall of the rotary cylinder to crush the caked acidification material; The acidification kiln and the calcination kiln are connected in series, and the acidification kiln and the calcination kiln are connected in series. The calcination kiln comprises a calcination kiln cylinder, a second heating assembly, a calcination kiln discharge box and a second feeding device, the second feeding device is used to convey the acidification material discharged from the acidification kiln into the calcination kiln cylinder; the second heating assembly is arranged on the calcination kiln cylinder and used to heat the calcination kiln cylinder; The cooling kiln comprises a cooling kiln cylinder, a cooling kiln discharge box and a third feeding device, the third feeding device is used to convey the calcination material discharged from the calcination kiln into the cooling kiln cylinder, cool the calcination material through the cooling kiln and discharge; A dust removal assembly is in communication with the exhaust pipe of the acidification kiln and the exhaust pipe of the roasting kiln, and is used for removing dust from the acidification flue gas discharged by the acidification kiln and the roasting flue gas discharged by the roasting kiln.

6. The ternary battery black powder acidification roasting device according to claim 5, characterized in that, A plurality of lifting plates are arranged on the inner side of the discharge port of the rotary cylinder, and the lifting plates are arranged along the radial direction of the rotary cylinder.

7. The ternary battery black powder acidification and calcination device according to claim 5, characterized in that, The dust removal assembly comprises a dry dust removal assembly and a wet dust removal assembly.

8. The ternary battery black powder acid roasting device according to claim 7, characterized in that, The dry dust removal assembly is in communication with the exhaust pipe of the acidification kiln and the exhaust pipe of the roasting kiln, and is used for dry dust removal of the acidification flue gas discharged by the acidification kiln and the roasting flue gas discharged by the roasting kiln. The dry dust removal assembly comprises: A first cyclone dust collector is in communication with the exhaust pipe, and is used for dust removal of the acidification flue gas entering through the exhaust pipe.

9. The ternary battery black powder acid roasting device according to claim 8, characterized in that, A second cyclone dust collector is in communication with the interior of the roasting kiln cylinder through a flue gas pipeline, and is used for dust removal of the roasting flue gas discharged by the roasting kiln cylinder. The wet dust removal assembly comprises: A Venturi dust collector is in communication with the outlets of the first and second cyclone dust collectors, and is used for wet dust removal of the acidification flue gas and the roasting flue gas discharged by the first and second cyclone dust collectors. A spray washing tower is in communication with the outlet of the Venturi dust collector, and is used for wet dust removal of the acidification flue gas and the roasting flue gas discharged by the Venturi dust collector. A Venturi circulating tank is used for containing spray liquid, and is in communication with the bottom of the spray washing tower. A Venturi circulating pump is in communication with the Venturi circulating tank, and is used for pumping the spray liquid.

10. The ternary battery black powder acid roasting device according to claim 9, characterized in that, A heat exchanger is connected with the outlet of the Venturi circulating pump, and is used for cooling the spray liquid pumped by the Venturi circulating pump. The top of the spray washing tower is provided with a raw water inlet, and the wet dust removal assembly further comprises: A washing pump is in communication with the bottom of the spray washing tower, and is used for conveying the washing liquid at the bottom of the spray washing tower to the top of the spray washing tower for wet dust removal.

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