CN116851135A - Preparation device and recovery process of mixed lithium iron phosphate electrode flotation inhibitor - Google Patents
Preparation device and recovery process of mixed lithium iron phosphate electrode flotation inhibitor Download PDFInfo
- Publication number
- CN116851135A CN116851135A CN202310936004.XA CN202310936004A CN116851135A CN 116851135 A CN116851135 A CN 116851135A CN 202310936004 A CN202310936004 A CN 202310936004A CN 116851135 A CN116851135 A CN 116851135A
- Authority
- CN
- China
- Prior art keywords
- stirring
- iron phosphate
- lithium iron
- mixed
- beaker
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
- B03B9/06—General arrangement of separating plant, e.g. flow sheets specially adapted for refuse
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
- B01F27/85—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with two or more stirrers on separate shafts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
- B01F27/90—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of electrode recovery, in particular to a preparation device and a recovery process of a mixed lithium iron phosphate electrode flotation inhibitor, comprising the following steps: the lower surface of the sealing cover is provided with a hollow cylinder positioned in the beaker, the periphery of the hollow cylinder is rotatably provided with a stirring support cylinder, the surface of the stirring main shaft is provided with stirring plates, and the stirring rods and the stirring plates are mutually staggered; the driven gear meshed with the driving gear is arranged on the outer side of the driving gear, and the driven gear is fixedly sleeved at the upper end of the stirring support cylinder; the beneficial effects are as follows: the preparation method has the advantages that the preparation method adopts the easily biodegradable starch and cellulose natural high polymer as main medicines as selective flocculation medicines and lithium iron phosphate flotation inhibitors, has the characteristics of being green, environment-friendly, pollution-free and environment-friendly, reduces the influence of the binder PVDF and electrolyte on the positive and negative electrode separation of the mixed electrode of the waste lithium battery, does not need to adopt a roasting method to remove the binder and the electrolyte, and reduces the separation cost and is environment-friendly.
Description
Technical Field
The invention relates to the technical field of electrode recovery, in particular to a preparation device and a recovery process of a mixed lithium iron phosphate electrode flotation inhibitor.
Background
The main components of the lithium iron phosphate mixed electrode are lithium iron phosphate and graphite, and the secondary components are electrolyte ethylene carbonate, a binder PVDF, a diaphragm and the like.
The traditional recovery method of the lithium iron phosphate mixed electrode generally comprises chemical and metallurgical processes (roasting, acid leaching and alkaline leaching), or wet and fire recovery, and the recovery process has high energy consumption and cost and is easy to produce secondary pollution; for example, in the process of fire recovery, the metal recovery rate is low, the equipment requirement is high, lithium cannot be recovered, further refining is required for metal recovery in the alloy, and the environmental influence comprises the production of smelting slag, dust, harmful gas and the like; for example, in the wet recycling process, the battery cells must be crushed, the consumption of reagents is large, and a large amount of salt-containing wastewater must be treated. Therefore, the invention provides a preparation device and a recovery process of a mixed lithium iron phosphate electrode flotation inhibitor, which are used for solving the problems.
Disclosure of Invention
The invention aims to provide a preparation device and a recovery process of a mixed lithium iron phosphate electrode flotation inhibitor, so as to solve the problems of high energy consumption, high cost and serious secondary pollution in the recovery process of the traditional lithium iron phosphate mixed electrode in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: a device for preparing a mixed lithium iron phosphate electrode flotation suppressant, comprising a stirring assembly, wherein the stirring assembly comprises:
the sealing cover covers the opening end of the beaker, a hollow cylinder positioned in the beaker is arranged on the lower surface of the sealing cover, a stirring support cylinder is rotatably arranged on the periphery of the hollow cylinder, stirring rods are arranged on the surface of the stirring support cylinder, a stirring main shaft is rotatably arranged in the middle of the inner cavity of the hollow cylinder, stirring plates are arranged on the surface of the stirring main shaft, the stirring rods and the stirring plates are mutually staggered, an avoidance groove for the stirring rods to pass through is formed in the surface of the hollow cylinder, and a discharge hole is formed in the surface of the stirring support cylinder;
the driving gear is positioned at the outer side of the beaker and fixedly connected with the upper end of the stirring main shaft, a driven gear meshed with the driving gear is arranged at the outer side of the driving gear, and the driven gear is fixedly sleeved at the upper end of the stirring support barrel.
Preferably, the lower surface of closing cap is fixed and is provided with the sealing bench, the lateral wall of sealing bench is laminated and is bonded with the sealing layer with the inner wall of beaker, the stirring support section of thick bamboo is provided with a plurality of and is annular array distribution around hollow section of thick bamboo.
Preferably, the upper ends of the stirring main shaft and the stirring support cylinder all penetrate through the sealing cover, the upper surface of the sealing cover is provided with the mounting groove, the driving gear and the driven gear are both located in the inner cavity of the mounting groove, the opening end of the mounting groove is covered with the top cover, the surface of the top cover is connected with the plugs through the flexible connecting rope, the plugs are provided with a plurality of upper opening ends which are respectively plugged on the stirring support cylinders, and the upper end of the stirring main shaft is provided with a handle rod for driving the stirring main shaft to rotate.
The recovery process of the mixed lithium iron phosphate electrode comprises the steps of preparing the mixed lithium iron phosphate electrode flotation inhibitor by using the preparation device, and specifically comprises the following steps of:
step one, mixing: mixing a lithium iron phosphate electrode with water, adding a dispersing agent, and grinding to obtain mixed electrode powder;
step two, stirring and flocculating: pouring the ground mixed electrode powder into a stirring barrel for stirring, adding a selective flocculant, continuing stirring, uniformly mixing, and standing to obtain ore pulp;
step three, magnetic separation: separating the ore pulp into a graphite negative electrode and lithium iron phosphate and graphite by using a high-gradient strong magnetic separator;
step four, floatation: adding water into the ore pulp to obtain an underflow product A and a foam product A (roughing), continuously adding the dispersing agent, the inhibitor, the collector and the foaming agent into the underflow product A in sequence, wherein the dosage of the dispersing agent, the inhibitor, the collector and the foaming agent is half of that of the roughing agent to obtain a foam product B and an underflow product B (selecting one), and continuously adding the dispersing agent, the inhibitor, the collector and the foaming agent into the underflow product B in sequence, wherein the dosage of the agent is half of that of the selecting one to obtain an underflow product C and a foam product C (selecting two), and the underflow product C is a lithium iron phosphate anode;
step five, scavenging operation: and sequentially adding a dispersing agent and an inhibitor into the ore pulp of the foam product A, wherein the dosage of the agent is 1/4 of that of the roughing agent, so as to obtain a foam product D and an underflow product D, and the foam product D is a graphite negative electrode.
Preferably, in the fourth step and the fifth step, the foam product B and the underflow product D are mixed, returned to the roughing step, mixed with the magnetic concentrate to form a closed circuit, and the foam product C is returned to the concentrating step, mixed with the underflow product a to be concentrated.
Preferably, in the second step and the fourth step, the selective flocculant and the inhibitor are the same substance, and the preparation method comprises the following steps:
adding water, starch, cellulose salt, polyacrylamide and polyvinyl alcohol into a beaker, and stirring the mixture by using a stirring assembly until the solution is uniform and has no particles;
heating the beaker, adding sodium hydroxide and sodium sulfite, and continuing heating until substances in the beaker react completely;
and (8) diluting the solution in the beaker after the beaker is cooled.
Preferably, in the step (1), starch: cellulose salt: polyacrylamide: the mass ratio of the polyvinyl alcohol is 50-80:5-9:0.01-0.05:2-7.
Preferably, in the first step, the dispersing agent is sodium tripolyphosphate, guar gum and water glass, and the mass ratio is 2-10:1-8:1-15, the consumption of the dispersing agent is 500-1000 g/ton, the grinding concentration is 60-80%, the grinding time is 15-30min, and the rotating speed of the mill is 20-40r/min.
Preferably, in the second step, the first stirring time is 5-15min, the dosage of the selective flocculant is 800-1500 g/ton, the second stirring time is 5-15min, the magnetic field strength is 0.5-0.8T, and the pulse size is 100-300 times/min.
Preferably, in the fourth step, the dispersant is used in an amount of 200-1000 g/ton, the inhibitor is used in an amount of 500-1500 g/ton, the collector is used in an amount of 100-300 g/ton, and the foaming agent is used in an amount of 10-50 g/ton.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts the agents which are mainly biodegradable starch and cellulose natural high polymer as selective flocculation agents and lithium iron phosphate flotation inhibitors, and has the characteristics of green, environment protection, no pollution and environmental protection;
2. the selective flocculation selectively bridges the positive electrode of the lithium iron phosphate battery, reduces the inclusion of graphite as a negative electrode material before magnetic separation, optimizes the magnetic separation effect and provides a good separation basis for subsequent flotation;
3. because the granularity of the battery powder is smaller and is usually 10-50 mu m, the phenomenon of entrainment is extremely easy to form in the flotation process, and the addition of the inhibitor selectively inhibits the floating of the lithium iron phosphate positive electrode material, reduces the generation of the phenomenon of entrainment in the flotation, and is beneficial to improving the flotation index;
4. the process flow of selective flocculation, magnetic separation and floatation is adopted, so that the influence of the binder PVDF and electrolyte on the positive and negative electrode separation of the mixed electrode of the waste lithium battery is reduced, the binder and the electrolyte are not required to be removed by a roasting method, the separation cost is reduced, and the method is environment-friendly.
Drawings
FIG. 1 is a schematic perspective view of a stirring assembly according to the present invention;
FIG. 2 is a schematic view of the hollow cylinder structure installation of the present invention;
FIG. 3 is a schematic perspective view of the hollow cylinder structure of the invention;
FIG. 4 is a schematic view of the installation of the roof structure of the present invention;
FIG. 5 is a schematic view showing the internal structure of the installation groove of the present invention;
FIG. 6 is a schematic diagram of a flocculation-magnetic separation process flow of the present invention;
fig. 7 is a schematic diagram of the flotation process flow of the present invention.
In the figure: 1. a cover; 11. a sealing table; 12. a mounting groove; 13. a top cover; 14. a plug; 15. a flexible connecting rope; 2. a hollow cylinder; 21. a stirring support cylinder; 22. a stirring rod; 23. an avoidance groove; 24. a discharge port; 3. a stirring main shaft; 31. a stirring plate; 32. a handle bar; 4. a drive gear; 5. a driven gear.
Detailed Description
In order to make the objects, technical solutions, and advantages of the present invention more apparent, the embodiments of the present invention will be further described in detail with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are some, but not all, embodiments of the present invention, are intended to be illustrative only and not limiting of the embodiments of the present invention, and that all other embodiments obtained by persons of ordinary skill in the art without making any inventive effort are within the scope of the present invention.
In the description of the present invention, it should be noted that the terms "center," "middle," "upper," "lower," "left," "right," "inner," "outer," "top," "bottom," "side," "vertical," "horizontal," and the like indicate orientations or positional relationships based on the orientation or positional relationships shown in the drawings, merely to facilitate description of the present invention and simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "a," an, "" the first, "" the second, "" the third, "" the fourth, "" the fifth, "and the sixth" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
For purposes of brevity and description, the principles of the embodiments are described primarily by reference to examples. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the embodiments. It will be apparent, however, to one of ordinary skill in the art that the embodiments may be practiced without limitation to these specific details. In some instances, well-known methods and structures have not been described in detail so as not to unnecessarily obscure the embodiments. In addition, all embodiments may be used in combination with each other.
Referring to fig. 1 to 7, the present invention provides a technical solution:
in a first embodiment, a device for preparing a mixed lithium iron phosphate electrode flotation suppressant includes a stirring assembly, the stirring assembly including: a cover 1 and a drive gear 4.
The sealing cover 1 covers the open end of the beaker, the hollow cylinder 2 positioned in the beaker is arranged on the lower surface of the sealing cover 1, the stirring support cylinder 21 is rotatably arranged on the periphery of the hollow cylinder 2, the stirring rod 22 is arranged on the surface of the stirring support cylinder 21, the stirring main shaft 3 is rotatably arranged in the middle of the inner cavity of the hollow cylinder 2, the stirring plate 31 is arranged on the surface of the stirring main shaft 3, the stirring rod 22 and the stirring plate 31 are mutually staggered, the avoiding groove 23 for the stirring rod 22 to pass through is formed in the surface of the hollow cylinder 2, the discharge hole 24 is formed in the surface of the stirring support cylinder 21, and as shown in fig. 2, 3 and 4, when the stirring main shaft 3 and the stirring support cylinder 21 rotate, the stirring plate 31 and the stirring rod 22 can mix and stir the solution in the beaker, and the solution in the beaker cannot overflow from the open end of the beaker due to the excessively high rotation speed;
secondly, the driving gear 4 is located outside the beaker and fixedly connected with the upper end of the stirring main shaft 3, the driven gear 5 meshed with the driving gear 4 is arranged outside the driving gear 4, the driven gear 5 is fixedly sleeved at the upper end of the stirring support 21, and as shown in fig. 5, the stirring support 21 can be driven to rotate through the meshing transmission of the driven gear 5 when the driving gear 4 rotates, so that the stirring main shaft 3 can be ensured to drive the stirring support 21 to synchronously rotate when rotating.
Further, a sealing table 11 is fixedly arranged on the lower surface of the sealing cover 1, the side wall of the sealing table 11 is attached to the inner wall of the beaker, and a sealing layer is adhered to the side wall of the sealing table 11, so that the sealing performance of the sealing cover 1 to the opening end of the beaker is improved, and a plurality of stirring support cylinders 21 are arranged and distributed in an annular array around the hollow cylinder 2.
In addition, the upper ends of the stirring main shaft 3 and the stirring support cylinders 21 are all penetrated through the sealing cover 1, the upper surface of the sealing cover 1 is provided with the mounting groove 12, the driving gear 4 and the driven gear 5 are all positioned in the inner cavity of the mounting groove 12, the opening end of the mounting groove 12 is covered with the top cover 13, the surface of the top cover 13 is connected with the plugs 14 through the flexible connecting ropes 15, the plugs 14 are provided with a plurality of plugs respectively at the upper opening ends of the plurality of stirring support cylinders 21, the upper end of the stirring main shaft 3 is provided with the handle rods 32 for driving the stirring main shaft 3 to rotate, as shown in fig. 5, 4 and 1, staff can drive the stirring main shaft 3 to rotate through the handle rods 32, and then drive the plurality of stirring support cylinders 21 to synchronously rotate through the meshing between the driving gear 4 and the plurality of driven gears 5, so that the full mixing of solution in the beaker is realized.
The invention also discloses a recovery process of the mixed lithium iron phosphate electrode, which comprises the steps of using the preparation device to prepare the mixed lithium iron phosphate electrode flotation inhibitor, and specifically comprises the following steps:
step one, mixing: mixing a lithium iron phosphate electrode with water, adding a dispersing agent, and grinding to obtain mixed electrode powder;
step two, stirring and flocculating: pouring the ground mixed electrode powder into a stirring barrel for stirring, adding a selective flocculant, continuing stirring, uniformly mixing, and standing to obtain ore pulp;
step three, magnetic separation: separating the ore pulp into a graphite negative electrode and lithium iron phosphate and graphite by using a high-gradient strong magnetic separator;
step four, floatation: adding water into the ore pulp to obtain an underflow product A and a foam product A (roughing), continuously adding the dispersing agent, the inhibitor, the collector and the foaming agent into the underflow product A in sequence, wherein the dosage of the dispersing agent, the inhibitor, the collector and the foaming agent is half of that of the roughing agent to obtain a foam product B and an underflow product B (selecting one), and continuously adding the dispersing agent, the inhibitor, the collector and the foaming agent into the underflow product B in sequence, wherein the dosage of the agent is half of that of the selecting one to obtain an underflow product C and a foam product C (selecting two), and the underflow product C is a lithium iron phosphate anode;
step five, scavenging operation: and sequentially adding a dispersing agent and an inhibitor into the ore pulp of the foam product A, wherein the dosage of the agent is 1/4 of that of the roughing agent, so as to obtain a foam product D and an underflow product D, and the foam product D is a graphite negative electrode.
In the fourth step and the fifth step, the foam product B and the underflow product D are mixed, returned to the rough concentration step, mixed with the magnetic concentrate to form a closed circuit, and the foam product C is returned to the fine concentration step, mixed with the underflow product A to carry out fine concentration.
In the second step and the fourth step, the selective flocculant and the inhibitor are the same substance, and the preparation method comprises the following steps:
adding water, starch, cellulose salt, polyacrylamide and polyvinyl alcohol into a beaker, and stirring the mixture by using a stirring assembly until the solution is uniform and has no particles;
heating the beaker, adding sodium hydroxide and sodium sulfite, and continuing heating until substances in the beaker react completely;
and (8) diluting the solution in the beaker after the beaker is cooled.
The action mechanism of the selective flocculant and the flotation inhibitor is as follows:
I. the carboxylic acid anions of the modified carboxymethyl cellulose salt and the metal cations on the surface of the lithium iron phosphate positive electrode material are electrostatically attracted, the hydroxyl groups in the modified carboxymethyl cellulose salt and water form a water film through hydrogen bonds, and the electrostatic force attraction generated by the opposite electricity can reach the degree of forming chemical bonds, so that a chemical adsorption effect is formed to a certain extent, in addition, the modified carboxymethyl cellulose salt forms a molecular flocculation state in water, and the micelle adsorbs the lithium iron phosphate positive electrode material in the micelle, so that the granularity of the lithium iron phosphate is increased. The entrainment of the foam on the lithium iron phosphate positive electrode material is reduced in the flotation process when the collector and the foaming agent are used for flotation and aeration;
II. The starch has large molecules, each glucose unit in the molecule contains 3 hydroxyl groups, and after the starch is modified, the modified starch contains other hydrophilic groups besides the hydroxyl groups, and the modified starch can be adsorbed on the surface of minerals by virtue of the hydrogen bond action, so that the mineral particles firstly wrap a layer of starch colloid and then wrap a layer of water film, and the lithium iron phosphate anode material is hydrophilic and inhibited;
III, under the combined action of agents such as modified starch, modified carboxymethyl cellulose and the like, the surface property and the particle state of the lithium iron phosphate positive electrode material are changed, and the hydrophilicity of the lithium iron phosphate positive electrode material is enhanced, so that the inhibition effect on the lithium iron phosphate positive electrode material is achieved.
In step (1), starch: cellulose salt: polyacrylamide: the mass ratio of the polyvinyl alcohol is 50-80:5-9:0.01-0.05:2-7.
In the first step, the dispersing agent is sodium tripolyphosphate, guar gum and water glass, and the mass ratio is 2-10:1-8:1-15, the consumption of the dispersing agent is 500-1000 g/ton, the grinding concentration is 60-80%, the grinding time is 15-30min, and the rotating speed of the mill is 20-40r/min.
In the second step, the first stirring time is 5-15min, the dosage of the selective flocculant is 800-1500 g/ton, the second stirring time is 5-15min, the magnetic field strength is 0.5-0.8T, and the pulse size is 100-300 times/min.
In the fourth step, the consumption of the dispersing agent is 200-1000 g/ton, the consumption of the inhibitor is 500-1500 g/ton, the consumption of the collecting agent is 100-300 g/ton, and the consumption of the foaming agent is 10-50 g/ton.
In the second embodiment, experiments are performed by using a mixed electrode of a waste lithium battery with a fixed carbon content of 23.21% as a raw material, wherein the main materials are lithium iron phosphate and graphite:
1. adding water into the mixed electrode powder, adjusting the concentration to 70%, adding 600g/t dispersing agent (sodium tripolyphosphate, guar gum and water glass in a mass ratio of 7:5:10), grinding for 20min, and grinding at a rotating speed of 30r/min.
2. Pouring the ground mixed electrode powder into a stirring barrel for stirring at the stirring speed of 80r/min for 7min, and then adding the prepared selective flocculant, wherein the dosage of the selective flocculant is 500 g/ton; stirring is continued at a stirring speed of 15r/min for 10min, and then stirring is stopped and the mixture is allowed to stand for 1min.
3. And (3) carrying out magnetic separation on the ore pulp subjected to selective flocculation, wherein the magnetic field intensity is 0.65T, the pulse size is 250 times/min, and separating a magnetic separation tailing graphite product (fixed carbon content 90.86%) and a magnetic separation concentrate (lithium iron phosphate+graphite product).
4. Adding water into the concentrate lithium iron phosphate and graphite mixed material to prepare flotation concentration of 5%, sequentially adding a dispersing agent, an inhibitor, a collector and a foaming agent (the dispersing agent dosage is 480 g/ton, the inhibitor dosage is 830 g/ton, the collector dosage is 150 g/ton, and the foaming agent dosage is 30 g/ton) into ore pulp to obtain an underflow product A and a foam product A, sequentially adding the dispersing agent, the inhibitor, the collector and the foaming agent into the underflow product A, wherein the dosage of the dispersing agent, the inhibitor, the collector and the foaming agent is half of the dosage of the roughing agent, to obtain a foam product B and an underflow product B, sequentially adding the dispersing agent, the inhibitor, the collector and the foaming agent into the underflow product B, wherein the dosage of the agent is half of the dosage of the agent, to obtain an underflow product C and a foam product C, and the underflow product C is a lithium iron phosphate anode.
5. And (3) scavenging the foam product A, sequentially adding a dispersing agent and an inhibitor into the ore pulp, wherein the dosage of the agent is 1/4 of that of the roughing agent, so as to obtain a foam product D and an underflow product D, wherein the foam product D is a graphite cathode, and the fixed carbon content is 92.49%.
6. And mixing the foam product B and the underflow product D, sequentially returning to roughing, mixing with the magnetic concentrate to form a closed circuit, sequentially returning to concentrating the foam product C, and mixing with the underflow product A to concentrate.
7. Finally, two groups of graphite cathodes are mixed to form a graphite cathode product, the fixed carbon content is 91.92%, the graphite recovery rate is 95.35%, the flotation concentrate is a lithium iron phosphate cathode product, the purity of the lithium iron phosphate is 96.17%, the fixed carbon content is 1.43%, and the recovery rate of the lithium iron phosphate is 93.81%.
In the third embodiment, experiments are performed by using a mixed electrode of a certain waste lithium battery in Hubei with a fixed carbon content of 18.98% as a raw material, wherein the main materials are lithium iron phosphate and graphite:
this example corresponds to the second example, with the following main differences:
1. after adding water, the concentration is adjusted to 65%, 800g/t of dispersing agent (sodium tripolyphosphate, guar gum and water glass in mass ratio of (3:2:6)) is added, the grinding time is 15min, and the rotating speed of the grinding machine is 20r/min;
2. the first stirring speed is 60r/min, the stirring time is 10min, and the dosage of the selective flocculant is 800 g/ton; the second stirring time is 5min;
3. the magnetic field strength is 0.6T, the pulse size is 150 times/min, and the fixed carbon content of the separated graphite product is 93.27%;
4. the dispersant dosage is 300 g/ton, the inhibitor dosage is 500 g/ton, the collector dosage is 100 g/ton, and the foamer dosage is 20 g/ton;
5. obtaining a fixed carbon content 90.43% in foam product D;
6. consistent;
7. the graphite cathode product has a fixed carbon content of 91.42%, a graphite recovery rate of 87.68%, a purity of 95.58% of lithium iron phosphate, a fixed carbon content of 2.86% and a recovery rate of 94.26%.
In the fourth embodiment, experiments are carried out by taking a certain high-aluminum low-grade phosphorite in Henan with 18.29% fixed carbon as a raw material, wherein the main materials are lithium iron phosphate and graphite:
the present embodiment is identical to the steps in the second and third embodiments, and the main differences are as follows:
1. after adding water, the concentration is adjusted to be 75%, 1000g/t of dispersing agent (sodium tripolyphosphate, guar gum and water glass in mass ratio of (6:7:11)) is added, the grinding time is 25min, and the rotating speed of a grinding machine is 30r/min;
2. the first stirring speed is 100r/min, the stirring time is 5min, and the dosage of the selective flocculant is 800 g/ton; the second stirring speed is 25r/min, and the time is 15min;
3. the magnetic field strength is 0.80T, the pulse size is 250 times/min, and the fixed carbon content of the separated graphite product is 95.28%;
4. the dispersant dosage is 900 g/ton, the inhibitor dosage is 1200 g/ton, the collector dosage is 250 g/ton, and the foamer dosage is 40 g/ton;
5. obtaining a fixed carbon content of 92.33% in foam product D;
6. consistent;
7. the graphite cathode product has 93.45% of fixed carbon content, 95.98% of graphite recovery rate, 94.14% of purity of lithium iron phosphate, 1.56% of fixed carbon content and 96.52% of recovery rate of lithium iron phosphate.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The utility model provides a preparation facilities of mixed lithium iron phosphate electrode flotation inhibitor, includes stirring subassembly, its characterized in that: the stirring assembly includes:
the sealing cover (1), the sealing cover (1) covers the beaker opening end, a hollow cylinder (2) positioned in the beaker is arranged on the lower surface of the sealing cover (1), a stirring support cylinder (21) is rotatably arranged on the periphery of the hollow cylinder (2), a stirring rod (22) is arranged on the surface of the stirring support cylinder (21), a stirring main shaft (3) is rotatably arranged in the middle of an inner cavity of the hollow cylinder (2), stirring plates (31) are arranged on the surface of the stirring main shaft (3), the stirring rods (22) and the stirring plates (31) are mutually staggered, a avoiding groove (23) for the stirring rod (22) to pass through is formed in the surface of the hollow cylinder (2), and a discharge hole (24) is formed in the surface of the stirring support cylinder (21);
the stirring device comprises a driving gear (4), wherein the driving gear (4) is positioned at the outer side of the beaker and fixedly connected with the upper end of the stirring main shaft (3), a driven gear (5) meshed with the driving gear (4) is arranged at the outer side of the driving gear (4), and the driven gear (5) is fixedly sleeved at the upper end of the stirring support tube (21).
2. The apparatus for preparing the mixed lithium iron phosphate electrode flotation suppressant according to claim 1, wherein: the lower surface of closing cap (1) is fixed and is provided with sealing platform (11), the lateral wall of sealing platform (11) is laminated and is bonded with the sealing layer with the inner wall of beaker, stirring a plurality of section of thick bamboo (21) are provided with and are annular array distribution around hollow section of thick bamboo (2).
3. The apparatus for preparing the mixed lithium iron phosphate electrode flotation suppressant according to claim 2, wherein: the upper ends of stirring main shaft (3) and stirring section of thick bamboo (21) all run through closing cap (1), mounting groove (12) have been seted up to the upper surface of closing cap (1), driving gear (4) and driven gear (5) all are located mounting groove (12) inner chamber, the open end of mounting groove (12) is covered with top cap (13), the surface of top cap (13) is connected with end cap (14) through flexible coupling rope (15), end cap (14) are provided with a plurality of and shutoff respectively in the upper portion open end of a plurality of stirring section of thick bamboo (21), the upper end of stirring main shaft (3) is provided with handle (32) that are used for driving stirring main shaft (3).
4. A recovery process of a mixed lithium iron phosphate electrode is characterized in that: comprising the preparation of a mixed lithium iron phosphate electrode flotation suppressor by using the preparation device of any one of claims 1-3, and specifically comprising the following steps:
step one, mixing: mixing a lithium iron phosphate electrode with water, adding a dispersing agent, and grinding to obtain mixed electrode powder;
step two, stirring and flocculating: pouring the ground mixed electrode powder into a stirring barrel for stirring, adding a selective flocculant, continuing stirring, uniformly mixing, and standing to obtain ore pulp;
step three, magnetic separation: separating the ore pulp into a graphite negative electrode and lithium iron phosphate and graphite by using a high-gradient strong magnetic separator;
step four, floatation: adding water into the ore pulp to obtain an underflow product A and a foam product A (roughing), continuously adding the dispersing agent, the inhibitor, the collector and the foaming agent into the underflow product A in sequence, wherein the dosage of the dispersing agent, the inhibitor, the collector and the foaming agent is half of that of the roughing agent to obtain a foam product B and an underflow product B (selecting one), and continuously adding the dispersing agent, the inhibitor, the collector and the foaming agent into the underflow product B in sequence, wherein the dosage of the agent is half of that of the selecting one to obtain an underflow product C and a foam product C (selecting two), and the underflow product C is a lithium iron phosphate anode;
step five, scavenging operation: and sequentially adding a dispersing agent and an inhibitor into the ore pulp of the foam product A, wherein the dosage of the agent is 1/4 of that of the roughing agent, so as to obtain a foam product D and an underflow product D, and the foam product D is a graphite negative electrode.
5. The process for recycling a mixed lithium iron phosphate electrode according to claim 4, wherein: in the fourth step and the fifth step, the foam product B and the underflow product D are mixed, returned to the roughing step and mixed with the magnetic concentrate to form a closed circuit, and the foam product C is returned to the selecting step and mixed with the underflow product A for selecting.
6. The process for recycling a mixed lithium iron phosphate electrode according to claim 4, wherein: in the second step and the fourth step, the selective flocculant and the inhibitor are the same substance, and the preparation method comprises the following steps:
adding water, starch, cellulose salt, polyacrylamide and polyvinyl alcohol into a beaker, and stirring the mixture by using a stirring assembly until the solution is uniform and has no particles;
heating the beaker, adding sodium hydroxide and sodium sulfite, and continuing heating until substances in the beaker react completely;
and (8) diluting the solution in the beaker after the beaker is cooled.
7. The process for recycling a mixed lithium iron phosphate electrode according to claim 6, wherein: in the step (1), starch: cellulose salt: polyacrylamide: the mass ratio of the polyvinyl alcohol is 50-80:5-9:0.01-0.05:2-7.
8. The process for recycling a mixed lithium iron phosphate electrode according to claim 4, wherein: in the first step, the dispersing agent is sodium tripolyphosphate, guar gum and water glass, the mass ratio is 2-10:1-8:1-15, the dispersing agent dosage is 500-1000 g/ton, the grinding concentration is 60% -80%, the grinding time is 15-30min, and the grinding speed is 20-40r/min.
9. The process for recycling a mixed lithium iron phosphate electrode according to claim 4, wherein: in the second step, the first stirring time is 5-15min, the dosage of the selective flocculant is 800-1500 g/ton, the second stirring time is 5-15min, the magnetic field strength is 0.5-0.8T, and the pulse size is 100-300 times/min.
10. The process for recycling a mixed lithium iron phosphate electrode according to claim 4, wherein: in the fourth step, the consumption of the dispersing agent is 200-1000 g/ton, the consumption of the inhibitor is 500-1500 g/ton, the consumption of the collecting agent is 100-300 g/ton, and the consumption of the foaming agent is 10-50 g/ton.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310936004.XA CN116851135A (en) | 2023-07-27 | 2023-07-27 | Preparation device and recovery process of mixed lithium iron phosphate electrode flotation inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310936004.XA CN116851135A (en) | 2023-07-27 | 2023-07-27 | Preparation device and recovery process of mixed lithium iron phosphate electrode flotation inhibitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116851135A true CN116851135A (en) | 2023-10-10 |
Family
ID=88225049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310936004.XA Pending CN116851135A (en) | 2023-07-27 | 2023-07-27 | Preparation device and recovery process of mixed lithium iron phosphate electrode flotation inhibitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116851135A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5525212A (en) * | 1995-06-07 | 1996-06-11 | Cytec Technology Corp. | Method of depressing non-sulfide silicate gangue minerals |
| CN212189105U (en) * | 2020-04-23 | 2020-12-22 | 苏州浩迈纺织股份有限公司 | Energy-efficient reation kettle |
| CN214261719U (en) * | 2020-10-26 | 2021-09-24 | 上海拜高高分子材料有限公司 | Dispersion tank with multi-shaft stirring function |
| CN115863822A (en) * | 2023-02-09 | 2023-03-28 | 湖南五创循环科技股份有限公司 | Method for efficiently separating and recovering valuable substances in waste lithium battery electrode powder |
| US20230107938A1 (en) * | 2020-03-13 | 2023-04-06 | Dowa Eco-System Co., Ltd. | Method for recovering valuable substance |
-
2023
- 2023-07-27 CN CN202310936004.XA patent/CN116851135A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5525212A (en) * | 1995-06-07 | 1996-06-11 | Cytec Technology Corp. | Method of depressing non-sulfide silicate gangue minerals |
| US20230107938A1 (en) * | 2020-03-13 | 2023-04-06 | Dowa Eco-System Co., Ltd. | Method for recovering valuable substance |
| CN212189105U (en) * | 2020-04-23 | 2020-12-22 | 苏州浩迈纺织股份有限公司 | Energy-efficient reation kettle |
| CN214261719U (en) * | 2020-10-26 | 2021-09-24 | 上海拜高高分子材料有限公司 | Dispersion tank with multi-shaft stirring function |
| CN115863822A (en) * | 2023-02-09 | 2023-03-28 | 湖南五创循环科技股份有限公司 | Method for efficiently separating and recovering valuable substances in waste lithium battery electrode powder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115213023B (en) | A method for improving the flotation separation efficiency of positive and negative electrode materials of waste lithium batteries | |
| CN102921559A (en) | Selective flotation collector for spodumene and application thereof | |
| CN102284372A (en) | Flotation method for carbonate minerals | |
| CN109467261A (en) | Waste lithium cell electrolyte wastewater treatment method | |
| CN105214853B (en) | A kind of brown coal floatation method | |
| CN115591658A (en) | A kind of beneficiation method of lithium-containing china clay ore magnetic-flotation joint extraction lithium | |
| CN112916582B (en) | Gasification fly ash decarbonization method by combined flotation of mechanical activation and compound reagent | |
| CN116851135A (en) | Preparation device and recovery process of mixed lithium iron phosphate electrode flotation inhibitor | |
| CN114273088B (en) | Mud-control flotation beneficiation process | |
| CN110976099A (en) | Flotation method and collector composition of lithium ore | |
| CN108461859A (en) | A method of from extraction lithium in waste liquid containing lithium | |
| CN202516696U (en) | Single-cylinder vertical stirring concentrating machine | |
| CN205873974U (en) | Novel board -like rotary electrode electricity flocculation electrolysis device | |
| CN106492940B (en) | The technique that a kind of mechanical activation improves boron concentrate leaching boron rate | |
| CN221085976U (en) | Recycling device for lithium manganese iron phosphate positive electrode material in lithium ion battery waste | |
| CN118179758A (en) | Method for promoting lepidolite and feldspar full-size-fraction flotation separation by surface pretreatment | |
| CN207016608U (en) | Heavy metal containing sewage treatment reactor tank | |
| CN117019408A (en) | Flotation inhibitor and preparation method and application thereof | |
| CN216964944U (en) | Novel cylindrical magnet sorting machine capable of working in all directions | |
| CN117282545A (en) | Composite flotation reagent and application thereof in lepidolite flotation | |
| CN116273445B (en) | Method for improving separation efficiency of mixed materials of waste lithium manganate batteries | |
| CN219291083U (en) | Dissolving tank | |
| CN217190167U (en) | Prevent fine iron powder extraction equipment that splashes | |
| CN207108770U (en) | A kind of sludge treatment equipment with Double stirring function | |
| CN116651910B (en) | Selective flocculation flotation separation method for anode and cathode materials of lithium iron phosphate battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |