Lithium and aluminum hydroxyfluoride extraction equipment and low-grade cathode carbon block recovery process

Abstract

The invention provides lithium and aluminum hydroxyfluoride extraction equipment and a low-grade cathode carbon block recovery process, and relates to the technical field of metal recycling, the lithium and aluminum hydroxyfluoride extraction equipment comprises a bracket, a tank body, a mounting plate, a driving mechanism, a reciprocating mechanism, a water washing liquid discharging mechanism and an acid leaching liquid discharging mechanism; the tank body is installed in the support, a top plate is installed at the top end of the tank body through bolts, and a supporting frame is installed on the upper surface of the top plate through bolts. According to the scheme, a layer of pickle liquor is covered and injected after water washing liquid enters, so that the two extracting solutions can be added in a laminated manner, and the water washing liquid and the pickle liquor are quantitatively added in the laminated adding process, so that layered mixing is realized in the adding process of the device, and the efficiency of the device is improved. According to the device, the subsequent stirring time can be shortened, electric power is saved, meanwhile, it is guaranteed that two kinds of liquid are mixed more sufficiently and stably, and meanwhile the internal alkaline balance can be guaranteed through a stacked adding mode.

Description

Technical Field

[0001] The present invention relates to the technical field of metal recovery and utilization, in particular to lithium and hydroxyaluminum fluoride extraction equipment and a low-grade cathode carbon block recovery process. Background Art

[0002] The technologies for recovering valuable metals from aluminum electrolytic waste slag are mainly divided into three categories: wet recovery, pyrolysis recovery, and combined recovery. The wet treatment is a method of using strong acid (HCl, HNO, etc.), strong base (NaOH) and salt substances (CaCl2) to dissolve and leach soluble and insoluble substances in the waste aluminum electrolyte, while treating fluorides and oxides, separating valuable metal elements and recovering the electrolyte.

[0003] In recent years, the combined treatment of aluminum electrolytic waste slag by wet and pyrolysis has attracted more and more attention. The combined treatment of burning and leaching can alleviate the problems caused by the use of wet or pyrolysis alone to a certain extent, and realize the harmless disposal and resource utilization of aluminum electrolyte waste slag.

[0004] During the leaching and extraction stage of traditional equipment, since lithium and hydroxyaluminum fluoride need to be extracted in water washing liquid and acid leaching liquid, traditional equipment requires continuous stirring to adjust the acidity and alkalinity of the two liquids. This not only wastes electricity resources, but also is not conducive to full contact between the two liquids, easily causing alkaline imbalance, which in turn affects the extraction effect.

[0005] Therefore, it is necessary to provide lithium and hydroxyaluminum fluoride extraction equipment and low-grade cathode carbon block recovery process to solve the above technical problems. Summary of the Invention

[0006] The present invention provides lithium and hydroxyaluminum fluoride extraction equipment and a low-grade cathode carbon block recovery process, which solves the technical problem in the related art that water washing solution and acid leaching solution are not conducive to fusion and easily affect the extraction effect.

[0007] In order to solve the above technical problems, the present invention provides a lithium and aluminum hydroxyfluoride extraction device, which includes a bracket, a tank body, a mounting plate, a driving mechanism, a reciprocating mechanism, a water washing liquid discharge mechanism and an acid leaching liquid discharge mechanism;

[0008] The tank body is installed inside the bracket, a top plate is installed on the top of the tank body by bolts, a support frame is installed on the upper surface of the top plate by bolts, and the mounting plate is fixed on the top of the support frame;

[0009] The driving mechanism includes a mounting seat and a limiting plate, the mounting seat is mounted on the upper surface of the top plate, the limiting plate is fixed to the top of the mounting seat, a double-headed motor is installed inside the mounting seat by bolts, the top output shaft keyway of the double-headed motor is connected to the upper ratchet, the upper ratchet ring is rotatably connected inside the limiting plate, the top of the upper ratchet ring is fixed with an upper plate, and the top axis of the upper plate is fixed with a rotating shaft;

[0010] The reciprocating mechanism includes a turntable connected to the top of the rotating shaft by a keyway, the top of the turntable is rotatably connected to a limit wheel, two slides are fixedly provided on the upper surface of the mounting plate, rack rods are slidably connected inside the two slides, and a toothed plate is rotatably connected on the upper surface of the mounting plate and located on the opposite side of the two slides, and a notch is opened inside the toothed plate;

[0011] The water washing liquid discharge mechanism includes a first sleeve mounted on the upper surface of the mounting plate, a first piston is slidably connected to the interior of the first sleeve, a first one-way valve and a second one-way valve are installed inside the first sleeve and on one side of the first piston, and a first hose is sealed at the outlet of the second one-way valve;

[0012] The pickling liquid discharge mechanism includes a second sleeve installed on the upper surface of the mounting plate, a second piston is slidably connected to the interior of the second sleeve, a third one-way valve and a fourth one-way valve are installed inside the second sleeve and on one side of the second piston, and a second hose is sealed at the outlet of the fourth one-way valve.

[0013] Preferably, the upper ratchet wheel and the upper ratchet ring are engaged with each other, and the upper ratchet ring, the upper plate, the upper ratchet wheel and the rotating shaft are on the same axis.

[0014] Preferably, the limiting wheel is located inside the notch, and the outer wall of the limiting wheel is in contact with the inside of the notch, and the tooth plate and the rack rod are engaged with each other.

[0015] Preferably, both ends of the rack rod are fixedly connected to the axis of the first piston and the second piston, and the output ends of the first hose and the second hose extend to the inside of the top plate and pass through the top plate.

[0016] Preferably, the bottom output shaft keyway of the double-headed motor is connected to a lower ratchet, and the axis of the top plate is rotatably connected to a lower ratchet ring;

[0017] The bottom end of the lower ratchet ring is fixed with a rotating rod, the outer wall of the rotating rod is fixed with stirring rods distributed in an equidistant ring, the outer wall of the rotating rod and above the stirring rod is fixed with a rotating ring, the bottom of the rotating ring is fixed with an ejection plate, the inner wall of the tank body and below the rotating ring is fixed with a positioning plate, the interior of the positioning plate is slidably connected to the alkaline detector, the top of the alkaline detector is fixed with a baffle, the top of the baffle is fixed with a roller, and the outer wall of the alkaline detector is sleeved with a reset spring;

[0018] An end cover is rotatably connected to the top of the tank body and located on the side of the top plate through a hinge. Two locking rods are rotatably connected to the outer wall of the tank body and located below the end cover. Knobs are installed on the top of the two locking rods. A handle is fixedly provided at the middle position of the top of the end cover. A discharge pipe is installed at the bottom of the tank body, and four movable wheels are installed at the bottom of the bracket.

[0019] Preferably, the upper surface of the roller is in contact with the bottom surface of the rotating ring, and the upper and lower ends of the reset spring are fixedly connected to the baffle and the positioning plate.

[0020] Preferably, it further comprises a third sleeve;

[0021] The third sleeve is installed at the bottom of the mounting plate, and the third piston is slidably connected to the interior of the third sleeve. A fifth one-way valve and a sixth one-way valve are respectively installed inside the third sleeve and on one side of the third piston. An injection pipe is sealed at the outlet of the sixth one-way valve. A connecting plate is fixed at the axis of the third piston and on the outside of the third sleeve. A guide wheel is fixed on the outer wall of the connecting plate, and a limit spring is sleeved between the connecting plate and the third piston.

[0022] Preferably, the bottom of the injection pipe extends to the upper surface of the top plate and penetrates the top plate, and the outer wall of the guide wheel is in contact with the outer wall of the cam.

[0023] The low-grade cathode carbon block recovery process includes the following steps:

[0024] S1: Crush and grind the cathode carbon block and sieve it to 200 mesh;

[0025] S2: Place the sieved cathode carbon block in a tube furnace and pass oxygen-inert gas for decarburization at a temperature of 500-670°C for 1 hour. The decarburized material is gray, and there is little loss of fluorine and lithium.

[0026] S3: calcining the decarburized material and aluminum sulfate additive at a low temperature, with a raw material to auxiliary ratio of 5:1-10:1, a calcination temperature of 300-700°C, and a calcination time of 0.5 hours;

[0027] S4: placing the roasted clinker in a constant temperature water bath for immersion to leach out the soluble fluoride and lithium, with a solid-liquid ratio of 1:3-4;

[0028] S5: Finally, the silica, aluminate and other refractory substances in the water leaching residue are further acid-leached, and the pH is controlled at 1-2;

[0029] S6: The two stages of leachate are mixed, and the pH of the mixed solution is adjusted with sodium hydroxide solution to obtain hydroxyaluminum fluoride and precipitated liquid. The pH adjustment precision range is 4.3-4.5, and the sodium hydroxide concentration is 6 mol / L. This step needs to be performed in a tank.

[0030] Compared with related technologies, the equipment for extracting lithium and aluminum hydroxyfluoride and the process for recovering low-grade cathode carbon blocks provided by the present invention have the following beneficial effects:

[0031] Compared with the traditional design, this design uses a rack rod with the first and second pistons fixedly mounted at both ends, and uses a turntable that continuously rotates clockwise to influence the eccentric rotation of the limit wheel, so that the limit wheel can influence the notch to drive the tooth plate to rotate back and forth, meshing and controlling the rack rod to influence the reciprocating movement of the first and second pistons;

[0032] When the rack rod moves to the left, the first piston squeezes the water washing liquid in the first sleeve into the tank body, and the second sleeve will suck the acid leaching liquid at this time. When the rack rod moves to the right, the acid leaching liquid in the second sleeve is squeezed into the tank body, and the water washing liquid is sucked into the first sleeve at this time.

[0033] Through reciprocating motion, regular switching control of the two states of suction and extrusion is achieved to ensure that after some water washing liquid enters, a layer of acid extract is added to cover it. Therefore, this design allows the two extracts to be added in a layered manner. At the same time, the water washing liquid and the acid extract are added in a quantitative manner during the layered addition process, so that the device can achieve layered mixing during the addition process, which can reduce the subsequent stirring time, save electricity, and ensure that the mixing of the two liquids is more sufficient and stable. At the same time, the layered addition method can also ensure the internal alkaline balance. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0035] Figure 1 A schematic diagram of the best structure provided by the present invention;

[0036] Figure 2 for Figure 1 Schematic diagram of the back structure shown;

[0037] Figure 3 for Figure 2 The enlarged structural diagram of point A is shown;

[0038] Figure 4 for Figure 2 Schematic diagram of the driving mechanism structure shown;

[0039] Figure 5 for Figure 2 Schematic diagram of the initial working state of the reciprocating mechanism, the water washing liquid feeding mechanism and the acid immersion liquid feeding mechanism shown;

[0040] Figure 6 for Figure 5 Schematic diagram of the working status of the reciprocating mechanism, the water washing liquid feeding mechanism and the acid immersion liquid feeding mechanism shown;

[0041] Figure 7 for Figure 2 Schematic diagram of the detailed internal structure of the tank shown;

[0042] Figure 8 for Figure 7 The enlarged structural diagram of point B is shown;

[0043] Figure 9 A schematic diagram of the working state of the cam provided by the present invention without interfering with the guide wheel;

[0044] Figure 10 for Figure 9 The schematic diagram of the working state of the cam against the guide wheel shown;

[0045] Figure 11 This is the XRD pattern of the by-product (hydroxyaluminum fluoride) of the low-grade cathode carbon block recovery process shown in the present invention.

[0046] Description of Figure Numbers:

[0047] 1. Bracket, 2. Tank body, 3. Top plate, 4. Support frame;

[0048] 5. Mounting plate;

[0049] 6. Driving mechanism, 61. Mounting seat, 62. Limiting plate, 63. Double-headed motor, 64. Upper ratchet, 65. Upper ratchet ring, 66. Upper plate, 67. Rotating shaft, 68. Cam, 69. Lower ratchet, 610. Lower ratchet ring;

[0050] 7. Reciprocating mechanism, 71. Turntable, 72. Limiting wheel, 73. Slide, 74. Tooth plate, 75. Notch, 76. Rack rod;

[0051] 8. Wash liquid discharging mechanism, 81. First sleeve, 82. First piston, 83. First one-way valve, 84. Second one-way valve, 85. First hose;

[0052] 9. Pickling liquid discharging mechanism, 91. Second sleeve, 92. Second piston, 93. Third one-way valve, 94. Fourth one-way valve, 95. Second hose;

[0053] 10. Moving wheel;

[0054] 11. End cap, 12. Locking rod, 13. Knob, 14. Handle;

[0055] 15. Rotating rod, 16. Rotating ring, 17. Ejector plate, 18. Stirring rod, 19. Positioning plate, 20. Discharge pipe, 21. Alkaline detector, 22. Baffle, 23. Roller;

[0056] 24. Return spring, 25. Third sleeve, 26. Third piston, 27. Fifth one-way valve, 28. Sixth one-way valve, 29. Injection pipe, 30. Connecting plate, 31. Limit spring, 32. Guide wheel.

[0057] The purpose, features and advantages of the present invention will be further described with reference to the accompanying drawings and in conjunction with the embodiments. DETAILED DESCRIPTION

[0058] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0059] The present invention provides lithium and hydroxyaluminum fluoride extraction equipment and a low-grade cathode carbon block recovery process.

[0060] First embodiment:

[0061] See also Figure 1 、 Figure 2 、 Figures 4 to 6 , lithium and hydroxyaluminum fluoride extraction equipment, including a bracket 1, a tank body 2, a mounting plate 5, a driving mechanism 6, a reciprocating mechanism 7, a water washing liquid feeding mechanism 8 and an acid leaching liquid feeding mechanism 9;

[0062] The tank body 2 is installed inside the bracket 1, and a top plate 3 is installed on the top of the tank body 2 by bolts. A support frame 4 is installed on the upper surface of the top plate 3 by bolts, and the mounting plate 5 is fixed on the top of the support frame 4;

[0063] The driving mechanism 6 includes a mounting seat 61 and a limiting plate 62. The mounting seat 61 is mounted on the upper surface of the top plate 3. The limiting plate 62 is fixed to the top of the mounting seat 61. A double-headed motor 63 is installed inside the mounting seat 61 by bolts. The top output shaft keyway of the double-headed motor 63 is connected to an upper ratchet 64. The upper ratchet ring 65 is rotatably connected inside the limiting plate 62. An upper plate 66 is fixed to the top of the upper ratchet ring 65. A rotating shaft 67 is fixed to the top axis of the upper plate 66.

[0064] See also Figure 4 : The upper and lower output shafts of the double-headed motor 63 are respectively connected to the upper ratchet 64 and the lower ratchet 69 by keyways. Secondly, the internal output shafts of the double-headed motor 63 are coaxially designed, so the rotation direction is also consistent. When the user starts the double-headed motor 63 to rotate clockwise, the upper ratchet 64 and the lower ratchet 69 will rotate clockwise synchronously. The upper ratchet 64 will rotate clockwise to affect the upper ratchet ring 65 to drive the upper plate 66 and the rotating shaft 67 to achieve linked synchronous clockwise rotation;

[0065] However, the teeth of the lower ratchet 69 and the upper ratchet 64 are arranged in opposite directions. Therefore, when the lower ratchet 69 rotates clockwise, it will not affect the rotation of the lower ratchet ring 610.

[0066] It can be seen from the above working state that when the double-headed motor 63 rotates clockwise, it can only control the rotation of the upper ratchet 64, and when the double-headed motor 63 rotates counterclockwise, it can only control the rotation of the lower ratchet 69.

[0067] The reciprocating mechanism 7 includes a turntable 71 connected to the top of the rotating shaft 67 by a keyway. The top of the turntable 71 is rotatably connected to a limit wheel 72. Two slides 73 are fixed to the upper surface of the mounting plate 5. Rack rods 76 are slidably connected to the interiors of the two slides 73. A toothed plate 74 is rotatably connected to the upper surface of the mounting plate 5 and located on the opposite side of the two slides 73. A notch 75 is formed inside the toothed plate 74.

[0068] The washing liquid discharge mechanism 8 includes a first sleeve 81 mounted on the upper surface of the mounting plate 5. A first piston 82 is slidably connected to the interior of the first sleeve 81. A first one-way valve 83 and a second one-way valve 84 are installed inside the first sleeve 81 and on one side of the first piston 82. A first hose 85 is sealed at the outlet of the second one-way valve 84.

[0069] The pickling liquid discharge mechanism 9 includes a second sleeve 91 installed on the upper surface of the mounting plate 5, and a second piston 92 is slidably connected to the interior of the second sleeve 91. A third one-way valve 93 and a fourth one-way valve 94 are installed inside the second sleeve 91 and on one side of the second piston 92. A second hose 95 is sealed at the outlet of the fourth one-way valve 94.

[0070] See also Figure 5 : In the initial state, the tooth plate 74 and the rack rod 76 are in meshing state, and the limiting wheel 72 is installed inside the slot 75. When the rotating shaft 67 rotates clockwise, the rotating shaft 67 will control the turntable 71 to rotate clockwise synchronously. At the same time, the rotating turntable 71 will control the limiting wheel 72 to rotate eccentrically. At this time, the eccentric rotation force generated by the limiting wheel 72 controls the force-bearing slot 75 to affect the tooth plate 74. Therefore, the clockwise rotating limiting wheel 72 will drive the tooth plate 74 to adaptively rotate back and forth on the mounting plate 5.

[0071] See also Figure 6 : The reciprocatingly rotating gear plate 74 engages the transmission control rack rod 76 to reciprocate along the slide 73. When the rack rod 76 drives the first piston 82 and the second piston 92 to move to the left, the first piston 82 squeezes and compresses the inside of the first sleeve 81, and the water washing liquid inside the first sleeve 81 is injected into the tank body 2 through the second one-way valve 84, the first hose 85, and the top plate 3;

[0072] At the same time, the second piston 92 moves to the left inside the second sleeve 91, generating a suction force to draw the pickling liquid into the second sleeve 91 through the third one-way valve 93;

[0073] When the rack rod 76 completes its leftward movement, it moves to the right. At this time, the second piston 92 squeezes the pickling liquid in the second sleeve 91 and squeezes it out of the fourth one-way valve 94 and injects it into the tank body 2 through the second hose 95.

[0074] At the same time, the first piston 82 moves to the right in the first sleeve 81 , generating a suction force to draw the washing liquid into the first sleeve 81 through the first one-way valve 83 .

[0075] The upper ratchet 64 and the upper ratchet ring 65 are engaged with each other, and the upper ratchet ring 65, the upper plate 66, the upper ratchet 64 and the rotating shaft 67 are on the same axis.

[0076] The limiting wheel 72 is located inside the notch 75 , and the outer wall of the limiting wheel 72 contacts the inside of the notch 75 , and the tooth plate 74 and the rack rod 76 are engaged with each other.

[0077] Both ends of the rack rod 76 are fixedly connected to the axis of the first piston 82 and the second piston 92 . The output ends of the first hose 85 and the second hose 95 extend to the interior of the top plate 3 and pass through the top plate 3 .

[0078] from Figure 5 and Figure 6It can be seen that the slot 75 is designed with a certain length, which can ensure that the limiting wheel 72 can stably rotate and move inside the slot 75, thereby effectively controlling the tooth plate 74 and avoiding interference between the limiting wheel 72 and the slot 75.

[0079] Secondly, the first one-way valve 83 and the third one-way valve 93 are for one-way passage from the outside to the inside, and the second one-way valve 84 and the fourth one-way valve 94 are for one-way passage from the inside to the outside;

[0080] During the suction process, the water washing liquid and the acid leaching liquid will not leak, and during the squeezing process, the water washing liquid and the acid leaching liquid will not flow back.

[0081] This embodiment:

[0082] Compared with the traditional design, the present invention adopts a rack rod 76 with the first piston 82 and the second piston 92 fixedly mounted at both ends, and adopts a turntable 71 that continuously rotates clockwise to influence the eccentric rotation of the limit wheel 72, so that the limit wheel 72 can influence the notch 75 to drive the tooth plate 74 to rotate back and forth and engage with the rack rod 76 to influence the reciprocating movement of the first piston 82 and the second piston 92;

[0083] When the rack rod 76 moves to the left, the first piston 82 squeezes the water washing liquid in the first sleeve 81 into the tank body 2, and the second sleeve 91 sucks the acid leaching liquid. When the rack rod 76 moves to the right, the acid leaching liquid in the second sleeve 91 is squeezed into the tank body 2, and the water washing liquid is sucked into the first sleeve 81.

[0084] Through reciprocating motion, regular switching control of the two states of suction and extrusion is achieved to ensure that after some water washing liquid enters, a layer of acid extract is added to cover it. Therefore, this design allows the two extracts to be added in a layered manner. At the same time, the water washing liquid and the acid extract are added in a quantitative manner during the layered addition process, so that the device can achieve layered mixing during the addition process, which can reduce the subsequent stirring time, save electricity, and ensure that the mixing of the two liquids is more sufficient and stable. At the same time, the layered addition method can also ensure the internal alkaline balance.

[0085] Second embodiment:

[0086] See also Figures 1 to 4 、 Figures 7 and 8 The bottom output shaft keyway of the double-headed motor 63 is connected to a lower ratchet 69, and the axis of the top plate 3 is rotatably connected to a lower ratchet ring 610;

[0087] The bottom end of the lower ratchet ring 610 is fixed with a rotating rod 15, and the outer wall of the rotating rod 15 is fixed with stirring rods 18 distributed in an equidistant ring. A rotating ring 16 is fixed on the outer wall of the rotating rod 15 and located above the stirring rod 18. A knockout plate 17 is fixed at the bottom of the rotating ring 16. A positioning plate 19 is fixed on the inner wall of the tank body 2 and located below the rotating ring 16. An alkaline detector 21 is slidably connected to the interior of the positioning plate 19. A baffle 22 is fixed on the top of the alkaline detector 21. A roller 23 is fixed on the top of the baffle 22. A return spring 24 is sleeved on the outer wall of the alkaline detector 21.

[0088] See also Figure 4 : During the operation of the first embodiment, if the double-headed motor 63 rotates counterclockwise, the upper ratchet ring 65 will not be affected, and only the lower ratchet ring 610 can rotate counterclockwise. In combination with the working state of the first embodiment, it can be seen that when the mixed liquid inside the tank body 2 rises to the threshold value, stirring and extraction is required.

[0089] See also Figure 7 : During the rotation of the lower ratchet ring 610, the rotating rod 15 is synchronously driven to rotate, and the rotating rod 15 synchronously controls the rotation of the stirring rod 18 and the rotating ring 16. During the rotation of the stirring rod 18, the water washing liquid and the acid leaching liquid in the tank body 2 are stirred and mixed to ensure that aluminum hydroxyfluoride and the precipitated liquid can be formed inside the tank body 2 later;

[0090] Aluminum hydroxyfluoride is dried to obtain a finished product, and the precipitated liquid is collected to prepare lithium carbonate;

[0091] The main recovered product ① is lithium-rich brine, containing 98% elemental lithium and low in impurities;

[0092] The recovered by-product ② is hydroxyaluminum fluoride, containing 94% fluorine.

[0093] The XRD diffraction peaks of this sample are consistent with those of the standard aluminum hydroxyfluoride PDF card, and there are no other impurity peaks.

[0094] See also Figure 7 and Figure 8 : When the rotating ring 16 drives the ejector plate 17 at the bottom to move to the position of the roller 23, the roller 23 will follow the shape of the ejector plate 17 to adaptively control the alkalinity detector 21 to move downward along the vertical direction of the positioning plate 19. During the downward movement, the alkalinity detector 21 will enter the mixed liquid inside the tank body 2 to detect its alkalinity number. As the rotating ring 16 continues to rotate, when the ejector plate 17 moves away from the roller 23, the alkalinity detector 21 will automatically reset to its initial state.

[0095] An end cover 11 is rotatably connected to the top of the tank body 2 and located on the side of the top plate 3 through a hinge. Two locking rods 12 are rotatably connected to the outer wall of the tank body 2 and located below the end cover 11. Knobs 13 are installed on the top of the two locking rods 12. A handle 14 is fixed to the middle position of the top of the end cover 11. A discharge pipe 20 is installed at the bottom of the tank body 2, and four moving wheels 10 are installed at the bottom of the bracket 1.

[0096] The upper surface of the roller 23 contacts the bottom surface of the rotating ring 16 , and the upper and lower ends of the return spring 24 are fixedly connected to the baffle 22 and the positioning plate 19 .

[0097] This embodiment: Compared with the traditional design, this case adopts a double-headed motor 63 that can switch between two working modes by forward and reverse rotation. Clockwise rotation is the feeding mode, and when it rotates counterclockwise, it will drive the stirring rod 18 to rotate to fully mix and stir the mixed liquid in the tank body 2, ensuring efficient reaction extraction. Secondly, the rotating ring 16 drives the ejection plate 17 to control the roller 23 to control the alkalinity detector 21 to intermittently penetrate into the mixed liquid in the tank body 2, so that the alkalinity value inside the tank body 2 can be intermittently detected during the extraction process. Therefore, such a design can not only realize the switching of multiple modes, but also facilitate the detection of the alkalinity value of the mixed liquid in the tank body 2, so that the internal alkalinity value can be judged in time, which is convenient for the user to adjust in time.

[0098] Third embodiment:

[0099] See also Figure 4 、 Figures 9 and 10 , further comprising a third sleeve 25;

[0100] The third sleeve 25 is installed at the bottom of the mounting plate 5. The third piston 26 is slidably connected to the inside of the third sleeve 25. A fifth one-way valve 27 and a sixth one-way valve 28 are installed inside the third sleeve 25 and on one side of the third piston 26. An injection pipe 29 is sealed at the outlet of the sixth one-way valve 28. A connecting plate 30 is fixed at the axis of the third piston 26 and on the outside of the third sleeve 25. A guide wheel 32 is fixed on the outer wall of the connecting plate 30. A limit spring 31 is sleeved between the connecting plate 30 and the third piston 26.

[0101] The bottom of the injection pipe 29 extends to the upper surface of the top plate 3 and penetrates the top plate 3 , and the outer wall of the guide wheel 32 contacts the outer wall of the cam 68 .

[0102] Preferably, the third piston 26 and the connecting plate 30 can be installed and connected by a connecting rod.

[0103] See also Figure 4During operation of the first embodiment, since the cam 68 is mounted on the rotating shaft 67, the rotation of the rotating shaft 67 drives the cam 68 to rotate synchronously.

[0104] See also Figure 9 : In the initial state, the guide wheel 32 is attached to the outer wall of the cam 68. At this time, the limit spring 31 is in an extended state, and the third piston 26 is located at the left end position of the third sleeve 25.

[0105] See also Figure 10 When the cam 68 operates according to the first embodiment, the cam 68 rotates clockwise. At this time, the long end of the cam 68 contacts the control guide wheel 32, driving the connecting plate 30 to compress the limit spring 31. At the same time, the third piston 26 pushes inside the third sleeve 25, so that the sodium hydroxide solution inside the third sleeve 25 passes through the sixth one-way valve 28 and the injection pipe 29 and is injected into the interior of the tank body 2.

[0106] When the cam 68 continues to rotate and reset, the limit spring 31 automatically resets to the initial state. At this time, the third piston 26 will suck the sodium hydroxide solution into the third sleeve 25 through the fifth one-way valve 27 in the third sleeve 25.

[0107] This embodiment:

[0108] Compared with the traditional design, this case is designed with an independently moving driven cam 68. During the operation of the first embodiment, when the water washing liquid and the acid leaching liquid are added and mixed in layers, the synchronously rotating cam 68 will squeeze the sodium hydroxide solution in the third sleeve 25 into the tank body 2, so that during the layered filling of the water washing liquid and the acid leaching liquid, the sodium hydroxide solution is added synchronously to achieve mixing, thereby realizing three-layered filling, ensuring that the required sodium hydroxide solution can be added in layers, and also using a quantitative addition method. Compared with the direct filling method, this design further ensures alkaline balance, thereby further ensuring the final extraction effect.

[0109] Fourth embodiment:

[0110] Low-grade cathode carbon block recovery process

[0111] S1: Crush and grind the cathode carbon block and sieve it to 200 mesh;

[0112] S2: Place the sieved cathode carbon block in a tube furnace and pass oxygen-inert gas (nitrogen) for decarburization at a temperature of 500-670°C for 1 hour. The decarburized material is gray and there is little loss of fluorine and lithium.

[0113] S3: calcining the decarburized material and aluminum sulfate additive at a low temperature, with a raw material to auxiliary ratio of 5:1-10:1, a calcination temperature of 300-700°C, and a calcination time of 0.5 hours;

[0114] S4: placing the roasted clinker in a constant temperature water bath for immersion to leach out the soluble fluoride and lithium, with a solid-liquid ratio of 1:3-4;

[0115] S5: Finally, the silica, aluminate and other refractory substances in the water leaching residue are further acid-leached, and the pH is controlled at 1-2;

[0116] S6: The two stages of leachate are mixed, and the pH of the mixed solution is adjusted with sodium hydroxide solution to obtain hydroxyaluminum fluoride and a precipitated solution. The pH adjustment precision range is 4.3-4.5, and the sodium hydroxide concentration is 6 mol / L. This step needs to be performed in tank 2.

[0117] The operation steps in this embodiment can be specifically transformed into three types, and the specific operation steps are as follows:

[0118] The first one:

[0119] Step 1: Pre-treat the cathode carbon block (crush, grind, and sieve to 200 mesh);

[0120] Step 2: Place 100g of the pretreated material in a tube furnace, introduce oxygen and inert gas (nitrogen), and roast at 500°C for 1 hour. After cooling, take it out and send it for testing and analysis to analyze the loss of the material before and after roasting;

[0121] Step 3: Mix 80g of the decarbonized clinker with anhydrous aluminum sulfate in a ratio of 5:1, place it in a muffle furnace in an air atmosphere and roast it at 300°C for 0.5 hours. After cooling, take it out for use;

[0122] Step 4: Mix the roasted clinker and pure water at a solid-liquid ratio of 1:3 at 60°C for leaching to obtain washed slag;

[0123] Step 5: Mix the washed slag and sulfuric acid solution at a solid-liquid ratio of 1:3 for leaching (the amount of sulfuric acid used accounts for 30%; for example, 120g of washed slag and 30g of 98% concentrated sulfuric acid);

[0124] Step 6: mixing the water washing solution and the acid leaching solution to obtain a mixed solution;

[0125] Step 7: Use 6 mol / L sodium hydroxide solution to adjust the mixed solution to 4.3 to obtain hydroxyaluminum fluoride and precipitated liquid. The precipitated liquid is a lithium-rich solution that can be used to prepare lithium carbonate.

[0126] The second type:

[0127] Step 1: Pre-treat the cathode carbon block (crush, grind, and sieve to 200 mesh);

[0128] Step 2: Place 150g of the pretreated material in a tube furnace, introduce oxygen and inert gas (nitrogen), and roast at 600°C for 1 hour. After cooling, take it out and send it for testing and analysis to analyze the loss of the material before and after roasting;

[0129] Step 3: Mix 130g of the decarbonized clinker with anhydrous aluminum sulfate in a ratio of 6:1, place it in a muffle furnace in an air atmosphere and roast it at 500°C, cool it for 0.5 hours, and then take it out for use;

[0130] Step 4: Mix the roasted clinker and pure water at a solid-liquid ratio of 1:3 at 60°C for leaching to obtain washed slag;

[0131] Step 5: Mix the washed slag with sulfuric acid solution at a solid-liquid ratio of 1:3 for leaching (the amount of sulfuric acid used accounts for 30%; for example, 120g of washed slag and 30g of 98% concentrated sulfuric acid);

[0132] Step 6: mixing the water washing solution and the acid leaching solution to obtain a mixed solution;

[0133] Step 7: Use 6 mol / L sodium hydroxide solution to adjust the mixed solution to 4.5 to obtain hydroxyaluminum fluoride and a precipitated solution. The precipitated solution is a lithium-rich solution that can be used to prepare lithium carbonate.

[0134] The third type:

[0135] Step 1: Pre-treat the cathode carbon block (crush, grind, and sieve to 200 mesh);

[0136] Step 2: Place 200g of the pretreated material in a tube furnace, introduce oxygen and inert gas (nitrogen), and roast at 670°C for 1 hour. After cooling, take it out and send it for testing and analysis to analyze the loss of the material before and after roasting;

[0137] Step 3: 180g of the decarbonized clinker was mixed with anhydrous aluminum sulfate in a ratio of 6:1, and the mixture was placed in a muffle furnace and calcined at 700°C in an air atmosphere. The mixture was cooled for 0.5h and then taken out for use;

[0138] Step 4: Mix the roasted clinker and pure water at a solid-liquid ratio of 1:3 at 60°C for leaching to obtain washed slag;

[0139] Step 5: Mix the washed slag and sulfuric acid solution at a solid-liquid ratio of 1:3 for leaching (the amount of sulfuric acid used accounts for 30%; for example, 120g of washed slag and 30g of 98% concentrated sulfuric acid);

[0140] Step 6: mixing the water washing solution and the acid leaching solution to obtain a mixed solution;

[0141] Step 7: Use 6 mol / L sodium hydroxide solution to adjust the mixed solution to 4.7 to obtain hydroxyaluminum fluoride and precipitated liquid. The precipitated liquid is a lithium-rich solution that can be used to prepare lithium carbonate.

[0142] The present invention mainly introduces inert gas and oxygen into low-grade cathode carbon blocks in a vacuum atmosphere for low-temperature decarburization treatment, thereby destroying the unit packaging structure and converting it into soluble lithium fluoride. On the other hand, harmful substances such as cyanide are removed. Subsequently, aluminum salt additives are used for low-temperature roasting. After water leaching and acid leaching, a leachate is obtained, and finally 94% of fluorine is recovered from the solution in the form of hydroxyaluminum fluoride.

[0143] Existing technologies utilize a sodium hydroxide molten salt roasting method, all performed under high-temperature inert gas conditions. This method requires high equipment requirements and is not environmentally friendly or economical. The present invention pre-treats the raw ore for decarburization, reducing the activation energy for lithium fluoride dissolution. This allows for subsequent low-temperature roasting and leaching in air. The leachate is pH-adjusted to precipitate aluminum hydroxyfluoride, leaving 98% of the lithium in the precipitated solution for subsequent use in lithium carbonate production, achieving low-cost and efficient recovery of the valuable metal lithium fluoride.

[0144] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made by using the contents of the present invention description and drawings under the concept of the present invention, or direct / indirect application in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. Lithium and aluminum hydroxyfluoride extraction equipment, characterized in that, It includes a bracket, a tank body, a mounting plate, a driving mechanism, a reciprocating mechanism, a water washing liquid unloading mechanism and an acid immersion liquid unloading mechanism; The tank body is installed inside the bracket, a top plate is installed on the top of the tank body by bolts, a support frame is installed on the upper surface of the top plate by bolts, and the mounting plate is fixed on the top of the support frame; The driving mechanism includes a mounting seat and a limiting plate, the mounting seat is mounted on the upper surface of the top plate, the limiting plate is fixed to the top of the mounting seat, a double-headed motor is installed inside the mounting seat by bolts, the top output shaft keyway of the double-headed motor is connected to the upper ratchet, the upper ratchet ring is rotatably connected inside the limiting plate, the top of the upper ratchet ring is fixed with an upper plate, and the top axis of the upper plate is fixed with a rotating shaft; The reciprocating mechanism includes a turntable connected to the top of the rotating shaft by a keyway, the top of the turntable is rotatably connected to a limit wheel, two slides are fixedly provided on the upper surface of the mounting plate, rack rods are slidably connected inside the two slides, and a toothed plate is rotatably connected on the upper surface of the mounting plate and located on the opposite side of the two slides, and a notch is opened inside the toothed plate; The water washing liquid discharge mechanism includes a first sleeve mounted on the upper surface of the mounting plate, a first piston is slidably connected to the interior of the first sleeve, a first one-way valve and a second one-way valve are installed inside the first sleeve and on one side of the first piston, and a first hose is sealed at the outlet of the second one-way valve; The pickling liquid discharge mechanism includes a second sleeve installed on the upper surface of the mounting plate, a second piston is slidably connected to the interior of the second sleeve, a third one-way valve and a fourth one-way valve are installed inside the second sleeve and on one side of the second piston, and a second hose is sealed at the outlet of the fourth one-way valve.

2. The lithium and aluminum hydroxyfluoride extraction device according to claim 1, characterized in that The upper ratchet wheel and the upper ratchet ring are meshed with each other, and the upper ratchet ring, the upper plate, the upper ratchet wheel and the rotating shaft are on the same axis.

3. The lithium and aluminum hydroxyfluoride extraction device according to claim 1, characterized in that The limiting wheel is located inside the notch, and the outer wall of the limiting wheel is in contact with the inside of the notch, and the tooth plate and the rack rod are meshed with each other.

4. The lithium and aluminum hydroxyfluoride extraction device according to claim 1, characterized in that Both ends of the rack rod are fixedly connected to the axis of the first piston and the second piston, and the output ends of the first hose and the second hose extend to the inside of the top plate and pass through the top plate.

5. The lithium and aluminum hydroxyfluoride extraction device according to claim 1, characterized in that The bottom output shaft keyway of the double-headed motor is connected to a lower ratchet, and the axis of the top plate is rotatably connected to a lower ratchet ring; The bottom end of the lower ratchet ring is fixed with a rotating rod, the outer wall of the rotating rod is fixed with stirring rods distributed in an equidistant ring, the outer wall of the rotating rod and above the stirring rod is fixed with a rotating ring, the bottom of the rotating ring is fixed with an ejection plate, the inner wall of the tank body and below the rotating ring is fixed with a positioning plate, the interior of the positioning plate is slidably connected to the alkaline detector, the top of the alkaline detector is fixed with a baffle, the top of the baffle is fixed with a roller, and the outer wall of the alkaline detector is sleeved with a reset spring; An end cover is rotatably connected to the top of the tank body and located on the side of the top plate through a hinge. Two locking rods are rotatably connected to the outer wall of the tank body and located below the end cover. Knobs are installed on the top of the two locking rods. A handle is fixedly provided at the middle position of the top of the end cover. A discharge pipe is installed at the bottom of the tank body, and four movable wheels are installed at the bottom of the bracket.

6. The lithium and aluminum hydroxyfluoride extraction device according to claim 5, characterized in that The upper surface of the roller is in contact with the bottom surface of the rotating ring, and the upper and lower ends of the reset spring are fixedly connected to the baffle and the positioning plate.

7. The lithium and aluminum hydroxyfluoride extraction device according to claim 1, characterized in that Also included is a third sleeve; The third sleeve is installed at the bottom of the mounting plate, and the third piston is slidably connected to the interior of the third sleeve. A fifth one-way valve and a sixth one-way valve are respectively installed inside the third sleeve and on one side of the third piston. An injection pipe is sealed at the outlet of the sixth one-way valve. A connecting plate is fixed at the axis of the third piston and on the outside of the third sleeve. A guide wheel is fixed on the outer wall of the connecting plate, and a limit spring is sleeved between the connecting plate and the third piston.

8. The lithium and aluminum hydroxyfluoride extraction device according to claim 7, characterized in that The bottom of the injection pipe extends to the upper surface of the top plate and penetrates the top plate, and the outer wall of the guide wheel is in contact with the outer wall of the cam.

9. Low-grade cathode carbon block recovery process, characterized in that: The low-grade cathode carbon block recovery process comprises the lithium and aluminum hydroxyfluoride extraction apparatus according to any one of claims 1 to 8, comprising the following steps: S1: Crush and grind the cathode carbon block and sieve it to 200 mesh; S2: Place the sieved cathode carbon block in a tube furnace and pass oxygen-inert gas for decarburization at a temperature of 500-670°C for 1 hour. The decarburized material is gray, and there is little loss of fluorine and lithium. S3: calcining the decarburized material and aluminum sulfate additive at a low temperature, with a raw material to auxiliary ratio of 5:1-10:1, a calcination temperature of 300-700°C, and a calcination time of 0.5 hours; S4: placing the roasted clinker in a constant temperature water bath for immersion to leach out the soluble fluoride and lithium, with a solid-liquid ratio of 1:3-4; S5: Finally, the silica, aluminate and other refractory substances in the water leaching residue are further acid-leached, and the pH is controlled at 1-2; S6: The two stages of leachate are mixed, and the pH of the mixed solution is adjusted with sodium hydroxide solution to obtain hydroxyaluminum fluoride and precipitated liquid. The pH adjustment precision range is 4.3-4.5, and the sodium hydroxide concentration is 6 mol / L. This step needs to be performed in a tank.

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