Lithium and hydroxy aluminum fluoride extraction apparatus and low-grade cathode carbon block recovery process

Abstract

The application provides lithium and hydroxyl aluminum fluoride extraction equipment and low-grade cathode carbon block recovery process, relates to the technical field of metal recycling, and comprises a support, a tank body, a mounting plate, a driving mechanism, a reciprocating mechanism, a water washing liquid discharging mechanism and an acid immersion liquid discharging mechanism. The tank body is mounted in the interior of the support, a top plate is mounted at the top end of the tank body through bolts, and a support frame is mounted on the upper surface of the top plate through bolts. The water washing liquid enters first, and then a layer of acid immersion liquid is added, so that the two extraction liquids can be added in a stacked manner, the water washing liquid and the acid immersion liquid are added quantitatively in the process of stacked addition, the device realizes layered mixing in the process of addition, the subsequent stirring time is reduced, the power is saved, the mixing of the two liquids is more sufficient and stable, and the internal alkaline balance is ensured.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of metal recycling, in particular to lithium and hydroxyl aluminum fluoride extraction equipment and low-grade cathode carbon block recovery process. BACKGROUND

[0002] The technology for recovering valuable metals from aluminum electrolysis waste slag mainly falls into three categories: wet recovery, pyrometallurgical recovery, and combined recovery. Wet processing is a method of dissolving and leaching soluble and insoluble substances in waste aluminum electrolyte using strong acids (HCl, HNO3, etc.), strong alkalis (NaOH), and salt substances (CaCl2), while treating fluorides and chlorides to separate valuable metal elements and recover electrolyte.

[0003] In recent years, the combined wet and pyrometallurgical treatment of aluminum electrolysis waste slag has been increasingly focused on. The combined burning-leaching treatment can alleviate the problems caused by the use of wet or pyrometallurgical methods alone to some extent, achieving harmless disposal and resource utilization of aluminum electrolyte waste slag.

[0004] In the process of the traditional equipment leaching extraction stage, lithium and hydroxyl aluminum fluoride extraction needs to be extracted in water washing liquid and acid leaching liquid. The traditional equipment needs continuous stirring for acid-base adjustment of the two liquids, which not only wastes power resources, but also is not conducive to the full contact of the two liquids, easily causing alkaline imbalance, thereby affecting the extraction effect.

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

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

[0007] To solve the above technical problems, the lithium and hydroxyl aluminum fluoride extraction equipment provided by the present application includes a support, 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.

[0008] The tank body is installed inside the support, the top end of the tank body is provided with a top plate through bolts, the upper surface of the top plate is provided with a support frame through bolts, and the mounting plate is fixed to the top of the support frame.

[0009] The driving mechanism comprises a mounting seat and a limiting plate, the mounting seat is installed on the upper surface of the top plate, the limiting plate is fixed on the top of the mounting seat, a double-head motor is installed in the mounting seat through bolts, an upper ratchet wheel is connected with the top end output shaft key groove of the double-head motor, an upper ratchet ring is rotationally connected in the limiting plate, an upper plate is fixed on the top of the upper ratchet ring, and a rotating shaft is fixed on the top axial center of the upper plate;

[0010] The reciprocating mechanism comprises a rotating disc connected with the top end of the rotating shaft through a key groove, a limiting wheel is rotationally connected on the top of the rotating disc, two sliding seats are fixed on the upper surface of the mounting plate, rack rods are slidingly connected in the two sliding seats, a toothed plate is rotationally connected on the upper surface of the mounting plate and located on the opposite side of the two sliding seats, and a slot is formed in the toothed plate;

[0011] The water washing liquid discharging mechanism comprises a first sleeve installed on the upper surface of the mounting plate, a first piston is slidingly connected in the first sleeve, a first one-way valve and a second one-way valve are installed on one side of the first piston in the first sleeve, and a first hose is sealingly installed on the outlet of the second one-way valve;

[0012] The acid immersion liquid discharging mechanism comprises a second sleeve installed on the upper surface of the mounting plate, a second piston is slidingly connected in the second sleeve, a third one-way valve and a fourth one-way valve are installed on one side of the second piston in the second sleeve, and a second hose is sealingly installed on the outlet of the fourth one-way valve.

[0013] Preferably, the upper ratchet wheel and the upper ratchet ring are in meshing relationship, and the upper ratchet ring, the upper plate, the upper ratchet wheel and the rotating shaft are on the same axial line.

[0014] Preferably, the limiting wheel is located in the slot, the outer wall of the limiting wheel and the inner part of the slot are in contact with each other, and the toothed plate and the rack rod are in meshing relationship.

[0015] Preferably, the two ends of the rack rod are fixedly connected with the axial centers of the first piston and the second piston, and the output ends of the first hose and the second hose extend into the top plate and penetrate through the top plate.

[0016] Preferably, a lower ratchet wheel is connected with the bottom output shaft key groove of the double-head motor, and a lower ratchet ring is rotationally connected with the axial center of the top plate.

[0017] The bottom end of the lower ratchet ring is fixedly provided with a rotating rod, the outer wall of the rotating rod is fixedly provided with stirring rods distributed in an equidistant annular manner, the outer wall of the rotating rod and above the stirring rods is fixedly provided with a rotating ring, the bottom of the rotating ring is fixedly provided with an ejection plate, the inner wall of the tank and below the rotating ring is fixedly provided with a positioning plate, the inside of the positioning plate is slidingly connected with an alkalinity detector, the top of the alkalinity detector is fixedly provided with a baffle, the top of the baffle is fixedly provided with a roller, and the outer wall of the alkalinity detector is sleeved with a reset spring.

[0018] The upper side of the tank and at the side of the top plate is rotationally connected with an end cover through a hinge, the outer wall of the tank and below the end cover is rotationally connected with two lock rods, the top of the two lock rods is provided with a knob, the top of the end cover is fixedly provided with a handle in the middle, the bottom of the tank is provided with a discharge pipe, and the bottom of the support is provided with four moving wheels.

[0019] Preferably, the upper surface of the roller and the bottom surface of the rotating ring are in contact with each other, and the upper and lower ends of the reset spring are fixedly connected with 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, the inside of the third sleeve is slidingly connected with a third piston, the inside of the third sleeve and at one side of the third piston is respectively provided with a fifth one-way valve and a sixth one-way valve, the outlet of the sixth one-way valve is sealingly provided with an injection pipe, the shaft center of the third piston and outside the third sleeve is fixedly provided with an adapter plate, the outer wall of the adapter plate is fixedly provided with a guide wheel, and a limit spring is sleeved between the adapter plate and the third piston.

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

[0023] A low-grade cathode carbon block recovery process, comprising the following steps:

[0024] S1: crushing, grinding and sieving the cathode carbon block below 200 meshes;

[0025] S2: placing the sieved cathode carbon block in a tube furnace to perform decarburization treatment by passing oxygen-inert gas, the temperature is 500-670 DEG C, the time is maintained for 1H hours, the material after decarburization is gray, and fluorine and lithium are basically not lost;

[0026] S3: low-temperature calcination of the decarburized material and aluminum sulfate aluminum salt additive, the ratio of raw materials and auxiliaries is 5:1-10:1, the calcination temperature is 300-700 DEG C, and the time is 0.5 hours;

[0027] S4: the calcined clinker is placed in a constant temperature water bath for water immersion to leach soluble fluorine lithium, with a solid-liquid ratio of 1:3-4;

[0028] S5: the silica and aluminate in the water immersion residue are further acid leached, with a pH controlled at 1-2;

[0029] S6: the two-stage leaching solutions are mixed, and the mixed solution is adjusted in pH by a sodium hydroxide solution to obtain hydroxyl aluminum fluoride and a post-precipitation solution, the pH is adjusted in an accurate range of 4.3-4.5, and the concentration of the sodium hydroxide solution is 6 mol / L, and this step needs to be implemented in a tank.

[0030] Compared with the related art, the lithium and hydroxyl aluminum fluoride extraction device and the low-grade cathode carbon block recovery process provided by the application have the following beneficial effects:

[0031] Compared with the traditional design, the rack rod is fixedly installed with the first piston and the second piston at two ends, and the continuous clockwise rotating movement of the rotating disc affects the eccentric rotating movement of the limiting wheel, so that the limiting wheel can affect the notch to drive the rack rod to reciprocatingly rotate and mesh to control the first piston and the second piston to reciprocate.

[0032] When the rack rod moves to the left side, the first piston extrudes the water washing liquid in the first sleeve into the tank, and at this time, the second sleeve sucks the acid leaching liquid; when the rack rod moves to the right side, the acid leaching liquid in the second sleeve is extruded into the tank, and at this time, the first sleeve sucks the water washing liquid.

[0033] The two states of suction and extrusion are regularly switched by the reciprocating movement, so that the water washing liquid enters and then a layer of acid leaching liquid is added, so that the two kinds of extraction liquids can be added in a stacked manner, and the water washing liquid and the acid leaching liquid are added quantitatively during the stacked addition, so that the device realizes layered mixing during the addition, which can reduce the subsequent stirring time, save power, and ensure that the mixing of the two liquids is more sufficient and stable, and the stacked addition can also ensure the internal alkaline balance. BRIEF DESCRIPTION OF DRAWINGS

[0034] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are only some embodiments of the application, and for those skilled in the art, other drawings can also be obtained from the structures shown in the drawings without creative labor.

[0035] Figure 1 The best structure schematic diagram provided by the application;

[0036] Figure 2 for Figure 1 The diagram shows the back structure.

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

[0038] Figure 4 for Figure 2 The diagram shows the structure of the drive mechanism.

[0039] Figure 5 for Figure 2 The diagram shows the initial working state of the reciprocating mechanism, the washing liquid feeding mechanism, and the acid leaching liquid feeding mechanism.

[0040] Figure 6 for Figure 5 The diagram shows the working status of the reciprocating mechanism, the washing liquid feeding mechanism, and the acid leaching liquid feeding mechanism.

[0041] Figure 7 for Figure 2 The diagram shows a detailed internal structure of the tank.

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

[0043] Figure 9 This is a schematic diagram of the working state of the cam not contacting the guide wheel provided by the present invention;

[0044] Figure 10 for Figure 9 The diagram shows the working state of the cam abutting the guide wheel.

[0045] Figure 11 The image shows the XRD pattern of the byproduct (aluminum hydroxyfluoride) from the low-grade cathode carbon block recycling process of this invention.

[0046] Explanation of icon numbers:

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

[0048] 5. Mounting plate;

[0049] 6. Drive mechanism; 61. Mounting base; 62. Limiting plate; 63. Dual-head 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. Limit wheel; 73. Slide; 74. Gear plate; 75. Groove; 76. Rack and pinion.

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

[0052] 9. Acid immersion 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 cover, 12. Locking rod, 13. Knob, 14. Handle;

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

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

[0057] The purposes, functional features and advantages of the present application will be further described with reference to the embodiments and the accompanying drawings. DETAILED DESCRIPTION

[0058] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0059] The present application provides a lithium and hydroxyl aluminum fluoride extraction device and a low-grade cathode carbon block recovery process.

[0060] First embodiment:

[0061] Please refer to Figure 1 , Figure 2 , Figures 4 to 6 , a lithium and hydroxyl aluminum fluoride extraction device, comprising a support 1, a tank body 2, a mounting plate 5, a driving mechanism 6, a reciprocating mechanism 7, a water washing liquid discharging mechanism 8 and an acid immersion liquid discharging mechanism 9;

[0062] The tank body 2 is installed inside the support 1, the top end of the tank body 2 is provided with a top plate 3 through bolts, the upper surface of the top plate 3 is provided with a support frame 4 through bolts, and the mounting plate 5 is fixedly arranged on the top of the support frame 4;

[0063] The driving mechanism 6 comprises 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 fixedly arranged on the top of the mounting seat 61, the inside of the mounting seat 61 is provided with a double-head motor 63 through bolt mounting, the top end output shaft key groove of the double-head motor 63 is connected with an upper ratchet wheel 64, the inside of the limiting plate 62 is rotatably connected with an upper ratchet tooth ring 65, the top of the upper ratchet tooth ring 65 is fixedly arranged with an upper plate 66, the top shaft center of the upper plate 66 is fixedly arranged with a rotating shaft 67;

[0064] Please refer to Figure 4 The upper and lower end output shafts of the double-head motor 63 are respectively connected with the upper ratchet wheel 64 and the lower ratchet wheel 69 through key grooves, and the inside output shaft of the double-head motor 63 is coaxial, so the rotation directions are consistent, when the double-head motor 63 is rotated clockwise by the user, the upper ratchet wheel 64 and the lower ratchet wheel 69 will be synchronously rotated clockwise, the upper ratchet wheel 64 will rotate clockwise to affect the upper ratchet tooth ring 65 to drive the upper plate 66 and the rotating shaft 67 to realize linkage and synchronous clockwise rotation.

[0065] But the tooth type setting directions of the lower ratchet wheel 69 and the upper ratchet wheel 64 are opposite, so when the lower ratchet wheel 69 rotates clockwise, it will not affect the rotation of the lower ratchet tooth ring 610.

[0066] From the above working state, it can be known that the clockwise rotation of the double-head motor 63 can only control the rotation of the upper ratchet wheel 64, and the counterclockwise rotation of the double-head motor 63 can only control the rotation of the lower ratchet wheel 69.

[0067] The reciprocating mechanism 7 comprises a rotating disc 71 connected with the top end of the rotating shaft 67 through a key groove, the top of the rotating disc 71 is rotatably connected with a limiting wheel 72, the upper surface of the mounting plate 5 is fixedly arranged with two sliding seats 73, the inside of the two sliding seats 73 is slidably connected with a rack rod 76, the upper surface of the mounting plate 5 and located on the opposite side of the two sliding seats 73 is rotatably connected with a toothed plate 74, the inside of the toothed plate 74 is provided with a slot 75.

[0068] The water washing liquid discharging mechanism 8 comprises a first sleeve 81 mounted on the upper surface of the mounting plate 5, the inside of the first sleeve 81 is slidably connected with a first piston 82, the inside of the first sleeve 81 and located on one side of the first piston 82 is mounted with a first one-way valve 83 and a second one-way valve 84, the outlet of the second one-way valve 84 is sealingly mounted with a first hose 85.

[0069] The acid immersion liquid discharging mechanism 9 comprises a second sleeve 91 mounted on the upper surface of the mounting plate 5, the inside of the second sleeve 91 is slidably connected with a second piston 92, the inside of the second sleeve 91 and located on one side of the second piston 92 is mounted with a third one-way valve 93 and a fourth one-way valve 94, the outlet of the fourth one-way valve 94 is sealingly mounted with a second hose 95.

[0070] Please refer to Figure 5 : initial state, the toothed plate 74 and rack bar 76 is in meshing state, limit wheel 72 is installed in the notch 75 inside, when the rotating shaft 67 clockwise rotation, then the rotating shaft 67 will control the rotating disc 71 synchronous clockwise rotation movement, rotating rotating disc 71 will control the limit wheel 72 eccentric rotation movement at this time, the limit wheel 72 generated by the influence of the eccentric rotating force of the toothed plate 74, therefore, the limit wheel 72 will drive the toothed plate 74 to adapt to the reciprocating rotation of the mounting plate 5.

[0071] Please refer to Figure 6 : reciprocating rotation of the toothed plate 74 will engage transmission control rack bar 76 along the slide 73 inside reciprocating movement, when the rack bar 76 drive first piston 82 and second piston 92 to the left side, then the first piston 82 will be in the first sleeve 81 extrusion compression control the first sleeve 81 inside the water washing liquid through the second one-way valve 84 from the first hose 85 through the top plate 3 into the tank 2 inside;

[0072] At the same time, the second piston 92 will be in the second sleeve 91 to the left side, forming the suction force through the third one-way valve 93 will be acid leaching liquid suction to the second sleeve 91 inside;

[0073] When the left stroke of the rack bar 76 moves to the right side, the second piston 92 will be in the second sleeve 91 extrusion acid leaching liquid from the fourth one-way valve 94, through the second hose 95 into the tank 2 inside;

[0074] At the same time, the first piston 82 in the first sleeve 81 to the right side, forming the suction force will be water washing liquid through the first one-way valve 83 suction to the first sleeve 81 inside.

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

[0076] The limit wheel 72 is located in the inside of the notch 75, and the outer wall of the limit wheel 72 and the inside of the notch 75 are in contact with each other, the toothed plate 74 and the rack bar 76 are engaged with each other.

[0077] The two ends of the rack bar 76 are fixedly connected with the shafts 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 inside of the top plate 3 and penetrate through the top plate 3.

[0078] From Figure 5 and Figure 6It can be seen that the notch 75 has a certain length design, so that the limiting wheel 72 can stably rotate and move inside the notch 75, thereby effectively controlling the tooth plate 74, and avoiding interference between the limiting wheel 72 and the notch 75.

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

[0080] During the suction process, the water washing liquid and the acid immersion liquid will not leak, and during the extrusion process, the water washing liquid and the acid immersion liquid will not backflow.

[0081] The embodiment of the present application is as follows:

[0082] Compared with the traditional design, the rack bar 76 is fixedly installed at both ends of the first piston 82 and the second piston 92, and the rotating disc 71 is continuously rotated clockwise to affect the eccentric rotating motion of the limiting wheel 72, so that the limiting wheel 72 can drive the tooth plate 74 to reciprocatingly rotate and engage to control the rack bar 76 to reciprocatingly move the first piston 82 and the second piston 92.

[0083] When the rack bar 76 moves to the left, the first piston 82 will extrude the water washing liquid in the first sleeve 81 into the tank 2, and at this time the second sleeve 91 will suck the acid immersion liquid. When the rack bar 76 moves to the right, the acid immersion liquid in the second sleeve 91 is extruded into the tank 2, and at this time the first sleeve 81 sucks the water washing liquid.

[0084] The reciprocating motion realizes regular switching control of the suction and extrusion states, ensures that the water washing liquid enters and then a layer of acid immersion liquid is added, so that the two kinds of extraction liquids can be added in a stacked manner, and the water washing liquid and the acid immersion liquid are added quantitatively during the stacked addition, so that the device realizes layered mixing during the addition process, reduces the subsequent stirring time, saves power, and ensures that the mixing of the two liquids is more sufficient and stable. The stacked addition method can also ensure the internal alkaline balance.

[0085] The second embodiment of the present application is as follows:

[0086] Please refer to Figures 1 to 4 、 Figures 7 to 8 The bottom output shaft key groove of the double-head motor 63 is connected with the lower ratchet wheel 69, and the shaft center of the top plate 3 is rotationally connected with the lower ratchet ring 610.

[0087] The bottom end of the lower ratchet ring 610 is fixedly provided with a rotating rod 15, the outer wall of the rotating rod 15 is fixedly provided with stirring rods 18 distributed in an equidistant annular manner, the outer wall of the rotating rod 15 and above the stirring rods 18 is fixedly provided with a rotating ring 16, the bottom of the rotating ring 16 is fixedly provided with an ejection plate 17, the inner wall of the tank body 2 and below the rotating ring 16 is fixedly provided with a positioning plate 19, the inside of the positioning plate 19 is slidingly connected with an alkalinity detector 21, the top of the alkalinity detector 21 is fixedly provided with a baffle 22, the top of the baffle 22 is fixedly provided with a roller 23, the outer wall of the alkalinity detector 21 is sleeved with a reset spring 24.

[0088] Please refer to Figure 4 : During the working process of the first embodiment, if the double-head motor 63 rotates counterclockwise, the upper ratchet ring 65 will not be affected, only the lower ratchet ring 610 can rotate counterclockwise, and in combination with the working state of the first embodiment, when the mixed liquid in the tank body 2 rises to a threshold value, stirring extraction needs to be performed.

[0089] Please refer to Figure 7 : The rotating process of the lower ratchet ring 610 will synchronously drive the rotating rod 15 to rotate, the rotating rod 15 synchronously controls the rotating motion of the stirring rods 18 and the rotating ring 16, the stirring rods 18 rotate in the process of stirring and mixing the water washing liquid and the acid leaching liquid in the tank body 2, so that the hydroxyl aluminum fluoride and the post-precipitation liquid can be formed in the tank body 2 subsequently;

[0090] The hydroxyl aluminum fluoride is dried to obtain a finished product, and the post-precipitation liquid is collected to prepare lithium carbonate;

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

[0092] The by-product ② recovered is hydroxyl aluminum fluoride containing 94% of fluorine.

[0093] The XRD diffraction peak is consistent with the standard hydroxyl aluminum fluoride PDF card, and there is no other impurity peak.

[0094] Please refer to Figure 7 and Figure 8 : When the rotating ring 16 drives the bottom ejection plate 17 to move to the position of the roller 23, the roller 23 will follow the shape of the ejection plate 17 to adaptively control the alkalinity detector 21 to move downward along the vertical direction of the positioning plate 19, in the process of moving downward, the alkalinity detector 21 will enter the mixed liquid inside the tank body 2 to detect the alkalinity number, with the continuous rotating motion of the rotating ring 16, when the ejection plate 17 moves away from the roller 23, the alkalinity detector 21 will automatically reset to the initial state.

[0095] The upper part of the tank body 2 is connected with an end cover 11 through a hinge, the outer wall of the tank body 2 is connected with two lock rods 12 below the end cover 11, the top of the two lock rods 12 is installed with a knob 13, the top of the end cover 11 is fixedly provided with a handle 14, the bottom of the tank body 2 is installed with a discharge pipe 20, and the bottom of the support 1 is installed with four moving wheels 10.

[0096] The upper surface of the roller 23 is in contact with the bottom surface of the rotating ring 16, and the upper and lower ends of the reset spring 24 are fixedly connected with the baffle 22 and the positioning plate 19.

[0097] Compared with the traditional design, the double-head motor 63 of the embodiment can switch two working modes by rotating in the forward and reverse directions, and the clockwise rotation is the feeding mode, and when the counterclockwise rotation drives the stirring rod 18 to rotate, the mixed liquid in the tank body 2 is fully mixed and stirred, so that the efficient reaction extraction is ensured, and then 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 in the tank body 2 can be intermittently detected in the extraction process. Therefore, such a design not only can realize the switching of multiple modes, but also can detect the alkalinity value of the mixed liquid in the tank body 2, so that the alkalinity value in the tank body 2 can be judged in time, and the user can adjust in time.

[0098] Third embodiment

[0099] Please refer to Figure 4 , Figures 9 to 10 , and a third sleeve 25 is further included.

[0100] The third sleeve 25 is installed at the bottom of the mounting plate 5, the third sleeve 25 is slidably connected with a third piston 26 in the inside, the fifth one-way valve 27 and the sixth one-way valve 28 are respectively installed at one side of the third piston 26 in the inside of the third sleeve 25, the injection pipe 29 is sealingly installed at the outlet of the sixth one-way valve 28, the shaft center of the third piston 26 is fixedly provided with a link plate 30 outside the third sleeve 25, the outer wall of the link plate 30 is fixedly provided with a guide wheel 32, and the link plate 30 and the third piston 26 are sleeved with a limiting spring 31.

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

[0102] Preferably, the third piston 26 and the link plate 30 are installed and connected through a connecting rod.

[0103] Please refer to Figure 4In the working process of the first embodiment, since the cam 68 is installed on the rotating shaft 67, the rotating shaft 67 can drive the cam 68 to rotate synchronously when the rotating shaft 67 rotates;

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

[0105] Please refer to Figure 10 : When the cam 68 works in the first embodiment, the cam 68 rotates clockwise, and at this time, the long end of the cam 68 will touch the control guide wheel 32 to drive the abutment plate 30 to compress the limiting spring 31, and at the same time, the third piston 26 will push in the third sleeve 25 to make the sodium hydroxide solution in the third sleeve 25 pass through the sixth one-way valve 28 and be injected into the tank body 2 through the injection pipe 29.

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

[0107] The embodiment of the present application:

[0108] Compared with the traditional design, the present design has an independent motion driven cam 68. When the water washing liquid and the acid immersion liquid are layered and mixed in the working process of the first embodiment, the synchronously rotating cam 68 will squeeze and inject the sodium hydroxide solution in the third sleeve 25 into the tank body 2, so that the sodium hydroxide solution is synchronously injected and mixed during the layered injection of the water washing liquid and the acid immersion liquid, thereby realizing three-layered layered injection, ensuring that the required sodium hydroxide solution can be layered added, and also realizing quantitative addition. Compared with the direct injection method, such design further ensures the 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 to pass through a 200-mesh screen;

[0112] S2: Place the sieved cathode carbon block in a tube furnace and pass oxygen-inert gas (nitrogen) to perform decarburization treatment at a temperature of 500-670°C for 1H hours. The decarburized material is gray, and the fluorine and lithium are basically not lost.

[0113] S3: The decarburized material is low-temperature calcined with aluminum sulfate aluminum salt additive, the ratio of raw material to auxiliary is 5:1-10:1, the calcination temperature is 300-700℃, and the time is 0.5 hours;

[0114] S4: The calcined clinker is placed in a constant-temperature water bath for water immersion to leach soluble fluorine and lithium, and the solid-liquid ratio is 1:3-4;

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

[0116] S6: The two-stage leaching solutions are mixed, the mixed solution is adjusted to a pH of 4.3-4.5 with a 6 mol / L sodium hydroxide solution to obtain hydroxy aluminum fluoride and a post-precipitation solution, and this step needs to be implemented in tank 2.

[0117] The operation steps in the embodiment can be specifically implemented in three ways, and the specific operation steps are as follows:

[0118] Firstly:

[0119] Step 1: The cathode carbon block is pretreated (crushed, ground, and sieved to 200 mesh or less);

[0120] Step 2: 100g of the pretreated material is placed in a tube furnace, oxygen and inert gas (nitrogen) are introduced, and calcination is carried out at 500℃ for 1 hour. After cooling, the material is taken out for detection and analysis to analyze the loss of the material before and after calcination;

[0121] Step 3: 80g of the decarburized clinker is mixed with anhydrous aluminum sulfate in a ratio of 5:1, placed in a muffle furnace in an air atmosphere, and calcined at 300℃ for 0.5H. After cooling, it is taken out for standby use;

[0122] Step 4: The calcined clinker is mixed with pure water at a solid-liquid ratio of 1:3 at 60℃ to obtain a water washed residue;

[0123] Step 5: The water washed residue is mixed with sulfuric acid solution at a solid-liquid ratio of 1:3 (the amount of sulfuric acid accounts for 30%; for example, 120g of water washed residue and 30g of 98% concentrated sulfuric acid);

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

[0125] Step 7: The mixed solution is adjusted to 4.3 with a 6 mol / L sodium hydroxide solution to obtain hydroxy aluminum fluoride and a post-precipitation solution, and the post-precipitation solution is a lithium-rich solution which can be used to prepare lithium carbonate.

[0126] Secondly:

[0127] Step one: Pretreatment of cathode carbon block (crushing, grinding, and sieving to 200 mesh or less);

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

[0129] Step three: Mix 130 g of the decarburized clinker with anhydrous aluminum sulfate in a ratio of 6:1, and place in a muffle furnace in an air atmosphere and roast at 500°C for 0.5H. After cooling, take out and reserve for use;

[0130] Step four: Mix the roasted clinker with pure water in a solid-liquid ratio of 1:3 at 60°C to obtain a water washed residue;

[0131] Step five: Mix the water washed residue with a sulfuric acid solution in a solid-liquid ratio of 1:3. (The amount of sulfuric acid used is 30%; for example, 120 g of water washed residue and 30 g of 98% concentrated sulfuric acid);

[0132] Step six: Mix the water washed liquid and the acid leaching liquid to obtain a mixed liquid;

[0133] Step seven: Adjust the mixed liquid to 4.5 with a 6 mol / L sodium hydroxide solution to obtain hydroxyl aluminum fluoride and a post precipitation liquid. The post precipitation liquid is a lithium-rich solution that can be used to prepare lithium carbonate.

[0134] Third:

[0135] Step one: Pretreatment of cathode carbon block (crushing, grinding, and sieving to 200 mesh or less);

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

[0137] Step three: Mix 180 g of the decarburized clinker with anhydrous aluminum sulfate in a ratio of 6:1, and place in a muffle furnace in an air atmosphere and roast at 700°C for 0.5H. After cooling, take out and reserve for use;

[0138] Step four: Mix the roasted clinker with pure water in a solid-liquid ratio of 1:3 at 60°C to obtain a water washed residue;

[0139] Step five: Mix the water washed residue with a sulfuric acid solution in a solid-liquid ratio of 1:3. (The amount of sulfuric acid used is 30%; for example, 120 g of water washed residue and 30 g of 98% concentrated sulfuric acid);

[0140] Step six: Mix the water washed liquid and the acid leaching liquid to obtain a mixed liquid;

[0141] Step seven: adjust the mixture to 4.7 with 6 mol / L sodium hydroxide solution to obtain hydroxyl aluminum fluoride and precipitate after liquid, and the precipitate after liquid is a lithium-rich solution which can be used to prepare lithium carbonate.

[0142] The present application mainly passes low-quality cathode carbon blocks into inert gas and oxygen in a vacuum atmosphere for low-temperature decarburization treatment, destroys the unit wrapping structure to convert it into soluble fluorine lithium, removes harmful cyanide on the other hand, then uses aluminum salt additives for low-temperature calcination, and obtains leaching liquid through water immersion and acid immersion, and finally recovers 94% of fluorine from the solution in the form of hydroxyl aluminum fluoride.

[0143] The prior art is all sodium hydroxide molten salt calcination which is carried out at high temperature in inert gas, has high requirements for equipment, and is not environmentally friendly and economical. The present application first pretreats the raw ore for decarburization, reduces the activation energy of fluorine lithium dissolution, and thus can directly carry out low-temperature calcination and leaching in an air atmosphere. The leaching liquid is adjusted for precipitation of hydroxyl aluminum fluoride, 98% of lithium exists in the precipitate after liquid, and the precipitate after liquid is used for subsequent preparation of lithium carbonate, realizing low-cost and effective recovery of valuable metals fluorine and lithium.

[0144] The above only describes the preferred embodiments of the present application, and does not limit the patent scope of the present application, and any equivalent structural transformation made under the concept of the present application, using the content of the present application specification and drawings, or direct / indirect application in other related technical fields is included in the patent protection scope of the present application.

Claims

1. A lithium and hydroxy aluminum fluoride extraction plant, characterized in that, The device comprises a support, a tank body, a mounting plate, a driving mechanism, a reciprocating mechanism, a water washing liquid discharging mechanism and an acid immersion liquid discharging mechanism. The tank body is mounted in the support, the top end of the tank body is provided with a top plate through bolts, the upper surface of the top plate is provided with a support frame through bolts, and the mounting plate is fixed to the top of the support frame. The driving mechanism comprises 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-head motor is mounted in the mounting seat through bolts, the top end output shaft key groove of the double-head motor is connected with an upper ratchet wheel, an upper ratchet ring is rotatably connected in the limiting plate, an upper plate is fixed to the top of the upper ratchet ring, and a rotating shaft is fixed to the top axial center of the upper plate. The reciprocating mechanism comprises a rotating disc connected to the top end of the rotating shaft through a key groove, a limiting wheel is rotatably connected to the top of the rotating disc, two sliding seats are fixed to the upper surface of the mounting plate, two rack rods are slidably connected in the two sliding seats, a toothed plate is rotatably connected to the upper surface of the mounting plate and located on the opposite side of the two sliding seats, and a slot is formed in the toothed plate. The water washing liquid discharging mechanism comprises a first sleeve mounted on the upper surface of the mounting plate, a first piston is slidably connected in the first sleeve, a first one-way valve and a second one-way valve are mounted in the first sleeve and located on one side of the first piston, and a first hose is sealingly mounted at the outlet of the second one-way valve. The acid immersion liquid discharging mechanism comprises a second sleeve mounted on the upper surface of the mounting plate, a second piston is slidably connected in the second sleeve, a third one-way valve and a fourth one-way valve are mounted in the second sleeve and located on one side of the second piston, and a second hose is sealingly mounted at the outlet of the fourth one-way valve.

2. The lithium and hydroxy aluminum fluoride extraction apparatus of claim 1, wherein, The upper ratchet wheel and the upper ratchet ring are in meshing relationship, and the upper ratchet ring, the upper plate, the upper ratchet wheel and the rotating shaft are on the same axial line.

3. The lithium and hydroxy aluminum fluoride extraction apparatus of claim 1, wherein, The limiting wheel is located in the slot, the outer wall of the limiting wheel and the inner wall of the slot are in contact with each other, and the toothed plate and the rack rod are in meshing relationship.

4. The lithium and hydroxy aluminum fluoride extraction apparatus of claim 1, wherein, The two ends of the rack rod are fixedly connected with the axial centers of the first piston and the second piston, and the output ends of the first hose and the second hose extend into the inside of the top plate and penetrate through the top plate.

5. The lithium and hydroxy aluminum fluoride extraction apparatus of claim 1, wherein, The bottom output shaft key groove of the double-head motor is connected with a lower ratchet wheel, and a lower ratchet ring is rotatably connected to the axial center of the top plate. The bottom end of the lower ratchet ring is fixedly provided with a rotating rod, a plurality of stirring rods are equidistantly and annularly arranged on the outer wall of the rotating rod, a rotating ring is fixedly arranged on the outer wall of the rotating rod and located above the stirring rods, a ejection plate is fixedly arranged on the bottom of the rotating ring, a positioning plate is fixedly arranged on the inner wall of the tank body and located below the rotating ring, an alkalinity detector is slidably connected in the positioning plate, a baffle is fixedly arranged on the top of the alkalinity detector, a roller is fixedly arranged on the top of the baffle, and a return spring is arranged on the outer wall of the alkalinity detector. The upper side of the tank body and the side of the top plate are rotationally connected with an end cover through a hinge, the outer wall of the tank body and the lower side of the end cover are rotationally connected with two lock rods, the top of the two lock rods is provided with a knob, the top of the end cover is fixedly provided with a handle, the bottom of the tank body is provided with a discharge pipe, and the bottom of the support is provided with four moving wheels.

6. The lithium and hydroxy aluminum fluoride extraction apparatus of claim 5, wherein, 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 with the baffle and the positioning plate.

7. The lithium and hydroxy aluminum fluoride extraction apparatus of claim 1, wherein, A third sleeve is further included; The third sleeve is installed at the bottom of the mounting plate, a third piston is slidably connected in the third sleeve, a fifth one-way valve and a sixth one-way valve are respectively installed at one side of the third piston in the third sleeve, an injection pipe is sealingly installed at the outlet of the sixth one-way valve, an abutment plate is fixedly arranged at the shaft center of the third piston and outside the third sleeve, a guide wheel is fixedly arranged on the outer wall of the abutment plate, and a limiting spring is sleeved between the abutment plate and the third piston.

8. The lithium and hydroxy aluminum fluoride extraction apparatus of claim 7, wherein, The bottom of the injection pipe extends to the upper surface of the top plate and penetrates through the top plate, and the outer wall of the guide wheel is in contact with the outer wall of the cam.

9. A low-grade cathode carbon block recovery process characterized by, The low-quality cathode carbon block recovery process comprises the lithium and hydroxyl aluminum fluoride extraction equipment according to any one of claims 1-8, and comprises the following steps: S1: crushing, grinding and screening the cathode carbon block to 200 mesh; S2: placing the screened cathode carbon block in a tube furnace to perform decarburization treatment by oxygen-inert gas, the temperature is 500-670 DEG C, the time is maintained for 1 hour, the decarburized material is gray, and the fluorine and lithium are basically not lost; S3: adding aluminum sulfate aluminum salt additives to the decarburized material and performing low-temperature roasting, the ratio of the raw material to the auxiliary material is 5:1-10:1, the roasting temperature is 300-700 DEG C, and the time is 0.5 hours; S4: placing the roasted material in a constant-temperature water bath to perform water immersion, the soluble fluorine and lithium are leached out, and the solid-liquid ratio is 1:3-4; S5: further acid leaching of the silicon dioxide and aluminate refractory substances in the water immersion residue, the pH is controlled to be 1-2; S6: mixing the two-stage leaching solutions, adjusting the pH of the mixed solution by using a sodium hydroxide solution to obtain hydroxyl aluminum fluoride and a precipitate, the pH adjustment is accurate in the range of 4.3-4.5, the concentration of the sodium hydroxide is 6 mol / L, and this step needs to be operated in a tank.

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