A device for leaching tin from tin-containing waste slag and a method for enriching and recovering tin

Abstract

The present invention provides an apparatus for leaching tin from tin-containing waste slag and a method for enriching and recovering tin, which relates to the field of metal recycling technology, including a base, an end cover, a mounting seat, a drive motor, a leaching mechanism, a feeding pipe, and a feeding pipe; a heating seat is installed on the top of the base, a tank body is installed inside the heating seat, and the end cover is sealed and installed on the top of the tank body by bolts. In this case, the water and solid in the tank body are stirred up and down when the rotating vortex is switched and lifted, which can facilitate the layered stirring and mixing of the mixed acid and the tin-containing waste slag. Since the mixed acid is added to the tank body through an acid adding pipe in a fixed position, it is convenient for the mixed acid to dissolve with the tin-containing waste slag more quickly after addition. If it rotates in one direction of freedom for a long time, the heat will be concentrated in the corresponding vortex layer. The heat in the tank body can be evenly layered through the lifting auxiliary movement, which can avoid heat concentration and ensure the efficiency and safety of the leaching process.

Description

Technical Field

[0001] The invention relates to the technical field of metal recycling, in particular to a device for leaching tin from tin-containing waste slag and a method for enriching and recovering tin. Background Art

[0002] During the hydrometallurgical smelting of tantalum and niobium, tin, a byproduct of the tantalum-niobium ore, remains largely in the slag after tantalum and niobium are extracted. As a highly valuable metal resource, tin, thanks to its excellent physical and chemical properties, plays an irreplaceable and crucial role in numerous fields. Its exceptional ductility, corrosion resistance, and unique electrical and thermal properties have enabled its widespread and in-depth application in industrial manufacturing, the electronic information industry, medical devices, and new energy sectors.

[0003] At the same time, from an economic perspective, the rational development and utilization of tin resources can create considerable economic value and promote the development of related industries. Based on this, the present invention has carefully developed an effective method for enriching and recovering tin from tantalum-niobium waste residue, aiming to achieve efficient resource utilization and maximize economic value.

[0004] In the process of leaching tin, the first step is to use mixed acid to leach the tin-containing waste slag and perform the first impurity removal to obtain tin-rich acid leaching slag. However, in the process of mixed acid leaching, it is necessary to work under long-term rotation conditions. Long-term rotation is prone to overheating inside the tank, and the liquid and solid inside the tank are stirred in layers, which can easily cause uneven mixing and affect the leaching effect.

[0005] Therefore, it is necessary to provide a device for leaching tin from tin-containing waste slag and a method for enriching and recovering tin to solve the above technical problems. Summary of the Invention

[0006] The present invention provides an apparatus for leaching tin from tin-containing waste slag and a method for enriching and recovering tin, which solves the technical problems in the related art of easy overheating during long-term rotation during mixed acid leaching, poor leaching effect, and difficulty in uniform dissolution due to mixed acid.

[0007] In order to solve the above technical problems, the present invention provides an apparatus for leaching tin from tin-containing waste slag, comprising a base, an end cover, a mounting seat, a drive motor, a leaching mechanism, a feeding pipe and a discharging pipe;

[0008] A heating seat is installed on the top of the base, a tank body is installed inside the heating seat, the end cover is sealed and installed on the top of the tank body by bolts, the mounting seat is installed at the bottom axis of the end cover, and a reduction box is installed in the output direction of the drive motor;

[0009] The feeding pipe is installed on the top of the tank body, and the feeding pipe is installed on the bottom end of the tank body;

[0010] The leaching mechanism includes a driving key rod, two connecting rods, a first spring and a second spring, the first spring and the second spring are respectively sleeved on the outside of the driving key rod, the top and bottom ends of the two connecting rods are respectively fixed with a first slide plate and a second slide plate, the bottom end of the driving key rod is fixed with a bottom plate, the outer wall of the driving key rod and above the first spring are fixed with a fixing plate, the outer walls of the two connecting rods are fixed with four horizontally arranged rotating plates, the outer walls of the two connecting rods and directly below the rotating plates are fixed with two horizontally arranged side rods, the bottoms of the two side rods are fixed with lifting rings by bolts, and guide wheels are installed on both sides of the first slide plate;

[0011] A fixing ring is fixedly provided on the inner wall of the tank body, and an ejection plate is installed on the bottom of the fixing ring through bolts.

[0012] Preferably, the bottom of the reduction gear box is mounted to the top of the mounting seat by bolts, and the top end of the driving key rod extends to the interior of the reduction gear box and is connected to the keyway at the output end of the reduction gear box.

[0013] Preferably, the upper and lower ends of the first spring are fixedly connected to the fixed plate and the first slide plate, and the upper and lower ends of the second spring are fixedly connected to the second slide plate and the bottom plate.

[0014] Preferably, the upper surface of the guide wheel is continuously in contact with the bottom surface of the fixing ring, the protrusion of the ejector plate faces downward of the fixing ring, and the ejector plate is mirror-distributed about the axis of the fixing ring.

[0015] Preferably, a flip mechanism is further included, wherein the flip mechanism includes a mounting frame fixedly mounted on the lower inner wall of the tank body, a flap is rotatably connected to the interior of the mounting frame, and shift plates are fixedly provided on both sides of the flap.

[0016] Preferably, the mounting frame, the flap and the dial plate are distributed in an annular shape with equal distances about the axis of the tank body, and the upper surface of the flap is in contact with the bottom surface of the lifting ring.

[0017] Preferably, it further includes a linkage mechanism and an adding mechanism, the linkage mechanism includes a connecting frame and a ratchet, the connecting frame is fixed to the inner wall of the tank body, the ratchet keyway is connected to the outer wall of the driving key rod, the top of the connecting frame is rotatably connected to the ratchet ring, and the outer wall of the ratchet ring is fixed with a convex plate;

[0018] The adding mechanism includes a pipeline, a limiting plate and a sealing ring. The pipeline is fixed inside the tank body. An acid adding pipe is fixed inside the tank body and below the pipeline. The limiting plate and the sealing ring are respectively fixed to the inner wall of the pipeline. A sliding key rod is slidably connected to the axis of the limiting plate. Telescopic frames are installed on both sides of the pipeline. A sealing plate is fixed at one end of the sliding key rod close to the inner side of the pipeline. A wheel frame is fixed at one end of the sliding key rod close to the outside of the pipeline. A roller is rotatably connected to the inside of the wheel frame.

[0019] Preferably, the outer wall of the blocking plate fits tightly with the inner wall of the blocking ring, the limiting plate is semicircular in structure, the outer wall of the roller contacts the outer wall of the ratchet ring, the two sides of the wheel frame are fixedly mounted on the telescopic frame, and the driving key rod passes through the axis of the connecting frame and is not mounted on the connecting frame.

[0020] A method for enriching and recovering tin comprises the following steps:

[0021] S1: using mixed acid to stir and leach the tin-containing waste residue, and separating the tin-rich acid-leached residue into solid and liquid. This step needs to be carried out in a tank. The mixed acid is a 1:1 volume uniform mixture of 2 mol / L dilute sulfuric acid and 1 mol / L dilute hydrochloric acid. The liquid-solid ratio of the mixed acid to the tin-containing waste residue is 3-8:1. The acid leaching temperature is controlled by a heating block at 70-90°C, the acid leaching time is 1-3 hours, and the stirring speed is 150-400 r / min.

[0022] S2: mixing the tin-rich acid leaching residue with a certain amount of concentrated sulfuric acid and stirring them evenly, placing them in a heating furnace for sulfation roasting and defluorination reaction to obtain a roasted product;

[0023] The concentration of concentrated sulfuric acid is 98w%, the mass ratio of sulfuric acid to tin-rich acid leaching residue is 1-2:1, the roasting temperature is 260-310°C, and the roasting time is 0.5-3h;

[0024] The main reactions under sulfuric acid roasting are:

[0025] CaF2+H2SO4=CaSO4+2HF

[0026] 2AlF3+3H2O=Al2O3+3HF

[0027] Al2O3+3H2SO4=Al2(SO4)3+3H2O

[0028] This step can defluorinate insoluble calcium fluoride and aluminum fluoride, while cassiterite remains in the slag together with calcium sulfate because it is difficult to react with sulfuric acid;

[0029] S3: Evenly disperse the roasted product in a certain amount of water, add a certain amount of urea, stir and react at a high temperature, and collect the filter residue after the reaction is completed;

[0030] The liquid-solid ratio of the urea solution to the calcined product is 2-5:1, the amount of urea added is 3-7 times the theoretical stoichiometric amount, the reaction temperature is 80-100°C, the reaction time is 3-6 hours, and the stirring speed is 200-400 r / min;

[0031] The main reactions of urea leaching are:

[0032] CaSO4+CO(NH2)2+2H2O=CaCO3+(NH4)2SO4

[0033] This step converts the difficult-to-decompose calcium sulfate into calcium carbonate that can be decomposed by hydrochloric acid to remove calcium impurities in tin;

[0034] S4: using dilute hydrochloric acid to acid-leach the filter residue to remove calcium to obtain tin residue, wherein the dilute hydrochloric acid concentration is 0.1-1 mol / L, the liquid-solid ratio is 1-3:1, the reaction is carried out at room temperature, the reaction time is 10-30 minutes, and the stirring speed is 150-400 r / min;

[0035] The main reactions in S4 are:

[0036] CaCO3+2HCl=CaCl2+CO2+H2O;

[0037] S5: Use pure water to wash the tin slag, dry it, and then collect it. It should be noted that the washing times are twice.

[0038] Compared with the related art, the equipment for leaching tin from tin-containing waste slag and the method for enriching and recovering tin provided by the present invention have the following beneficial effects:

[0039] During the rotation, the lifting effect changes the vortex shape in the tank. The rotating vortex switches the lifting and lowering to stir the water and solid in the tank up and down. On the one hand, it is convenient to stir and mix the mixed acid and tin-containing waste residue in layers. Since the mixed acid is added to the tank through an acid adding tube at a fixed position, it is convenient for the mixed acid to dissolve with the tin-containing waste residue more quickly after addition. Secondly, if it rotates in one direction of freedom for a long time, the heat will be concentrated in the corresponding vortex layer. The lifting auxiliary movement can evenly layer the heat in the tank to avoid heat concentration and ensure the efficiency and safety of the leaching process. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] 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.

[0041] Figure 1 The best structural diagram provided by the present invention;

[0042] Figure 2 A schematic diagram of the cross-sectional structure of the tank provided by the present invention;

[0043] Figure 3 for Figure 2 Schematic diagram of the leaching mechanism structure shown;

[0044] Figure 4 for Figure 3 The schematic diagram of the working state of controlling the turn plate to move downward when the guide wheel rotates to the ejection plate position is shown;

[0045] Figure 5 for Figure 2 The schematic diagram of the flip mechanism structure shown;

[0046] Figure 6 for Figure 5 The flip mechanism shown is in a working state;

[0047] Figure 7 A schematic cross-sectional view of the linkage mechanism and the adding mechanism provided by the present invention;

[0048] Figure 8 for Figure 7 Schematic diagram of the connecting frame structure viewed from above

[0049] Figure 9 for Figure 7 The diagram shown is a schematic diagram of the working state in which the convex plate contacts the roller to control the opening of the sealing plate and the sealing ring.

[0050] Description of Figure Numbers:

[0051] 1. Base, 2. Heating seat, 3. Tank body;

[0052] 4. Mounting seat, 5. Gearbox;

[0053] 6. Leaching mechanism, 61. Driving key rod, 62. Fixed plate, 63. First slide plate, 64. First spring, 65. Guide wheel, 66. Second slide plate, 67. Bottom plate, 68. Second spring, 69. Connecting rod, 610. Rotating plate, 611. Side rod, 612. Lifting ring;

[0054] 7. Flipping mechanism, 71. Mounting frame, 72. Flip plate, 73. Dial plate;

[0055] 8. Linkage mechanism, 81. Connecting frame, 82. Ratchet, 83. Ratchet ring, 84. Convex plate;

[0056] 9. Adding mechanism, 91. Pipe, 92. Limiting plate, 93. Sliding key rod, 94. Telescopic frame, 95. Wheel frame, 96. Roller, 97. Blocking ring, 98. Blocking plate;

[0057] 10. Drive motor;

[0058] 11. Loading pipe, 12. Unloading pipe;

[0059] 13. Fixed ring, 14. Ejector plate, 15. Acid adding tube, 16. End cover.

[0060] 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

[0061] 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.

[0062] The invention provides a device for leaching tin from tin-containing waste slag and a method for enriching and recovering tin.

[0063] First embodiment:

[0064] See also Figures 1 to 4 , a device for leaching tin from tin-containing waste slag, comprising a base 1, an end cover 16, a mounting base 4, a drive motor 10, a leaching mechanism 6, a feeding pipe 11 and a discharging pipe 12;

[0065] A heating seat 2 is installed on the top of the base 1, a tank body 3 is installed inside the heating seat 2, the end cover 16 is sealed and installed on the top of the tank body 3 by bolts, the mounting seat 4 is installed at the bottom axis of the end cover 16, and a reduction box 5 is installed in the output direction of the drive motor 10;

[0066] The feeding pipe 11 is installed above the tank body 3, and the feeding pipe 12 is installed at the bottom end of the tank body 3;

[0067] The leaching mechanism 6 includes a driving key rod 61, two connecting rods 69, a first spring 64 and a second spring 68, the first spring 64 and the second spring 68 are respectively sleeved on the outside of the driving key rod 61, the top and bottom ends of the two connecting rods 69 are respectively fixed with a first slide 63 and a second slide 66, the bottom end of the driving key rod 61 is fixed with a bottom plate 67, the outer wall of the driving key rod 61 and above the first spring 64 are fixed with a fixing plate 62, the outer walls of the two connecting rods 69 are fixed with four horizontally arranged rotating plates 610, the outer walls of the two connecting rods 69 and directly below the rotating plates 610 are fixed with two horizontally arranged side rods 611, the bottoms of the two side rods 611 are fixed with lifting rings 612 by bolts, and guide wheels 65 are installed on both sides of the first slide 63;

[0068] A fixing ring 13 is fixed to the inner wall of the tank body 3 , and an ejector plate 14 is mounted on the bottom of the fixing ring 13 via bolts.

[0069] Preferably, the reduction box 5 may preferably be a bevel gear exchange reduction box 5, and the driving motor 10 may preferably be a three-phase asynchronous motor.

[0070] See also Figure 1 and Figure 2 : Start the drive motor 10 to rotate, and the speed of the drive motor 10 can be decelerated through the reduction gear box 5. Finally, the reduction gear box 5 can realize forward and reverse rotation movement by controlling the drive key rod 61.

[0071] See also Figure 3 : The driving key rod 61 has two working modes, the first is to drive the key rod 61 to rotate counterclockwise, and the second is to drive the key rod 61 to rotate clockwise;

[0072] In this embodiment, the driving key rod 61 mainly rotates counterclockwise. When rotating counterclockwise, it can drive the fixed plate 62 and the first slide plate 63 to rotate synchronously. Secondly, the first slide plate 63 also synchronously drives and controls the two connecting rods 69 to affect the rotation of the second slide plate 66 and the bottom plate 67.

[0073] Therefore, it can be seen that when the connecting rod 69 rotates, it will drive the external rotating plate 610 and the side rod 611 to rotate synchronously. The rotation of the rotating plate 610 can rotate and stir the mixed acid and tin-containing waste residue inside the tank body 3 to ensure that the mixed acid and tin-containing waste residue are evenly mixed and impurities are removed.

[0074] Please refer again Figure 3 : It can be seen that the tilt direction of the rotating plate 610 is staggered, so that during the rotation process, the tilt surface is always in contact with the medium in the tank body 3, ensuring that the medium can be evenly stirred and mixed under a fixed rotation direction.

[0075] The bottom of the reduction box 5 is mounted to the top of the mounting base 4 by bolts, and the top end of the driving key rod 61 extends to the interior of the reduction box 5 and is connected to the keyway of the output end of the reduction box 5 .

[0076] The upper and lower ends of the first spring 64 are fixedly connected to the fixed plate 62 and the first slide plate 63 , and the upper and lower ends of the second spring 68 are fixedly connected to the second slide plate 66 and the bottom plate 67 .

[0077] The upper surface of the guide wheel 65 is continuously attached to the bottom surface of the fixing ring 13 , the protrusion of the ejector plate 14 faces downward of the fixing ring 13 , and the ejector plate 14 is mirror-distributed about the axis of the fixing ring 13 .

[0078] See also Figure 3 When the first slide 63 rotates counterclockwise, the first slide 63 will synchronously drive the guide wheels 65 on both sides to rotate counterclockwise. During the rotation of the guide wheels 65, the top of the guide wheels 65 continues to contact the bottom of the fixing ring 13 while rotating.

[0079] See also Figure 4 : As the guide wheel 65 rotates from the bottom of the fixed ring 13 to the position of the ejection plate 14, the guide wheel 65 rotates downward along the inclined surface of the ejection plate 14, and then continues to rotate downward following the trajectory of the ejection plate 14, thereby controlling the first slide 63 to drive the connecting rod 69 and the second slide 66 to move downward along the vertical direction of the driving key rod 61. During the downward movement, the first spring 64 will follow the extension, while the second spring 68 will follow the compression;

[0080] In this way, the rotating plate 610 can synchronously achieve lifting motion during the rotation process.

[0081] The working principle of this embodiment is as follows:

[0082] Step 1: First, the user needs to add tin-containing waste residue into the tank body 3 through the feeding pipe 11;

[0083] Step 2: Then, the mixed acid and the mixed solution medium are added into the interior of the tank 3 through the acid adding pipe 15 to ensure that the medium and the mixed acid can contact and mix with the tin-containing waste residue;

[0084] Step 3: The user starts the drive motor 10 to control the drive key rod 61 to rotate counterclockwise. During the counterclockwise rotation, the rotating plate 610 can be driven to rotate to stir and mix the mixed acid and tin-containing waste slag inside the tank body 3. At the same time, when the guide wheel 65 rotates to the position of the ejection plate 14, it will affect the downward movement of the rotating plate 610 to assist in stirring and mixing.

[0085] It should be noted that the total amount of medium in the tank body 3 cannot exceed the bottom limit position of the ejector plate 14. After the leaching is completed, all the medium in the tank body 3 is discharged through the discharge pipe 12 to proceed to the next step.

[0086] This embodiment:

[0087] Compared with the traditional design, this case is provided with two sets of rotating plates 610 with a basic staggered design to rotate, mix and stir the mixed acid and tin-containing waste slag in the tank body 3. On the basis of fixed rotation, a set of arc-shaped ejector plates 14 are designed to cooperate with the rotating plates 610. When the guide wheel 65 rotates from the bottom surface position of the fixed ring 13 to the position of the ejector plate 14, it affects the rotating plate 610 to form a certain range of lifting movement, so that the lifting movement is not affected during the rotation process, thereby increasing the rotating plate 610 from one degree of freedom to two degrees of freedom, while not affecting the rotational freedom.

[0088] Therefore, during the rotation, the lifting effect can change the vortex shape in the tank body 3. When the rotating vortex switches to lifting, the water and solid in the tank body 3 are stirred up and down. On the one hand, it is convenient to stir and mix the mixed acid and the tin-containing waste residue in layers. Since the mixed acid is added to the tank body 3 through the acid adding pipe 15 at a fixed position, it is convenient for the mixed acid to dissolve with the tin-containing waste residue more quickly after addition. Secondly, if it rotates in one direction of freedom for a long time, the heat will be concentrated in the corresponding vortex layer. The heat in the tank body 3 can be evenly layered through the lifting auxiliary movement, which can avoid heat concentration and ensure the efficiency and safety of the leaching process.

[0089] Second embodiment:

[0090] See also Figures 4 to 6 , also includes a flip mechanism 7, the flip mechanism 7 includes a mounting frame 71 fixed to the inner wall below the tank body 3, the mounting frame 71 is internally rotatably connected to a flip plate 72, and a dial plate 73 is fixed on both sides of the flip plate 72.

[0091] The mounting frame 71 , the flap 72 and the dial plate 73 are equidistantly distributed in a ring shape around the axis of the tank body 3 , and the upper surface of the flap 72 contacts the bottom surface of the lifting ring 612 .

[0092] See also Figure 5 : During the operation of the first embodiment, if the guide wheel 65 rotates on the fixed ring 13, the lifting ring 612 will also follow the connecting rod 69 to rotate normally in one degree of freedom. During the rotation, the lifting ring 612 continues to fit on the flap 72, so it will not affect the movement of the flap 72.

[0093] See also Figure 6When the guide wheel 65 follows the ejection plate 14 in its downward movement, the connecting rod 69 also drives the lifting ring 612 to achieve the same amplitude of downward movement, so that the lifting ring 612 can downwardly abut one end of the control flap 72 when it descends, so that the flap 72 can be turned clockwise along the hinge position of the mounting frame 71, thereby turning the dial plate 73 from the bottom of the tank body 3 to the top;

[0094] Thereby, the tin-containing waste residue sediment at the bottom of the tank body 3 is caused to surge upward.

[0095] This embodiment: by providing a turnover mechanism 7, during the operation of the first embodiment, the lifting ring 612 can rise and fall along with the rise and fall of the rotating plate 610, and when the lifting ring 612 is descending, it drives the flip plate 72 to control the dial plate 73 to flip the tin-containing waste slag sediment at the bottom of the tank body 3 upward and continue to mix it in the mixed acid medium in the middle layer of the tank body 3. The flip plate 72 is driven to flip through the intermittent reciprocating lifting and lowering motion, and the flip plate 72 can be automatically reset to its initial state. Therefore, the bottom of the tank body 3 can be prevented from settling, which can effectively avoid the occurrence of sinking to the bottom, and is different from the traditional bottom-integrated stirring method design;

[0096] This design adopts an intermittent flipping design, which can effectively avoid overheating. At the same time, it can also reduce the excessive load on the drive motor 10 under long-term rotation working conditions. Secondly, the flipping freedom corresponds to the rotation freedom, which can further achieve full mixing and ensure that the leaching effect is further optimized.

[0097] It is understandable that there is a gap between the outer wall of the lifting ring 612 and the inner wall of the tank body 3, so as to avoid rotational friction between the lifting ring 612 and the tank body 3 and avoid excessive load.

[0098] Third embodiment:

[0099] See also Figures 7 to 9 , further comprising a linkage mechanism 8 and an adding mechanism 9, the linkage mechanism 8 comprising a connecting frame 81 and a ratchet 82, the connecting frame 81 being fixedly mounted on the inner wall of the tank body 3, the ratchet 82 being keyway-connected to the outer wall of the driving key rod 61, the top of the connecting frame 81 being rotatably connected to a ratchet ring 83, the outer wall of the ratchet ring 83 being fixedly provided with a convex plate 84;

[0100] The adding mechanism 9 includes a pipe 91, a limiting plate 92 and a sealing ring 97. The pipe 91 is fixed inside the tank body 3. An acid adding pipe 15 is fixed inside the tank body 3 and below the pipe 91. The limiting plate 92 and the sealing ring 97 are respectively fixed to the inner wall of the pipe 91. A sliding key rod 93 is slidably connected to the axis of the limiting plate 92. Telescopic frames 94 are installed on both sides of the pipe 91. A sealing plate 98 is fixed to one end of the sliding key rod 93 close to the inner side of the pipe 91. A wheel frame 95 is fixed to one end of the sliding key rod 93 close to the outside of the pipe 91. A roller 96 is rotatably connected to the inside of the wheel frame 95.

[0101] See also Figure 7 and Figure 8 As can be seen from the working principle of the first embodiment, the drive motor 10 has two working modes. In the first and second embodiments, the drive motor 10 mainly rotates counterclockwise, so the driving key rod 61 can drive the ratchet 82 to rotate counterclockwise, thereby not affecting the operation of the ratchet ring 83;

[0102] See also Figure 9 : When the driving key rod 61 rotates clockwise, the clockwise rotating driving key rod 61 will synchronously drive the ratchet 82 to rotate clockwise, and the clockwise rotating ratchet 82 will affect the ratchet ring 83 to form a rotational motion. During the rotation of the ratchet ring 83, the convex plate 84 will be synchronously driven to rotate. When the convex plate 84 rotates to the position of the roller 96, it will interfere with the control roller 96 to drive the wheel frame 95 to control the sliding key rod 93 to slide horizontally in the limit plate 92, thereby controlling the sliding key rod 93 to interfere with the blocking plate 98 and the blocking ring 97 to achieve separation;

[0103] After separation, the sealing ring 97 is in an open through-hole state. At this time, the mixed acid in the pipeline 91 will flow out from the pipe opening through the sealing ring 97 and into the tank body 3.

[0104] See also Figure 7 and Figure 8 : It can be understood that the limiting plate 92 is designed as a semicircular shape, which can ensure that the mixed acid flows out of the pipe 91 through the limiting plate 92. Because the bottom of the limiting plate 92 is open, it does not affect the filling of the mixed acid.

[0105] Secondly, the sealing plate 98 is of conical structure, so when the roller 96 loses the resistance of the convex plate 84, the mixed acid hydraulic pressure in the pipeline 91 can resist the sealing plate 98 to ensure sealing. At the same time, the telescopic frame 94 is a spring telescopic frame 94 to ensure that the sealing plate 98 is reset.

[0106] This embodiment:

[0107] There are two working modes. In the first mode, the user can control the driving key rod 61 to rotate continuously clockwise, which can continuously control the ratchet ring 83 to drive the convex plate 84 to rotate, intermittently interfering with the control roller 96 to ensure that the sealing ring 97 is opened. In this way, the pipeline 91 can be intermittently controlled to add mixed acid into the tank body 3.

[0108] The second type: when the convex plate 84 continuously contacts the roller 96, the sealing plate 98 controls the sealing ring 97 to open, and the continuous contact can achieve continuous separation, so that the pipeline 91 can continue to add the mixed acid solution to the inside of the tank body 3, and under the condition of fixed contact, the driving key rod 61 will not affect the normal operation of the convex plate 84 when rotating counterclockwise.

[0109] The outer wall of the blocking plate 98 fits tightly with the inner wall of the blocking ring 97, the limiting plate 92 is semicircular in structure, the outer wall of the roller 96 contacts the outer wall of the ratchet ring 83, the two sides of the wheel frame 95 are fixedly mounted on the telescopic frame 94, and the driving key rod 61 passes through the axis of the connecting frame 81 and is not mounted on the connecting frame 81.

[0110] The above technical solution has the following beneficial effects:

[0111] Since the mixed acid and tin-containing waste slag are rotated and mixed in the tank body 3 for a long period of time, the internal pH value may easily change due to the first addition of mixed acid during long-term mixing. In order to ensure that the tank body 3 can be maintained in a strong acid environment under long-term mixing, the linkage mechanism 8 and the adding mechanism 9 are designed. Only when the driving key rod 61 rotates clockwise will the linkage mechanism 8 be activated to control the adding mechanism 9 to open. The pipe 91 can be used to supplement the acid when the tank body 3 is working. Secondly, the two working modes of intermittent acid supplementation and continuous acid supplementation can be switched freely. The mixed acid can be supplemented in time to ensure that the tank body 3 is mixed in a strong acid environment for a long time, and the leaching effect can be continuously in the optimal environment. Secondly, the operation of the linkage mechanism 8 and the operation of the rotating plate 610 will not affect each other, and the integration of the working modes can be achieved.

[0112] Fourth embodiment:

[0113] A method for enriching and recovering tin

[0114] S1: using mixed acid to stir and leach the tin-containing waste residue, and separating the solid and liquid into tin-rich acid-leached residue. This step needs to be carried out in the tank body 3. The mixed acid is a 1:1 volume uniform mixture of 2 mol / L dilute sulfuric acid and 1 mol / L dilute hydrochloric acid. The liquid-solid ratio of the mixed acid to the tin-containing waste residue is 3-8:1. The acid leaching temperature is controlled by the heating base 2 to be 70-90°C, the acid leaching time is 1-3 hours, and the stirring speed is 150-400 r / min;

[0115] S2: mixing the tin-rich acid leaching residue with a certain amount of concentrated sulfuric acid and stirring them evenly, placing them in a heating furnace for sulfation roasting and defluorination reaction to obtain a roasted product;

[0116] The concentration of concentrated sulfuric acid is 98w%, the mass ratio of sulfuric acid to tin-rich acid leaching residue is 1-2:1, the roasting temperature is 260-310°C, and the roasting time is 0.5-3h;

[0117] The main reactions under sulfuric acid roasting are:

[0118] CaF2+H2SO4=CaSO4+2HF

[0119] 2AlF3+3H2O=Al2O3+3HF

[0120] Al2O3+3H2SO4=Al2(SO4)3+3H2O

[0121] This step can defluorinate insoluble calcium fluoride and aluminum fluoride, while cassiterite remains in the slag together with calcium sulfate because it is difficult to react with sulfuric acid;

[0122] S3: Evenly disperse the roasted product in a certain amount of water, add a certain amount of urea, stir and react at a high temperature, and collect the filter residue after the reaction is completed;

[0123] The liquid-solid ratio of the urea solution to the calcined product is 2-5:1, the amount of urea added is 3-7 times the theoretical stoichiometric amount, the reaction temperature is 80-100°C, the reaction time is 3-6 hours, and the stirring speed is 200-400 r / min;

[0124] The main reactions of urea leaching are:

[0125] CaSO4+CO(NH2)2+2H2O=CaCO3+(NH4)2SO4

[0126] This step converts the difficult-to-decompose calcium sulfate into calcium carbonate that can be decomposed by hydrochloric acid to remove calcium impurities in tin;

[0127] S4: using dilute hydrochloric acid to acid-leach the filter residue to remove calcium to obtain tin residue, wherein the dilute hydrochloric acid concentration is 0.1-1 mol / L, the liquid-solid ratio is 1-3:1, the reaction is carried out at room temperature, the reaction time is 10-30 minutes, and the stirring speed is 150-400 r / min;

[0128] The main reactions in S4 are:

[0129] CaCO3+2HCl=CaCl2+CO2+H2O;

[0130] S5: Use pure water to wash the tin slag, dry it, and then collect it. It should be noted that the washing times are twice.

[0131] The main components of the tin-containing waste slag in S1 are shown in the following table:

[0132] Sn(%) Fe(%) Mn (%) Ca(%) Al(％) Na(%) 24.153 9.811 2.599 3.382 1.269 0.057 Zn(%) K(％) Cu(%) Ta(%) Nb(%) F(％) 0.003 0.036 0.064 0.036 0.02 6.371

[0133] Example 1:

[0134] (1) using a 1:1 volume mixture of 2 mol / L dilute sulfuric acid and 1 mol / L dilute hydrochloric acid to stir and leach the tin-containing waste residue, separate the solid and liquid, and obtain a tin-rich acid leaching residue. The liquid-solid ratio of the mixed acid to the tin-containing waste residue is 5:1, the acid leaching temperature is 80°C, the acid leaching time is 2 hours, and the stirring speed is 300 r / min;

[0135] (2) mixing the tin-rich acid leaching residue with 2 times the mass of 98w% concentrated sulfuric acid and stirring evenly, and then placing it in a high-temperature furnace for sulfuric acid roasting and defluorination reaction to obtain a roasted product, wherein the roasting temperature is 280°C and the roasting time is 1 hour;

[0136] (3) The calcined product is uniformly dispersed in a fixed amount of water, a fixed amount of urea is added, and the reaction is stirred at a certain temperature. After the reaction is completed, the filter residue is collected. The liquid-solid ratio of the urea solution to the calcined product is 3:1, the amount of urea added is 5 times the theoretical stoichiometric number, the reaction temperature is 95°C, the reaction time is 4 hours, and the stirring speed is 300 r / min;

[0137] (4) using 0.5 mol / L dilute hydrochloric acid to acid-leach the filter residue to remove calcium to obtain tin residue, wherein the liquid-solid ratio of the dilute hydrochloric acid to the filter residue is 2:1, the reaction is carried out at room temperature, the reaction time is 20 min, and the stirring speed is 300 r / min;

[0138] (5) Wash the tin slag twice with pure water, dry it, and collect the tin concentrate.

[0139] Example 2:

[0140] (1) using a 1:1 volume mixture of 2 mol / L dilute sulfuric acid and 1 mol / L dilute hydrochloric acid to stir and leach the tin-containing waste residue, separate the solid and liquid, and obtain a tin-rich acid leaching residue. The liquid-solid ratio of the mixed acid to the tin-containing waste residue is 4:1, the acid leaching temperature is 80°C, the acid leaching time is 2.5 hours, and the stirring speed is 200 r / min;

[0141] (2) mixing the tin-rich acid leaching residue with 1.5 times the mass of 98w% concentrated sulfuric acid and stirring evenly, and then placing it in a high-temperature furnace for sulfuric acid roasting and defluorination reaction to obtain a roasted product, wherein the roasting temperature is 290°C and the roasting time is 2h;

[0142] (3) The calcined product is uniformly dispersed in a fixed amount of water, a fixed amount of urea is added, and the mixture is stirred at a certain temperature. After the reaction is completed, the filter residue is collected; the liquid-solid ratio of the urea solution to the calcined product is 4:1, the amount of urea added is 6 times the theoretical stoichiometric amount, the reaction temperature is 90°C, the reaction time is 4 hours, and the stirring speed is 200 r / min

[0143] (4) using 1 mol / L dilute hydrochloric acid to acid-leach the filter residue to remove calcium to obtain tin residue, wherein the liquid-to-solid ratio of the dilute hydrochloric acid to the filter residue is 1.5:1, the reaction is carried out at room temperature, the reaction time is 10 min, and the stirring speed is 200 r / min;

[0144] (5) Wash the tin oxide slag twice with pure water, dry it, and collect the tin concentrate.

[0145] Example 3:

[0146] (1) using a 1:1 volume mixture of 2 mol / L dilute sulfuric acid and 1 mol / L dilute hydrochloric acid to stir and leach the tin-containing waste residue, separate the solid and liquid, and obtain a tin-rich acid leaching residue. The liquid-solid ratio of the mixed acid to the tin-containing waste residue is 6:1, the acid leaching temperature is 70°C, the acid leaching time is 3 hours, and the stirring speed is 200 r / min;

[0147] (2) mixing the tin-rich acid leaching residue with 1 times the mass of 98w% concentrated sulfuric acid and stirring evenly, and then placing it in a high-temperature furnace for sulfuric acid roasting and defluorination reaction to obtain a roasted product, wherein the roasting temperature is 310°C and the roasting time is 2h;

[0148] (3) The calcined product is uniformly dispersed in a fixed amount of water, a fixed amount of urea is added, and the mixture is stirred at a certain temperature. After the reaction is completed, the filter residue is collected; the liquid-solid ratio of the urea solution to the calcined product is 5:1, the amount of urea added is 7 times the theoretical stoichiometric amount, the reaction temperature is 85°C, the reaction time is 4 hours, and the stirring speed is 300 r / min

[0149] (4) using 1 mol / L dilute hydrochloric acid to acid-leach the filter residue to remove calcium to obtain tin residue, wherein the liquid-solid ratio of the dilute hydrochloric acid to the filter residue is 2.5:1, the reaction is carried out at room temperature, the reaction time is 10 min, and the stirring speed is 200 r / min;

[0150] (5) Wash the tin oxide slag twice with pure water, dry it, and collect the tin concentrate.

[0151] Beneficial effects: iron and manganese are leached out by mixed acid leaching, the impurity removal process is simple and the separation efficiency is high; calcium fluoride and a small amount of aluminum fluoride impurities in tin-containing waste slag are removed by sulfuric acid roasting, and the fluorine removal rate reaches above 99.3%; urea is used to convert calcium sulfate impurities into calcium carbonate precipitates that can be decomposed by dilute hydrochloric acid, which is conducive to separation from tin; tin is enriched and recovered from tin-containing waste slag, which is a comprehensive utilization of the associated resources of tantalum-niobium ore and promotes the sustainable development of resources.

[0152] 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. A device for leaching tin from tin-containing waste slag, characterized in that: It includes a base, an end cover, a mounting base, a driving motor, a leaching mechanism, a feeding pipe and a discharging pipe; A heating seat is installed on the top of the base, a tank body is installed inside the heating seat, the end cover is sealed and installed on the top of the tank body by bolts, the mounting seat is installed at the bottom axis of the end cover, and a reduction box is installed in the output direction of the drive motor; The feeding pipe is installed on the top of the tank body, and the feeding pipe is installed on the bottom end of the tank body; The leaching mechanism includes a driving key rod, two connecting rods, a first spring and a second spring, the first spring and the second spring are respectively sleeved on the outside of the driving key rod, the top and bottom ends of the two connecting rods are respectively fixed with a first slide plate and a second slide plate, the bottom end of the driving key rod is fixed with a bottom plate, the outer wall of the driving key rod and above the first spring are fixed with a fixing plate, the outer walls of the two connecting rods are fixed with four horizontally arranged rotating plates, the outer walls of the two connecting rods and directly below the rotating plates are fixed with two horizontally arranged side rods, the bottoms of the two side rods are fixed with lifting rings by bolts, and guide wheels are installed on both sides of the first slide plate; A fixing ring is fixed on the inner wall of the tank body, and an ejector plate is installed on the bottom of the fixing ring through bolts; It also includes a linkage mechanism and an adding mechanism, the linkage mechanism includes a connecting frame and a ratchet, the connecting frame is fixed to the inner wall of the tank body, the ratchet keyway is connected to the outer wall of the driving key rod, the top of the connecting frame is rotatably connected to the ratchet ring, and the outer wall of the ratchet ring is fixed with a convex plate; The adding mechanism includes a pipeline, a limiting plate and a blocking ring. The pipeline is fixed inside the tank body. An acid adding pipe is fixed inside the tank body and below the pipeline. The limiting plate and the blocking ring are respectively fixed on the inner wall of the pipeline. A sliding key rod is slidably connected to the axis of the limiting plate. Telescopic frames are installed on both sides of the pipeline. A blocking plate is fixed on one end of the sliding key rod close to the inner side of the pipeline. A wheel frame is fixed on one end of the sliding key rod close to the outer side of the pipeline. A roller is rotatably connected to the inside of the wheel frame. The outer wall of the blocking plate fits tightly with the inner wall of the blocking ring, the limiting plate is semicircular in structure, the outer wall of the roller contacts the outer wall of the ratchet ring, the two sides of the wheel frame are fixedly mounted on the telescopic frame, and the driving key rod passes through the axis of the connecting frame and is not mounted on the connecting frame.

2. The device for leaching tin from tin-containing waste slag according to claim 1, characterized in that: The bottom of the reduction box is mounted on the top of the mounting seat via bolts, and the top end of the driving key rod extends into the interior of the reduction box and is connected to the output end keyway of the reduction box.

3. The device for leaching tin from tin-containing waste slag according to claim 1, characterized in that: The upper and lower ends of the first spring are fixedly connected to the fixed plate and the first slide plate, and the upper and lower ends of the second spring are fixedly connected to the second slide plate and the bottom plate.

4. The device for leaching tin from tin-containing waste slag according to claim 1, characterized in that: The upper surface of the guide wheel is continuously attached to the bottom surface of the fixing ring, the protrusion of the ejector plate faces downward of the fixing ring, and the ejector plate is mirror-distributed about the axis of the fixing ring.

5. The device for leaching tin from tin-containing waste slag according to claim 1, characterized in that: The utility model further comprises a turning mechanism, wherein the turning mechanism comprises a mounting frame fixedly mounted on the inner wall below the tank body, a turning plate is rotatably connected to the interior of the mounting frame, and dial plates are fixedly mounted on both sides of the turning plate.

6. The device for leaching tin from tin-containing waste slag according to claim 5, characterized in that: The mounting frame, the flap and the dial plate are distributed in an annular manner with equal distances about the axis of the tank body, and the upper surface of the flap is in contact with the bottom surface of the lifting ring.

7. A method for enriching and recovering tin, characterized in that: The method for enriching and recovering tin comprises the apparatus for leaching tin from tin-containing waste slag according to any one of claims 1 to 6, comprising the following steps: S1: using mixed acid to stir and leach the tin-containing waste residue, and separating the tin-rich acid-leached residue into solid and liquid. This step needs to be carried out in a tank. The mixed acid is a 1:1 volume uniform mixture of 2 mol / L dilute sulfuric acid and 1 mol / L dilute hydrochloric acid. The liquid-solid ratio of the mixed acid to the tin-containing waste residue is 3-8:

1. The acid leaching temperature is controlled by a heating block at 70-90°C, the acid leaching time is 1-3 hours, and the stirring speed is 150-400 r / min. S2: mixing the tin-rich acid leaching residue with a certain amount of concentrated sulfuric acid and stirring them evenly, placing them in a heating furnace for sulfation roasting and defluorination reaction to obtain a roasted product; The concentration of concentrated sulfuric acid is 98w%, the mass ratio of sulfuric acid to tin-rich acid leaching residue is 1-2:1, the roasting temperature is 260-310°C, and the roasting time is 0.5-3h; The main reactions under sulfuric acid roasting are: CaF2+H2SO4=CaSO4+2HF 2AlF3+3H2O=Al2O3+3HF Al2O3+3H2SO4=Al2(SO4)3+3H2O This step can defluorinate insoluble calcium fluoride and aluminum fluoride, while cassiterite remains in the slag together with calcium sulfate because it is difficult to react with sulfuric acid; S3: Evenly disperse the roasted product in a certain amount of water, add a certain amount of urea, stir and react at a high temperature, and collect the filter residue after the reaction is completed; The liquid-solid ratio of the urea solution to the calcined product is 2-5:1, the amount of urea added is 3-7 times the theoretical stoichiometric amount, the reaction temperature is 80-100°C, the reaction time is 3-6 hours, and the stirring speed is 200-400 r / min; The main reactions of urea leaching are: CaSO4+CO(NH2)2+2H2O=CaCO3+(NH4)2SO4 This step converts the difficult-to-decompose calcium sulfate into calcium carbonate that can be decomposed by hydrochloric acid to remove calcium impurities in tin; S4: using dilute hydrochloric acid to acid-leach the filter residue to remove calcium to obtain tin residue, wherein the dilute hydrochloric acid concentration is 0.1-1 mol / L, the liquid-solid ratio is 1-3:1, the reaction is carried out at room temperature, the reaction time is 10-30 minutes, and the stirring speed is 150-400 r / min; The main reactions in S4 are: CaCO3+2HCl=CaCl2+CO2+H2O; S5: Use pure water to wash the tin slag, dry it, and then collect it. It should be noted that the washing times are twice.

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