Equipment for leaching tin from tin-containing waste residues and method for enriching and recycling tin

Abstract

The invention provides equipment for leaching tin from tin-containing waste residues and a method for enriching and recovering tin through the equipment, and relates to the technical field of metal recycling. The equipment comprises a base, an end cover, a mounting base, a driving motor, a leaching mechanism, a feeding pipe and a discharging pipe; a heating base is installed on the top of the base, a tank body is installed in the heating base, and the end cover is installed at the top end of the tank body in a sealed mode through bolts. According to the device, water and solids in the tank body are stirred up and down when rotating eddy current is switched to ascend and descend, mixed acid and tin-containing waste residues can be conveniently stirred and mixed in a layered mode, and due to the fact that the mixed acid is added into the tank body through the acid adding pipe at the fixed position, the mixed acid can be more rapidly dissolved with the tin-containing waste residues after being added, and the stirring efficiency is improved. And if rotation is conducted in the direction of one degree of freedom for a long time, heat can be concentrated in the corresponding vortex layers, heat in the tank body can be evenly layered through lifting type auxiliary movement, heat concentration can be avoided, and high efficiency and safety in the leaching process are guaranteed.

Description

Technical Field

[0001] The present invention relates to the technical field of metal recycling, and particularly to an apparatus for leaching tin from tin-containing waste residue and a method for enriching and recycling tin. Background Art

[0002] In the wet smelting process of tantalum and niobium, tin, as an associated resource of tantalum and niobium ore, will remain in the slag in large quantities after tantalum and niobium are extracted by the wet smelting process. As a metal resource with extremely high value, tin plays an irreplaceable key role in many fields with its excellent physical and chemical properties. Its excellent ductility, corrosion resistance, and unique electrical and thermal properties enable it to be widely and deeply applied in the fields of industrial manufacturing, electronic information industry, medical devices, and new energy.

[0003] At the same time, from the perspective of economic benefits, the rational development and utilization of tin resources can create extremely 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 recycling tin from tantalum and niobium waste residue, aiming to achieve the efficient utilization of resources and the maximization of economic value.

[0004] In the process of leaching tin, the first step is to use mixed acid to leach the tin-containing waste residue for primary impurity removal, and a tin-rich acid leaching residue can be obtained. However, in the process of mixed acid leaching, it needs to work under long-term rotation conditions. Long-term rotation is likely to cause overheating inside the tank body, and the liquid and solid inside the tank body are stirred in a layered manner, which is likely to cause uneven mixing and affect the leaching effect.

[0005] Therefore, it is necessary to provide an apparatus for leaching tin from tin-containing waste residue and a method for enriching and recycling 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 residue and a method for enriching and recycling tin, which solve the technical problems in the related art that long-term rotation is likely to cause overheating during the process of mixed acid leaching, and secondly, the leaching effect is poor and the mixed acid is not conducive to uniform dissolution.

[0007] To solve the above technical problems, an apparatus for leaching tin from tin-containing waste residue provided by the present invention includes a base, an end cover, a mounting seat, a driving 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 hermetically installed on the top end of the tank body through bolts, the mounting seat is installed at the bottom center of the end cover, and a speed reducer is installed in the output direction of the driving motor;

[0009] The feeding pipe is installed above the tank body, and the discharging pipe is installed at 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 outside the driving key rod. A first sliding plate and a second sliding plate are fixedly arranged at the top end and the bottom end of the two connecting rods respectively. A bottom plate is fixedly arranged at the bottom end of the driving key rod. A fixing plate is fixedly arranged on the outer wall of the driving key rod and above the first spring. Four rotating plates are horizontally arranged on the outer walls of the two connecting rods. Two side rods are horizontally arranged on the outer walls of the two connecting rods and directly below the rotating plates. A lifting ring is installed at the bottom of the two side rods through bolts. Guide wheels are installed on both sides of the first sliding plate;

[0011] A fixing ring is fixedly arranged on the inner wall of the tank body, and a top plate is installed at the bottom of the fixing ring through bolts.

[0012] Preferably, the bottom of the reduction box is installed with the top of the mounting seat through bolts. The top end of the driving key rod extends into the reduction box and is keyed to the output end of the reduction box.

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

[0014] Preferably, the upper surface of the guide wheel continuously fits on the bottom surface of the fixing ring. The convex shape of the top plate faces downward of the fixing ring, and the top plates are mirror-symmetrically distributed about the axis of the fixing ring.

[0015] Preferably, a turning mechanism is further included. The turning mechanism includes a mounting frame fixedly arranged on the inner wall below the tank body. A turning plate is rotatably connected inside the mounting frame. Pushing plates are fixedly arranged on both sides of the turning plate.

[0016] Preferably, the mounting frame, the turning plate and the pushing plates are equidistantly and annularly distributed about the axis of the tank body. The upper surface of the turning plate is in contact with the bottom surface of the lifting ring.

[0017] Preferably, a linkage mechanism and an adding mechanism are further included. The linkage mechanism includes a connecting frame and a ratchet wheel. The connecting frame is fixedly arranged on the inner wall of the tank body. The ratchet wheel is keyed to the outer wall of the driving key rod. A ratchet ring is rotatably connected to the top of the connecting frame. A convex plate is fixedly arranged on the outer wall of the ratchet ring;

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

[0019] Preferably, the outer wall of the sealing plate is in close fit with the inner wall of the sealing ring. The limiting plate is in a semi-circular structure. The outer wall of the roller is in contact with the outer wall of the ratchet ring. Both sides of the wheel frame are fixedly installed with the telescopic frames. The driving key rod penetrates through the center of the connecting frame and is not installed with the connecting frame.

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

[0021] S1: Stir and leach the tin-containing waste residue with mixed acid, and perform solid-liquid separation on the tin-rich acid leaching residue. This step needs to be carried out in the tank body. The mixed acid is uniformly mixed by 2mol / L dilute sulfuric acid and 1mol / L dilute hydrochloric acid in a volume ratio of 1:1. The liquid-solid ratio of the mixed acid to the tin-containing waste residue is 3-8:1. The acid leaching temperature is controlled at 70-90°C by a heating seat, the acid leaching time is 1-3h, and the stirring speed is 150-400r / min;

[0022] S2: Mix the tin-rich acid leaching residue with a certain amount of concentrated sulfuric acid and stir evenly, and place it in a heating furnace for a sulfuric acid roasting defluorination reaction to obtain a roasting product;

[0023] The concentration of the concentrated sulfuric acid is 98w%, the mass ratio of sulfuric acid to the 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 as follows:

[0025] CaF2+H2SO4=CaSO4+2HF

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

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

[0028] This step can remove fluorine from the insoluble calcium fluoride and aluminum fluoride. Cassiterite remains in the residue together with calcium sulfate because it is difficult to react with sulfuric acid;

[0029] S3: Uniformly disperse the roasting product in a certain amount of water, add a certain amount of urea, and carry out a stirring reaction at a higher temperature. After the reaction is completed, collect the filter residue;

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

[0031] The main reaction of urea leaching is:

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

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

[0034] S4: Acid leaching the filter residue with dilute hydrochloric acid to obtain tin slag. The concentration of the dilute hydrochloric acid 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 min, and the stirring speed is 150-400 r / min;

[0035] The main reaction in S4 is:

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

[0037] S5: Wash the tin slag with pure water, dry it and then collect it. It should be noted that the number of washing times is two.

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

[0039] During the rotation process, the lifting affects and changes the eddy current form in the tank. When the rotating eddy current switches to lifting, the water body and solid in the tank are stirred up and down. On the one hand, it is convenient to stir and mix the mixed acid and tin-containing waste residues in a layered manner. Since the mixed acid is added to the tank through the acid addition pipe at a fixed position, it is convenient for the mixed acid to dissolve more quickly with the tin-containing waste residues after being added. Secondly, if it rotates in one degree-of-freedom direction for a long time, the heat will be concentrated in the corresponding eddy current layer. The auxiliary lifting motion can evenly layer the heat in the tank, avoid heat concentration, and ensure the high efficiency and safety during the leaching process. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on the structures shown in these drawings.

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

[0042] Figure 2 The sectional structural schematic diagram of the tank body provided for the present invention;

[0043] Figure 3 is Figure 2 The structural schematic diagram of the leaching mechanism shown in;

[0044] Figure 4 is Figure 3 The schematic diagram of the working state when the guide wheel rotates to the ejector plate position to control the downward movement of the rotating plate shown in;

[0045] Figure 5 is Figure 2 The structural schematic diagram of the flipping mechanism shown in;

[0046] Figure 6 is Figure 5 The schematic diagram of the working state of the flipping mechanism shown in;

[0047] Figure 7 The sectional structural schematic diagram of the linkage mechanism and the adding mechanism provided for the present invention;

[0048] Figure 8 is Figure 7 The schematic diagram of the upward view structure of the connecting frame shown in

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

[0050] Explanation of the reference numerals in the drawings:

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

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

[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. Link, 610. Rotating plate, 611. Side rod, 612. Lifting ring;

[0054] 7. Flipping mechanism, 71. Mounting frame, 72. Flap, 73. Pushing plate;

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

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

[0057] 10. Driving motor;

[0058] 11. Feeding pipe, 12. Discharging pipe;

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

[0060] The realization, functional features and advantages of the object of the present invention will be further described with reference to the embodiments and the accompanying drawings. Detailed implementation manners

[0061] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0062] The present invention provides an apparatus for leaching tin from tin-containing waste residues and a method for enriching and recovering tin therefrom.

[0063] First embodiment:

[0064] Please refer to Figures 1 to 4 , an apparatus for leaching tin from tin-containing waste residues, including a base 1, an end cover 16, a mounting seat 4, a driving 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 hermetically installed at the top end of the tank body 3 by bolts, the mounting seat 4 is installed at the bottom center of the end cover 16, and a speed reducer 5 is installed in the output direction of the driving motor 10;

[0066] The feeding pipe 11 is installed above the tank body 3, and the discharging 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 outside the driving key rod 61. A first sliding plate 63 and a second sliding plate 66 are fixedly provided at the top and bottom of the two connecting rods 69 respectively. A bottom plate 67 is fixedly provided at the bottom end of the driving key rod 61. A fixing plate 62 is fixedly provided on the outer wall of the driving key rod 61 and above the first spring 64. Four rotating plates 610 are horizontally provided on the outer walls of the two connecting rods 69. Two side rods 611 are horizontally provided on the outer walls of the two connecting rods 69 and directly below the rotating plates 610. A lifting ring 612 is installed at the bottom of the two side rods 611 through bolts. Guide wheels 65 are installed on both sides of the first sliding plate 63;

[0068] A fixing ring 13 is fixedly provided on the inner wall of the tank body 3. A top plate 14 is installed at the bottom of the fixing ring 13 through bolts.

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

[0070] Please refer to Figure 1 and Figure 2 : Start the driving motor 10 to rotate. The reduction gearbox 5 can be used to reduce the speed of the driving motor 10. Finally, the reduction gearbox 5 can achieve forward and reverse rotational motion by controlling the driving key rod 61.

[0071] Please refer to Figure 3 : The driving key rod 61 has two working modes. The first is that the driving key rod 61 rotates counterclockwise, and the second is that the driving key rod 61 rotates clockwise;

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

[0073] Therefore, it can be known that when the connecting rod 69 rotates, it will drive the external rotating plate 610 and the side rod 611 to rotate synchronously. By the rotation of the rotating plate 610, the mixed acid and tin-containing waste residue inside the tank body 3 can be rotated and stirred to ensure uniform mixing of the mixed acid and the tin-containing waste residue and remove impurities;

[0074] Please refer to Figure 3 : It can be seen that the inclination directions of the rotating plates 610 are arranged in a staggered manner. In this way, during the rotation process, the inclined surfaces are always in contact with the medium inside the tank body 3, ensuring uniform stirring and mixing in a fixed rotation direction.

[0075] The bottom of the speed reducer 5 is installed on the top of the mounting base 4 through bolts. The top end of the driving key rod 61 extends into the speed reducer 5 and is key-connected to the output keyway of the speed reducer 5.

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

[0077] The upper surface of the guide wheel 65 is continuously attached to the bottom surface of the fixed ring 13. The convex shape of the ejector plate 14 faces downward of the fixed ring 13, and the ejector plates 14 are mirror-symmetrically distributed about the axis of the fixed ring 13.

[0078] Please refer to Figure 3 : When the first sliding plate 63 rotates counterclockwise, the first sliding plate 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 continuously contacts the bottom of the fixed ring 13 while rotating;

[0079] Please refer to Figure 4 : As the guide wheel 65 rotates from the bottom of the fixed ring 13 to the position of the ejector plate 14, the guide wheel 65 will rotate downward along the inclined surface of the ejector plate 14 and then continuously rotate downward following the trajectory of the ejector plate 14, thereby controlling the first sliding plate 63 to drive the connecting rod 69 and the second sliding plate 66 to move downward along the vertical direction of the driving key rod 61. During the downward movement, the first spring 64 will extend accordingly, while the second spring 68 will be compressed;

[0080] In this way, the lifting movement can be synchronously realized during the rotation of the rotating plate 610.

[0081] The working principle of this embodiment:

[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, add mixed acid and mixed solution medium into the tank body 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 driving motor 10 to control the driving key rod 61 to rotate counterclockwise. During the counterclockwise rotation, it can drive the rotating plate 610 to rotate to stir and mix the mixed acid and the tin-containing waste residue inside the tank body 3. At the same time, when the guide wheel 65 rotates to the position of the ejector plate 14, it will affect the rotating plate 610 to move downward to assist in stirring and mixing.

[0085] Note: The total amount of the medium in the tank body 3 shall not exceed the bottom limit position of the ejector plate 14. After the final leaching is completed, all the medium in the tank body 3 is discharged through the blanking pipe 12 for the next step.

[0086] In this embodiment:

[0087] Compared with the traditional design, in this case, two groups of rotating plates 610 with staggered bases are provided to rotate and mix the mixed acid and tin-containing waste residue in the tank body 3. On the basis of fixed rotation, a set of arc-shaped ejector plates 14 are also designed to cooperate with the rotating plates 610. When the guide wheel 65 rotates from the bottom position of the fixed ring 13 to the position of the ejector plate 14, it will affect the rotating plate 610 to form a certain range of lifting motion, so that the lifting motion is not affected during the rotation process, increasing the degrees of freedom of the rotating plate 610 from one to two, and at the same time not affecting the rotational degree of freedom;

[0088] Therefore, during the rotation process, the lifting can affect and change the eddy current form in the tank body 3. When the rotating eddy current switches to lifting, the water body 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 tin-containing waste residue in a layered manner. 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 being added. Secondly, if it rotates in one degree of freedom direction for a long time, the heat will be concentrated in the corresponding eddy current layer. The auxiliary lifting motion can evenly layer the heat in the tank body 3, avoid heat concentration, and ensure the efficiency and safety during the leaching process.

[0089] Second embodiment:

[0090] Please refer to Figures 4 to 6 , and it further includes a flipping mechanism 7. The flipping mechanism 7 includes a mounting frame 71 fixedly arranged on the inner wall below the tank body 3. A turning plate 72 is rotatably connected inside the mounting frame 71, and shifting plates 73 are fixedly arranged on both sides of the turning plate 72.

[0091] The mounting frame 71, the turning plate 72 and the shifting plates 73 are annularly distributed equidistantly about the axis of the tank body 3, and the upper surface of the turning plate 72 is in contact with the bottom surface of the lifting ring 612.

[0092] Please refer to Figure 5 : During the working process of the first embodiment, if the guide wheel 65 rotates on the fixed ring 13, the lifting ring 612 will also normally rotate in one degree of freedom following the connecting rod 69. During the rotation process, the lifting ring 612 continuously fits on the turning plate 72, so it will not affect the movement of the turning plate 72.

[0093] Please refer to Figure 6: When the guide wheel 65 follows the ejection plate 14 to descend, the connecting rod 69 will also drive the lifting ring 612 to achieve the same amplitude of the downward movement, so that the lifting ring 612 can downwardly resist one end of the control flap 72 when descending, so that the flap 72 can be turned clockwise along the hinge position of the mounting frame 71, so that the dial plate 73 can be turned upward from the bottom of the tank body 3;

[0094] Thereby, the tin-containing waste slag 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 flap 72 to control the paddle 73 to roll 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, and drives the flap 72 to flip through intermittent reciprocating lifting and lowering motion, and at the same time, the flap 72 can be automatically reset to the initial state, so that the bottom of the tank body 3 can be prevented from settling, and the bottom sinking can be effectively avoided, which 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 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 can be understood 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, wherein the linkage mechanism 8 comprises a connecting frame 81 and a ratchet 82, wherein the connecting frame 81 is fixedly arranged on the inner wall of the tank body 3, the ratchet 82 is keyway connected to the outer wall of the driving key rod 61, the top of the connecting frame 81 is rotatably connected to a ratchet ring 83, and a convex plate 84 is fixedly arranged on the outer wall of the ratchet ring 83;

[0100] The addition 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 on the inner wall of the pipe 91. A sliding key rod 93 is slidably connected to the center 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 the end of the sliding key rod 93 close to the outside of the pipe 91. A roller 96 is rotatably connected inside the wheel frame 95.

[0101] Please refer to 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 embodiment and the second embodiment, the drive motor 10 mainly rotates counterclockwise. Therefore, the drive key rod 61 can drive the ratchet wheel 82 to rotate counterclockwise, thus not affecting the operation of the ratchet tooth ring 83.

[0102] Please refer to Figure 9 : When the drive key rod 61 rotates clockwise, the clockwise rotating drive key rod 61 will synchronously drive the ratchet wheel 82 to rotate clockwise. The clockwise rotating ratchet wheel 82 will affect and drive the ratchet tooth ring 83 to form a rotational movement. During the rotation of the ratchet tooth 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 contact and control the roller 96 to drive the wheel frame 95 to control the horizontal sliding of the sliding key rod 93 in the limiting plate 92, thereby controlling the sliding key rod 93 to contact the sealing plate 98 and the sealing ring 97 to achieve separation.

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

[0104] Please refer to Figure 7 and Figure 8 : It can be understood that the limiting plate 92 is designed as a semicircle, which can ensure that the mixed acid flows out of the pipe 91 through the limiting plate 92. Since the bottom of the limiting plate 92 is in an open state, it will not affect the filling of the mixed acid.

[0105] Secondly, the sealing plate 98 is of a conical structure. In this way, when the roller 96 loses the contact of the convex plate 84, the hydraulic pressure of the mixed acid in the pipe 91 against the sealing plate 98 can ensure sealing. At the same time, the telescopic frame 94 is a spring telescopic frame 94 to ensure the reset of the sealing plate 98.

[0106] This embodiment:

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

[0108] The second mode: when the convex plate 84 continuously touches the roller 96, the sealing plate 98 controls the sealing ring 97 to open, and continuous contact can achieve continuous separation. In this way, the pipeline 91 can continuously inject the mixed acid solution into the tank body 3, and in the case of fixed contact, when the driving lever 61 rotates counterclockwise, it will not affect the normal operation of the convex plate 84.

[0109] The outer wall of the sealing plate 98 is closely attached to the inner wall of the sealing ring 97. The limiting plate 92 is of a semicircular structure. The outer wall of the roller 96 is in contact with the outer wall of the ratchet ring 83. Both sides of the wheel frame 95 are fixedly installed with the telescopic frame 94. The driving lever 61 passes through the axis of the connecting frame 81 and is not installed with the connecting frame 81.

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

[0111] Since the rotation mixing time of the mixed acid and the tin-containing waste residue in the tank body 3 is long periodically, when adding the mixed acid for the first time and under long-term mixing, it is easy to cause the change of the internal acidity and alkalinity. In order to ensure that the tank body 3 can still maintain a strong acid environment under long-term mixing, through the design of the linkage mechanism 8 and the adding mechanism 9, only when the driving lever 61 rotates clockwise will the linkage mechanism 8 be activated to control the adding mechanism 9 to open, and the pipeline 91 can supplement the acid while the tank body 3 is working. Secondly, it can freely switch between two working modes of intermittent acid supplementation and continuous acid supplementation, and can realize the timely supplementation of the mixed acid in the tank body 3, so as to ensure that the tank body 3 is maintained in a strong acid environment for long-term mixing, ensure that 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 mode can be realized.

[0112] Fourth Embodiment:

[0113] A method for enriching and recovering tin

[0114] S1: Use mixed acid to stir and leach the tin-containing waste residue, and perform solid-liquid separation on the tin-rich acid leaching residue. This step needs to be carried out in the tank body 3. The mixed acid is uniformly mixed in a volume ratio of 1:1 of 2mol / L dilute sulfuric acid and 1mol / 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 at 70-90°C by the heating seat 2, the acid leaching time is 1-3h, and the stirring speed is 150-400r / min.

[0115] S2: Mix the stanniferous acid leaching residue with a quantified amount of concentrated sulfuric acid and stir evenly, then place it in a heating furnace for sulfation roasting to remove fluorine, obtaining a roasted product;

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

[0117] The main reactions under sulfation roasting are as follows:

[0118] CaF2 + H2SO4 = CaSO4 + 2HF

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

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

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

[0122] S3: Uniformly disperse the roasted product in a quantified amount of water, add a certain amount of urea, and carry out a stirring reaction at a relatively high temperature. After the reaction ends, collect the filter residue;

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

[0124] The main reaction of urea leaching is:

[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: Use dilute hydrochloric acid to leach calcium from the filter residue to obtain a tin residue. The concentration of the dilute hydrochloric acid 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 min, and the stirring speed is 150 - 400 r / min;

[0128] The main reaction in S4 is:

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

[0130] S5: Wash the tin residue with pure water, dry it, and then collect it. It should be noted that the number of washing times is two.

[0131] The main components in the tin-containing waste residue 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) Use 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, followed by solid-liquid separation to 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 h, and the stirring speed is 300 r / min;

[0135] (2) Mix the tin-rich acid leaching residue with 2 times its mass of 98 w% concentrated sulfuric acid and stir evenly, then place it in a high-temperature furnace for a sulfuric acid roasting defluorination reaction to obtain a roasted product. The roasting temperature is 280 °C and the roasting time is 1 h;

[0136] (3) Uniformly disperse the roasted product in a certain amount of water, add a fixed amount of urea, and carry out a stirring reaction at a certain temperature. After the reaction ends, collect the filter residue. The liquid-solid ratio of the urea solution to the roasted product is 3:1, the urea addition amount is 5 times the theoretical stoichiometric number, the reaction temperature is 95 °C, the reaction time is 4 h, and the stirring speed is 300 r / min;

[0137] (4) Use 0.5 mol / L dilute hydrochloric acid to acid leach the filter residue to remove calcium to obtain a tin residue. 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 residue twice with pure water, dry it, and collect the tin concentrate.

[0139] Example 2:

[0140] (1) Use 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, followed by solid-liquid separation to 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 h, and the stirring speed is 200 r / min;

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

[0142] (3) Uniformly disperse the calcined product in a certain amount of water, add a fixed amount of urea, stir at a certain temperature, and collect the filter residue after the reaction; the liquid-solid ratio of the urea solution to the calcined product liquid is 4:1, the urea addition amount is 6 times the theoretical stoichiometry, the reaction temperature is 90 °C, the reaction time is 4 h, and the stirring speed is 200 r / min

[0143] (4) Use 1 mol / L dilute hydrochloric acid to leach calcium from the filter residue to obtain tin slag. The liquid-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) Use 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, perform solid-liquid separation to obtain the 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 h, and the stirring speed is 200 r / min;

[0147] (2) Mix the tin-rich acid leaching residue with 98 w% concentrated sulfuric acid with a mass of 1 time, stir evenly, and then place it in a high-temperature furnace for a sulfuric acid roasting defluorination reaction to obtain a calcined product. The roasting temperature is 310 °C and the roasting time is 2 h;

[0148] (3) Uniformly disperse the calcined product in a certain amount of water, add a fixed amount of urea, stir at a certain temperature, and collect the filter residue after the reaction; the liquid-solid ratio of the urea solution to the calcined product liquid is 5:1, the urea addition amount is 7 times the theoretical stoichiometry, the reaction temperature is 85 °C, the reaction time is 4 h, and the stirring speed is 300 r / min

[0149] (4) Use 1 mol / L dilute hydrochloric acid to leach calcium from the filter residue to obtain tin slag. 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: The mixed acid leaching is adopted to leach iron and manganese, and the impurity removal process is simple with high separation efficiency; the calcium fluoride and a small amount of aluminum fluoride impurities in the tin-containing waste residue are removed by means of sulfation roasting, and the defluorination rate reaches over 99.3%; urea is used to convert the calcium sulfate impurity into calcium carbonate precipitate that can be decomposed by dilute hydrochloric acid, which is beneficial to the separation from tin; tin is enriched and recovered from the tin-containing waste residue, which is the comprehensive utilization of the associated resources of tantalum-niobium ore and promotes the sustainable development of resources.

[0152] The above are only the preferred embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. Any equivalent structural transformation made under the concept of the present invention by using the content of the specification and drawings of the present invention, or any direct / indirect application in other related technical fields is included in the patent protection scope of the present invention.

Claims

1. An apparatus for leaching tin from tin-containing waste residues, characterized in that, It includes a base, an end cover, a mounting seat, 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 hermetically installed at the top end of the tank body by bolts, the mounting seat is installed at the bottom center of the end cover, and a reduction gearbox is installed in the output direction of the driving motor; The feeding pipe is installed above the tank body, and the discharging pipe is installed at 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 outside the driving key rod. First sliding plates and second sliding plates are fixedly provided at the top and bottom ends of the two connecting rods respectively. A bottom plate is fixedly provided at the bottom end of the driving key rod. A fixing plate is fixedly provided on the outer wall of the driving key rod and above the first spring. Four rotating plates are horizontally provided on the outer walls of the two connecting rods. Two side rods are horizontally provided on the outer walls of the two connecting rods and directly below the rotating plates. A lifting ring is installed at the bottom of the two side rods by bolts. Guide wheels are installed on both sides of the first sliding plate; A fixing ring is fixedly provided on the inner wall of the tank body, and a top plate is installed at the bottom of the fixing ring by bolts.

2. The device for leaching tin from tin-containing waste residues according to claim 1, wherein The bottom of the reduction gearbox is installed with the top of the mounting seat by bolts. The top end of the driving key rod extends into the inside of the reduction gearbox and is keyed to the output end of the reduction gearbox.

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

4. The apparatus for leaching tin from tin-containing waste residue according to claim 1, wherein, The upper surface of the guide wheel continuously fits against the bottom surface of the fixing ring. The convex shape of the top plate faces downward of the fixing ring, and the top plates are mirror-symmetrically distributed about the axis of the fixing ring.

5. The device for leaching tin from tin-containing waste residues according to claim 1, wherein It further includes a turning mechanism. The turning mechanism includes a mounting frame fixedly provided on the inner wall below the tank body. A turning plate is rotatably connected inside the mounting frame. Dial plates are fixedly provided on both sides of the turning plate.

6. The equipment for leaching tin from tin-containing waste residues according to claim 5, wherein, The mounting frame, the turning plate and the dial plates are equidistantly and annularly distributed about the axis of the tank body. The upper surface of the turning plate is in contact with the bottom surface of the lifting ring.

7. The device for leaching tin from tin-containing waste residue according to claim 1, wherein It further includes a linkage mechanism and an adding mechanism. The linkage mechanism includes a connecting frame and a ratchet wheel. The connecting frame is fixedly provided on the inner wall of the tank body. The ratchet wheel is keyed to the outer wall of the driving key rod. A ratchet ring is rotatably connected to the top of the connecting frame. A convex plate is fixedly provided on the outer wall of the ratchet ring; The adding mechanism includes a pipeline, a limiting plate and a sealing ring. The pipeline is fixedly provided inside the tank body. An acid adding pipe is fixedly provided inside the tank body and below the pipeline. The limiting plate and the sealing ring are respectively fixedly provided 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 sealing plate is fixedly provided at one end of the sliding key rod close to the inner side of the pipeline. A wheel frame is fixedly provided at one end of the sliding key rod close to the outside of the pipeline. A roller is rotatably connected inside the wheel frame.

8. The device for leaching tin from tin-containing waste residues according to claim 7, characterized in that, The outer wall of the plugging plate is in close fit with the inner wall of the plugging ring. The limiting plate is semicircular in configuration. The outer wall of the roller is in contact with the outer wall of the ratchet ring. Both sides of the wheel frame are fixedly installed with the telescopic frame. The driving key rod passes through the axis of the connecting frame and is not installed with the connecting frame.

9. A method for enriching and recovering tin, characterized in that, The method for enriching and recovering tin includes the equipment for leaching tin from tin-containing waste residues as described in any one of claims 1-8, and includes the following steps: S1: Stir and leach the tin-containing waste residues with a mixed acid, and perform solid-liquid separation on the tin-rich acid leaching residues. This step needs to be carried out in a tank. The mixed acid is uniformly mixed by 2 mol / L dilute sulfuric acid and 1 mol / L dilute hydrochloric acid at a volume ratio of 1:

1. The liquid-solid ratio of the mixed acid to the tin-containing waste residues is 3-8:

1. The acid leaching temperature is controlled at 70-90 °C by a heating seat, the acid leaching time is 1-3 h, and the stirring speed is 150-400 r / min; S2: Mix the tin-rich acid leaching residues with a quantitative concentrated sulfuric acid and stir evenly, and place them in a heating furnace for a sulfuric acid roasting defluorination reaction to obtain a roasting product; The concentration of the concentrated sulfuric acid is 98 w%, the mass ratio of sulfuric acid to the tin-rich acid leaching residues is 1-2:1, the roasting temperature is 260-310 °C, and the roasting time is 0.5-3 h; 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 remove fluorine from the insoluble calcium fluoride and aluminum fluoride, and cassiterite remains in the residue together with calcium sulfate because it is difficult to react with sulfuric acid; S3: Uniformly disperse the roasting product in a quantitative amount of water, add a certain amount of urea, and carry out a stirring reaction at a relatively high temperature. After the reaction ends, collect the filter residue; The liquid-solid ratio of the urea solution to the roasting product is 2-5:1, the addition amount of urea is 3-7 times the theoretical stoichiometry, the reaction temperature is 80-100 °C, the reaction time is 3-6 h, and the stirring speed is 200-400 r / min; The main reaction of urea leaching is: 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: Use dilute hydrochloric acid to leach and remove calcium from the filter residue to obtain tin residues. The concentration of the dilute hydrochloric acid 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 min, and the stirring speed is 150-400 r / min; The main reaction in S4 is: CaCO3 + 2HCl = CaCl2 + CO2 + H2O; S5: Wash the tin residues with pure water, dry them, and collect them. It should be noted that the number of washing times is two.

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