Tantalum-niobium extraction device and method for preparing highly selective tantalum-niobium extractant

Abstract

The present invention provides a tantalum-niobium extraction device and a method for preparing a highly selective tantalum-niobium extractant thereof, which relates to the field of hydrometallurgical technology and includes a base, an extraction mechanism, and an auxiliary mechanism; a heating seat is installed above the base, an extraction barrel is installed inside the heating seat, a top plate is installed on the top of the extraction barrel by bolts, and a cylinder is installed on the top of the top plate by bolts. In this case, recycled metal parts (abandoned metal parts, electronic products, and all other waste recycling materials containing tantalum and niobium) are placed in a storage barrel, and the extraction solvent is stored in the extraction barrel. The raw material and the solvent are mixed by a reciprocating lifting storage barrel, and when the storage barrel is lifted and lowered, a flap can be linked to control four linkage plates to perform a clockwise and counterclockwise reciprocating flipping motion, so that the solvent in the extraction barrel can be stirred during the flipping process, ensuring sufficient mixing and contact between the solvent and the raw material.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrometallurgy, and in particular to a tantalum-niobium extraction device and a method for preparing a highly selective tantalum-niobium extractant thereof. Background Art

[0002] Tantalum and niobium are important strategic metals, widely used in electronics, aerospace and other fields. Traditional tantalum-niobium separation processes mostly use solvent extraction, using hydrometallurgical methods to extract the tantalum-niobium components in the materials to be processed. Since tantalum and niobium are important strategic metals, in addition to extraction from concentrates, tantalum and niobium substances in some industrial scrap metals and recycled metal electronic devices also need to be extracted during recycling. Therefore, hydrometallurgical extraction can be applied to multi-directional tantalum-niobium extraction.

[0003] Announcement No. CN220926882U provides a tantalum-niobium two-phase extraction tank, comprising a mounting frame, an extraction tank disposed within a mounting opening defined within the mounting frame, a discharge pipe disposed at the discharge port defined at the lower end of the extraction tank, a first solenoid valve connected in series to the middle of the discharge pipe, a feed pipe disposed at the feed port defined at the upper end of the extraction tank, a second solenoid valve connected in series to the middle of the feed pipe, and a stirring mechanism disposed within the extraction tank. By stirring the tantalum-niobium raw material and solvent while scraping the tantalum-niobium raw material from the inner wall of the extraction tank, the tantalum-niobium raw material can be effectively prevented from adhering to the inner wall of the extraction tank, thereby enabling comprehensive extraction of the tantalum-niobium.

[0004] However, in actual use of the above-mentioned device, the extraction raw materials and various solvents are extracted inside a carrier. In this way, the extracted tantalum and niobium substances are still mixed with the raw materials. At the same time, there are too many impurities in the recovered raw materials, and the co-extraction phenomenon of impurity metals (such as iron and titanium) is significant, resulting in low extraction efficiency and poor extraction effect.

[0005] Therefore, it is necessary to provide a tantalum-niobium extraction device and a method for preparing a highly selective tantalum-niobium extractant to solve the above technical problems. Summary of the Invention

[0006] The present invention provides a tantalum-niobium extraction device and a method for preparing a highly selective tantalum-niobium extractant, which solves the technical problem in the related art that impurity metals (such as iron and titanium) in the recovered raw materials are significantly co-extracted, resulting in low extraction efficiency and poor extraction effect.

[0007] In order to solve the above technical problems, the present invention provides a tantalum-niobium extraction device, comprising a base, an extraction mechanism and an auxiliary mechanism;

[0008] A heating seat is installed above the base, an extraction barrel is installed inside the heating seat, a top plate is installed on the top of the extraction barrel by bolts, a cylinder is installed on the top of the top plate by bolts, and a lifting rod that can be lifted vertically is installed inside the cylinder;

[0009] The extraction mechanism includes a storage barrel, a top frame is fixed to the top of the storage barrel by bolts, a middle plate is fixed to the inner wall of the top frame, a rotating seat is fixed to the middle position of the top of the middle plate by bolts, a flange seat is fixed to the bottom end of the lifting rod by bolts, a mounting seat is fixed to the side wall of the top frame, and a guide wheel is rotatably connected to the inside of the mounting seat;

[0010] The auxiliary mechanism includes a flap, a through connecting groove is provided inside the flap, two first positioning seats are installed on the inner bottom of the extraction barrel, sleeves are fixed inside the two first positioning seats, rotating shafts are fixed on both sides of the flap, torsion springs are sleeved on the inner sides of the two sleeves and on the outer walls of the two rotating shafts, second positioning seats are installed on the inner bottom of the extraction barrel and on both sides of the flap, a linkage plate is rotatably connected to the interior of the second positioning seat, a through hole is provided inside the linkage plate, and a connecting wheel is rotatably connected to the side wall of the linkage plate.

[0011] Preferably, the two rotating shafts are rotatably connected to the axes of the two sleeves through bearings, the two sides of the torsion spring respectively contact the inner wall of the sleeve and the rotating shaft, and the connecting wheel is slidably connected to the connecting groove.

[0012] Preferably, the flange seat and the rotating seat are rotatably connected, and the bottom surface of the storage bucket is in contact with the upper surface of the flap.

[0013] Preferably, it further comprises a scraping mechanism, the scraping mechanism comprising positioning plates installed on both sides of the lifting rod and located above the flange seat, a scraping ring is installed on the inner bottom of the storage barrel, and connecting plates are fixed on both sides of the inner wall of the scraping ring;

[0014] The two positioning plates are both slidably connected to the two connecting plates via a "T"-shaped block.

[0015] Preferably, a corrugated plate is fixed on the inner wall of the storage barrel and located in the vertical direction of the guide wheel, a discharge pipe is installed at the internal axis of the storage barrel, and sealing plates are rotatably installed above the storage barrel and on both sides of the top plate, and the upper and lower sides of the corrugated plate are both inclined structures.

[0016] Preferably, it also includes an air-increasing mechanism, which includes a positioning frame installed on one side of the cylinder, an extrusion barrel installed inside the positioning frame, a piston rod slidingly connected to the inside of the extrusion barrel, a return spring sleeved on the outer wall of the piston rod, a first one-way valve installed on the inner bottom of the extrusion barrel, a second one-way valve installed on the side of the extrusion barrel and on one side of the first one-way valve, a connecting pipe installed on the air outlet end of the second one-way valve, two bottom plates installed on the inner bottom of the storage barrel by bolts, annular tubes installed inside the two bottom plates, four air outlet pipes installed on the outer wall of the annular tube, and a lifting plate installed on the top of the lifting rod by bolts.

[0017] Preferably, the upper surface of the lifting plate and the upper surface of the piston rod are in contact with each other, the first one-way valve is unidirectional from outside to inside, and the second one-way valve is unidirectional from inside to outside.

[0018] Preferably, the air outlet end of the connecting pipe passes through the interior of the top plate and the bottom plate and is sealed with the annular tube, and the upper and lower ends of the return spring are in contact with the piston rod and the extrusion cylinder.

[0019] A method for preparing a highly selective tantalum-niobium extractant comprises the following steps:

[0020] S1: Synthesis of diquaternary ammonium salt intermediates

[0021] N,N'-dimethylpiperazine is reacted with a brominated long-chain alkane (such as 1-bromododecane) in ethanol under reflux for 12 hours to generate a diquaternary ammonium bromide.

[0022] The bromide ion is replaced with a nitrate ion by an ion exchange resin (such as D201 type strong basic anion resin) to obtain a diquaternary ammonium salt nitrate intermediate.

[0023] CH3-N(CH2CH2N + CH3)2+2C 12 H 25 Br 乙醇,回流 →

[0024] [C 12 H 25 N + CH2CH2N + C 12 H 25 ]·2Br+C3H8

[0025] Conditions: ethanol solvent, reflux for 12 hours.

[0026] S2: Phosphonate functionalization

[0027] The intermediate reacts with triethyl phosphite in tetrahydrofuran, the temperature is controlled at 60-80° C., and a catalyst (such as aluminum chloride) is added to generate a phosphonated diquaternary ammonium salt precursor.

[0028] A long-chain fatty alcohol (such as n-octanol) is added to carry out an ester exchange reaction, and the pH is adjusted to neutral to generate a crude target extractant.

[0029] [R1N + CH2CH2N + R2]·2NO 3- +2PO(OEt)2→

[0030] AlCl3,60-80℃ [R1N + CH2CH2N + R2]·2NO 3- ·(PO(OEt)2)2

[0031] Conditions: tetrahydrofuran (THF) solvent, aluminum chloride catalyst.

[0032] S3: Introduction of long-chain fatty alcohols by transesterification

[0033] The phosphonated diquaternary ammonium salt precursor is mixed with excess n-octanol, the catalyst PTSA is added, heated to 80-100 ° C, stirred for 2-3 hours, and the generated short-chain alcohol (such as ethanol) is removed by distillation. After the reaction is completed, it is cooled to room temperature, and the organic phase is washed with saturated sodium bicarbonate solution to remove the residual catalyst, and then the unreacted n-octanol is removed by reduced pressure distillation.

[0034] [R1N + CH2CH2N + R2]·2NO 3- (PO(OEt)2)2+2C8H 17 OH→

[0035] p H=7[R1N + CH2CH2N + R2]·2NO 3- ·(PO(OC8H 17 )2)2+2EtOH

[0036] Conditions: neutral pH, excess fatty alcohol, catalyst PTSA, temperature 80-100°C.

[0037] S4: Synthesis of diester-based quaternary ammonium salt surfactants

[0038] Synthesis of intermediate (Ⅰ)

[0039] Nylon acid (HOOC-(CH2) n-COOH) + epichlorohydrin (acidic cationic resin, 130℃) → dibasic acid ester intermediate (Cl-OOC-(CH2) n -COO-Cl)

[0040] Conditions: Epichlorohydrin as solvent, reaction time 12 hours

[0041] Adipic acid and excess epichlorohydrin (molar ratio 1:3) were added to a reactor, followed by the addition of an acidic cation exchange resin (catalyst, 5% of the total mass), heated to 130-140°C, stirred for reaction for 12 hours, and finally filtered to remove the catalyst. Unreacted epichlorohydrin was recovered by vacuum distillation to obtain a white solid intermediate (I).

[0042] Synthesis of final product (II)

[0043] Dibasic acid ester intermediate + 2C12H25N(CH3)2 →

[0044] Na2CO3, acetone diester quaternary ammonium salt surfactant + 2HCl

[0045] Conditions: Acetone solvent, reflux for 5 hours

[0046] Dissolve intermediate (I) in acetone, add an excess of a long-chain alkyl tertiary amine (molar ratio of 1:2.2), and add sodium carbonate (molar ratio twice that of the intermediate) to neutralize the generated HCl. Heat to 60-70°C and stir for 5 hours. Remove the generated NaCl by filtration, and remove the acetone by vacuum distillation. The crude product is recrystallized from n-hexane to obtain the final diester quaternary ammonium salt surfactant (II).

[0047] S5: Synthesis of tertiary amine extractants

[0048] Diester-based quaternary ammonium salt surfactants are produced through the esterification reaction of a dibasic acid with epichlorohydrin to form an intermediate, which is then quaternized with a long-chain alkyl tertiary amine. The diester structure of these surfactants enhances their hydrophobicity and interfacial activity.

[0049] C8H 17 Br+α-methylbenzylamine KOH,乙醇 C8H 17 N(CH2C6H5)CH3+KBr

[0050] Conditions: base catalysis, heating under reflux

[0051] α-Methylbenzylamine and 1-bromooctane (molar ratio 1:1.2) were added to a three-necked flask. Ethanol was added as the solvent, and KOH (molar ratio 1.5 times that of the alkyl bromide) was added. Heat to ethanol reflux (80-90°C) and stir to react for 8-10 hours. After the reaction, cool to room temperature and filter to remove the KBr precipitate. Ethanol was removed by vacuum distillation, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10:1). The target fraction was collected to obtain a colorless liquid tertiary amine extractant.

[0052] S6: Purification and modification

[0053] The unreacted fatty alcohol and by-products were removed by silica gel column chromatography, and the target component was collected.

[0054] The specific steps are as follows: dissolving the crude reaction product in a small amount of dichloromethane, separating the target product by silica gel column chromatography, using dichloromethane and methanol as eluents, collecting the target component, and removing the solvent by reduced pressure distillation.

[0055] Antioxidants (such as 2,6-di-tert-butyl-p-cresol) are added to improve the chemical stability of the extractant.

[0056] The specific operation steps are to add 0.1%-0.5% antioxidant (such as BHT) to the purified extractant and stir until it is completely dissolved to ensure the chemical stability of the extractant.

[0057] Compared with related technologies, the tantalum-niobium extraction device and the method for preparing the highly selective tantalum-niobium extractant provided by the present invention have the following beneficial effects:

[0058] Through the design of internal and external storage barrels and extraction barrels, recycled metal parts (waste metal parts, electronic products and all other waste recycling materials containing tantalum and niobium) are placed in the storage barrel, and the extraction solvent is stored in the extraction barrel. The raw materials and solvent are mixed by the reciprocating lifting storage barrel, and when the storage barrel is in the process of lifting, a flip plate can be linked to control the four linkage plates to perform clockwise and counterclockwise reciprocating flipping movements, so that the solvent in the extraction barrel can be stirred during the flipping process to ensure sufficient mixing and contact between the solvent and the raw materials. Secondly, the linkage plate can realize the formation of a flip vortex along the inner wall of the through hole by flipping the through hole during the flipping process. Therefore, this design realizes efficient mixing and sufficient extraction. At the same time, it can extract in different areas to ensure that the raw materials and extracts can be distinguished separately. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] 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.

[0060] Figure 1 The best structural diagram provided by the present invention;

[0061] Figure 2 A bottom-up structural diagram of the present invention;

[0062] Figure 3 for Figure 1 The schematic diagram of the cross-sectional structure of the extraction barrel shown;

[0063] Figure 4 for Figure 3 The schematic diagram of the extraction mechanism and scraping mechanism shown;

[0064] Figure 5 for Figure 4 The schematic diagram of the structure viewed from above is shown;

[0065] Figure 6 This is a schematic diagram of the bottom structure of the auxiliary mechanism and the gas-increasing mechanism after the extraction barrel provided by the present invention is cut away;

[0066] Figure 7 A schematic cross-sectional view of the first positioning seat and sleeve provided by the present invention;

[0067] Figure 8 Schematic diagram of the initial extraction process of the storage bucket provided by the present invention, wherein (a) is a schematic diagram showing the bottom of the storage bucket and the upper surface of the flap fitting together in the working state, and (b) is a stereoscopic diagram of the initial state of the auxiliary mechanism;

[0068] Figure 9 for Figure 8 The schematic diagram of the storage barrel extraction operation is shown, wherein (c) is a schematic diagram of the control flap linkage control linkage plate flipping working state when the storage barrel is reciprocatingly raised and lowered, wherein (d) is a three-dimensional diagram of the auxiliary mechanism linkage flipping;

[0069] Figure 10 for Figure 9 The enlarged structural diagram of point A is shown;

[0070] Figure 11 for Figure 9 The lifting rod shown drives the storage barrel to extract the work diagram;

[0071] Figure 12 for Figure 11The schematic diagram of the storage barrel rising after the extraction is completed is shown;

[0072] Figure 13 for Figure 12 The schematic diagram of the storage barrel rising to the material taking state after the extraction is completed is shown;

[0073] Figure 14 A schematic diagram of the detailed structure of the scraping mechanism provided by the present invention;

[0074] Figure 15 A schematic diagram of the working state of the air-increasing mechanism provided by the present invention;

[0075] Figure 16 for Figure 15 Schematic diagram of the split ring tube and base plate shown.

[0076] Description of Figure Numbers:

[0077] 1. Base, 2. Heating base, 3. Extraction barrel;

[0078] 4. Extraction mechanism, 41. Storage barrel, 42. Top frame, 43. Middle plate, 44. Rotating seat, 45. Flange seat, 46. Mounting seat, 47. Guide wheel;

[0079] 5. Auxiliary mechanism, 51. Flip plate, 52. Linkage plate, 53. First positioning seat, 54. Connecting groove; 55. Second positioning seat, 56. Sleeve, 57. Rotating shaft, 58. Torsion spring, 59. Through hole, 510. Connecting wheel,

[0080] 6. Scraping mechanism, 61. Positioning plate, 62. Connecting plate, 63. Scraping ring;

[0081] 7. Air inflator, 71. Positioning frame, 72. Extrusion barrel, 73. Bottom plate, 74. Ring pipe, 75. Air outlet pipe, 76. Piston rod, 77. Return spring, 78. First one-way valve, 79. Second one-way valve, 710. Connecting pipe;

[0082] 8. Top plate, 9. Cylinder, 10. Lifting rod, 11. Sealing plate, 12. Lifting plate, 13. Discharge pipe, 14. Corrugated plate.

[0083] 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

[0084] 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.

[0085] The present invention provides a tantalum-niobium extraction device and a method for preparing a high-selectivity tantalum-niobium extractant.

[0086] First embodiment:

[0087] See also Figures 1 to 10 , a tantalum-niobium extraction device, comprising a base 1, an extraction mechanism 4 and an auxiliary mechanism 5;

[0088] A heating seat 2 is installed above the base 1, an extraction barrel 3 is installed inside the heating seat 2, a top plate 8 is installed on the top of the extraction barrel 3 by bolts, a cylinder 9 is installed on the top of the top plate 8 by bolts, and a lifting rod 10 that can be lifted vertically is installed inside the cylinder 9;

[0089] The extraction mechanism 4 includes a storage bucket 41. A top frame 42 is fixed to the top of the storage bucket 41 via bolts. A middle plate 43 is fixed to the inner wall of the top frame 42. A rotating seat 44 is fixed to the middle position of the top of the middle plate 43 via bolts. A flange seat 45 is fixed to the bottom end of the lifting rod 10 via bolts. A mounting seat 46 is fixed to the side wall of the top frame 42. A guide wheel 47 is rotatably connected to the inner portion of the mounting seat 46.

[0090] See also Figures 2 to 4 : When working, the cylinder 9 is started to drive the lifting rod 10 to move up and down. Since the lifting rod 10 is installed inside the cylinder 9 in a through-type manner, the upper and lower ends of the lifting rod 10 can move up and down in a linked manner;

[0091] Before extraction, the user can raise the storage bucket 41 to the upper end of the extraction bucket 3 by raising the lifting rod 10. Then, it is necessary to place recycled metal parts (waste metal parts, electronic products, and all other waste recycling materials containing tantalum and niobium) inside the storage bucket 41 on both sides of the top plate 8 and then lower the storage bucket 41 to the inside of the extraction bucket 3. After that, the extraction agent and solvent are added to the inside of the extraction bucket 3 for wet extraction.

[0092] The auxiliary mechanism 5 includes a flap 51, the interior of which is provided with a through connecting groove 54, two first positioning seats 53 are installed on the inner bottom of the extraction barrel 3, and sleeves 56 are fixedly provided inside the two first positioning seats 53, and rotating shafts 57 are fixedly provided on both sides of the flap 51. Torsion springs 58 are sleeved on the interiors of the two sleeves 56 and on the outer walls of the two rotating shafts 57, and second positioning seats 55 are installed on the inner bottom of the extraction barrel 3 and on both sides of the flap 51, and a linkage plate 52 is rotatably connected to the interior of the second positioning seat 55, a through hole 59 is opened inside the linkage plate 52, and a connecting wheel 510 is rotatably connected to the side wall of the linkage plate 52.

[0093] See also Figure 4 and Figure 5 : The storage barrel 41 needs to be lowered into the extraction barrel 3, and the bottom surface of the storage barrel 41 needs to be in contact with the upper surface of the flap 51. During the extraction process, the storage barrel 41 needs to be controlled to move back and forth up and down in the extraction barrel 3 to ensure that the solvent can be fully mixed with the raw materials in the storage barrel 41.

[0094] See also Figure 8 (a) and (b): In the initial state, the upper surfaces of the storage bucket 41 and the flap 51 are in contact with each other, and the flap 51 and the linkage plate 52 are in the initial flip state.

[0095] See also Figure 9 (c) and (d) in it: When the storage barrel 41 is in the process of reciprocating lifting, the bottom surface of the storage barrel 41 will resist the flip plate 51 and rotate clockwise along the first positioning seat 53. When the flip plate 51 moves, it can drive the internal connecting groove 54 to flip in a linked manner to control the sliding of the internal connecting wheel 510 to affect the corresponding linkage plate 52 to flip counterclockwise along the second positioning seat 55. When the storage barrel 41 is reciprocated and reset upward, the flip plate 51 will drive the linkage plate 52 to reset to the initial state. The reciprocating flipping movement of the flip plate 51 and the linkage plate 52 is achieved through the linkage of the reciprocating lifting storage barrel 41, so that the raw materials are fully mixed with the solvent, thereby achieving efficient extraction.

[0096] The two rotating shafts 57 are rotatably connected to the axes of the two sleeves 56 through bearings. The two sides of the torsion spring 58 respectively contact the inner wall of the sleeve 56 and the rotating shaft 57. The connecting wheel 510 is slidably connected to the connecting groove 54.

[0097] The flange seat 45 and the rotating seat 44 are rotatably connected, and the bottom surface of the storage bucket 41 and the upper surface of the flap 51 are in contact with each other.

[0098] Understandable: Combined Figure 7It can be seen that through the setting of the torsion spring 58, when the flap 51 flips on the first positioning seat 53, the flap 51 will drive the rotating shaft 57 to rotate in the sleeve 56. When the rotating shaft 57 rotates, it will control the torsion spring 58 to be subjected to force and twist. When the flap 51 loses the force, the torsion spring 58 will drive the flap 51 to return to the state before flipping when it is reset, so that automatic flipping and reset can be achieved.

[0099] In this embodiment: through the design of the inner and outer storage barrels 41 and the extraction barrel 3, the recycled metal parts (waste metal parts, electronic products, and all other waste recycling materials containing tantalum and niobium) are placed in the storage barrel 41, and the extraction solvent is stored in the extraction barrel 3. The raw materials and the solvent are mixed by the reciprocating lifting storage barrel 41, and when the storage barrel 41 is in the process of lifting, a flip plate 51 can be linked to control the four linkage plates 52 to perform clockwise and counterclockwise reciprocating flipping movements, so that the solvent in the extraction barrel 3 can be stirred during the flipping process to ensure that the solvent and the raw materials are fully mixed and contacted. Secondly, the linkage plate 52 can realize the formation of a flip vortex along the inner wall of the through hole 59 by flipping the through hole 59 during the flipping process. Therefore, this design realizes efficient mixing and sufficient extraction, and can also perform partitioned extraction to ensure that the raw materials and the extract can be distinguished separately.

[0100] Second embodiment:

[0101] See also Figures 11 to 14 , further comprising a scraper mechanism 6, the scraper mechanism 6 comprising positioning plates 61 mounted on both sides of the lifting rod 10 and located above the flange seat 45, a scraper ring 63 is mounted on the inner bottom of the storage bucket 41, and connecting plates 62 are fixed on both sides of the inner wall of the scraper ring 63;

[0102] The two positioning plates 61 are slidably connected to the two connecting plates 62 via a “T”-shaped block.

[0103] See also Figure 11 and Figure 14 : During the operation of the first embodiment, when the lifting rod 10 drives the storage bucket 41 to lift and lower back and forth, the positioning plates 61 on both sides of the lifting rod 10 will also move with the movement of the lifting rod 10. When descending, the positioning plates 61 are controlled to slide inside the connecting plate 62. At this time, the scraper ring 63 is located at the bottom end of the extraction barrel 3. Therefore, during the operation of the first embodiment, the up and down movement of the storage bucket 41 will not affect the scraper ring 63. The sliding connection between the positioning plates 61 and the connecting plates 62 can eliminate the interference of the lifting rod 10 on the scraper ring 63.

[0104] A corrugated plate 14 is fixedly provided on the inner wall of the storage barrel 41 and located in the vertical direction of the guide wheel 47. A discharge pipe 13 is installed at the internal axis of the storage barrel 41. Sealing plates 11 are rotatably installed above the storage barrel 41 and on both sides of the top plate 8. The upper and lower sides of the corrugated plate 14 are both inclined structures.

[0105] See also Figure 12 When the extraction process is completed, the user needs to control the storage bucket 41 to rise by using the lifting rod 10. During the rising process, the guide wheel 47 will follow the storage bucket 41 along the bottom slope of the corrugated plate 14 and enter the interior of the corrugated plate 14. As the storage bucket 41 continues to rise, the guide wheel 47 will follow the trajectory of the corrugated plate 14 to control the top frame 42 and the storage bucket 41 to rotate along the rotating seat 44 and the flange seat 45 to form polarization, thereby vibrating the raw materials in the storage bucket 41.

[0106] When the lifting rod 10 is rising, the positioning plate 61 is controlled to drive the connecting plate 62 to control the scraper ring 63 to rise. When the scraper ring 63 rises, the extract stuck on the inner wall of the extraction barrel 3 can be scraped out into the interior of the extraction barrel 3.

[0107] See also Figure 13 : As the storage barrel 41 continues to rise, the guide wheel 47 and the corrugated plate 14 are finally separated, and the storage barrel 41 is reset to a vertical state. Finally, the storage barrel 41 rises to the top of the extraction barrel 3. The user can use a robotic arm to take out the extraction raw materials inside the storage barrel 41. After taking them out, new recycled raw materials can be added for subsequent extraction.

[0108] Understandable: Combined Figure 14 It can be seen that the connecting plate 62 does not adopt a through-slot design, so the stability of the scraper ring 63 can be guaranteed when the lifting rod 10 is raised or lowered, and the scraper ring 63 can be driven to rise when the lifting rod 10 rises.

[0109] In this embodiment, after the extraction is completed, the storage barrel 41 can be driven to rise during the process of switching from the extraction working state to the initial working state. During the rising process of the storage barrel 41, the guide wheel 47 can enter the corrugated plate 14 and control the storage barrel 41 to flip and vibrate along the trajectory of the corrugated plate 14. In this way, the extract remaining on the raw material inside the storage barrel 41 can be vibrated into the interior of the extraction barrel 3 by flipping and vibrating, thereby ensuring a cleaner and more thorough extraction. Secondly, during the rising process of the storage barrel 41, the scraper ring 63 can be synchronously driven to rise to scrape off the extract stuck on the inner wall of the extraction barrel 3.

[0110] Secondly, when the raw materials inside the storage barrel 41 are placed, and thus move from the top of the extraction barrel 3 to the bottom, the guide wheel 47 will also vibrate the storage barrel 41 through the corrugated plate 14, so that the raw materials inside can be vibrated to ensure uniform distribution and facilitate extraction.

[0111] Third embodiment:

[0112] See also Figure 3 、 Figure 6 、 Figures 15 and 16 , also includes an air-increasing mechanism 7, which includes a positioning frame 71 installed on one side of the cylinder 9, an extrusion cylinder 72 installed inside the positioning frame 71, a piston rod 76 slidably connected inside the extrusion cylinder 72, an outer wall of the piston rod 76 is sleeved with a return spring 77, a first one-way valve 78 is installed on the inner bottom of the extrusion cylinder 72, a second one-way valve 79 is installed on the side of the extrusion cylinder 72 and on one side of the first one-way valve 78, a connecting pipe 710 is installed on the air outlet end of the second one-way valve 79, two bottom plates 73 are installed on the inner bottom of the storage barrel 41 by bolts, an annular tube 74 is installed inside the two bottom plates 73, four air outlet pipes 75 are installed on the outer wall of the annular tube 74, and a lifting plate 12 is installed on the top of the lifting rod 10 by bolts.

[0113] See also Figure 6 and Figure 15 During operation of the first embodiment, the lifting rod 10 is lifted and lowered in a reciprocating manner. Therefore, when the lifting rod 10 descends, the lifting plate 12 is driven to descend. The descending lifting plate 12 can press the piston rod 76 downward in the extrusion cylinder 72. During the downward pressing process, the gas inside the extrusion cylinder 72 can be squeezed through the second one-way valve 79 and then enter the annular pipe 74 through the connecting pipe 710. Thereafter, the gas is generated through the four outlet pipes 75 and impacts the bottom of the storage barrel 41 from bottom to top.

[0114] When the lifting rod 10 rises and resets, the reset spring 77 acts to push the piston rod 76 to reset. During the reset process, the external gas is sucked into the extrusion cylinder 72 through the first one-way valve 78. Therefore, as the piston rod 76 rises and falls, the gas in the extraction barrel 3 can be continuously increased.

[0115] The upper surface of the lifting plate 12 is in contact with the upper surface of the piston rod 76 . The first one-way valve 78 is unidirectional from outside to inside, and the second one-way valve 79 is unidirectional from inside to outside.

[0116] The air outlet end of the connecting tube 710 passes through the interior of the top plate 8 and the bottom plate 73 and is sealed with the annular tube 74 . The upper and lower ends of the return spring 77 are in contact with the piston rod 76 and the extrusion cylinder 72 .

[0117] Understandable: From Figure 16It can be seen that the bottom plate 73 is installed on the ring tube 74 in a sandwich manner, and secondly, the bottom plate 73 can be installed on the inner bottom of the extraction barrel 3 by bolts, so that the ring tube 74 can be stably installed on the extraction barrel 3.

[0118] Compared with the traditional design, this embodiment is designed with an air-increasing mechanism 7. When the lifting rod 10 is lifted and lowered in a reciprocating manner, it can drive the piston rod 76 to lift and lower the extrusion barrel 72, so that the gas in the extrusion barrel 72 can be squeezed into the connecting pipe 710, and then the gas in the extraction barrel 3 is increased through the ring pipe 74 and the outlet pipe 75.

[0119] During the gasification process, the flow rate of the solvent in the extraction barrel 3 can be changed. Compared with the traditional stirring method, it works stably and saves production costs, ensuring sufficient extraction and mixing. Secondly, by increasing the gas content in the solvent, the molecular gap between the solvent and the raw material can be changed, thereby ensuring that the extraction solvent can be fully utilized and achieving efficient extraction.

[0120] Fourth embodiment:

[0121] A method for preparing a highly selective tantalum-niobium extractant

[0122] S1: Synthesis of diquaternary ammonium salt intermediates

[0123] N,N'-dimethylpiperazine is reacted with a brominated long-chain alkane (such as 1-bromododecane) in ethanol under reflux for 12 hours to generate a diquaternary ammonium bromide.

[0124] The bromide ion is replaced with a nitrate ion by an ion exchange resin (such as D201 type strong basic anion resin) to obtain a diquaternary ammonium salt nitrate intermediate.

[0125] CH3-N(CH2CH2N + CH3)2+2C 12 H 25 Br 乙醇,回流 →

[0126] [C 12 H 25 N + CH2CH2N + C 12 H 25 ]·2Br+C3H8

[0127] Conditions: ethanol solvent, reflux for 12 hours.

[0128] S2: Phosphonate functionalization

[0129] The intermediate reacts with triethyl phosphite in tetrahydrofuran, the temperature is controlled at 60-80° C., and a catalyst (such as aluminum chloride) is added to generate a phosphonated diquaternary ammonium salt precursor.

[0130] A long-chain fatty alcohol (such as n-octanol) is added to carry out an ester exchange reaction, and the pH is adjusted to neutral to generate a crude target extractant.

[0131] [R1N + CH2CH2N + R2]·2NO 3- +2PO(OEt)2→

[0132] AlCl3,60-80℃ [R1N + CH2CH2N + R2]·2NO 3- ·(PO(OEt)2)2

[0133] Conditions: tetrahydrofuran (THF) solvent, aluminum chloride catalyst.

[0134] S3: Introduction of long-chain fatty alcohols by transesterification

[0135] The phosphonated diquaternary ammonium salt precursor is mixed with excess n-octanol, the catalyst PTSA is added, heated to 80-100 ° C, stirred for 2-3 hours, and the generated short-chain alcohol (such as ethanol) is removed by distillation. After the reaction is completed, it is cooled to room temperature, and the organic phase is washed with saturated sodium bicarbonate solution to remove the residual catalyst, and then the unreacted n-octanol is removed by reduced pressure distillation.

[0136] [R1N + CH2CH2N + R2]·2NO 3- (PO(OEt)2)2+2C8H 17 OH→

[0137] pH＝7 [R1N + CH2CH2N + R2]·2NO 3- ·(PO(OC8H 17 )2)2+2EtOH

[0138] Conditions: neutral pH, excess fatty alcohol, catalyst PTSA, temperature 80-100°C.

[0139] S4: Synthesis of diester-based quaternary ammonium salt surfactants

[0140] Synthesis of intermediate (Ⅰ)

[0141] Nylon acid (HOOC-(CH2) n -COOH) + epichlorohydrin (acidic cationic resin, 130℃) → dibasic acid ester intermediate (Cl-OOC-(CH2) n -COO-Cl)

[0142] Conditions: Epichlorohydrin as solvent, reaction time 12 hours

[0143] Adipic acid and excess epichlorohydrin (molar ratio 1:3) were added to a reactor, followed by the addition of an acidic cation exchange resin (catalyst, 5% of the total mass), heated to 130-140°C, stirred for reaction for 12 hours, and finally filtered to remove the catalyst. Unreacted epichlorohydrin was recovered by vacuum distillation to obtain a white solid intermediate (I).

[0144] Synthesis of final product (II)

[0145] Dibasic acid ester intermediate + 2C12H25N(CH3) → Na2CO3, acetone diester quaternary ammonium salt surfactant + 2HCl

[0146] Conditions: Acetone solvent, reflux for 5 hours

[0147] Dissolve intermediate (I) in acetone, add an excess of a long-chain alkyl tertiary amine (molar ratio of 1:2.2), and add sodium carbonate (molar ratio twice that of the intermediate) to neutralize the generated HCl. Heat to 60-70°C and stir for 5 hours. Remove the generated NaCl by filtration, and remove the acetone by vacuum distillation. The crude product is recrystallized from n-hexane to obtain the final diester quaternary ammonium salt surfactant (II).

[0148] S5: Synthesis of tertiary amine extractants

[0149] Diester-based quaternary ammonium salt surfactants are produced through the esterification reaction of a dibasic acid with epichlorohydrin to form an intermediate, which is then quaternized with a long-chain alkyl tertiary amine. The diester structure of these surfactants enhances their hydrophobicity and interfacial activity.

[0150] C8H 17 Br+α-methylbenzylamine KOH,乙醇 C8H 17 N(CH2C6H5)CH3+KBr

[0151] Conditions: base catalysis, heating under reflux

[0152] α-Methylbenzylamine and 1-bromooctane (molar ratio 1:1.2) were added to a three-necked flask. Ethanol was added as the solvent, and KOH (molar ratio 1.5 times that of the alkyl bromide) was added. Heat to ethanol reflux (80-90°C) and stir to react for 8-10 hours. After the reaction, cool to room temperature and filter to remove the KBr precipitate. Ethanol was removed by vacuum distillation, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10:1). The target fraction was collected to obtain a colorless liquid tertiary amine extractant.

[0153] S6: Purification and modification

[0154] The unreacted fatty alcohol and by-products were removed by silica gel column chromatography, and the target component was collected.

[0155] The specific steps are as follows: dissolving the crude reaction product in a small amount of dichloromethane, separating the target product by silica gel column chromatography, using dichloromethane and methanol as eluents, collecting the target component, and removing the solvent by reduced pressure distillation.

[0156] Antioxidants (such as 2,6-di-tert-butyl-p-cresol) are added to improve the chemical stability of the extractant.

[0157] The specific operation steps are to add 0.1%-0.5% antioxidant (such as BHT) to the purified extractant and stir until it is completely dissolved to ensure the chemical stability of the extractant.

[0158] This embodiment: This highly selective tantalum-niobium extractant is mainly used for recycling waste metal parts. Traditional tantalum-niobium separation processes mostly use solvent extraction, but existing extractants (such as MIBK, TBP, etc.) have problems such as low selectivity, easy emulsification, and the need for a high acidity environment. In recent years, diquaternary ammonium salt extractants have attracted attention due to their high coordination ability, but their separation efficiency for tantalum-niobium still needs to be improved. In addition, the extractants in traditional processes are easily oxidized and ineffective, and the co-extraction phenomenon of impurity metals (such as iron and titanium) is significant, resulting in high subsequent purification costs;

[0159] Core skeleton: diquaternary ammonium salt structure (such as N,N'-dimethylpiperazine diquaternary ammonium salt), linked by straight chain or cyclic aliphatic chain segments (C8-C12), to enhance the miscibility with organic solvents.

[0160] Functional groups: Phosphonate groups (—PO(OR3)2) are introduced at both ends of the quaternary ammonium salt to enhance the complexing ability for high-valent metal ions; long-chain fatty alcohols (such as n-octanol and isodecyl alcohol) are modified on the side chain to inhibit the co-extraction of impurity metals through steric hindrance effects.

[0161] Molecular formula example:

[0162] [R1N+CH2CH2N + R2]·2X - ·(PO(OR3)2)2

[0163]

[0164] Wherein R1 and R2 are methyl or ethyl, and R3 is C8-C12 alkyl.

[0165] Please refer to the Figures 1 to 16 The working principle of the tantalum-niobium extraction device provided by the present invention is as follows:

[0166] Step S1: Before extraction, the user can raise the storage bucket 41 to the top of the extraction bucket 3 by raising the lifting rod 10. Recycled metal parts (such as scrap metal parts, electronic products, and other waste containing tantalum and niobium) are then placed inside the storage bucket 41 on both sides of the top plate 8. The storage bucket 41 is then lowered into the extraction bucket 3.

[0167] In step S2, when the storage barrel 41 is in the process of reciprocating lifting, the bottom surface of the storage barrel 41 will resist the flip plate 51 and rotate clockwise along the first positioning seat 53. When the flip plate 51 moves, it can drive the internal connecting groove 54 to rotate in a linked manner to control the sliding of the internal connecting wheel 510, affecting the corresponding linkage plate 52 to rotate counterclockwise along the second positioning seat 55. When the storage barrel 41 is reciprocated and reset upward, the flip plate 51 will drive the linkage plate 52 to reset to the initial state. The reciprocating lifting storage barrel 41 is linked to realize the reciprocating rotation of the flip plate 51 and the linkage plate 52, so that the raw material and the solvent are fully mixed, and efficient extraction is achieved;

[0168] Step S3, when the extraction work is completed, the user needs to control the storage barrel 41 to rise through the lifting rod 10. During the rising process, the guide wheel 47 will follow the storage barrel 41 along the bottom slope of the corrugated plate 14 and enter the interior of the corrugated plate 14. As the storage barrel 41 continues to rise, the guide wheel 47 will follow the trajectory of the corrugated plate 14 to control the top frame 42 and the storage barrel 41 to rotate along the rotating seat 44 along the flange seat 45 to form polarization, thereby vibrating the raw materials in the storage barrel 41. Finally, the user needs to open the discharge pipe 13 to discharge all the extracts.

[0169] 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 tantalum-niobium extraction device, characterized in that: It includes a base, an extraction mechanism and an auxiliary mechanism; A heating seat is installed above the base, an extraction barrel is installed inside the heating seat, a top plate is installed on the top of the extraction barrel by bolts, a cylinder is installed on the top of the top plate by bolts, and a lifting rod that can be lifted vertically is installed inside the cylinder; The extraction mechanism includes a storage barrel, a top frame is fixed to the top of the storage barrel by bolts, a middle plate is fixed to the inner wall of the top frame, a rotating seat is fixed to the middle position of the top of the middle plate by bolts, a flange seat is fixed to the bottom end of the lifting rod by bolts, a mounting seat is fixed to the side wall of the top frame, and a guide wheel is rotatably connected to the inside of the mounting seat; The auxiliary mechanism includes a flap, a through-connecting groove is provided in the interior of the flap, two first positioning seats are installed on the inner bottom of the extraction barrel, sleeves are fixed in the interiors of the two first positioning seats, rotating shafts are fixed on both sides of the flap, torsion springs are sleeved on the interiors of the two sleeves and on the outer walls of the two rotating shafts, second positioning seats are installed on the inner bottom of the extraction barrel and on both sides of the flap, a linkage plate is rotatably connected to the interior of the second positioning seat, a through hole is provided in the interior of the linkage plate, and a connecting wheel is rotatably connected to the side wall of the linkage plate; The air-increasing mechanism further includes a positioning frame installed on one side of the cylinder, an extrusion barrel installed inside the positioning frame, a piston rod slidably connected to the inside of the extrusion barrel, a return spring sleeved on the outer wall of the piston rod, a first one-way valve installed on the inner bottom of the extrusion barrel, a second one-way valve installed on the side of the extrusion barrel and on one side of the first one-way valve, a connecting pipe installed on the air outlet end of the second one-way valve, two bottom plates installed on the inner bottom of the storage barrel by bolts, annular tubes installed inside the two bottom plates, four air outlet pipes installed on the outer wall of the annular tube, and a lifting plate installed on the top of the lifting rod by bolts.

2. The tantalum-niobium extraction device according to claim 1, characterized in that: The two rotating shafts are rotatably connected to the axes of the two sleeves through bearings. The two sides of the torsion spring respectively contact the inner wall of the sleeve and the rotating shaft. The connecting wheel is slidably connected to the connecting groove.

3. The tantalum-niobium extraction device according to claim 1, characterized in that: The flange seat and the rotating seat are rotatably connected, and the bottom surface of the storage bucket and the upper surface of the flap are in contact with each other.

4. The tantalum-niobium extraction device according to claim 1, characterized in that: It also includes a scraping mechanism, which includes positioning plates installed on both sides of the lifting rod and located above the flange seat. A scraping ring is installed on the inner bottom of the storage bucket, and connecting plates are fixed on both sides of the inner wall of the scraping ring. The two positioning plates are slidably connected to the two connecting plates through "T"-shaped blocks.

5. The tantalum-niobium extraction device according to claim 1, characterized in that: A corrugated plate is fixed on the inner wall of the storage barrel and located in the vertical direction of the guide wheel. A discharge pipe is installed at the internal axis of the storage barrel. Sealing plates are rotatably installed above the storage barrel and on both sides of the top plate. The upper and lower sides of the corrugated plate are both inclined structures.

6. The tantalum-niobium extraction device according to claim 1, characterized in that: The upper surface of the lifting plate and the upper surface of the piston rod are in contact with each other, the first one-way valve is unidirectional from outside to inside, and the second one-way valve is unidirectional from inside to outside.

7. The tantalum-niobium extraction device according to claim 1, characterized in that: The air outlet end of the connecting pipe passes through the interior of the top plate and the bottom plate and is sealed with the ring pipe. The upper and lower ends of the return spring are in contact with the piston rod and the extrusion cylinder.

8. A method for preparing a highly selective tantalum-niobium extractant, characterized in that: The method for preparing a highly selective tantalum-niobium extractant is used in the tantalum-niobium extraction device according to any one of claims 1 to 7, comprising the following steps: S1: Synthesis of diquaternary ammonium salt intermediates; N,N'-dimethylpiperazine and brominated long-chain alkane were refluxed in ethanol for 12 hours to generate diquaternary ammonium bromide; The bromide ion is replaced by nitrate by ion exchange resin to obtain a diquaternary ammonium nitrate intermediate; CH3−N(CH2CH2N+CH3)2+2C 12 H 25 Br ethanol, reflux → [C 12 H 25 N+CH2CH2N+C 12 H 25 ]·2Br+ C3H8 Conditions: ethanol solvent, reflux for 12 hours; S2: phosphonate functionalization; The intermediate is reacted with triethyl phosphite in tetrahydrofuran, the temperature is controlled at 60-80°C, and a catalyst is added to generate a phosphonated diquaternary ammonium salt precursor; Adding long-chain fatty alcohol to carry out transesterification reaction, adjusting the pH to neutral, and generating the target extractant crude product; [R1N+CH2CH2N+R2]·2NO3−+2PO(OEt)2→ <h2 style=";text-align:left;direction:ltr">AlCl3,60−80℃[R1N+CH2CH2N+R2]·2NO3−·(PO(OE<h2 style=";text-align:left;direction:ltr"> t <h2 style=";text-align:left;direction:ltr"> )2)2 Conditions: tetrahydrofuran solvent, aluminum chloride catalyst; S3: transesterification reaction introduces long-chain fatty alcohols; The phosphonated diquaternary ammonium salt precursor is mixed with excess n-octanol, the catalyst PTSA is added, and the mixture is heated to 80-100°C and stirred for 2-3 hours. The generated short-chain alcohol is removed by distillation. After the mixture is cooled to room temperature, the organic phase is washed with saturated sodium bicarbonate solution to remove the residual catalyst, and the unreacted n-octanol is removed by distillation under reduced pressure; [R1N+CH2CH2N+R2]·2NO3-·(PO(OEt)2)2+2C8H 17 OH→ pH=7[R1N+CH2CH2N+R2]·2NO3-·(PO(OC8H 17 )2)2+2EtOH Conditions: neutral pH, excess fatty alcohol, catalyst PTSA, temperature 80-100°C; S4: Synthesis of diester-based quaternary ammonium salt surfactants; Synthesis of intermediate Ⅰ; Nylon acid (HOOC-(CH2) n -COOH) + epichlorohydrin → dibasic acid ester intermediate (Cl-OOC-(CH2) n -COO-Cl) Conditions: epichlorohydrin as solvent, reaction time 12 hours; Adipic acid and excess epichlorohydrin were added to a reaction kettle, followed by addition of an acidic cation exchange resin. The mixture was heated to 130-140°C and stirred for 12 hours. The catalyst was finally removed by filtration and the unreacted epichlorohydrin was recovered by vacuum distillation to obtain a white solid intermediate I. Synthesis of final product II; Dibasic acid ester intermediate + 2C 12 H 25 N(CH3)2→ Na2CO3, acetone diester quaternary ammonium salt surfactant + 2HCl; Conditions: Acetone solvent, reflux for 5 hours; The intermediate I is dissolved in acetone, an excess of a long-chain alkyl tertiary amine is added, sodium carbonate is added to neutralize the generated HCl, the mixture is heated to 60-70°C, stirred and reacted for 5 hours, the generated NaCl is removed by filtration, the acetone is removed by vacuum distillation, and the crude product is recrystallized from n-hexane to obtain the final product, a diester quaternary ammonium salt surfactant II; S5: Synthesis of tertiary amine extractants; Diester-based quaternary ammonium salt surfactants are prepared by esterification of dibasic acid with epichlorohydrin to form an intermediate, which is then quaternized with long-chain alkyl tertiary amines. The surfactant has a diester structure, which enhances its hydrophobicity and interfacial activity. C8H 17 Br+α-methylbenzylamine KOH, ethanol C8H 17 N(CH2C6H5)CH3+KBr Conditions: base catalysis, heating under reflux; α-Methylbenzylamine and 1-bromooctane are added to a three-necked flask, ethanol is added as a solvent, and KOH is added. The mixture is heated at 80-90°C until the ethanol refluxes, and the mixture is stirred and reacted for 8-10 hours. After the reaction is completed, the mixture is cooled to room temperature, the KBr precipitate is removed by filtration, and the ethanol is removed by vacuum distillation. The crude product is purified by silica gel column chromatography, and the target component is collected to obtain a colorless liquid tertiary amine extractant. S6: purification and modification; The unreacted fatty alcohol and by-products were removed by silica gel column chromatography to collect the target component; The specific steps are as follows: dissolving the crude reaction product in a small amount of dichloromethane, separating the target product by silica gel column chromatography, using dichloromethane and methanol as eluents, collecting the target component, and removing the solvent by reduced pressure distillation; Adding antioxidants to improve the chemical stability of the extractant; The specific operation steps are to add 0.1%-0.5% antioxidant to the purified extractant and stir until it is completely dissolved to ensure the chemical stability of the extractant.

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