Method for recovering and extracting vanadium from high-chromium vanadium slag

Abstract

The invention provides a method for recovering and extracting vanadium from high-chromium vanadium slag, and relates to the technical field of extracting vanadium from solid waste. The invention discloses a method for recovering and extracting vanadium from high-chromium vanadium slag. The method comprises the following steps: step S1, mixing treatment; step S2, water immersion treatment; step S3, evaporative crystallization; step S4, carrying out leaching treatment; step S5, oscillating and mixing: merging the filtrates obtained by the three-stage countercurrent leaching in the step S4, adding the prepared organic phase, oscillating, standing and separating to obtain a loaded organic phase and raffinate; and step S6, reverse extraction treatment: further reverse extraction, pH adjustment and calcination are carried out on the loaded organic phase in the step S5, and V2O5 is obtained. Through three-section countercurrent leaching, the sulfuric acid can be utilized more effectively, the consumption of the sulfuric acid is reduced, the concentration of vanadium in the leachate is improved, and the content of impurities is reduced, that is, the countercurrent acid leaching process not only reduces the acid consumption by 50%, but also reduces the leaching rate of the impurities, and more favorable conditions are provided for subsequent vanadium separation.

Description

Technical Field

[0001] This invention relates to the field of vanadium extraction technology from solid waste, and more particularly to a method for recovering and extracting vanadium from high-chromium vanadium slag. Background Technology

[0002] High-chromium vanadium slag refers to vanadium slag with a chromium content greater than 5% by mass. It is an important metallurgical by-product produced in the blast furnace-converter smelting process of high-chromium vanadium-titanium magnetite, and is rich in both vanadium and chromium, two key metal resources.

[0003] Vanadium and chromium are important industrial resources, with approximately 88% of global vanadium production originating from vanadium slag. However, during the smelting process, due to the similar chemical properties of chromium and vanadium, chromium often accumulates in vanadium slag, especially in high-chromium vanadium slag, where the chromium content is significantly increased, posing a significant challenge to the recovery and separation of vanadium and chromium.

[0004] Traditional hydrometallurgy and pyrometallurgy suffer from problems such as high acid consumption, severe impurity interference, and high energy consumption, resulting in low vanadium extraction efficiency and low purity.

[0005] Therefore, it is necessary to provide a method for recovering and extracting vanadium from high-chromium vanadium slag to solve the above-mentioned technical problems. Summary of the Invention

[0006] This invention provides a method for recovering and extracting vanadium from high-chromium vanadium slag, which solves the problems of low extraction efficiency and low purity of vanadium in related technologies.

[0007] To solve the above-mentioned technical problems, the present invention provides a method for recovering and extracting vanadium from high-chromium vanadium slag, comprising the following steps:

[0008] Step S1, mixing process: high chromium vanadium slag, calcium oxide and sodium carbonate are mixed, roasted and ground to obtain a mixture.

[0009] Step S2, water immersion treatment: the mixture from step S1 is sequentially immersed in water and filtered to obtain a chromium-containing solution and a vanadium-containing slag.

[0010] Step S3, Evaporation and Crystallization: The chromium-containing solution in step S2 is evaporated, concentrated, and crystallized sequentially, then filtered, washed, and dried to obtain sodium chromate.

[0011] Step S4, Leaching Treatment:

[0012] First stage leaching: The vanadium-containing slag is mixed with the leaching solution from the second stage, and after the reaction, filtrate 1 and filter residue 1 are obtained;

[0013] Second stage leaching: Mix filter residue 1 with the leachate from the third stage, heat and stir, separate solid and liquid, and obtain filtrate 2 and filter residue 2 after the reaction;

[0014] Third stage leaching: Mix filter residue 2 with fresh sulfuric acid solution, heat and stir, separate solid and liquid, and obtain filtrate 3 and vanadium-free filter residue after reaction;

[0015] Step S5: Shake and mix, combine the filtrates obtained from the three countercurrent leaching stages in step S4, add the prepared organic phase, shake, let stand, and separate to obtain the loaded organic phase and raffinate.

[0016] Step S6, back-extraction treatment: the supported organic phase in step S5 is further back-extracted, the pH is adjusted, and calcined to obtain V2O5.

[0017] Preferably, in step S1, the calcination environment is calcination at 900°C for 90 minutes under air at a flow rate of 20 L / min.

[0018] Preferably, the grinding fineness is ground to a particle size of -74μm.

[0019] Preferably, the fresh sulfuric acid solution in step S4 is a sulfuric acid solution with a concentration of 0.3 g / g.

[0020] Preferably, the temperature during heating and stirring in step S4 is 50°C, and the stirring time is 75 min.

[0021] Preferably, in step S5, the ratio of the combined solution to the organic phase is 2:1, and the shaking time is 5 min.

[0022] Preferably, the organic phase prepared in step S5 is a mixture of Mextral-5640H and sulfonated kerosene at a volume ratio of 15:1.

[0023] Preferably, the method further includes the following steps:

[0024] Step S7, Mix and calcine: Mix V2O5 and lithium carbonate from step S6, ball mill, calcine, grind, and calcine again to obtain Li3VO4 powder;

[0025] Step S8, negative electrode treatment: Li3VO4 powder, conductive agent Ketjen black and binder lithium polyacrylic acid are mixed, N-methylpyrrolidone is added, and the mixture is prepared, coated, dried and cut to obtain Li3VO4 negative electrode.

[0026] Step S9, solution preparation: Naphthalene is dissolved in dimethyl ether and mixed, and lithium metal is added to react and obtain Li-naphthalene solution;

[0027] Step S10, pre-lithiation treatment: Immerse the Li3VO4 negative electrode in Li-naphthalene solution and perform pre-lithiation treatment in a glove box. Then clean and dry to obtain the pre-lithiated electrode.

[0028] Preferably, in step S7, V2O5 and lithium carbonate are mixed at a Li:V molar ratio of 1:3, ball milling is performed for 20 minutes, calcination is carried out at 600°C for 2 hours, and the second calcination is carried out at 900°C for 3 hours.

[0029] Preferably, the binder lithium polyacrylic acid in step S8 is synthesized by reacting acrylic acid and lithium hydroxide monohydrate in a molar ratio of 1:1 and then sealed and stored.

[0030] Compared with related technologies, the method for recovering and extracting vanadium from high-chromium vanadium slag provided by the present invention has the following beneficial effects:

[0031] By using three-stage countercurrent leaching, sulfuric acid can be utilized more effectively, sulfuric acid consumption can be reduced, and the concentration of vanadium in the leachate can be increased, while the impurity content can be reduced. In other words, the countercurrent acid leaching process not only reduces acid consumption by 50%, but also reduces the impurity leaching rate, providing more favorable conditions for subsequent vanadium separation.

[0032] The pre-lithiation process is carried out directly on the electrode sheet, without affecting the battery assembly process. It is simple to operate and has economic and environmental benefits. Attached Figure Description

[0033] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0034] Figure 1 A flowchart illustrating a preferred embodiment of the method for recovering and extracting vanadium from high-chromium vanadium slag provided by the present invention;

[0035] Figure 2 A flowchart illustrating another preferred embodiment of the method for recovering and extracting vanadium from high-chromium vanadium slag provided by the present invention;

[0036] Figure 3 A three-dimensional diagram of a first embodiment of the oscillation device provided by the present invention;

[0037] Figure 4 for Figure 3 The front view of the AA cross-sectional structure shown;

[0038] Figure 5 for Figure 4 Left view of the cam section connection structure shown;

[0039] Figure 6 for Figure 4 A schematic diagram of the cross-sectional structure of section BB shown;

[0040] Figure 7 for Figure 6 The diagram shows the structure of the support frame adjusted to a synchronous oscillation state.

[0041] Figure 8 for Figure 3 A three-dimensional diagram showing the oscillating tank mounted on the support frame;

[0042] Figure 9 A schematic diagram of the structure of a second embodiment of the oscillation device provided by the present invention;

[0043] Figure 10 for Figure 9 A cross-sectional view of the movable sleeve connection shown;

[0044] Figure 11 for Figure 10 The diagram shows a cross-sectional view of the CC section.

[0045] Explanation of icon numbers:

[0046] 1. Fixing box;

[0047] 2. Vibration assembly; 21. First drive component; 22. Rotary shaft; 23. Cam; 24. Telescopic block; 25. Elastic support tube;

[0048] 3. Rotating assembly; 31. Rotating frame; 310. Buffer groove; 32. Second driving component; 33. Sliding shaft; 34. Spring component;

[0049] 4. Installation components; 41. Support frame; 42. Connecting frame; 43. Torsion plate;

[0050] 5. Feeding assembly; 51. Feeding rack; 52. Limiting plate; 53. Gear pump; 54. Third drive component;

[0051] 100. Vibrating tank;

[0052] 6. Storage tank; 601. Liquid storage chamber;

[0053] 541. Synchronous shaft; 542. First bevel gear; 543. Movable sleeve; 544. Second bevel gear;

[0054] 7. Connecting components; 71. Flexible shrink tubing; 72. Synchronizing frame; 73. Slide plate.

[0055] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0056] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0057] This invention provides a method for recovering and extracting vanadium from high-chromium vanadium slag.

[0058] Please refer to the following: Figure 1 The method for recovering and extracting vanadium from high-chromium vanadium slag in this invention includes the following steps:

[0059] Step S1, mixing process: high chromium vanadium slag, calcium oxide and sodium carbonate are mixed, roasted and ground to obtain a mixture.

[0060] Step S2, water immersion treatment, the mixture is sequentially immersed in water and filtered to obtain a chromium-containing solution and a vanadium-containing slag;

[0061] Step S3, Evaporation and Crystallization: The chromium-containing solution is evaporated, concentrated, crystallized, filtered, washed, and dried in sequence to obtain sodium chromate;

[0062] Step S4, Leaching Treatment:

[0063] First stage leaching: The vanadium-containing slag is mixed with the medium-acid leachate from the second stage. After the reaction, filtrate 1 (low vanadium, low acid, because the vanadium has not been fully dissolved) and filter residue 1 are obtained.

[0064] Second stage leaching: Filter residue 1 is mixed with the high acidity leaching solution of the third stage, heated and stirred, and the solid and liquid are separated. After the reaction, filtrate 2 (medium vanadium, medium acid, vanadium further dissolved) and filter residue 2 are obtained.

[0065] Third stage leaching: Mix filter residue 2 with fresh sulfuric acid solution, heat and stir, separate solid and liquid, and obtain filtrate 3 (high vanadium, high acid, vanadium dissolution to the maximum extent) and vanadium-free filter residue after the reaction;

[0066] Step S5: Shake and mix, combine the filtrates obtained from the three countercurrent leaching stages (filtrate 1, filtrate 2, and filtrate 3), add the prepared organic phase, shake, let stand, and separate to obtain the loaded organic phase and raffinate.

[0067] Step S6, back-extraction treatment: the supported organic phase in step S5 is further back-extracted, the pH is adjusted, and calcined to obtain V2O5.

[0068] The fresh sulfuric acid is added from the third stage (high acid) and flows step by step to the second stage (medium acid) and the first stage (low acid), realizing the reverse utilization of acidity; the vanadium content in the vanadium-containing slag decreases step by step in the positive direction, which is matched with the sulfuric acid concentration gradient in the reverse direction to ensure the leaching efficiency of each stage is maximized; the three-stage countercurrent can be recycled.

[0069] Specifically, in step S1, the calcination environment is calcination at 900°C for 90 minutes under air with a flow rate of 20 L / min.

[0070] Specifically, the grinding fineness is grinding to a particle size of -74μm.

[0071] Specifically, the fresh sulfuric acid solution in step S4 is a sulfuric acid solution with a concentration of 0.3 g / g.

[0072] Specifically, in step S4, the temperature during heating and stirring is 50°C, and the stirring time is 75 minutes.

[0073] Specifically, in step S5, the ratio of the combined solution to the organic phase is 2:1, and the shaking time is 5 minutes.

[0074] Specifically, in step S5, the prepared organic phase is a mixture of Mextral-5640H and sulfonated kerosene at a volume ratio of 15:1.

[0075] The method for recovering and extracting vanadium from high-chromium vanadium slag further includes the following steps:

[0076] Step S7, Mix and calcine: Mix V2O5 and lithium carbonate from step S6, ball mill, calcine, grind, and calcine again to obtain Li3VO4 powder;

[0077] Step S8, negative electrode treatment: Li3VO4 powder, conductive agent Ketjen black and binder lithium polyacrylic acid are mixed, N-methylpyrrolidone is added, and the mixture is prepared, coated, dried and cut to obtain Li3VO4 negative electrode.

[0078] Step S9, solution preparation: Naphthalene is dissolved in dimethyl ether and mixed, and lithium metal is added to react and obtain Li-naphthalene solution;

[0079] Step S10, pre-lithiation treatment: Immerse the Li3VO4 negative electrode in Li-naphthalene solution and perform pre-lithiation treatment in a glove box. Then clean and dry to obtain the pre-lithiated electrode.

[0080] The pre-lithiated electrode can be assembled with lithium iron phosphate electrode, electrolyte, and separator into a coin cell.

[0081] Specifically, in step S7, V2O5 and lithium carbonate are mixed at a Li:V molar ratio of 1:3, ball milling is performed for 20 minutes, calcination is carried out at 600℃ for 2 hours, and the second calcination is carried out at 900℃ for 3 hours.

[0082] Specifically, in step S8, Li3VO4 powder, conductive agent Ketjen black, and binder lithium polyacrylic acid are mixed in a mass ratio of 7:2:1.

[0083] Specifically, the binder lithium polyacrylic acid is synthesized by reacting acrylic acid and lithium hydroxide monohydrate in a molar ratio of 1:1 and stored in a sealed container.

[0084] Specifically, in step S9, 0.01 mol of naphthalene is dissolved in 10 ml of dimethyl ether, and after adding 0.01 mol of metallic lithium, the reaction time is 2 h.

[0085] Specifically, in step S10, the pre-lithiation treatment time is 5 minutes, and the cleaning is performed by washing with dimethyl ether 3 times.

[0086] Beneficial effects:

[0087] By using three-stage countercurrent leaching, sulfuric acid can be utilized more effectively, sulfuric acid consumption can be reduced, and the concentration of vanadium in the leachate can be increased, while the impurity content can be reduced. In other words, the countercurrent acid leaching process not only reduces acid consumption by 50%, but also reduces the impurity leaching rate, providing more favorable conditions for subsequent vanadium separation.

[0088] The pre-lithiation process is carried out directly on the electrode sheet, without affecting the battery assembly process. It is simple to operate and has economic and environmental benefits.

[0089] Implementation plan:

[0090] Step 1: Mix 10g of high-chromium vanadium slag with stoichiometric amounts of calcium oxide and sodium carbonate, calcine at 900℃ for 90min under air at 20L / min, and grind to a particle size of -74μm to obtain a mixture;

[0091] Step 2: Soak the mixture in water at room temperature, filter, and obtain a chromium-containing solution and vanadium-containing slag;

[0092] Step 3: Evaporate, concentrate, and crystallize the chromium-containing solution, filter, wash three times with deionized water, and dry at low temperature to obtain sodium chromate;

[0093] Step 4: First stage leaching: Mix the vanadium-containing slag with the medium-acid leachate from the second stage. After the reaction, filtrate 1 (low vanadium, low acid, because vanadium has not been fully dissolved) and filter residue 1 are obtained.

[0094] Second stage leaching: Filter residue 1 is mixed with the high acidity leaching solution of the third stage, heated and stirred at 50°C for 75 min, solid and liquid are separated, and filtrate 2 (medium vanadium, medium acid, vanadium further dissolved) and filter residue 2 are obtained after the reaction.

[0095] Third stage leaching: Mix filter residue 2 with 0.3 g / g fresh sulfuric acid solution, heat and stir at 50°C for 75 min, separate solid and liquid, and obtain filtrate 3 (high vanadium, high acid, vanadium dissolution to the maximum extent) and vanadium-free filter residue after the reaction;

[0096] The fresh sulfuric acid is added from the third stage (high acid) and flows step by step to the second stage (medium acid) and the first stage (low acid), realizing the reverse utilization of acidity; the vanadium content in the vanadium-containing slag decreases step by step, which is inversely matched with the sulfuric acid concentration gradient to ensure that the leaching efficiency of each stage is maximized; the three-stage countercurrent can be recycled;

[0097] Step 5: Combine the filtrates obtained from the three countercurrent leaching stages (filtrates 1, 2, and 3), add the prepared organic phase with an O / A ratio of 2:1, shake for 5 minutes, let stand, and separate to obtain the loaded organic phase and raffinate; the prepared organic phase is a mixture of Mextral-5640H and sulfonated kerosene at a volume ratio of 15:1.

[0098] Step 6: Further back-extract the supported organic phase obtained in Step 5, adjust the pH, and calcine to obtain V2O5;

[0099] Step 7: Mix the V2O5 obtained in Step 6 and lithium carbonate at a Li:V molar ratio of 1:3, ball mill for 20 min, calcine at 600℃ for 2 h, grind, and calcine again at 900℃ for 3 h to obtain Li3VO4 powder.

[0100] Step 8: Mix Li3VO4 powder, conductive agent Ketjen black, and binder lithium polyacrylic acid in a mass ratio of 7:2:1, add N-methylpyrrolidone, prepare a slurry, coat it on copper foil, dry and cut it to obtain the Li3VO4 negative electrode; the binder lithium polyacrylic acid is synthesized by reacting acrylic acid and lithium hydroxide monohydrate in a molar ratio of 1:1 and stored in a sealed container.

[0101] Step 9: Dissolve 0.01 mol naphthalene in 10 ml dimethyl ether, add 0.01 mol lithium metal and react for 2 h to obtain Li-naphthalene solution;

[0102] Step 10: Immerse the Li3VO4 negative electrode in Li-naphthalene solution, perform pre-lithiation treatment for 5 min in an argon glove box, wash with dimethyl ether 3 times, and dry to obtain the pre-lithiation electrode.

[0103] The pre-lithiated electrode can be assembled with a lithium iron phosphate electrode, electrolyte, and separator into a coin cell, achieving an initial coulombic efficiency of 100% in the first week and increasing the reversible capacity to 146.3 mAh / g.

[0104] The present invention also provides an oscillation device for oscillating the combined filtrate in the method for recovering and extracting vanadium from high-chromium vanadium slag.

[0105] First embodiment:

[0106] Please refer to the following: Figures 3 to 6 In this invention, the oscillation device includes:

[0107] Fixing box 1;

[0108] Vibration component 2, which is mounted on the fixed box 1;

[0109] The rotating assembly 3 includes a rotating frame 31, a second driving member 32, a sliding shaft 33, and a spring member 34. The bottom of the rotating frame 31 is rotatably mounted on the vibrating part of the vibration assembly 2. The fixing part of the second driving member 32 is embedded in the vibration assembly 2. The driving part of the second driving member 32 is fixedly connected to the bottom of the rotating frame 31. The rotating frame 31 has a buffer groove 310. The sliding shaft 33 is fixed on the rotating frame 31 and located within the range of the buffer groove 310. The spring member 34 is sleeved on the sliding shaft 33.

[0110] Mounting assembly 4 includes a support frame 41, a connecting frame 42, and a torsion plate 43. One end of the support frame 41 is sleeved on the sliding shaft 33 and slidably connected to the rotating frame 31. The bottom of the connecting frame 42 is fixed to the support frame 41. The torsion plate 43 is rotatably mounted on the connecting frame 42 by a torsion spring. Both ends of the spring member 34 are fixedly connected to the rotating frame 31 and the support frame 41.

[0111] The feeding assembly 5 includes a feeding frame 51, a limiting plate 52, a gear pump 53, and a third driving component 54. The feeding frame 51 is fixed to one side of the fixed box 1, the limiting plate 52 is fixed to the feeding frame 51, the gear pump 53 is fixed to the top of the feeding frame 51, and the third driving component 54 is mounted on the gear pump 53. The driving part of the third driving component 54 is fixedly connected to the shaft end of the gear pump 53.

[0112] The vibration component 2 is used to drive the rotating frame 31 to vibrate up and down for adjustment. There are four buffer grooves 310. The number of buffer grooves 310, sliding shafts 33, springs 34 and mounting components 4 are equal and they are set in a one-to-one correspondence.

[0113] like Figure 8As shown, each of the support frames 41 is equipped with an oscillating tank 100. The bottom of the oscillating tank 100 is supported on the support frame 41, and the torsion plate 43 is pressed against the top of the oscillating tank 100 to ensure the stability of the oscillation after the oscillating tank 100 is installed.

[0114] In this embodiment, the second driving component 32 is a motor structure used to drive the rotating frame 31 to rotate and adjust on the vibration assembly 2, so as to adjust the use positions of the four mounting components 4.

[0115] The third driving component 54 can be a motor structure, used to directly drive the gear pump 53 to rotate and adjust, so as to facilitate the extraction and conveying of materials; the material is a solution that needs to be shaken.

[0116] In this embodiment, the installation component 4 includes two usage states:

[0117] Feeding status, such as Figure 6 As shown, one end of the support frame 41 is aligned with the clamping range of the limiting plate 52 to facilitate maintaining the stability of the material receiving after the vibrating tank 100 is installed.

[0118] Synchronous oscillation state, such as Figure 7 As shown, the limiting ranges of the support frame 41 and the limiting plate 52 are staggered, which facilitates the simultaneous vibration operation of the four vibration tanks 100 on the mounting components 4.

[0119] In this embodiment, the input pipe of the gear pump 53 is connected to an external raw material storage device, and the output pipe of the gear pump 53 passes through the feeding rack 51 and is aligned directly above the opening of the oscillating tank 100 at the feeding station.

[0120] Operating principle:

[0121] During synchronous oscillation, the vibration component 2 controls the rotating frame 31 to vibrate up and down. The rotating frame 31 drives the support frame 41 to rise and fall synchronously through the spring 34. The support frame 41 drives the installed oscillation tank 100 to oscillate and adjust, so as to drive the oscillation operation of four oscillation tanks 100 at the same time.

[0122] When switching workstations, if it is necessary to inject raw materials into the vibrating tank 100, the second drive unit 32 is activated. The second drive unit 32 drives the rotating frame 31 to rotate, and the rotating frame 31 drives the support frames 41 of the four workstations to rotate synchronously, so that the support frames 41 rotate and insert into the blocking range of the limiting plate 52, so that the opening of the vibrating tank 100 is aligned with the output pipe of the gear pump 53. While the other three support frames 41 continue to vibrate, the support frame 41 in the feeding state does not vibrate, maintaining stability during feeding.

[0123] When adding material, the third driving component 54 is activated, which drives the gear pump 53 to rotate. The gear pump 53 draws material through the input pipe and delivers material through the output pipe, injecting the required material into the vibrating tank 100 in the feeding state, so that the feeding process of one vibrating tank 100 does not affect the continuous vibration processing of other vibrating tanks 100.

[0124] Please refer to the following: Figure 4 and Figure 5 The vibration assembly 2 includes a first driving member 21, a rotating shaft 22, a cam 23, a telescopic block 24, and an elastic support tube 25. The first driving member 21 is fixedly installed in the fixed box 1. One end of the rotating shaft 22 is fixedly connected to the driving part of the first driving member 21. The cam 23 is fixedly installed on the rotating shaft 22. The top of the telescopic block 24 passes through the fixed box 1 and is slidably connected. The two ends of the elastic support tube 25 are fixedly connected to the fixed box 1 and the telescopic block 24. The bottom of the telescopic block 24 abuts against the cam 23.

[0125] The bottom of the rotating frame 31 is rotatably mounted on the top of the telescopic block 24, and the bottom of the second driving member 32 is embedded in the top of the telescopic block 24.

[0126] In this embodiment, the first driving component 21 can be a motor structure, used to directly drive the rotating shaft 22 to rotate and adjust, providing a power source for the oscillation of the rotating frame 31.

[0127] In this embodiment, the elastic support tube 25 is used to maintain the bottom of the telescopic block 24 and the top of the cam 23 in stable contact, thereby ensuring the stability of the telescopic block 24 during up-and-down oscillation.

[0128] Oscillation principle:

[0129] The first drive unit 21 is activated, and the first drive unit 21 drives the cam 23 to rotate through the rotating shaft 22. When the cam 23 rotates, it drives the telescopic block 24 to oscillate up and down. At the same time, the telescopic block 24 oscillates up and down, and drives the rotating frame 31 to oscillate up and down. The rotating frame 31 drives the installation assembly 4 of the four workstations to oscillate up and down as a whole (in synchronous oscillation state).

[0130] Please refer to the following: Figure 3 and Figure 4 The oscillation device also includes a storage tank 6, which is integrated on the feeding rack 51, and a liquid storage chamber 601 is formed between the storage tank 6 and the feeding rack 51.

[0131] The input pipe of the gear pump 53 passes through the feeding rack 51 and the storage box 6 and is completely inserted into the range of the liquid storage chamber 601.

[0132] By adding the storage box 6 to one side of the feeding rack 51, it is convenient to temporarily store the materials that need to be injected. After storage, the materials are pumped out by the gear pump 53, which facilitates the storage and pumping of materials.

[0133] The working principle of the oscillation device provided in this embodiment is as follows:

[0134] like Figure 7 As shown, it can be defined that in the initial state, the installation component 4 is in a synchronous oscillation state, and the support frame 41 and the limiting plate 52 are in a staggered distribution state, so as to facilitate the synchronous driving of the four support frames 41 to oscillate through the vibration component 2.

[0135] When a vibrating tank 100 needs to be filled with raw materials:

[0136] A1, workstation adjustment: first, start the second drive component 32, the second drive component 32 drives the rotating frame 31 to rotate, the rotating frame 31 drives the four mounting components 4 to rotate synchronously (no oscillation during rotation adjustment); so that one of the support frames 41 rotates and inserts into the range of the limiting plate 52, then turn off the second drive component 32;

[0137] A2, Material filling: Start the third drive unit 54, which drives the gear pump 53 to run. The gear pump 53 draws material from the storage chamber 601 through the input pipe and delivers the drawn material through the output pipe, so that the material is vertically conveyed downward to the inside of the oscillating tank 100, so as to facilitate the automatic filling of material in the oscillating tank 100.

[0138] A3, synchronous oscillation, during the material filling process, the first drive component 21 is activated, the rotating shaft 22 drives the cam 23 to rotate, the cam 23 pushes the telescopic block 24 to oscillate up and down, the telescopic block 24 synchronously drives the rotating frame 31 to oscillate up and down as a whole, and the rotating frame 31 synchronously drives the three mounting components 4 to oscillate up and down as a whole through the sliding shaft 33 and the spring component 34;

[0139] The support frame 41, which is blocked by the limiting plate 52, is allowed to slide relative to the sliding shaft 33 and the rotating frame 31 under the elastic action of the spring 34. The support frame 41 maintains a stable limiting state and will not oscillate up and down with the rotating frame 31.

[0140] Ultimately, during the period when one oscillating tank 100 is stably fed, the other three oscillating tanks 100 can continuously oscillate up and down without affecting the oscillating tank 100 that is feeding.

[0141] Second embodiment:

[0142] Please refer to the following: Figure 9 , Figure 10 and Figure 11 Based on the oscillation device provided in the first embodiment of the present invention, the second embodiment of the present invention proposes another oscillation device. The second embodiment is merely a preferred embodiment of the first embodiment, and the implementation of the second embodiment will not affect the separate implementation of the first embodiment.

[0143] Specifically, the difference in the oscillation device provided in the second embodiment of the present invention is that the third driving component 54 includes a synchronous shaft 541, a first bevel gear 542, a movable sleeve 543, and a second bevel gear 544. The top of the synchronous shaft 541 is fixedly connected to the shaft end of the gear pump 53. The first bevel gear 542 is fixedly mounted on the synchronous shaft 541. One end of the movable sleeve 543 passes through the feeding frame 51 and the fixed box 1 and is inserted into the left end of the rotating shaft 22. The left end of the rotating shaft 22 has a rectangular structure. The movable sleeve 543 is connected to the rotating shaft 22 by a sliding key. The second bevel gear 544 is fixedly mounted on the movable sleeve 543.

[0144] The oscillation device further includes a connecting assembly 7, which includes an elastic shrink tube 71, a synchronization frame 72, and a sliding plate 73. The fixed end of the elastic shrink tube 71 is installed through the feeding frame 51. The synchronization frame 72 is fixed to the telescopic end of the elastic shrink tube 71. One end of the sliding plate 73 is fixedly connected to the top of the synchronization frame 72. The other end of the sliding plate 73 passes through the feeding frame 51 and is inserted into the blocking range of the limiting plate 52. The bottom of the synchronization frame 72 is sleeved on the movable sleeve 543 and rotatably connected.

[0145] In this embodiment, "sliding key connection" means that the movable sleeve 543 and the rotating shaft 22 can be adjusted relative to each other; and when the rotating shaft 22 rotates, it also drives the movable sleeve 543 to rotate synchronously.

[0146] In this embodiment, the elastic contraction tube 71 provides an elastic contraction force to the synchronization frame 72. When the support frame 41 abuts against the slide plate 73, the second bevel gear 544 engages with the first bevel gear 542, and the elastic contraction tube 71 pulls the synchronization frame 72 and the slide plate 73 to maintain stable contact with the support frame 41.

[0147] When the support frame 41 separates from the slide plate 73, the elastic contraction tube 71 pulls the synchronization frame 72, the slide plate 73 and the movable sleeve 543 to the right, so that the movable sleeve 543 drives the second bevel gear 544 to separate from the first bevel gear 542 to avoid collision.

[0148] During the process of the installation component 4 switching from the synchronous oscillation state to the feeding state, the support frame 41 also synchronously pushes the slide plate 73 to retract. The slide plate 73 drives the movable sleeve 543 to retract through the synchronous frame 72. The movable sleeve 543 drives the second bevel gear 544 to mesh with the first bevel gear 542, so that while the rotating frame 31 is driven to oscillate up and down by the first driving member 21, the rotation of the gear pump 53 is also driven for material pumping.

[0149] Similarly, during the process of the installation assembly 4 switching from the feeding state to the synchronous oscillation state, while the support frame 41 and the slide plate 73 rotate and separate, the elastic shrink tube 71 drives the synchronous frame 72 and the slide plate 73 to extend synchronously, and the movable sleeve 543 drives the second bevel gear 544 to separate from the first bevel gear 542, so that when the installation assembly 4 is in the synchronous oscillation state, the first drive member 21 is only used for the up and down oscillation operation of the rotating frame 31.

[0150] The working principle of the oscillation device provided in this embodiment is as follows:

[0151] Let us define it as follows: In the initial state, the mounting assembly 4 is in a synchronous oscillation state, the support frame 41 is separated from the slide plate 73, the second bevel gear 544 is separated from the first bevel gear 542, and the first drive member 21 only provides power for the oscillation of the rotating frame 31.

[0152] B1, workstation adjustment, start the second drive component 32, the second drive component 32 drives the rotating frame 31 to rotate, the rotating frame 31 drives the four installation components 4 to switch from synchronous oscillation state to feeding state;

[0153] B2, synchronous switching: when the support frame 41 rotates and inserts into the blocking range of the limiting plate 52, the support frame 41 pushes the slide plate 73 to retract. The slide plate 73 drives the synchronous frame 72, the movable sleeve 543 and the second bevel gear 544 to move to the left. While the movable sleeve 543 maintains its connection with the rotating shaft 22, it also causes the second bevel gear 544 to move toward the first bevel gear 542. When the support frame 41 and the slide plate 73 are fully abutted, the second bevel gear 544 and the first bevel gear 542 engage.

[0154] B3, synchronous operation, start the first drive component 21, the first drive component 21 drives the rotating shaft 22 to rotate, on the one hand, the rotating shaft 22 drives the cam 23 to rotate, the cam 23 drives the telescopic block 24 to oscillate stably up and down on the fixed box 1, the telescopic block 24 synchronously drives the rotating frame 31 to oscillate up and down, the rotating frame 31 synchronously drives the three mounting components 4 to maintain oscillation operation;

[0155] On the other hand, the rotating shaft 22 also synchronously drives the movable sleeve 543 to rotate, the movable sleeve 543 drives the second bevel gear 544 to rotate, the second bevel gear 544 drives the first bevel gear 542 to rotate, the first bevel gear 542 drives the synchronous shaft 541 to rotate, and the synchronous shaft 541 drives the gear pump 53 to rotate. The gear pump 53 draws material from the liquid storage chamber 601 through the input pipe for transportation, and the gear pump 53 pumps material to the vibrating tank 100 at the feeding station through the output pipe.

[0156] Ultimately, under the driving action of the first driving component 21, the oscillation of the three oscillating tanks 100 and the feeding of one oscillating tank 100 are realized simultaneously.

[0157] 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 under the concept of the present invention using the contents of the present invention specification and drawings, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A method for recovering and extracting vanadium from high-chromium vanadium slag, characterized in that, Includes the following steps: Step S1, mixing process: high chromium vanadium slag, calcium oxide and sodium carbonate are mixed, roasted and ground to obtain a mixture. Step S2, water immersion treatment: the mixture from step S1 is sequentially immersed in water and filtered to obtain a chromium-containing solution and a vanadium-containing slag. Step S3, Evaporation and Crystallization: The chromium-containing solution in step S2 is evaporated, concentrated, and crystallized sequentially, then filtered, washed, and dried to obtain sodium chromate. Step S4, Leaching Treatment: First stage leaching: The vanadium-containing slag is mixed with the leaching solution from the second stage, and after the reaction, filtrate 1 and filter residue 1 are obtained; Second stage leaching: Mix filter residue 1 with the leachate from the third stage, heat and stir, separate solid and liquid, and obtain filtrate 2 and filter residue 2 after the reaction; Third stage leaching: Mix filter residue 2 with fresh sulfuric acid solution, heat and stir, separate solid and liquid, and obtain filtrate 3 and vanadium-free filter residue after reaction; Step S5: Shake and mix, combine the filtrates obtained from the three countercurrent leaching stages in step S4, add the prepared organic phase, shake, let stand, and separate to obtain the loaded organic phase and raffinate. Step S6, back-extraction treatment: the supported organic phase in step S5 is further back-extracted, the pH is adjusted, and calcined to obtain V2O5.

2. The method for recovering and extracting vanadium from high-chromium vanadium slag according to claim 1, characterized in that, In step S1, the calcination environment is calcination at 900°C for 90 minutes under air at a flow rate of 20 L / min.

3. The method for recovering and extracting vanadium from high-chromium vanadium slag according to claim 2, characterized in that, The grinding fineness is ground to a particle size of -74μm.

4. The method for recovering and extracting vanadium from high-chromium vanadium slag according to claim 1, characterized in that, In step S4, the fresh sulfuric acid solution is a 0.3 g / g sulfuric acid solution.

5. The method for recovering and extracting vanadium from high-chromium vanadium slag according to claim 4, characterized in that, In step S4, the temperature during heating and stirring is 50°C, and the stirring time is 75 minutes.

6. The method for recovering and extracting vanadium from high-chromium vanadium slag according to claim 1, characterized in that, In step S5, the ratio of the combined solution to the organic phase is 2:1, and the shaking time is 5 min.

7. The method for recovering and extracting vanadium from high-chromium vanadium slag according to claim 6, characterized in that, In step S5, the prepared organic phase is a mixture of Mextral-5640H and sulfonated kerosene at a volume ratio of 15:

1.

8. The method for recovering and extracting vanadium from high-chromium vanadium slag according to claim 1, characterized in that, It also includes the following steps: Step S7, Mix and calcine: Mix V2O5 and lithium carbonate from step S6, ball mill, calcine, grind, and calcine again to obtain Li3VO4 powder; Step S8, negative electrode treatment: Li3VO4 powder, conductive agent Ketjen black and binder lithium polyacrylic acid are mixed, N-methylpyrrolidone is added, and the mixture is prepared, coated, dried and cut to obtain Li3VO4 negative electrode. Step S9, solution preparation: Naphthalene is dissolved in dimethyl ether and mixed, and lithium metal is added to react and obtain Li-naphthalene solution; Step S10, pre-lithiation treatment: Immerse the Li3VO4 negative electrode in Li-naphthalene solution and perform pre-lithiation treatment in a glove box. Then clean and dry to obtain the pre-lithiated electrode.

9. The method for recovering and extracting vanadium from high-chromium vanadium slag according to claim 8, characterized in that, In step S7, V2O5 and lithium carbonate are mixed at a Li:V molar ratio of 1:3, ball milling is performed for 20 minutes, calcination is carried out at 600℃ for 2 hours, and the second calcination is carried out at 900℃ for 3 hours.

10. The method for recovering and extracting vanadium from high-chromium vanadium slag according to claim 8, characterized in that, The binder lithium polyacrylic acid in step S8 is synthesized by reacting acrylic acid and lithium hydroxide monohydrate in a molar ratio of 1:1 and then sealed and stored.

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