Method for extracting lithium resource by using spodumene impurity removal slag
By employing a multi-step process for removing impurities from spodumene and freezing the slurry, including stirred leaching, pH adjustment, ion exchange, and lithium precipitation, the problem of low lithium recovery rate has been solved, achieving efficient recovery of lithium resources and maximizing economic benefits.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- FENGCHENG JIULING LITHIUM IND CO LTD
- Filing Date
- 2025-12-23
- Publication Date
- 2026-04-21
AI Technical Summary
Existing methods for treating spodumene residue have problems such as low lithium recovery rate, high cost, significant environmental pollution, and insufficient utilization of lithium in the cryogenic solution.
The process involves weighing spodumene (after removing impurities) and mixing it with a cryogenic solution for stirring and leaching. The pH value is then adjusted for constant-temperature stirring. The mixture is purified using ion exchange resin, evaporated and concentrated, and precipitated with saturated sodium phosphate solution. Finally, the mixture is washed with water and dried to obtain battery-grade lithium phosphate.
This technology enables the efficient recovery of lithium elements, converting them into high-value-added lithium phosphate products, thereby improving resource utilization and reducing processing costs.
Smart Images
Figure CN121896450A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of lithium extraction technology from solid waste, and in particular to a method for extracting lithium resources using spodumene residue after impurity removal. Background Technology
[0002] With the rapid development of the new energy industry, the demand for lithium has increased dramatically. Spodumene is an important mineral resource for lithium extraction. The process of preparing lithium carbonate from spodumene generates a large amount of byproducts and waste liquid. The spodumene residue contains magnesium hydroxide, calcium hydroxide, lithium hydroxide, calcium carbonate, and lithium carbonate, while the cryogenic liquid mainly contains sulfate, lithium, sodium, and potassium, and has an overall alkaline pH.
[0003] Currently, most treatments for these byproducts and waste liquids employ traditional methods, which suffer from low lithium recovery rates, high costs, and significant environmental pollution. Traditional methods for treating spodumene slag often focus on removing impurities while neglecting lithium recovery, leading to a waste of lithium resources. In treating cryogenic liquids, simple neutralization or discharge is typically performed without fully utilizing the lithium content.
[0004] Therefore, it is necessary to provide a method for extracting lithium resources using spodumene residue to solve the above-mentioned technical problems. Summary of the Invention
[0005] This invention provides a method for extracting lithium resources using spodumene residue, which solves the problem in related technologies where it is necessary to study how to effectively improve the sufficiency of lithium element recovery and extraction.
[0006] To solve the above-mentioned technical problems, the present invention provides a method for extracting lithium resources using spodumene residue, comprising the following steps:
[0007] Step S1, material leaching treatment: Weigh the spodumene residue and mix it with the frozen clear liquid. Stir and leaching reaction is carried out at room temperature. After the reaction is completed, filter to obtain lithium-rich filtrate A and filter residue A.
[0008] Step S2, calcium removal and purification treatment: Sodium hydroxide is added to lithium-rich filtrate A to adjust the pH, and the solution is transferred to a constant temperature water bath for constant temperature stirring reaction. After the reaction is completed, a uniform sample is taken and sent for analysis of calcium and magnesium components. Sodium carbonate is added according to the calcium concentration to continue the reaction to remove calcium. Solid-liquid separation is performed to obtain filter residue B and filtrate B. Filter residue B is reused in step S1. Filtrate B is passed through an ion exchange resin at a certain flow rate for deep purification to remove residual impurity ions and obtain purified solution.
[0009] Step S3, lithium extraction treatment: the purified liquid is evaporated and concentrated to control the lithium concentration in the liquid. The concentrated liquid is sent for analysis of its components. Saturated sodium phosphate solution is added according to the lithium ion concentration. The mixture is transferred to a constant temperature water bath and stirred at a constant temperature to precipitate lithium. After the reaction is completed, the mixture is filtered to obtain filtrate C and filter residue C. Filter residue C is mixed with deionized water and washed three times. After washing, it is dried to obtain battery-grade lithium phosphate.
[0010] Preferably, in step S1, the solid-liquid ratio of spodumene impurity removal residue to cryogenic liquid is 1:4~5.
[0011] Preferably, the stirring speed of the stirring leaching reaction in step S1 is 350 rpm, and the reaction time is 2 h.
[0012] Preferably, the pH adjustment range in step S2 is 11.5~12.5.
[0013] Preferably, in step S2, the isothermal stirring reaction is carried out at 350 rpm at 68°C for 30 min.
[0014] Preferably, in step S2, sodium carbonate is added at a calcium concentration of 1.1 to 1.2, and the reaction continues for 45 minutes.
[0015] Preferably, in step S2, filtrate B is passed through the ion exchange resin at a flow rate of 5 mL / min.
[0016] Preferably, the lithium concentration in step S3 is controlled at 15~19 g / L.
[0017] Preferably, in step S3, a saturated sodium phosphate solution is added at a coefficient of 1.1 to 1.2 according to the lithium ion concentration.
[0018] Preferably, in step S3, the constant temperature stirring reaction is carried out at a stirring speed of 350 rpm at 90~95℃ for 3~4 hours; the filter residue C is mixed with deionized water at a solid-liquid ratio of 1:3.
[0019] Compared with related technologies, the method for extracting lithium resources from spodumene residue provided by this invention has the following beneficial effects:
[0020] This method efficiently recovers lithium from spodumene impurities and cryogenic liquid, converting it into high-value-added lithium phosphate products, thereby maximizing resource recycling and economic benefits. Attached Figure Description
[0021] 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.
[0022] Figure 1 A three-dimensional view of the first embodiment of the water washing equipment provided by the present invention;
[0023] Figure 2 for Figure 1 A schematic diagram of the structure of section AA shown;
[0024] Figure 3 for Figure 1 The diagram shows a cross-section of section BB.
[0025] Figure 4 for Figure 3 A schematic diagram of the CC cross-section shown;
[0026] Figure 5 for Figure 3 The diagram shows the structure with the switch cover in the open position.
[0027] Figure 6 for Figure 5 The diagram shown illustrates the structure of the stirring rod adjusted to the discharge mode.
[0028] Figure 7 A three-dimensional view of a second embodiment of the water washing equipment provided by the present invention;
[0029] Figure 8 for Figure 7 A three-dimensional diagram showing the distribution of the buffer box and stirring rods;
[0030] Figure 9 A three-dimensional view of the third embodiment of the water washing equipment provided by the present invention;
[0031] Figure 10 for Figure 9 The diagram shows the structure of the switch component blocking the switch port.
[0032] Figure 11 for Figure 10 The diagram shows the structure after the switch has been completely moved upwards.
[0033] Explanation of icon numbers:
[0034] 1. Bracket;
[0035] 2. Tank body; 201. Isolation panel; 202. Filter hole; 21. Switch cover; 22. Feed inlet; 23. Observation port;
[0036] 3. Stirring mechanism; 31. Mounting frame; 32. Drive component; 33. First telescopic component; 34. Slide; 35. Stirring rod; 350. Connecting groove;
[0037] 4. Pumping mechanism; 41. Gear pump; 42. First switching valve; 421. Inlet pipe; 43. Second switching valve; 431. Water supply pipe; 432. Drain pipe;
[0038] 5. Conveying pipe fittings;
[0039] 6. Hose;
[0040] 7. Switching mechanism; 71. Second telescopic component; 72. Rotating arm;
[0041] 8. Buffer box; 801. Switch port; 81. Switch component.
[0042] 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
[0043] 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.
[0044] This invention provides a method for extracting lithium resources from spodumene residue after impurity removal. The method includes the following steps:
[0045] Step S1, material leaching treatment: Weigh the spodumene residue and mix it with the frozen clear liquid. Stir and leaching reaction is carried out at room temperature. After the reaction is completed, filter to obtain lithium-rich filtrate A and filter residue A.
[0046] Step S2, calcium removal and purification treatment: Sodium hydroxide is added to lithium-rich filtrate A to adjust the pH, and the solution is transferred to a constant temperature water bath for constant temperature stirring reaction. After the reaction is completed, a uniform sample is taken and sent for analysis of calcium and magnesium components. Sodium carbonate is added according to the calcium concentration to continue the reaction to remove calcium. Solid-liquid separation is performed to obtain filter residue B and filtrate B. Filter residue B is reused in step S1. Filtrate B is passed through an ion exchange resin at a certain flow rate for deep purification to remove residual impurity ions and obtain purified solution.
[0047] Step S3, lithium extraction treatment: the purified liquid is evaporated and concentrated to control the lithium concentration in the liquid. The concentrated liquid is sent for analysis of its components. Saturated sodium phosphate solution is added according to the lithium ion concentration. The mixture is transferred to a constant temperature water bath and stirred at a constant temperature to precipitate lithium. After the reaction is completed, the mixture is filtered to obtain filtrate C and filter residue C. Filter residue C is mixed with deionized water and washed three times. After washing, it is dried to obtain battery-grade lithium phosphate.
[0048] In this embodiment, since the cryosol is slightly alkaline, it can inhibit the decomposition of calcium and magnesium ions in the impurity residue, which is beneficial to the selective leaching of lithium.
[0049] This method efficiently recovers lithium from spodumene impurities and cryogenic liquid, converting it into high-value-added lithium phosphate products, thereby maximizing resource recycling and economic benefits.
[0050] Specifically, in step S1, the solid-liquid ratio of spodumene impurity removal residue to cryogenic liquid is 1:4~5.
[0051] Specifically, in step S1, the stirring speed of the leaching reaction is 350 rpm, and the reaction time is 2 hours.
[0052] Specifically, the pH adjustment range in step S2 is 11.5~12.5.
[0053] Specifically, in step S2, the isothermal stirring reaction is carried out at 350 rpm at 68°C for 30 min.
[0054] Specifically, in step S2, sodium carbonate is added at a calcium concentration of 1.1 to 1.2, and the reaction continues for 45 minutes.
[0055] Specifically, in step S2, filtrate B is passed through the ion exchange resin at a flow rate of 5 mL / min.
[0056] Specifically, in step S3, the lithium concentration is controlled at 15~19 g / L.
[0057] Specifically, in step S3, saturated sodium phosphate solution is added according to the lithium ion concentration at a coefficient of 1.1 to 1.2.
[0058] Specifically, in step S3, the constant temperature stirring reaction is carried out at a stirring speed of 350 rpm at 90~95℃ for 3~4 hours; the filter residue C is mixed with deionized water at a solid-liquid ratio of 1:3.
[0059] The method for extracting lithium resources using spodumene residue further includes the following steps:
[0060] Step S4: Add an appropriate amount of concentrated hydrochloric acid to filtrate C to adjust the pH of the solution to 3-4. Transfer the solution to a constant temperature water bath and react for a period of time at a certain stirring speed and temperature to carry out the decarbonation reaction and remove carbonate ions. The solubility product of barium sulfate is much smaller than that of barium phosphate. Under acidic conditions, phosphate ions have a weaker ability to combine with barium ions and can preferentially precipitate sulfate ions. Add excess barium chloride solution to the decarbonized liquid to generate white barium sulfate precipitate. Filter to obtain filtrate D and filter residue D, which is mainly composed of barium sulfate.
[0061] Step S5: Add calcium oxide to filtrate D to adjust the pH of the liquid to 8-9, transfer it to a constant temperature water bath, and react it for a period of time at a certain stirring speed and a specific temperature to generate calcium phosphate precipitate. Filter to obtain filtrate E and filter residue E whose main component is calcium phosphate.
[0062] Step S6: Filtrate E mainly contains K + Na + Cl - and a small amount of excess reagent (such as Ca) 2 Ba 2+ ), filtrate E can be recovered by evaporation and crystallization to recover potassium chloride and sodium chloride salts.
[0063] Beneficial effects:
[0064] In the process of producing lithium carbonate from spodumene, the cryogenic liquid provides an alkaline environment and a free lithium carrier, while the impurity residue provides solid-phase adsorbed lithium. The two work synergistically to achieve bidirectional enrichment of lithium. The cryogenic liquid after lithium carbonate production from spodumene is used to leach the impurity residue from spodumene. By cleverly utilizing the slightly alkaline properties of the cryogenic liquid, the decomposition of calcium and magnesium ions in the impurity residue is inhibited during the leaching process, thereby improving the selectivity of lithium leaching and reducing the cost of subsequent impurity removal. This achieves the synergistic treatment of the two wastes, reducing waste emissions and improving the recovery rate of lithium.
[0065] Option 1:
[0066] Step S1: Weigh 1000g of spodumene residue and mix it with the cryogenic liquid at a solid-liquid ratio of 1:4. At room temperature, carry out the leaching reaction at a stirring speed of 350rpm for 2 hours. After the reaction is completed, filter to obtain lithium-rich filtrate A and filter residue A.
[0067] Step S2: Add sodium hydroxide to lithium-rich filtrate A to adjust the pH to 11.5, transfer it to a constant temperature water bath and react at 68°C with a stirring speed of 350 rpm for 30 min. After the reaction, take a uniform sample for analysis of calcium and magnesium components. Add sodium carbonate according to the calcium concentration at a coefficient of 1.2 and continue the reaction for 45 min to remove calcium. Separate the solid and liquid to obtain filter residue B and filtrate B. Filter residue B can be returned to step S1. Filtrate B is passed through an ion exchange resin at a flow rate of 8 mL / min for deep purification to remove residual impurity ions and obtain purified solution.
[0068] Step S3: The purified liquid is evaporated and concentrated to control the lithium concentration in the liquid at 17 g / L. The concentrated liquid is sent for component testing. Saturated sodium phosphate solution is added according to the lithium ion concentration at a coefficient of 1.1. The solution is transferred to a constant temperature water bath and reacted at 95°C for 3 hours with stirring at 350 rpm to precipitate lithium. After the reaction, the solution is filtered to obtain filtrate C and filter residue C. Filter residue C is mixed with deionized water at a solid-liquid ratio of 1:3 and washed three times. After washing, the solution is dried at 100°C for 4 hours to obtain battery-grade lithium phosphate.
[0069] Step S4: Add an appropriate amount of concentrated hydrochloric acid to filtrate C to adjust the pH to 3. Transfer the solution to a constant temperature water bath and react at 80°C for 60 minutes with stirring at 350 rpm to carry out the decarbonation reaction and remove carbonate ions. The solubility product of barium sulfate is much smaller than that of barium phosphate. Under acidic conditions, phosphate ions have a weaker binding ability with barium ions and can preferentially precipitate sulfate ions. Add excess barium chloride solution to the decarbonized liquid to generate white barium sulfate precipitate. Filter to obtain filtrate D and filter residue D, which is mainly composed of barium sulfate.
[0070] Step S5: Add calcium oxide to filtrate D to adjust the pH of the liquid to 8.5, transfer it to a constant temperature water bath and react at 68°C with stirring at 350 rpm for a period of time to generate calcium phosphate precipitate, filter to obtain filtrate E and filter residue E whose main component is calcium phosphate.
[0071] Step S6: Filtrate E mainly contains K + Na + Cl - and a small amount of excess reagent (such as Ca) 2 Ba 2+ ), filtrate E can be recovered by evaporation and crystallization to recover potassium chloride and sodium chloride salts.
[0072] Option 2:
[0073] Step S1: Weigh 1000g of spodumene impurity removal residue and freeze-dried liquid and mix them in a solid-liquid ratio of 1:5. At room temperature, carry out the leaching reaction at a stirring speed of 350rpm for 2 hours. Since the freeze-dried liquid is slightly alkaline, it can inhibit the decomposition of calcium and magnesium ions in the impurity removal residue, which is conducive to the selective leaching of lithium. After the reaction is completed, filter to obtain lithium-rich filtrate A and filter residue A.
[0074] Step S2: Add sodium hydroxide to lithium-rich filtrate A to adjust the pH to 12, transfer it to a constant temperature water bath and react at 68°C with stirring at 350 rpm for 30 min. After the reaction, take a uniform sample and send it for testing of calcium and magnesium components. Add sodium carbonate according to the calcium concentration at a coefficient of 1.1 and continue the reaction for 45 min to remove calcium. Separate the solid and liquid to obtain filter residue B and filtrate B. Filter residue B can be returned to step S1. Filtrate B is passed through an ion exchange resin at a flow rate of 5 mL / min for deep purification to remove residual impurity ions and obtain purified solution.
[0075] Step S3: The purified liquid is evaporated and concentrated to control the lithium concentration in the liquid at 19 g / L. The concentrated liquid is sent for component testing. Saturated sodium phosphate solution is added according to the lithium ion concentration at a coefficient of 1.2. The solution is transferred to a constant temperature water bath and reacted at 90°C for 4 hours with stirring at 350 rpm to precipitate lithium. After the reaction, the solution is filtered to obtain filtrate C and filter residue C. Filter residue C is mixed with deionized water at a solid-liquid ratio of 1:3 and washed three times. After washing, the solution is dried at 100°C for 4 hours to obtain battery-grade lithium phosphate.
[0076] Step S4: Add an appropriate amount of concentrated hydrochloric acid to filtrate C to adjust the pH to 3.5, transfer it to a constant temperature water bath, and react at 80°C for 60 minutes with stirring at 350 rpm to carry out the decarbonation reaction and remove carbonate ions. The solubility product of barium sulfate is much smaller than that of barium phosphate. Under acidic conditions, phosphate ions have a weaker binding ability with barium ions and can preferentially precipitate sulfate ions. Add excess barium chloride solution to the decarbonized liquid to generate white barium sulfate precipitate. Filter to obtain filtrate D and filter residue D, which is mainly composed of barium sulfate.
[0077] Step S5: Add calcium oxide to filtrate D to adjust the pH of the liquid to 9, transfer it to a constant temperature water bath and react at 68°C with stirring at 350 rpm for a period of time to generate calcium phosphate precipitate, filter to obtain filtrate E and filter residue E whose main component is calcium phosphate.
[0078] Step S6: Filtrate E mainly contains K + Na + Cl - and a small amount of excess reagent (such as Ca) 2 Ba 2+ ), filtrate E can be recovered by evaporation and crystallization to recover potassium chloride and sodium chloride salts.
[0079] This invention provides a water washing device for water washing treatment in the method of extracting lithium resources by removing impurities from spodumene.
[0080] First embodiment:
[0081] Please refer to the following: Figures 1 to 3 In this invention, the water washing equipment includes:
[0082] Bracket 1;
[0083] Tank 2, which is fixed on the support 1, has an isolation plate 201 fixed inside the tank 2. The isolation plate 201 is funnel-shaped and has filter holes 202. The bottom of the tank 2 is provided with a switch cover 21 and the top of the tank 2 is provided with a feed inlet 22.
[0084] The stirring mechanism 3 includes a mounting frame 31, a driving component 32, a first telescopic component 33, a slide 34, and a stirring rod 35. The bottom of the mounting frame 31 is fixed to the top of the tank body 2. The driving component 32 is mounted on the mounting frame 31. The fixed part of the first telescopic component 33 is fixed to the mounting frame 31. The slide 34 is slidably mounted on the mounting frame 31. The top of the slide 34 is fixedly connected to the telescopic part of the first telescopic component 33. The top of the stirring rod 35 passes through the top of the tank body 2 and is rotatably connected to the slide 34. The top of the stirring rod 35 has a connecting groove 350. The driving shaft of the driving component 32 is inserted into the connecting groove 350 and is connected to the top of the stirring rod 35 via a sliding key.
[0085] Pumping mechanism 4 is installed on the top of the tank 2 and is used to pump the solution within the range of the switch cover 21 upward.
[0086] A switching mechanism 7 is mounted on the bracket 1 and is used to control the opening and closing of the switch cover 21 relative to the tank body 2.
[0087] Specifically, when the bottom of the stirring rod 35 is inserted into the bottom of the isolation plate 201, the isolation plate 201 is in a closed state; when the bottom of the stirring rod 35 is completely separated from the bottom of the isolation plate 201, the isolation plate 201 is in an open state.
[0088] In this embodiment, the "sliding key connection" simply means that while the drive shaft of the drive member 32 rotates, it can stably drive the stirring rod 35 to rotate synchronously and adjust; at the same time, the stirring rod 35 can also be adjusted in height and sliding relative to the drive shaft of the drive member 32.
[0089] In this embodiment, the driving component 32 is a motor structure used to drive the stirring rod 35 to rotate and adjust.
[0090] The first telescopic member 33 can be any one of an electric telescopic rod, a hydraulic telescopic cylinder, or a telescopic cylinder, used to drive the lifting and lowering adjustment of the slide 34. The lifting and lowering adjustment of the slide 34 can synchronously drive the stirring rod 35 to lift and lower relative to the driving part of the first telescopic member 33.
[0091] In this embodiment, the stirring rod 35 includes two usage modes:
[0092] See also Figure 2 and Figure 3 Stirring and mixing mode: the first telescopic member 33 is in the extended state, the bottom of the stirring rod 35 is fully inserted into the output port of the isolation plate 201, the output port of the isolation plate 201 is in the closed state, and the switch cover 21 is in the closed state; facilitating the washing of materials;
[0093] like Figure 6 As shown, the discharge mode is as follows: the first telescopic member 33 is in a retracted state, the bottom of the stirring rod 35 is completely detached from the output port of the isolation enclosure 201, the output port of the isolation enclosure 201 is in an open state, and the switch cover 21 is in an open state; this facilitates the discharge of materials.
[0094] During material washing, the isolation plate 201 is provided inside the tank body 2. When the bottom of the stirring rod 35 is inserted into the outlet of the isolation plate 201, the material injected into the tank body 2 is easily isolated above the isolation plate 201. The stirring rod 35 can also fully mix the material and deionized water.
[0095] When discharging materials, the deionized water in the tank 2 is completely discharged first, and then the switch cover 21 is opened by the switch mechanism 7; the stirring rod 35 is moved upward by the first telescopic member 33 to realize the automatic opening of the outlet of the isolation plate 201;
[0096] After the isolation enclosure 201 is opened, the driving component 32 controls the stirring rod 35 to rotate, so as to facilitate the turbulence of the material after washing, so that the material can pass through the opened isolation enclosure 201 and the opened switch cover 21 to discharge downwards.
[0097] In this embodiment, the mixed deionized water is filtered through the filter hole 202 and stored below the isolation plate 201, while the material is blocked above by the isolation plate 201. The material will not directly communicate with the liquid outlet of the switch cover 21, thus preventing the material from being extracted when the deionized water is drawn out.
[0098] When the feed inlet 22 is open, it is convenient to add materials into the interior of the tank 2;
[0099] When the feed inlet 22 is closed, it facilitates stable water washing of the material inside the tank 2.
[0100] Specifically, the pumping mechanism 4 includes a gear pump 41, a first switching valve 42, and a second switching valve 43. The gear pump 41 is fixed to the top of the tank 2. The two input ends of the first switching valve 42 are respectively connected to the water inlet pipe 421 and the conveying pipe 5. The output end of the first switching valve 42 is connected to the input end of the gear pump 41.
[0101] The input end of the second switching valve 43 is connected to the output end of the gear pump 41. The two output ends of the second switching valve 43 are respectively connected to the water supply pipe 431 and the drain pipe 432. The output end of the water supply pipe 431 passes through the tank 2 and communicates with the interior of the tank 2.
[0102] The conveying pipe 5 is fixed on the bracket 1, and the input end of the conveying pipe 5 is fixedly connected to the output pipe of the switch cover 21 through the hose 6.
[0103] The gear pump 41 conveniently pumps deionized water through the first switching valve 42;
[0104] The inlet pipe 421 is connected to an external deionized water storage device. When the inlet pipe 421 is connected to the gear pump 41 through the first switching valve 42, it is convenient to add external deionized water into the tank 2.
[0105] When the conveying pipe 5 is connected to the gear pump 41 through the first switching valve 42, it facilitates the circulation and conveying of the deionized water after washing inside the tank 2 within the tank 2.
[0106] In this embodiment, the gear pump 41 includes three pumping modes:
[0107] Deionized water filling mode: The inlet pipe 421 is connected to the input end of the gear pump 41 through the first switching valve 42, and the supply pipe 431 is connected to the output end of the gear pump 41 through the second switching valve 43, so as to facilitate the filling of external deionized water into the inside of the tank 2;
[0108] Deionized water circulation mode: The conveying pipe 5 is connected to the input end of the gear pump 41 through the first switching valve 42, and the water supply pipe 431 is connected to the output end of the gear pump 41 through the second switching valve 43, which facilitates the circulation and delivery of deionized water inside the tank 2 during the water washing process, improves the fluidity of deionized water, and improves the water washing efficiency.
[0109] Deionized water discharge mode: The conveying pipe 5 is connected to the input end of the gear pump 41 through the first switching valve 42, and the drain pipe 432 is connected to the output end of the gear pump 41 through the second switching valve 43, which facilitates the discharge of deionized water inside the tank 2 after washing, and provides support for the discharge of materials after washing.
[0110] In this embodiment, the first switching valve 42 is a three-way solenoid valve in the prior art, which is a two-inlet and one-outlet type. The principle is: when energized, one inlet is open and the other inlet is closed; when de-energized, the order is reversed, which will not be elaborated on here.
[0111] The second switching valve 43 is a three-way solenoid valve in the prior art, which is a one-inlet, two-outlet type. When energized, one outlet opens and the other outlet closes; when de-energized, the order is reversed, which will not be elaborated on here.
[0112] In this embodiment, the hose 6 connects the delivery pipe 5 and the switch cover 21, providing support for the rotational opening of the switch cover 21.
[0113] Specifically, the switching mechanism 7 includes a second telescopic member 71 and a rotating arm 72. The fixed part of the second telescopic member 71 is hinged to the bracket 1. The middle part of the rotating arm 72 is rotatably mounted on the bracket 1. The telescopic part of the second telescopic member 71 is hinged to one end of the rotating arm 72. The other end of the rotating arm 72 is fixedly connected to the switch cover 21.
[0114] In this embodiment, the second telescopic member 71 is a hydraulic telescopic cylinder, which provides a power source for the rotational adjustment of the rotating arm 72.
[0115] The second telescopic component 71 facilitates the control of the rotational arm 72 on the bracket 1 for rotational adjustment.
[0116] When the rotating arm 72 rotates counterclockwise, it facilitates switching the switch cover 21 from the closed state to the open state.
[0117] When the rotating arm 72 rotates clockwise, it facilitates switching the switch cover 21 from the open state to the closed state.
[0118] This allows for convenient control of the switch cover 21's opening and closing via the second telescopic member 71, facilitating the discharge of materials after washing.
[0119] Specifically, the tank body 2 is also provided with an observation port 23.
[0120] The observation port 23 allows for convenient and direct observation of the washing process of the materials inside the tank 2.
[0121] The working principle of the water washing equipment provided in this embodiment is as follows:
[0122] A1, Material addition: Open the switch cover 21 and add the material to be washed into the tank 2 through the switch cover 21. After the material enters, it is stored above the isolation panel 201. Then close the switch cover 21.
[0123] A2, Add deionized water, switch the pumping mode of the gear pump 41 to the deionized water adding mode, start the gear pump 41, the gear pump 41 draws deionized water from the outside through the water inlet pipe 421 and pumps it into the inside of the tank 2, so that the material and deionized water are fully mixed.
[0124] A3, water washing treatment, start the drive unit 32, the drive unit 32 drives the stirring rod 35 to rotate, and the stirring rod 35 stirs and mixes the material and deionized water when it rotates;
[0125] While the materials are being stirred and mixed, the pumping mode of the gear pump 41 is switched to the deionized water circulation mode, the gear pump 41 is started, and the gear pump 41 draws water from the area of the switch cover 21 and delivers it to the top of the tank 2, forming a circulation of deionized water in the tank 2, thereby improving the washing efficiency.
[0126] A4, material discharge: First, switch the pumping mode of the gear pump 41 to the deionized water discharge mode, start the gear pump 41, and the gear pump 41 will completely extract the deionized water from the tank 2.
[0127] Then, the second telescopic component 71 is activated, which drives the rotating arm 72 to rotate counterclockwise. The rotating arm 72 drives the switch cover 21 to rotate counterclockwise, so that the switch cover 21 separates from the bottom of the tank body 2, thereby opening the bottom of the tank body 2.
[0128] Reactivate the first telescopic component 33, which drives the slide 34 to move upward. The slide 34 drives the stirring rod 35 to slide upward relative to the drive shaft of the drive component 32. As the stirring rod 35 slides upward, it gradually disengages from the output port of the isolation enclosure 201, causing the output port of the isolation enclosure 201 to open automatically.
[0129] After the outlet of the isolation panel 201 is opened, the material above the isolation panel 201 falls stably under the action of gravity and the rotation of the stirring rod 35, so that the material can be discharged stably.
[0130] Second embodiment:
[0131] Please refer to the following: Figure 7 and Figure 8 Based on the water washing device provided in the first embodiment of the present invention, the second embodiment of the present invention proposes another water washing 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.
[0132] Specifically, the difference in the water washing equipment provided in the second embodiment of the present invention is that the conveying pipe 5 is a filter pipe structure, and the filter pipe structure integrates an activated carbon filter layer and a quartz sand filter layer.
[0133] The washing equipment also includes a buffer box 8, which is fixed inside the tank 2. A switch 81 is provided at the bottom of the buffer box 8. The buffer box 8 is arranged around the stirring rod 35. The top opening of the buffer box 8 is aligned with the output end of the water supply pipe 431.
[0134] In this embodiment, the installation position of the buffer box 8 is staggered with the feeding range of the feed inlet 22, so that the material passing through the range of the feed inlet 22 can be stably fed downward into the tank 2.
[0135] In this embodiment, the switch 81 can be an electromagnetic switch valve structure, used to control the switch of the output terminal of the buffer box 8, so as to facilitate the independent control of the output terminal of the buffer box 8.
[0136] By using the conveying pipe fitting 5 with a filter structure, it is convenient to purify the circulating deionized water, so as to ensure the quality of the mixing of deionized water and materials and improve the quality and efficiency of water washing.
[0137] The buffer box 8 allows for the temporary storage of purified deionized water when materials need to be replaced, ensuring stable separation between the mixed deionized water and the materials. After separation, it facilitates the discharge and replacement of materials. After material replacement, the stored deionized water can be easily re-introduced into the tank 2 by opening the switch 81. This allows the previously used deionized water to be fully purified and reused, reducing the consumption and usage of deionized water and achieving the recycling of deionized water.
[0138] In this embodiment, the water washing area inside the tank 2 is located below the buffer box 8, so the washing of the material will not be affected by the buffer box 8, thus ensuring the stability of the equipment operation.
[0139] Specifically, when the output end of the buffer box 8 is opened, the deionized water entering the buffer box 8 through the water supply pipe 431 is discharged naturally downwards after passing through the switch 81, ensuring the circulation of deionized water in the tank 2 from bottom to top.
[0140] During the deionized water circulation process, as the deionized water passes through the conveying pipe 5, the conveying pipe 5 filters and purifies the deionized water after the mixed water washing, ensuring the quality of the deionized water after each circulation, thereby improving the washing quality and efficiency.
[0141] When the output end of the buffer box 8 is closed, the deionized water entering the buffer box 8 through the water supply pipe 431 can be temporarily stored within the buffer box 8, achieving the isolation and separation of materials and deionized water. This eliminates the need to discharge and replace the deionized water before material discharge, reducing the consumption of deionized water.
[0142] The working principle of the water washing equipment provided in this embodiment:
[0143] B1, when adding or circulating deionized water, the output end of the buffer box 8 is kept open by the switch 81, so that the deionized water entering the buffer box 8 through the water supply pipe 431 can be stably transported downward and mixed with the material in the tank 2, so as to facilitate stable water washing of the material.
[0144] B2, Deionized water circulation filtration treatment: While the deionized water is being transported by the conveying pipe 5, the activated carbon layer and quartz sand layer inside the conveying pipe 5 purify the deionized water, so that the deionized water pumped in circulation can ensure the quality after use, improve the washing efficiency, and reduce the total amount of deionized water required during the material washing process.
[0145] B3. When deionized water is discharged, the second switching valve 43 does not need to be switched. It is only necessary to control the output end of the buffer box 8 to be adjusted to the closed state through the switch 81, so that the deionized water delivered through the water supply pipe 431 is stably stored in the buffer box 8 until the deionized water above the switch cover 21 is completely extracted, and only the washed material is left above the isolation plate 201, so as to temporarily store the purified deionized water during discharge.
[0146] Third embodiment:
[0147] Please see Figure 9 Based on the water washing device provided in the second embodiment of the present invention, the third embodiment of the present invention proposes another water washing device. The third embodiment is merely a preferred embodiment of the first embodiment, and the implementation of the third embodiment will not affect the separate implementation of the first embodiment.
[0148] Specifically, the washing device provided in the third embodiment of the present invention is different in that the bottom of the buffer box 8 is provided with a switch port 801, the switch member 81 is a piston shaft structure, the top of the switch member 81 passes through the switch port 801 and then through the top of the tank body 2, and the top of the switch member 81 is fixedly connected to the bottom of the slide 34.
[0149] When the piston portion of the switch element 81 separates from the switch port 801, the switch port 801 opens; when the piston portion of the switch element 81 slides and seals with the switch port 801, the switch port 801 closes.
[0150] In this embodiment, the switch 81 adopts a piston shaft structure and is connected to the slide 34, which facilitates the simultaneous movement and adjustment of the switch 81 while the first telescopic member 33 controls the lifting and lowering of the slide 34.
[0151] During the process of the slide 34 driving the stirring rod 35 to switch from the stirring and mixing mode to the discharge mode, the slide 34 simultaneously drives the switch 81 to move upward and slides to seal at the switch port 801, so as to realize the adaptive closing of the buffer box 8, so as to facilitate the storage of deionized water after washing and the discharge of materials.
[0152] Similarly, during the process of the slide 34 driving the stirring rod 35 to switch from the discharge mode to the mixing mode, the slide 34 simultaneously drives the switch 81 to move down and away from the switch port 801, so as to realize the adaptive opening of the buffer box 8, so as to facilitate the addition of the next round of materials, mix the stored deionized water with the materials, facilitate the continuous use of deionized water, and extend the service life of deionized water.
[0153] The working principle of the water washing equipment provided in this embodiment:
[0154] C1, When it is necessary to drain the deionized water used for washing in the tank 2, please refer to [reference needed]. Figures 9 to 10 First, the first telescopic component 33 is activated, which drives the slide 34 to move upward. The slide 34, on the one hand, drives the stirring rod 35 to move upward, thus keeping the outlet of the isolation panel 201 closed.
[0155] On the other hand, the slide 34 drives the switch 81 to move upward, so that the switch 81 blocks the area of the switch opening 801, and the switch opening 801 switches from the open state to the closed state.
[0156] C2, start the gear pump 41, the gear pump 41 circulates and pumps the deionized water after washing the tank 2 to the buffer box 8 for temporary storage of the purified deionized water.
[0157] C3, after the deionized water and the material are completely separated, first open the switch cover 21. Please refer to the following: Figure 10 and Figure 11 The first telescopic component 33 is activated again, and the first telescopic component 33 drives the slide 34 to continue to move upward. The slide 34 drives the stirring rod 35 to move upward, so that the outlet of the isolation panel 201 opens.
[0158] On the other hand, the slide 34 drives the switch 81 to move upward, so that the switch 81 maintains a sliding block with the switch opening 801, so that the switch opening 801 remains closed, facilitating the discharge of materials.
[0159] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention specification and drawings under the concept of the present invention, 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 extracting lithium resources using spodumene residue, characterized in that, Includes the following steps: Step S1, material leaching treatment: Weigh the spodumene residue and mix it with the frozen clear liquid. Stir and leaching reaction is carried out at room temperature. After the reaction is completed, filter to obtain lithium-rich filtrate A and filter residue A. Step S2, calcium removal and purification treatment: Sodium hydroxide is added to lithium-rich filtrate A to adjust the pH, and the solution is transferred to a constant temperature water bath for constant temperature stirring reaction. After the reaction is completed, a uniform sample is taken and sent for analysis of calcium and magnesium components. Sodium carbonate is added according to the calcium concentration to continue the reaction to remove calcium. Solid-liquid separation is performed to obtain filter residue B and filtrate B. Filter residue B is reused in step S1. Filtrate B is passed through an ion exchange resin at a certain flow rate for deep purification to remove residual impurity ions and obtain purified solution. Step S3, lithium extraction treatment: the purified liquid is evaporated and concentrated to control the lithium concentration in the liquid. The concentrated liquid is sent for analysis of its components. Saturated sodium phosphate solution is added according to the lithium ion concentration. The mixture is transferred to a constant temperature water bath and stirred at a constant temperature to precipitate lithium. After the reaction is completed, the mixture is filtered to obtain filtrate C and filter residue C. Filter residue C is mixed with deionized water and washed three times. After washing, it is dried to obtain battery-grade lithium phosphate.
2. The method for extracting lithium resources using spodumene residue according to claim 1, characterized in that, In step S1, the solid-liquid ratio of spodumene impurity removal residue to cryogenic liquid is 1:4~5.
3. The method for extracting lithium resources using spodumene residue according to claim 1, characterized in that, In step S1, the stirring speed of the leaching reaction is 350 rpm, and the reaction time is 2 hours.
4. The method for extracting lithium resources using spodumene residue according to claim 1, characterized in that, The pH adjustment range in step S2 is 11.5~12.
5.
5. The method for extracting lithium resources using spodumene residue according to claim 1, characterized in that, In step S2, the isothermal stirring reaction is carried out at 350 rpm at 68°C for 30 min.
6. The method for extracting lithium resources using spodumene residue according to claim 1, characterized in that, In step S2, sodium carbonate is added at a calcium concentration of 1.1 to 1.2, and the reaction continues for 45 minutes.
7. The method for extracting lithium resources using spodumene residue according to claim 1, characterized in that, In step S2, filtrate B is passed through the ion exchange resin at a flow rate of 5 mL / min.
8. The method for extracting lithium resources using spodumene residue according to claim 7, characterized in that, In step S3, the lithium concentration is controlled at 15~19 g / L.
9. The method for extracting lithium resources using spodumene residue according to claim 8, characterized in that, In step S3, saturated sodium phosphate solution is added according to the lithium ion concentration at a coefficient of 1.1 to 1.
2.
10. The method for extracting lithium resources using spodumene residue according to claim 9, characterized in that, In step S3, the constant temperature stirring reaction is carried out at a stirring speed of 350 rpm at 90~95℃ for 3~4 hours; the filter residue C is mixed with deionized water at a solid-liquid ratio of 1:3.