Brine adsorbent preparation wastewater treatment device and preparation method

Abstract

This invention provides a wastewater treatment device and preparation method for brine adsorbent preparation. The wastewater treatment device includes: a support frame; and a treatment vessel mounted on the support frame. The treatment vessel is used to add wastewater and treatment reagents for reaction. A feed trough is installed at the top of the treatment vessel, and a discharge trough is installed at the bottom. The wastewater treatment device and preparation method provided by this invention, through the two extensions of the pushing component, can transform the device from a mixing state to a filtering state and then to a cleaning state, integrating multiple functions into one unit and enabling rapid wastewater treatment. When the device is in the filtering state, it can be used with a cleaning structure to sweep away the filtered sediment, preventing sediment accumulation at the filter pores of the filter plate, improving the filtration efficiency of the pores, and avoiding filter clogging.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment, and more particularly to a wastewater treatment device and preparation method for preparing brine adsorbent. Background Technology

[0002] Lithium, as a strategic metal in the new energy field, is crucial for the global energy transition due to its efficient development. Salt lake brines account for over 60% of global lithium reserves, but my country's salt lakes generally exhibit high magnesium-to-lithium ratios and low lithium concentrations. The magnesium-to-lithium ratio often reaches over 40, even hundreds of times, with only a small amount of lithium. + With a large amount of Mg 2+ The coexistence of magnesium and lithium makes their separation extremely difficult. Adsorption methods, due to their simple operation, high selectivity, environmental friendliness, and applicability to low-grade brine, are considered one of the most promising technologies for lithium extraction from high-magnesium-to-lithium ratio salt lakes. The core of this approach lies in the development of high-performance adsorbents. Currently, lithium-ion sieve adsorbents are mainly divided into manganese-based and titanium-based systems. While manganese-based ion sieves have high adsorption capacity, they suffer from manganese dissolution due to the Jahn-Teller effect, and their crystal structure is prone to collapse during acid leaching and desorption, resulting in poor cycle stability. In contrast, titanium-based ion sieves, due to their stable Ti-O bonds, exhibit low titanium dissolution rates and excellent structural stability during acid leaching, and have received widespread attention in recent years.

[0003] However, the large-scale preparation of titanium-based ion sieve adsorbents inevitably generates a large amount of industrial wastewater. If directly discharged or treated inadequately, it will cause serious harm to the ecological environment and human health. The pollutants in this type of preparation wastewater mainly come from raw material residues, reaction byproducts, and process auxiliary reagents during the preparation process. With the deepening of the global industrial green development concept and increasingly stringent environmental regulations, the compliant discharge and resource recycling of industrial wastewater have become a key bottleneck for the sustainable development of the titanium-based ion sieve adsorbent industry.

[0004] Currently, most wastewater treatment methods involve neutralization, sedimentation, and filtration. However, in traditional wastewater treatment devices, the filter pores of the filter plate are easily covered by impurities during the filtration process, resulting in low liquid throughput and affecting water filtration performance. This can also easily cause filter plate blockage, making it unsuitable for continuous production needs. Furthermore, sediment will adhere to the vessel wall during discharge, leading to scale buildup that is difficult to clean over time.

[0005] Therefore, it is necessary to provide a wastewater treatment device and preparation method for brine adsorbent preparation to solve the above-mentioned technical problems. Summary of the Invention

[0006] This invention provides a wastewater treatment device and preparation method for brine adsorbent preparation, which solves the problem that the filter pores of the filter plate are easily covered by impurities, resulting in low liquid throughput efficiency, affecting water filtration performance, and also easily causing filter plate blockage.

[0007] To solve the above-mentioned technical problems, the wastewater treatment device for brine adsorbent preparation provided by the present invention includes: a support frame;

[0008] The treatment vessel is mounted on the support frame. The treatment vessel is used to add wastewater and add treatment agents to carry out the reaction. The top of the treatment vessel is equipped with a feed chute and the bottom of the treatment vessel is equipped with a discharge chute.

[0009] A stirring assembly is installed on the treatment vessel and is used for mixing and stirring during wastewater treatment.

[0010] A blocking assembly is mounted on the support frame and is in close contact with the discharge chute to block the discharge chute. In use, the blocking assembly opens the discharge chute through vertical linear movement.

[0011] A filter assembly, which is mounted on the support frame, is used for solid-liquid separation after wastewater treatment.

[0012] A drive assembly is mounted on the processing vessel and is used to drive the stirring assembly, the sealing assembly, and the filtering assembly.

[0013] Preferably, the stirring assembly includes a sleeve rod, a stirring disc, and a wall scraping structure. The sleeve rod is rotatably connected to the processing vessel, and the top end of the sleeve rod penetrates the processing vessel and extends to the top of the processing vessel. The stirring disc is fixed to the outer surface of the sleeve rod, and the wall scraping structure is installed on the outer surface of the sleeve rod.

[0014] Preferably, the scraping structure includes a hollow rod, a fixing block, a connecting rod, a first inclined block, a first elastic element, and a scraper. The hollow rod is fixed to the sleeve rod, the fixing block is fixed inside the hollow rod, the connecting rod is slidably connected to the fixing block, the first inclined block is fixed to one end of the connecting rod, the first elastic element is installed between the fixing block and the first inclined block, and the scraper is fixed to the other end of the connecting rod.

[0015] Preferably, the sealing assembly includes a movable plate, a sealing plate, a pressing block, and a support plate. The movable plate is slidably connected to the support frame, the sealing plate is fixed to the movable plate, the sealing plate abuts against the discharge chute, the pressing block is fixed to the bottom of the movable plate, the support plate is fixed to the bottom of the movable plate, and the support plate is located outside the pressing block.

[0016] Preferably, the filter assembly includes a mounting block, a fixing frame, a sliding rod, a filter plate, a cleaning structure, and a limiting structure. The mounting block is fixed to the support frame, the fixing frame is fixed to the mounting block, the sliding rod is slidably connected to the fixing frame, the filter plate is fixed to the bottom of the sliding rod, the cleaning structure is mounted on the filter plate, and the limiting structure is mounted on the fixing frame. The limiting structure is used to fix the sliding rod.

[0017] Preferably, the cleaning structure includes a rotating shaft, a groove, and a cleaning component. The rotating shaft is rotatably connected to the filter plate, the groove is formed on the rotating shaft, and the cleaning component is mounted on the rotating shaft.

[0018] Preferably, the limiting structure includes a connecting block, a sliding block, a second elastic element, a limiting block, and a second inclined block. The connecting block is fixed to the fixed frame, the sliding block is slidably connected to the fixed frame, the second elastic element is installed between the connecting block and the sliding block, the limiting block is fixed to the sliding block, and the second inclined block is fixed to the top of the sliding block.

[0019] Preferably, the drive assembly includes a fixed frame, a sliding plate, a pusher, a drive member, a drive rod, a conical block, and a protrusion. The fixed frame is fixed to the processing vessel, the sliding plate is slidably connected to the fixed frame, the pusher is fixed to the fixed frame, and the output end of the pusher is fixed to the sliding plate. The drive member is fixed to the sliding plate, the drive rod is fixed to the output shaft of the drive member, the conical block is fixed to the outer surface of the drive rod, and the protrusion is fixed to the bottom end of the drive rod.

[0020] This invention also provides a method for preparing a brine adsorbent, comprising the following steps:

[0021] Step 1, Preparation of mixed-crystal TiO2 support: using metatitanic acid as raw material, calcination is carried out to obtain anatase TiO2; then the obtained anatase TiO2 is heated and held at that temperature to form rutile phase on the surface of anatase grains, thus obtaining a TiO2 support with mixed-crystal effect.

[0022] Step 2, Synthesis of doped titanium-based ion sieve precursor: The mixed-crystal TiO2 obtained in Step 1 is dispersed in deionized water, lithium source and doped element precursor are added, and the mixture is stirred and mixed evenly to obtain a mixed slurry; the mixed slurry is dried, pulverized and sieved to obtain a mixed powder; the mixed powder is calcined to obtain a titanium-based lithium ion sieve precursor doped with heterogeneous elements.

[0023] Step 3, Acid washing to remove lithium and create pores: Add the doped precursor obtained in step 2 to an inorganic acid solution and shake to react; after the reaction is completed, filter and wash until neutral to obtain wet material of doped H2TiO3 ion sieve. The acidic wastewater generated during the washing process is treated by the wastewater treatment device as described in any one of claims 1-8 and then discharged.

[0024] Step 4, surface hydrophilic modification: The wet material of doped H2TiO3 ion sieve obtained in step 3 is redispersed in anhydrous ethanol or toluene, and a silane coupling agent containing sulfonic acid group, carboxyl group or phosphate group is added for reflux reaction. After the reaction is completed, the material is filtered, washed and vacuum dried to obtain the surface-modified doped titanium ion sieve adsorbent.

[0025] Compared with related technologies, the wastewater treatment device and preparation method for brine adsorbent preparation provided by the present invention have the following beneficial effects:

[0026] This invention provides a wastewater treatment device and preparation method for brine adsorbent preparation. Through the two-stage extension of the pushing component, the device can switch from a mixing state to a filtering state and then to a cleaning state, integrating multiple functions into one unit to achieve rapid wastewater treatment. When the device is in the filtering state, it can be used with a cleaning structure to sweep away the filtered sediment, preventing sediment buildup at the filter plate pores, improving filtration efficiency, and avoiding pore blockage. When the device is in the cleaning state, it can be used with a wall scraping structure and a cleaning structure to clean the treatment vessel and filter plate, preventing scale formation caused by prolonged sediment adhesion and reducing subsequent maintenance costs. Attached Figure Description

[0027] Figure 1 A schematic diagram of a preferred embodiment of the wastewater treatment device for preparing brine adsorbent provided by the present invention;

[0028] Figure 2 for Figure 1 A schematic cross-sectional view of the processing vessel shown;

[0029] Figure 3 for Figure 2 The diagram shows the structure of the stirring assembly.

[0030] Figure 4 for Figure 2 A cross-sectional schematic diagram of the stirring assembly shown;

[0031] Figure 5 for Figure 1 The diagram shows the structure of the sealing assembly.

[0032] Figure 6 for Figure 1 The diagram shows the structure of the filter assembly.

[0033] Figure 7 for Figure 6 A cross-sectional view of the fixed frame shown;

[0034] Figure 8 for Figure 1 The diagram shows the structure of the driving component.

[0035] Figure 9 Initial state diagram of the wastewater treatment device for preparing brine adsorbent provided by the present invention;

[0036] Figure 10 This is a schematic diagram showing the state of the pusher component after its initial extension.

[0037] Figure 11 This is a schematic diagram showing the state of the pusher component after its secondary extension.

[0038] Numbering on the map:

[0039] 1. Support frame; 2. Processing vessel; 3. Feed chute; 4. Discharge chute;

[0040] 5. Stirring assembly; 51. Sleeve rod; 52. Stirring disc; 53. Scraper structure; 531. Hollow rod; 532. Fixing block; 533. Connecting rod; 534. First inclined block; 535. First elastic element; 536. Scraper.

[0041] 6. Sealing assembly; 61. Moving plate; 62. Sealing plate; 63. Pressing block; 64. Support plate;

[0042] 7. Filter assembly; 71. Mounting block; 72. Fixing frame; 73. Sliding rod; 74. Filter plate; 75. Cleaning structure; 751. Rotating shaft; 752. Groove; 753. Cleaning component; 76. Limiting structure; 761. Connecting block; 762. Sliding block; 763. Second elastic element; 764. Limiting block; 765. Second inclined block;

[0043] 8. Drive assembly; 81. Fixing frame; 82. Sliding plate; 83. Pushing component; 84. Drive component; 85. Drive rod; 86. Conical block; 87. Protrusion. Detailed Implementation

[0044] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0045] Please refer to the following: Figures 1-11 The present invention provides a wastewater treatment device for the preparation of brine adsorbent, comprising: a support frame 1;

[0046] The treatment vessel 2 is mounted on the support frame 1. The treatment vessel 2 is used to add wastewater and add treatment agents for reaction. The top of the treatment vessel 2 is equipped with a feed chute 3 and the bottom of the treatment vessel 2 is equipped with a discharge chute 4.

[0047] A stirring assembly 5 is installed on the treatment vessel 2 and is used for mixing and stirring during wastewater treatment.

[0048] A sealing component 6 is mounted on the support frame 1 and is in close contact with the discharge chute 4 to seal the discharge chute 4. In use, the sealing component 6 opens the discharge chute 4 through vertical linear movement.

[0049] Filter assembly 7, which is mounted on the support frame 1, is used for solid-liquid separation after wastewater treatment;

[0050] A drive assembly 8 is installed on the processing vessel 2 and is used to drive the stirring assembly 5, the sealing assembly 6, and the filtering assembly 7.

[0051] In this embodiment, the feed trough 3 is provided with a cover, which enables the feed trough 3 to be opened and closed.

[0052] In this embodiment, all electrical devices of this device are connected to an external power source through a control panel. This is a relatively mature existing technology and will not be described in detail here.

[0053] Please refer to the following: Figure 3 and Figure 4 The stirring assembly 5 includes a sleeve rod 51, a stirring disc 52, and a wall scraping structure 53. The sleeve rod 51 is rotatably connected to the processing vessel 2. The top end of the sleeve rod 51 passes through the processing vessel 2 and extends to the top of the processing vessel 2. The stirring disc 52 is fixed to the outer surface of the sleeve rod 51, and the wall scraping structure 53 is installed on the outer surface of the sleeve rod 51.

[0054] In this embodiment, the sleeve 51 includes a thin section and a thick section, and the tapered block 86 is located within the thick section.

[0055] In this embodiment, the sleeve 51 is slidably connected to the drive rod 85, and the sliding direction is vertical.

[0056] In other embodiments, a groove (vertical) is formed inside the sleeve rod 51, and a slider is fixed on the surface of the drive rod 85, and the slider is slidably connected in the groove, which can ensure that the drive rod 85 can drive the sleeve rod 51 to rotate when it rotates, and the drive rod 85 can slide vertically inside the sleeve rod 51.

[0057] When in use, the rotation of the drive rod 85 can drive the sleeve rod 51 to rotate, which in turn drives the stirring plate 52 to rotate, realizing the stirring during wastewater treatment. During stirring, the scraper structure 53 does not contact the inner wall of the treatment vessel 2, reducing wear.

[0058] Please refer to it again. Figure 4 The scraping structure 53 includes a hollow rod 531, a fixing block 532, a connecting rod 533, a first inclined block 534, a first elastic element 535, and a scraper 536. The hollow rod 531 is fixed to the sleeve rod 51, the fixing block 532 is fixed inside the hollow rod 531, the connecting rod 533 is slidably connected to the fixing block 532, the first inclined block 534 is fixed to one end of the connecting rod 533, the first elastic element 535 is installed between the fixing block 532 and the first inclined block 534, and the scraper 536 is fixed to the other end of the connecting rod 533.

[0059] In this embodiment, the first elastic element 535 may include, but is not limited to, a spring, an elastic rib, or a negative pressure telescopic cylinder, etc., as long as it provides a reverse elastic force to the first inclined block 534 when the first inclined block 534 moves toward the fixed block 532.

[0060] Furthermore, the elastic force of the first elastic element 535 needs to overcome the centrifugal force when the sleeve rod 51 rotates, so that the scraper 563 will not be thrown out when the sleeve rod 51 is rotating.

[0061] In use, when the drive rod 85 moves downward, it will drive the conical block 86 to move downward, thereby squeezing the first inclined block 534 through the inclined surface of the first inclined block 534, causing the first inclined block 534 to move toward the fixed block 532, thereby causing the connecting rod 533 to extend outward, and then causing the scraper 536 to come into contact with the inner wall of the processing vessel 2. Then, with the rotation of the drive rod 85, the sleeve rod 51 rotates, thereby indirectly causing the scraper 536 to move in a circular motion, scraping off the sediment attached to the inner wall of the processing vessel 2.

[0062] In other embodiments, the scraper 536 can be detachably mounted on the connecting rod 533 by means of bolts or clips, which facilitates the replacement of the scraper 536 after it wears out.

[0063] Please refer to the following: Figure 5 The sealing assembly 6 includes a movable plate 61, a sealing plate 62, a pressing block 63, and a support plate 64. The movable plate 61 is slidably connected to the support frame 1. The sealing plate 62 is fixed to the movable plate 61 and abuts against the discharge chute 4. The pressing block 63 is fixed to the bottom of the movable plate 61. The support plate 64 is fixed to the bottom of the movable plate 61 and is located outside the pressing block 63.

[0064] In this embodiment, the sealing plate 62 is rotatably connected to the drive rod 85, and the sealing plate 62 is provided with a sealing element to ensure the sealing performance of the sealing plate 62 when sealing the discharge chute 4.

[0065] In this embodiment, the pressing block 63 is located above the limiting structure 76;

[0066] In one embodiment, the lower pressure block 63 may also be provided with a roller to facilitate rolling on the limiting structure 76 and reduce friction.

[0067] In this embodiment, the tray 64 is L-shaped, and in the initial state, the bottom of the tray 64 abuts against the bottom of the filter plate 74.

[0068] Please refer to the following: Figure 10 In the filtering state, after the sealing component 6 moves downward, the discharge chute 4 opens to discharge material. At this time, the tray 64 no longer contacts the filter plate 74, and the filter plate 74 is fixed by the limiting structure 76.

[0069] Please refer to the following: Figure 11 In the cleaning state, the sealing component 6 continues to move downward, causing the pressing block 63 to press down and open the limiting structure 76. After the sliding rod 73 loses its limit, the filter plate 74 will fall.

[0070] The support plate 64 can lift the filter plate 74. When the pusher 83 retracts and resets, it will drive the drive rod 85 to move upward, thereby causing the sealing component 6 to move upward. Then, the support plate 64 moves upward and touches the filter plate 74, lifting the filter plate 74 upward and resetting it. After the sliding rod 73 slides upward, it is fixed again by the limiting structure 76.

[0071] Please refer to the following: Figure 6 and Figure 7 The filter assembly 7 includes a mounting block 71, a fixing frame 72, a sliding rod 73, a filter plate 74, a cleaning structure 75, and a limiting structure 76. The mounting block 71 is fixed to the support frame 1, the fixing frame 72 is fixed to the mounting block 71, the sliding rod 73 is slidably connected to the fixing frame 72, the filter plate 74 is fixed to the bottom of the sliding rod 73, the cleaning structure 75 is installed on the filter plate 74, and the limiting structure 76 is installed on the fixing frame 72. The limiting structure 76 is used to fix the sliding rod 73.

[0072] In this embodiment, the filter plate 74 is umbrella-shaped, which facilitates the conduction of the filtered sediment to the edge.

[0073] In other embodiments, the filter plate 74 is detachably mounted on the bottom of the sliding rod 73 for easy replacement of the filter plate 74.

[0074] In this embodiment, the mounting block 71 has a through groove, which allows the tray 64 to pass through and provides space for the tray 64 to move downward.

[0075] In this embodiment, a filter structure is formed by a fixed frame 72 and a filter plate 74. When the filter plate 74 is in close contact with the fixed frame 72, it can play a solid-liquid separation role. When the filter plate 74 leaves the fixed frame 72, the two are connected by a sliding rod 73, and the separated sediment will be discharged from the gap between the filter plate 74 and the fixed frame 72.

[0076] Please refer to it again. Figure 7 The cleaning structure 75 includes a rotating shaft 751, a groove 752, and a cleaning component 753. The rotating shaft 751 is rotatably connected to the filter plate 74, the groove 752 is formed on the rotating shaft 751, and the cleaning component 753 is installed on the rotating shaft 751.

[0077] In this embodiment, the cleaning component 753 includes, but is not limited to, a cleaning brush, a scraper, or a soft rubber strip, as long as it can sweep away the sediment on the surface of the filter plate 74.

[0078] In this embodiment, the groove 752 is adapted to the protrusion 87.

[0079] In this embodiment, the number of cleaning components 753 is at least one.

[0080] In use, when the protrusion 87 aligns with the groove 752, the rotation of the drive component 84 drives the drive rod 85 to rotate, thereby causing the protrusion 87 to rotate, which in turn drives the rotating shaft 751 to rotate, causing the cleaning component 753 to perform a circular motion. This sweeps away the filtered sediment, causing it to slide off to the edge of the filter plate 74, exposing the filter holes and preventing it from remaining at the filter holes of the filter plate 74 and affecting water filtration.

[0081] Please refer to it again. Figure 7 The limiting structure 76 includes a connecting block 761, a sliding block 762, a second elastic element 763, a limiting block 764, and a second inclined block 765. The connecting block 761 is fixed to the fixed frame 72, the sliding block 762 is slidably connected to the fixed frame 72, the second elastic element 763 is installed between the connecting block 761 and the sliding block 762, the limiting block 764 is fixed to the sliding block 762, and the second inclined block 765 is fixed to the top of the sliding block 762.

[0082] In this embodiment, the sliding rod 73 has a through hole that matches the limiting block 764. The limiting block 764 is inserted into the through hole to fix the sliding rod 73.

[0083] In this embodiment, the top of the sliding rod 73 is a slope. When the sliding rod 73 moves upward to reset, the limiting block 764 can be squeezed to one side through the slope. When the limiting block 764 is aligned with the through hole, it will be locked in the through hole, which facilitates reset.

[0084] In other embodiments, one side of the limiting block 764 may also be an arc surface, which facilitates its use in conjunction with the sliding rod 73.

[0085] In this embodiment, the second elastic element 763 includes, but is not limited to, a spring, an elastic rib, or a negative pressure telescopic cylinder, etc., as long as it provides a reverse elastic force to the sliding block 762 when the sliding block 762 moves toward the connecting block 761.

[0086] In the initial state, the limiting block 764 is inserted into the through hole of the sliding rod 73 to fix the sliding rod 73. When in use, after the pressing block 63 moves down and abuts against the second inclined block 765, the inclined surface of the second inclined block 765 pushes the second inclined block 765 outward, so that the sliding block 762 slides toward the connecting block 761. At this time, the limiting block 764 will move out of the through hole of the sliding rod 73 and no longer limit the sliding rod 73.

[0087] Please refer to the following: Figure 8 The drive assembly 8 includes a fixed frame 81, a sliding plate 82, a pusher 83, a drive member 84, a drive rod 85, a conical block 86, and a protrusion 87. The fixed frame 81 is fixed to the processing vessel 2. The sliding plate 82 is slidably connected to the fixed frame 81. The pusher 83 is fixed to the fixed frame 81, and the output end of the pusher 83 is fixed to the sliding plate 82. The drive member 84 is fixed to the sliding plate 82. The drive rod 85 is fixed to the output shaft of the drive member 84. The conical block 86 is fixed to the outer surface of the drive rod 85, and the protrusion 87 is fixed to the bottom end of the drive rod 85.

[0088] In this embodiment, the pushing component 83 may include, but is not limited to, electric push rods, cylinders, hydraulic cylinders or linear motors, etc., as long as it can drive the sliding plate 82 to move linearly in the vertical direction.

[0089] In this embodiment, the driving component 84 may include, but is not limited to, a motor, a pneumatic motor, or a hydraulic motor, as long as it can provide rotational power to the driving rod 84.

[0090] In use, the rotation of the driving component 84 can drive the driving rod 85 to rotate, which in turn can drive the protrusion 87 to rotate. When the protrusion 87 is engaged with the cleaning structure 75, the cleaning structure can be driven.

[0091] The extension of the pusher 83 can cause the sliding plate 82 to slide downward, which in turn can cause the drive rod 85 to slide downward, thereby causing the conical block 86 and the protrusion 87 to move downward. This can control the expansion of the scraping structure 53 and the docking of the protrusion 87 with the cleaning structure 75. The drive rod 85 is rotatably connected to the sealing plate 62, which can also control the sealing assembly 6 to achieve the sealing or opening function.

[0092] The working principle of the wastewater treatment device and preparation method for brine adsorbent preparation provided by this invention is as follows:

[0093] Wastewater and treatment agents are added into the treatment vessel 2 from the feed tank 3. Then, the rotation of the drive component 84 drives the drive rod 85 to rotate, thereby causing the sleeve rod 51 to rotate and drive the stirring plate 52 to rotate, so that the wastewater and treatment agents are evenly mixed and precipitate is produced after the reaction.

[0094] After the reaction is completed, the extension of the pusher 83 can drive the sliding plate 82 to move downward, which in turn causes the drive rod 85 to move downward, causing the sealing component 6 to slide downward, thereby opening the discharge trough 4. The material is discharged from the discharge trough 4 into the filter component 7 for solid-liquid separation. As the drive rod 85 moves downward, the protrusion 87 will dock with the cleaning structure 75 downward. With the rotation of the drive member 84, the drive rod 85 will drive the cleaning structure 75 to rotate, which can sweep the filtered sediment and prevent it from standing in the filter holes of the filter plate 74.

[0095] After filtration, the extension of the pusher 83 causes the sliding plate 82 to continue moving downward, which in turn causes the drive rod 85 to continue moving downward. This causes the conical block 86 to press against the scraping structure 53, making the scraping structure 53 abut against the inner wall of the treatment vessel 2. After the drive rod 85 moves downward, it causes the sealing assembly 6 to move downward, causing the pressing block 63 to abut against the limiting structure 76, opening the limiting structure 76. This allows the limiting structure 76 to no longer restrict the sliding rod 73. At this time, the filter plate 74 will fall, and the filtered sediment will be discharged from the area between the filter plate 74 and the fixed frame 72. The protrusion 87 remains connected to the cleaning structure 75. In conjunction with the rotation of the driveer 84, the drive rod 85 rotates, causing the scraping structure 53 to clean the inner wall of the treatment vessel 2, and causing the cleaning structure 75 to clean the filter plate 74.

[0096] Compared with related technologies, the wastewater treatment device and preparation method for brine adsorbent preparation provided by the present invention have the following beneficial effects:

[0097] This invention enables the device to switch from a mixing state to a filtering state and then to a cleaning state through the two extensions of the pusher 83, integrating multiple functions into one unit and enabling rapid wastewater treatment. When the device is in the filtering state, it can be used with the cleaning structure 75 to sweep away the filtered sediment, preventing sediment from accumulating at the filter holes of the filter plate 74, improving the filtration efficiency of the filter holes, and avoiding filter hole clogging. When the device is in the cleaning state, it can be used with the wall scraping structure 53 and the cleaning structure 75 to clean the treatment vessel 2 and the filter plate 74, avoiding the phenomenon of scale formation caused by long-term sediment adhesion and reducing subsequent maintenance costs.

[0098] In one instance, this wastewater treatment device can be used to treat acidic wastewater generated during the washing process in a method for preparing a brine adsorbent.

[0099] In another scenario, this wastewater treatment device can be used to treat lithium precipitation mother liquor wastewater after lithium extraction from salt lakes / oilfield brine.

[0100] This invention also provides a method for preparing a brine adsorbent, comprising the following steps:

[0101] Step 1: Preparation of mixed-crystal TiO2 support: Metatitanic acid is used as raw material and calcined in a muffle furnace at 500-600℃ for 3-8 hours to obtain anatase TiO2; then the obtained anatase TiO2 is heated to 850-950℃ and held for 0.5-2 hours to form rutile phase on the surface of anatase grains, thus obtaining a TiO2 support with mixed-crystal effect; the mass ratio of rutile phase in the mixed-crystal TiO2 is 15%-40%;

[0102] Step 2, Synthesis of Doped Titanium Ion Sieve Precursor: The mixed-crystal TiO2 obtained in Step 1 is dispersed in deionized water, and a lithium source and dopant precursor are added. The mixture is stirred and stirred until homogeneous to obtain a mixed slurry. The lithium source is at least one of lithium hydroxide, lithium carbonate, or lithium acetate, and the molar ratio of Li to Ti is (2.1-2.5):1. The dopant precursor is a nitrate, chloride, or alkoxide of lanthanum, cerium, scandium, yttrium, zirconium, niobium, or tantalum, and the dopant element accounts for 0.5%-8.0% of the molar amount of titanium.

[0103] The mixed slurry was dried at 120-150℃ for 6-10 hours, pulverized and sieved to obtain a mixed powder; the mixed powder was calcined at 650-850℃ for 3-8 hours at a heating rate of 4-6℃ / min to obtain a titanium-based lithium-ion sieve precursor doped with heterogeneous elements, with the chemical composition Li2Ti1-xMxO3, where M is the doping element, 0.005≤x≤0.08;

[0104] Step 3, Acid washing for lithium removal and pore formation: The doped precursor obtained in Step 2 is added to an inorganic acid solution with a concentration of 0.2-1.0 mol / L, with a solid-liquid ratio of 1:(20-100), and the reaction is carried out at 20-60℃ with shaking for 6-24 hours, during which the pH of the solution is maintained at 1.0-2.5. After the reaction is completed, the solution is filtered and washed until neutral to obtain wet material of doped H2TiO3 ion sieve. The acidic wastewater generated during the washing process is treated by the wastewater treatment device and then discharged.

[0105] Step 4, Surface hydrophilic modification: The wet material of the doped H2TiO3 ion sieve obtained in Step 3 is redispersed in anhydrous ethanol or toluene, and a silane coupling agent containing sulfonic acid group, carboxyl group or phosphate group is added. The silane coupling agent is selected from 3-mercaptopropyltriethoxysilane (which is converted to sulfonic acid group after oxidation), carboxyethyltrimethoxysilane, and 3-trihydroxysilane-1-phosphoric acid. The amount added is 1%-10% of the ion sieve mass. The reaction is refluxed at 50-80℃ for 6-12h. After the reaction is completed, the mixture is filtered, washed and vacuum dried to obtain the surface-modified doped titanium-based ion sieve adsorbent.

[0106] As a preferred option, the solid content of the mixed slurry in step 2 is 40%-60% to ensure uniform mixing of the lithium source, titanium source, and doped element precursor.

[0107] As a preferred embodiment, the doping element in step 2 is a composite doping of lanthanum (La) and zirconium (Zr), with a molar ratio of La to Zr of 1:(0.5-2), and the total doping amount is 2.0%-5.0% of the molar amount of titanium. The introduction of lanthanum can expand the lattice spacing and increase the lithium-ion diffusion channels, while the introduction of zirconium can enhance the stability of the Ti-O framework and improve its resistance to acid corrosion. The synergistic effect of the two can simultaneously improve the adsorption capacity and cycle stability.

[0108] As a preferred embodiment, the inorganic acid in step 3 is hydrochloric acid or sulfuric acid, with a concentration of 0.3-0.6 mol / L, a solid-liquid ratio of 1:40, a reaction temperature of 40℃, and a reaction time of 12 h.

[0109] As a preferred embodiment, the silane coupling agent in step 4 is oxidized 3-mercaptopropyltriethoxysilane (MPTES), which is treated with H2O2 before use to oxidize the mercapto group to a sulfonic acid group, so as to introduce a strongly hydrophilic -SO3H group on the surface of the ion sieve.

[0110] As an alternative, the surface hydrophilic modification in step 4 adopts a porous hydrophilic layer coating method: the doped H2TiO3 ion sieve obtained in step 3 is dispersed in a dilute acid solution of polyvinyl alcohol (PVA) or chitosan, stirred and adsorbed, crosslinked with glutaraldehyde, and then freeze-dried to form a three-dimensional porous hydrophilic network coating layer with a coating layer thickness of 5-15 nm.

[0111] Application of the above-mentioned titanium-based ion sieve adsorbent in lithium extraction from high magnesium-to-lithium ratio brine: The adsorbent is filled into an adsorption column, and the brine from the salt lake flows through the adsorption column at a flow rate of 2-10 BV / h. The adsorption temperature is 20-40℃. After adsorption, desorption is performed with 0.2-0.5 mol / L hydrochloric acid. The lithium ion concentration in the desorbate is enriched by 5-20 times, and the magnesium-to-lithium ratio is reduced to below 0.5.

[0112] Performance Testing: In simulated brine with a magnesium-to-lithium ratio of 120:1, the adsorbent prepared in this embodiment exhibited a lithium adsorption capacity of 32.5 mg / g and a magnesium adsorption capacity of only 0.032 mg / g, with a magnesium-to-lithium separation coefficient αLi / Mg = 8230. After 30 cycles, the adsorption capacity retention rate was 91.6%, and the average titanium dissolution rate was 0.055%. A lithium precipitation test was conducted on the lithium-rich desorption solution (magnesium-to-lithium ratio 0.25) treated with this adsorbent. The sodium carbonate excess coefficient was 1.2, and the soda ash consumption per ton of lithium carbonate was 1.45 t, a reduction of 32.6% compared to the control group (soda ash consumption of 2.15 t) without the process of this invention.

[0113] Compared with related technologies, the preparation method of brine adsorbent provided by the present invention has the following beneficial effects:

[0114] This invention introduces lattice distortion and oxygen vacancies into the Li₂TiO₃ lattice through rare earth element / high-valence transition metal doping, thereby modulating the Li₂TiO₃ crystal structure. + Diffusion channel size enhances Li + The surface hydrophilic modification enhances the specific recognition ability of ion sieve particles. Simultaneously, it constructs a hydrophilic microenvironment rich in functional groups such as -SO3H and -COOH at the particle interface, utilizing the hydrogen bonding between these functional groups and water molecules to form a hydration layer, physically blocking Mg. 2+ Approaching;

[0115] This invention uses mixed-crystal TiO2 as the titanium source and utilizes the mixed-crystal effect of anatase to rutile transformation at high temperature to break the regular rapid growth of [TiO6] octahedron and inhibit the excessive growth of β-Li2TiO3 grains during high-temperature calcination. This results in a fine-sized and uniformly distributed doped precursor under high-temperature conditions. This method solves the technical contradiction of "high temperature and high selectivity - low adsorption capacity" in traditional processes, enabling the adsorbent of this invention to have both high adsorption capacity and ultra-high magnesium-lithium selectivity.

[0116] Surface hydrophilic modification not only improves selectivity, but also significantly inhibits the aggregation behavior of nano-ion sieves in the aqueous phase through steric hindrance and electrostatic repulsion. The ion sieve modified with sulfonic acid groups has good dispersibility in water, with an absolute value of Zeta potential >35mV. After 30 adsorption-desorption cycles, the adsorption capacity retention rate is >92%, and the titanium dissolution rate is <0.06% / cycle, which is far superior to the level reported in the prior art.

[0117] The preparation process of this invention does not involve highly toxic reagents, and the reagents used in the acid washing and surface modification steps can be recycled. The raw materials, such as metatitanic acid and rare earth salts, are readily available in industry. The process route is highly compatible with existing titanium-based ion sieve production lines, requiring no additional large-scale equipment investment and possessing excellent industrialization prospects.

[0118] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A wastewater treatment device for brine adsorbent preparation, characterized in that, include: Support frame; The treatment vessel is mounted on the support frame. The treatment vessel is used to add wastewater and add treatment agents to carry out the reaction. The top of the treatment vessel is equipped with a feed chute and the bottom of the treatment vessel is equipped with a discharge chute. A stirring assembly is installed on the treatment vessel and is used for mixing and stirring during wastewater treatment. A blocking assembly is mounted on the support frame and is in close contact with the discharge chute to block the discharge chute. In use, the blocking assembly opens the discharge chute through vertical linear movement. A filter assembly, which is mounted on the support frame, is used for solid-liquid separation after wastewater treatment. A drive assembly is mounted on the processing vessel and is used to drive the stirring assembly, the sealing assembly, and the filtering assembly.

2. The wastewater treatment device for brine adsorbent preparation according to claim 1, characterized in that, The stirring assembly includes a sleeve rod, a stirring disc, and a wall scraping structure. The sleeve rod is rotatably connected to the processing vessel, and the top end of the sleeve rod penetrates the processing vessel and extends to the top of the processing vessel. The stirring disc is fixed to the outer surface of the sleeve rod, and the wall scraping structure is installed on the outer surface of the sleeve rod.

3. The wastewater treatment device for brine adsorbent preparation according to claim 2, characterized in that, The scraping structure includes a hollow rod, a fixed block, a connecting rod, a first inclined block, a first elastic element, and a scraper. The hollow rod is fixed to the sleeve rod, the fixed block is fixed inside the hollow rod, the connecting rod is slidably connected to the fixed block, the first inclined block is fixed to one end of the connecting rod, the first elastic element is installed between the fixed block and the first inclined block, and the scraper is fixed to the other end of the connecting rod.

4. The wastewater treatment device for brine adsorbent preparation according to claim 1, characterized in that, The sealing assembly includes a movable plate, a sealing plate, a pressing block, and a support plate. The movable plate is slidably connected to the support frame, the sealing plate is fixed on the movable plate, and the sealing plate abuts against the discharge chute. The pressing block is fixed to the bottom of the movable plate, and the support plate is fixed to the bottom of the movable plate, with the support plate located outside the pressing block.

5. The wastewater treatment device for brine adsorbent preparation according to claim 1, characterized in that, The filter assembly includes a mounting block, a fixing frame, a sliding rod, a filter plate, a cleaning structure, and a limiting structure. The mounting block is fixed to the support frame, the fixing frame is fixed to the mounting block, the sliding rod is slidably connected to the fixing frame, the filter plate is fixed to the bottom of the sliding rod, the cleaning structure is mounted on the filter plate, and the limiting structure is mounted on the fixing frame. The limiting structure is used to fix the sliding rod.

6. The wastewater treatment device for brine adsorbent preparation according to claim 5, characterized in that, The cleaning structure includes a rotating shaft, a groove, and a cleaning component. The rotating shaft is rotatably connected to the filter plate, the groove is formed on the rotating shaft, and the cleaning component is installed on the rotating shaft.

7. The wastewater treatment device for brine adsorbent preparation according to claim 5, characterized in that, The limiting structure includes a connecting block, a sliding block, a second elastic element, a limiting block, and a second inclined block. The connecting block is fixed to the fixed frame, the sliding block is slidably connected to the fixed frame, the second elastic element is installed between the connecting block and the sliding block, the limiting block is fixed to the sliding block, and the second inclined block is fixed to the top of the sliding block.

8. The wastewater treatment device for brine adsorbent preparation according to claim 1, characterized in that, The drive assembly includes a fixed frame, a sliding plate, a pusher, a drive member, a drive rod, a conical block, and a protrusion. The fixed frame is fixed to the processing vessel, the sliding plate is slidably connected to the fixed frame, the pusher is fixed to the fixed frame, and the output end of the pusher is fixed to the sliding plate. The drive member is fixed to the sliding plate, the drive rod is fixed to the output shaft of the drive member, the conical block is fixed to the outer surface of the drive rod, and the protrusion is fixed to the bottom end of the drive rod.

9. A method for preparing a brine adsorbent, characterized in that, Includes the following steps: Step 1, Preparation of mixed-crystal TiO2 support: using metatitanic acid as raw material, calcination is carried out to obtain anatase TiO2; then the obtained anatase TiO2 is heated and held at that temperature to form rutile phase on the surface of anatase grains, thus obtaining a TiO2 support with mixed-crystal effect. Step 2, Synthesis of doped titanium-based ion sieve precursor: The mixed-crystal TiO2 obtained in Step 1 is dispersed in deionized water, lithium source and doped element precursor are added, and the mixture is stirred and mixed evenly to obtain a mixed slurry; the mixed slurry is dried, pulverized and sieved to obtain a mixed powder; the mixed powder is calcined to obtain a titanium-based lithium ion sieve precursor doped with heterogeneous elements. Step 3, Acid washing to remove lithium and create pores: Add the doped precursor obtained in step 2 to an inorganic acid solution and shake to react; after the reaction is completed, filter and wash until neutral to obtain wet material of doped H2TiO3 ion sieve. The acidic wastewater generated during the washing process is treated by the wastewater treatment device as described in any one of claims 1-8 and then discharged. Step 4, surface hydrophilic modification: The wet material of doped H2TiO3 ion sieve obtained in step 3 is redispersed in anhydrous ethanol or toluene, and a silane coupling agent containing sulfonic acid group, carboxyl group or phosphate group is added for reflux reaction. After the reaction is completed, the material is filtered, washed and vacuum dried to obtain the surface-modified doped titanium ion sieve adsorbent.

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