Water pollution treatment equipment and process for recovering lithium, rubidium and cesium from leaching residue of lepidolite

Abstract

The application provides a water pollution treatment equipment and a process for recovering lithium, rubidium and cesium from leaching residue of lepidolite. The water pollution treatment equipment is related to the field of water pollution treatment and comprises a reaction tank, a bottom cover being fixedly installed at the bottom of the reaction tank. The water pollution treatment equipment and the process for recovering lithium, rubidium and cesium from leaching residue of lepidolite can make the distribution of the washing sewage more uniform when the washing sewage is initially filtered by arranging a water distributor and a water distribution pipe, can preliminarily intercept larger solid impurities and secondarily intercept heavy metal precipitates after precipitation, can obtain relatively pure mixed salt sewage, can reduce the consumption of alkali solution and the generation of sludge, can avoid fouling and pipeline blockage, can effectively reduce the concentration of heavy metals in the sewage by adjusting the pH to make heavy metal ions generate precipitates by arranging an alkali supply pump to extract alkali solution into the interior of the reaction tank, and can clean the filter screen one and the filter screen two by arranging two open-close plates.

Description

Technical Field

[0001] This invention relates to the field of water pollution treatment, and more particularly to a water pollution treatment device and a process for recovering lithium, rubidium, and cesium from lepidolite leaching residue. Background Technology

[0002] In the process of recovering lithium, rubidium, and cesium from lepidolite leaching residue, a washing solution with specific components is generated after washing with dilute sulfuric acid. This solution contains sodium sulfate and potassium sulfate metal ions. The washing wastewater has a complex composition, high acidity, and is prone to scaling. It is treated to achieve harmlessness through water pollution treatment equipment to reduce subsequent environmental pressure.

[0003] Existing water pollution treatment equipment removes heavy metal ions from washing wastewater by adding an alkaline solution to react with the wastewater, producing a precipitate, which is then filtered to obtain a relatively pure mixed salt solution.

[0004] However, existing water pollution treatment equipment does not filter particles generated after the calcined slag is crushed when treating washing wastewater, which leads to the need to add additional alkaline solution, increasing the amount of sludge and aggravating scaling and pipe blockage.

[0005] Therefore, it is necessary to provide a water pollution treatment device and a process for recovering lithium, rubidium, and cesium from lepidolite leaching residue to solve the above-mentioned technical problems. Summary of the Invention

[0006] This invention provides a water pollution treatment device and a process for recovering lithium, rubidium, and cesium from lepidolite leaching residue, which solves the problems of needing to add additional alkaline solution, increasing sludge volume, exacerbating scaling, and clogging pipelines.

[0007] To solve the above-mentioned technical problems, the present invention provides a water pollution treatment device, comprising: a reaction tank, wherein a bottom cover is fixedly installed at the bottom of the reaction tank and a top cover is fixedly installed at the top of the reaction tank;

[0008] A water distribution mechanism is connected to the top of the top cover. The water distribution mechanism includes a funnel connected to the top of the top cover. The bottom end of the funnel penetrates the top of the top cover and extends into the interior of the reaction vessel. The bottom end of the funnel is connected to a water distributor. The outer wall of the water distributor is connected to several water distribution pipes.

[0009] An alkali supply mechanism, used to supply alkali solution to the interior of the reaction tank;

[0010] Filter screen one, which is fixedly installed on the inner wall of the reaction vessel;

[0011] A drain pipe, wherein the drain pipe is connected to the bottom of the bottom cover;

[0012] Filter screen two, which is fixedly installed on the inner wall of the drain pipe;

[0013] Material collection troughs, both of which are located on one side of the reaction vessel;

[0014] Two opening and closing plates are fixedly installed on one side of the reaction vessel via a rotating frame, and the two opening and closing plates are respectively adapted to the two material receiving troughs.

[0015] Preferably, the alkali supply mechanism is connected to the outer wall of the reaction vessel. The alkali supply mechanism includes an alkali supply pipe, which is connected to the outer wall of the reaction vessel. One end of the alkali supply pipe is connected to an alkali supply pump, and the input end of the alkali supply pump is connected to an alkali supply tank through a connecting pipe.

[0016] Preferably, the end of the drain pipe is connected to a transfer mechanism, the transfer mechanism including a transfer pump, the transfer pump being connected to the end of the drain pipe, and the output end of the transfer pump being connected to the transfer pipe.

[0017] Preferably, the end of the transfer tube is connected to an evaporator, the evaporator is mounted on the ground by a bracket, and an evaporation chamber is fixedly installed on the top of the inner wall of the evaporator.

[0018] Preferably, a stirring mechanism is fixedly installed on the top of the evaporator. The stirring mechanism includes a stirring motor, which is fixedly installed on the top of the evaporator via a bracket. The output shaft of the stirring motor is fixedly connected to a stirring shaft. The bottom end of the stirring shaft passes through the top of the evaporator and extends into the interior of the evaporator chamber. Several stirring blades are fixedly installed on the surface of the stirring shaft.

[0019] Preferably, a heating mechanism is fixedly installed on both sides of the inner wall of the evaporator. The heating mechanism includes a fixed plate and a rotary motor. The two fixed plates are respectively fixedly installed on both sides of the inner wall of the evaporator. Two active turntables and two passive turntables are rotatably installed on opposite sides of the two fixed plates. A connecting shaft is fixedly installed inside each of the two active turntables. One end of each of the two connecting shafts passes through one side of the fixed plate, the inner wall of the evaporator, and the inner wall of the evaporator and extends to the outside. The two rotary motors are mounted on the ground by brackets. The output shafts of the two rotary motors are fixedly connected to the ends of the two connecting shafts located outside the evaporator. Two sets of heating tubes are fixedly installed between the two active turntables and the two passive turntables.

[0020] Preferably, a scraping mechanism is slidably mounted on the surfaces of the two sets of heating tubes. The scraping mechanism includes a scraper plate one, a scraper plate two, and a cylinder. The scraper plate one and the scraper plate two are slidably mounted on the surfaces of the two sets of heating tubes, respectively. The cylinder is mounted on the ground by a bracket. One end of the cylinder passes through the outer wall of the evaporator, the outer wall of the evaporator chamber, and one side of the fixing plate through the outer shell and extends into the interior of the evaporator chamber. The output end of the cylinder is fixedly mounted to the interior of the scraper plate one by a bearing. Both the scraper plate one and the scraper plate two have annular grooves on their peripheral surfaces. The scraper plate one and the scraper plate two are connected to a scraper through the annular grooves. The scraper is fitted and installed in accordance with the evaporator chamber.

[0021] Preferably, one side of the evaporator is connected to a discharge mechanism, which includes a discharge box and a second opening and closing plate. The discharge box is connected to one side of the evaporator, and one end of the discharge box penetrates the inner wall of the evaporator and extends to the outside. The second opening and closing plate is fixedly installed on the inner wall of the evaporator by a rotating bracket, and the second opening and closing plate is adapted to the discharge box.

[0022] Preferably, the inner wall of the evaporator is connected to two one-way pipes, and the top of the evaporator is connected to a steam pipe.

[0023] A process for recovering lithium, rubidium, and cesium from lepidolite leaching residue includes the following steps:

[0024] S1: Pre-treatment crushing, crushing the lepidolite sulfuric acid roasting residue to 200 mesh, in the lepidolite sulfuric acid roasting residue It accounts for 0.5-1.2%. It accounts for 0.3-0.8%. The solid-liquid ratio is 1:3. The solid-liquid ratio is 0.1-0.5%. The washing wastewater after washing with dilute sulfuric acid is sent to the water pollution treatment equipment for treatment and discharged in compliance with standards.

[0025] S2: Lithium preferential leaching, prepared with 1 mol / L... +0.5mol / L A mixed solution with a solid-liquid ratio of 1:5 was reacted at 90℃ for 2 hours, with the final pH controlled at 2.5. The solution was then filtered to obtain a lithium-containing leachate. The concentration is 8-12 g / L;

[0026] Reaction formula:

[0027]

[0028] ;

[0029] S3: Rubidium-cesium enhanced leaching, adding 2 mol / L of [unspecified substance] to the residue. +1mol / L The solution, with a solid-liquid ratio of 1:4, was subjected to high-pressure reaction at 120℃ for 3 hours. The pH was then adjusted to 1.0 to obtain a rubidium-cesium enriched solution. The concentration is 2-4 g / L. The concentration is 0.8-1.5 g / L;

[0030] Reaction formula:

[0031]

[0032] ;

[0033] S4: Stepwise precipitation separation, lithium precipitation: Add saturated sodium carbonate to the S2 leachate to pH=10 to form lithium carbonate; cesium preferential precipitation: Adjust the pH of the S3 solution to 3, add 0.1 mol / L sodium tetraphenylborate to form... Rubidium precipitation: Add 2 mol / L to the remaining solution Solution, formation ;

[0034] Reaction formula:

[0035]

[0036]

[0037] .

[0038] Compared with related technologies, the water pollution treatment equipment provided by the present invention has the following beneficial effects:

[0039] This invention provides a water pollution treatment device. By setting up a water distributor and water distribution pipe, the wastewater is distributed more evenly during the initial filtration. By setting up a first filter screen and a second filter screen to form a two-stage filtration, larger solid impurities are initially intercepted, and heavy metal precipitates are retained and settled in the second stage, resulting in purer mixed salt wastewater. This reduces the consumption of alkaline solution and the generation of sludge, avoiding scaling and pipe blockage. An alkaline supply pump draws alkaline solution into the reaction tank, adjusting the pH to promote the precipitation of heavy metal ions, effectively reducing the concentration of heavy metals in the wastewater. Two opening and closing plates allow for separate cleaning of the first and second filters screens. Attached Figure Description

[0040] Figure 1 A schematic diagram of a preferred embodiment of a water pollution treatment device provided by the present invention;

[0041] Figure 2 for Figure 1 The diagram shows the installation of filter screen one;

[0042] Figure 3 for Figure 2 The diagram shows the structure of the water distribution mechanism.

[0043] Figure 4 for Figure 1 The diagram shown is a structural schematic of the alkali supply mechanism.

[0044] Figure 5 A schematic diagram of the structure of a second embodiment of a water pollution treatment device;

[0045] Figure 6 for Figure 5 The diagram shows the installation of the discharge mechanism;

[0046] Figure 7 for Figure 5 The diagram shows the structure of the transfer mechanism.

[0047] Figure 8 for Figure 6 The diagram shown is a structural schematic of the stirring mechanism.

[0048] Figure 9 for Figure 6 The diagram shows the structure of the heating mechanism.

[0049] Figure 10 for Figure 9 Another schematic diagram of the heating mechanism shown;

[0050] Figure 11 for Figure 6 The diagram shows the structure of the scraping mechanism.

[0051] Figure 12 for Figure 6 The diagram shows the structure of the discharge mechanism.

[0052] Numbered in the diagram: 1. Reaction tank; 2. Bottom cover; 3. Top cover; 4. Water distribution mechanism; 401. Funnel; 402. Water distributor; 403. Water distribution pipe; 5. Alkali supply mechanism; 501. Alkali supply pipe; 502. Alkali supply pump; 503. Alkali supply tank; 6. Transfer mechanism; 601. Transfer pump; 602. Transfer pipe; 7. Stirring mechanism; 701. Stirring motor; 702. Stirring shaft; 703. Stirring blades; 8. Heating mechanism; 801. Fixed plate; 802. Rotary motor; 803. Driven turntable. 804. Connecting shaft; 805. Driven turntable; 806. Heating tube; 9. Scraping mechanism; 901. Cylinder; 902. Bearing; 903. Scraper plate one; 904. Annular groove; 905. Scraper; 906. Scraper plate two; 10. One-way pipe; 11. Discharge mechanism; 1101. Discharge box; 1102. Opening and closing plate two; 12. Filter screen one; 13. Filter screen two; 14. Drain pipe; 15. Material trough; 16. Opening and closing plate one; 17. Evaporator; 18. Evaporation chamber; 19. Steam pipe. Detailed Implementation

[0053] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0054] A water pollution treatment device

[0055] First Embodiment

[0056] Please refer to the following: Figures 1-4 A water pollution treatment device includes: a reaction tank 1, a bottom cover 2 fixedly installed at the bottom of the reaction tank 1, and a top cover 3 fixedly installed at the top of the reaction tank 1;

[0057] A water distribution mechanism 4 is connected to the top of the top cover 3. The water distribution mechanism 4 includes a funnel 401, which is connected to the top of the top cover 3. The bottom end of the funnel 401 penetrates the top of the top cover 3 and extends into the interior of the reaction tank 1. The bottom end of the funnel 401 is connected to a water distributor 402, and the outer wall of the water distributor 402 is connected to several water distribution pipes 403.

[0058] Alkali supply mechanism 5, which is used to supply alkali solution to the interior of the reaction tank 1;

[0059] Filter screen 12 is fixedly installed on the inner wall of the reaction vessel 1;

[0060] Drain pipe 14, the drain pipe 14 being connected to the bottom of the bottom cover 2;

[0061] Filter screen 2 13, which is fixedly installed on the inner wall of the drain pipe 14;

[0062] Material intake trough 15, both of the material intake troughs 15 are opened on one side of the reaction vessel 1;

[0063] The two opening and closing plates 16 are fixedly installed on one side of the reaction vessel 1 by means of a rotating frame, and the two opening and closing plates 16 are respectively adapted to the two material receiving troughs 15.

[0064] The alkali supply mechanism 5 is connected to the outer wall of the reaction tank 1. The alkali supply mechanism 5 includes an alkali supply pipe 501, which is connected to the outer wall of the reaction tank 1. One end of the alkali supply pipe 501 is connected to an alkali supply pump 502, and the input end of the alkali supply pump 502 is connected to an alkali supply tank 503 through a connecting pipe.

[0065] In practical use, the aforementioned water pollution treatment equipment can also be used in other related washing wastewater application fields; the alkaline solution inside the alkali supply tank 503 is a sodium hydroxide alkaline solution.

[0066] The working principle of the water pollution treatment equipment provided by this invention is as follows:

[0067] First, the washing wastewater is manually discharged into the water distributor 402 through the funnel 401. The washing wastewater is then distributed through the water distributor 402 and the water distribution pipe 403. After passing through the filter screen 12, the washing wastewater falls into the bottom of the inner wall of the reaction tank 1.

[0068] Then, the washing wastewater after preliminary filtration of impurities falls to the bottom of the inner wall of the reaction tank 1. The alkali supply pump 502 is started to extract the alkali solution inside the alkali supply tank 503 and discharge it into the interior of the reaction tank 1 through the alkali supply pipe 501. After adding the alkali solution, the pH is adjusted and the heavy metal ions are precipitated. When the pre-treated washing wastewater is discharged, the precipitate is filtered again by the filter screen 13. The drain pipe 14 is opened to discharge the pre-treated wastewater.

[0069] Finally, the two hinged plates 16 can be opened manually to clean the filter screens 12 and 13 regularly.

[0070] Compared with related technologies, the water pollution treatment equipment provided by the present invention has the following beneficial effects:

[0071] By setting up a water distributor 402 and a water distribution pipe 403, the initial filtration of washing wastewater is more evenly distributed. By setting up filter screen 12 and filter screen 2 13 to form a two-stage filtration, larger solid impurities are initially intercepted, and heavy metal precipitates are retained after secondary sedimentation, resulting in purer mixed salt wastewater. This reduces the consumption of alkaline solution and the generation of sludge, avoiding scaling and pipe blockage. By setting up an alkaline supply pump 502 to draw alkaline solution into the interior of the reaction tank 1, the pH is adjusted to promote the precipitation of heavy metal ions, effectively reducing the concentration of heavy metals in the wastewater. By setting up two opening and closing plates 16, filter screen 12 and filter screen 2 13 can be cleaned separately.

[0072] Second Embodiment

[0073] Please refer to the following: Figures 5-12 Based on the water pollution treatment device provided in the first embodiment of this application, the second embodiment of this application proposes another water pollution treatment 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.

[0074] Specifically, the water pollution treatment device provided in the second embodiment of this application differs in that the end of the drain pipe 14 is connected to a transfer mechanism 6, the transfer mechanism 6 includes a transfer pump 601, the transfer pump 601 is connected to the end of the drain pipe 14, and the output end of the transfer pump 601 is connected to a transfer pipe 602.

[0075] The end of the transfer tube 602 is connected to an evaporator 17, which is mounted on the ground by a bracket, and an evaporator chamber 18 is fixedly installed on the top of the inner wall of the evaporator 17.

[0076] A stirring mechanism 7 is fixedly installed on the top of the evaporator 17. The stirring mechanism 7 includes a stirring motor 701, which is fixedly installed on the top of the evaporator 17 by a bracket. The output shaft of the stirring motor 701 is fixedly connected to a stirring shaft 702. The bottom end of the stirring shaft 702 passes through the top of the evaporator 17 and extends into the interior of the evaporator chamber 18. Several stirring blades 703 are fixedly installed on the surface of the stirring shaft 702.

[0077] Heating mechanisms 8 are fixedly installed on both sides of the inner wall of the evaporator 18. The heating mechanism 8 includes a fixed plate 801 and a rotary motor 802. The two fixed plates 801 are fixedly installed on both sides of the inner wall of the evaporator 18. Two active turntables 803 and two driven turntables 805 are rotatably installed on opposite sides of the two fixed plates 801. A connecting shaft 804 is fixedly installed inside each of the two active turntables 803. One end of each of the two connecting shafts 804 passes through one side of the fixed plate 801, the inner wall of the evaporator 18, and the inner wall of the evaporator 17 and extends to the outside. The two rotary motors 802 are mounted on the ground by brackets. The output shafts of the two rotary motors 802 are fixedly connected to the ends of the two connecting shafts 804 located outside the evaporator 17. Two sets of heating tubes 806 are fixedly installed between the two active turntables 803 and the two driven turntables 805.

[0078] Scraping mechanisms 9 are slidably mounted on the surfaces of the two sets of heating tubes 806. The scraping mechanism 9 includes a first scraper 903, a second scraper 906, and a cylinder 901. The first scraper 903 and the second scraper 906 are slidably mounted on the surfaces of the two sets of heating tubes 806, respectively. The cylinder 901 is mounted on the ground by a bracket. One end of the cylinder 901 passes through the outer wall of the evaporator 17, the outer wall of the evaporator 18, and one side of the fixing plate 801 through the outer shell and extends into the interior of the evaporator 18. The output end of the cylinder 901 is fixedly mounted to the interior of the first scraper 903 by a bearing 902. The peripheral surfaces of the first scraper 903 and the second scraper 906 are provided with annular grooves 904. The first scraper 903 and the second scraper 906 are connected to a scraper 905 through the annular grooves 904. The scraper 905 is adapted to be installed in the evaporator 18.

[0079] One side of the evaporator 18 is connected to a discharge mechanism 11. The discharge mechanism 11 includes a discharge box 1101 and a second opening and closing plate 1102. The discharge box 1101 is connected to one side of the evaporator 18. One end of the discharge box 1101 penetrates the inner wall of the evaporator 17 and extends to the outside. The second opening and closing plate 1102 is fixedly installed on the inner wall of the evaporator 18 by a rotating bracket. The second opening and closing plate 1102 is adapted to the discharge box 1101.

[0080] The inner wall of the evaporator 18 is connected to two one-way pipes 10, and the top of the evaporator 17 is connected to a steam pipe 19.

[0081] In actual use, each group of heating tubes 806 consists of six tubes.

[0082] The working principle of the water pollution treatment equipment provided in this embodiment is as follows:

[0083] First, after the initial treatment is completed, the transfer pump 601 is started to extract the pre-treated washing wastewater through the drain pipe 14 and transfer it to the inside of the evaporator 17 through the transfer pipe 602. After the water level gradually rises, when it reaches the height of the one-way pipe 10, the washing wastewater is discharged into the inside of the evaporator 18 through the one-way pipe 10.

[0084] Then, the stirring motor 701 is started, which drives the stirring blades 703 to stir the washing wastewater through the stirring shaft 702. The two rotary motors 802 are started, which drive the two active turntables 803 to rotate through the two connecting shafts 804. As a result, the two sets of heating tubes 806 and the two driven turntables 805 also rotate. The two sets of heating tubes 806 are started to heat and evaporate the washing wastewater. At this time, the heated washing wastewater can also preheat the washing wastewater between the evaporation tank 18 and the evaporation tank 17 that has not yet evaporated, saving energy. The evaporated gas is discharged through the steam pipe 19 and condensed and recovered.

[0085] Then, after evaporation, the remaining solid sediment at the bottom of the inner wall of the evaporation tank 18 is mixed with high-concentration wastewater. The cylinder 901 is started, which drives the scraper 1 903 to move through the bearing 902. The scraper 1 903 drives the scraper 2 906 to move through the scraper 905. This allows the scraper 1 903 and the scraper 2 906 to simultaneously descale the surfaces of the two sets of heating tubes 806, preventing impurities from adhering to the surface after long-term use. At the same time, during the process of the cylinder 901 driving the scraper 1 903 and the scraper 2 906 to clean the two sets of heating tubes 806, the scraper 905 also cleans the remaining solid sediment at the bottom and the high-concentration wastewater. The scraper 905 also cleans the scale on the inner wall of the evaporation tank 18 to improve the heat transfer efficiency to the outside. When the scraper 905 is pushed to the position of the discharge box 1101, the opening and closing plate 2 1102 is opened manually from the outside of the equipment to collect hazardous waste and transfer it for treatment.

[0086] Finally, the above-mentioned scale removal process can also be started during the rotation of the heating tube 806 to complete the forced mixing of the high-concentration solution at the bottom and the low-concentration solution in the middle and upper layers.

[0087] Compared with related technologies, the water pollution treatment equipment provided in this embodiment has the following beneficial effects:

[0088] By setting the heating tube 806 to rotate with the active turntable 803, heat transfer uniformity is enhanced while the rotation promotes wastewater flow. Combined with the stirring blades 703, dynamic heating and mixing are achieved, shortening evaporation time and improving treatment efficiency. This integrates rotary heating and stirring. The heating tube 806 heats the washing wastewater inside the evaporation tank 18 while preheating the unevaporated wastewater located between the evaporation tank 18 and the evaporation vessel 17, achieving internal heat recycling and significantly reducing energy consumption. The cylinder 901 drives the scraper disc 903, scraper disc 906, and scraper 905 synchronously. The system completes multiple cleaning processes, including descaling the surface of heating tube 806, cleaning scale buildup on the inner wall of evaporator 18, and scraping away sediment at the bottom. During evaporation, the scraper 905 reciprocates, cleaning while simultaneously forcibly mixing high and low concentration solutions to prevent localized excessive concentrations. Impurities scraped by the scraper 905 can be removed by opening the external hinge plate 1102, eliminating the need for manual entry into the equipment and improving operational safety and convenience. Solid sediments and high-concentration wastewater are scraped into discharge box 1101 for centralized collection and professional treatment, reducing the risk of secondary pollution.

[0089] A process for recovering lithium, rubidium, and cesium from lepidolite leaching residue

[0090] A process for recovering lithium, rubidium, and cesium from lepidolite leaching residue includes the following steps:

[0091] S1: Pre-treatment crushing, crushing the lepidolite sulfuric acid roasting residue to 200 mesh, in the lepidolite sulfuric acid roasting residue It accounts for 0.5-1.2%. It accounts for 0.3-0.8%. The solid-liquid ratio is 1:3. The solid-liquid ratio is 0.1-0.5%. The washing wastewater after washing with dilute sulfuric acid is sent to the water pollution treatment equipment for treatment and discharged in compliance with standards.

[0092] S2: Lithium preferential leaching, prepared with 1 mol / L... +0.5mol / L A mixed solution with a solid-liquid ratio of 1:5 was reacted at 90℃ for 2 hours, with the final pH controlled at 2.5. The solution was then filtered to obtain a lithium-containing leachate. The concentration is 8-12 g / L;

[0093] Reaction formula:

[0094]

[0095] ;

[0096] S3: Rubidium-cesium enhanced leaching, adding 2 mol / L of [unspecified substance] to the residue. +1mol / L The solution, with a solid-liquid ratio of 1:4, was subjected to high-pressure reaction at 120℃ for 3 hours. The pH was then adjusted to 1.0 to obtain a rubidium-cesium enriched solution. The concentration is 2-4 g / L. The concentration is 0.8-1.5 g / L;

[0097] Reaction formula:

[0098]

[0099] ;

[0100] S4: Stepwise precipitation separation, lithium precipitation: Add saturated sodium carbonate to the S2 leachate to pH=10 to form lithium carbonate; cesium preferential precipitation: Adjust the pH of the S3 solution to 3, add 0.1 mol / L sodium tetraphenylborate to form... Rubidium precipitation: Add 2 mol / L to the remaining solution Solution, formation ;

[0101] Reaction formula:

[0102]

[0103]

[0104] .

[0105] In practical use, the functions of S1 are: 1. Increasing the reaction surface area: Crushing the leaching residue to 200 mesh (particle size approximately 75 μm) significantly increases the specific surface area of ​​the particles, improving the contact efficiency of subsequent leaching reactions; 2. Removing surface impurities: Washing with 5% dilute sulfuric acid dissolves residual sulfates (such as unreacted sodium sulfate and potassium sulfate) on the surface of the residue, preventing them from interfering with the purity of the subsequent leachate; 3. Optimizing solid-liquid separation: Removing soluble impurities by stirring and controlling the solid-liquid ratio (1:3), reducing the competitive reaction of impurity ions in subsequent steps; The functions of S2 are: 1. Selectively releasing lithium: Using low-concentration sulfuric acid (1 mol / L sulfuric acid) and... The mixed solution preferentially disrupts the lithium-bearing structure in lepidolite (e.g., This process leaches lithium as lithium sulfate, while rubidium and cesium minerals, due to their stable structure, are not completely destroyed. 2. It inhibits the formation of silica sol: the reaction produces... Precipitate in solid form to avoid silica sol clogging the filter material or encapsulating metal ions. 3. Control the endpoint pH (2.5): to prevent... Excessive dissolution ( Precipitation begins when pH > 3, reducing the difficulty of subsequent separation and preserving rubidium and cesium minerals (such as...). , To ensure stability and prevent premature dissolution, The addition was through The coordination effect promotes lithium release while avoiding excessive erosion of rubidium and cesium minerals by strong acids; the function of S3 is: 1. to disrupt the stable mineral structure: rubidium and cesium in the residue of S2 are mostly located in more stable aluminosilicates (such as... ) or sulfate double salts (such as In the middle, a higher acidity (2 mol / L) is required. 1) Temperature (120℃ high pressure) destroys the crystal structure; 2) Ion-enhanced leaching: Provide high concentration Promoting the dissolution of rubidium and cesium through ion exchange and coordination (e.g.) and 3. Inhibits silicon re-dissolution: Under high temperature and pressure, silicon forms stable complexes. The stable precipitation form reduces the interference of silicate on subsequent processes. The high-pressure reactor (120℃) increases the pressure of the reaction system, overcoming the kinetic limitations of acid leaching under normal pressure. The formation of byproducts such as calcium sulfate is suppressed by the common ion effect, reducing impurities in the leachate; the function of S3 is: lithium precipitation: utilizing... Low solubility under alkaline conditions ( Selective precipitation of lithium, preferential precipitation of cesium: sodium tetraphenylborate and Formation of sparingly soluble complexes ( ), with higher selectivity and Rubidium precipitation: utilizing and generate precipitation( ), to achieve interaction with the remaining solution , Separation.

[0106] First Embodiment

[0107] Take 1 kg of leaching residue ( 0.8%, 0.6%, 0.3%), the leachate obtained after S2 contains 9.2 g / L, lithium leaching rate 92%; S3 solution contains 3.5g / L With a concentration of 1.2 g / L, rubidium leaching rate of 88% and cesium leaching rate of 85%, the final lithium carbonate product obtained has a purity of 99.2%. Purity 98.5%, Purity 97.8%.

[0108] Second Embodiment

[0109] Take 2kg of high-silica slag ( >60%), S2 optimized conditions: adding 0.2% ammonium fluoride to inhibit silica dissolution, lithium leaching rate increased to 95%, S3 adopted gradient temperature increase (80℃→120℃), cesium recovery rate increased to 90%, final total metal recovery rate: 93.2% 89.5% 88.7%.

[0110] Compared with related technologies, the process for recovering lithium, rubidium, and cesium from lepidolite leaching residue provided by this invention has the following beneficial effects:

[0111] This invention innovatively proposes a stepwise gradient leaching process to improve metal recovery rate. Selective extraction is achieved by controlling the pH and ionic strength of the leaching system, avoiding the separation difficulties caused by the mixed acid leaching in traditional processes. Lithium is extracted first, then cesium is preferentially precipitated, and finally rubidium is precipitated.

[0112] 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 water pollution treatment device, characterized in that, include: The reaction vessel (1) is fixedly fitted with a bottom cover (2) at the bottom and a top cover (3) at the top. A water distribution mechanism (4) is connected to the top of the top cover (3). The water distribution mechanism (4) includes a funnel (401). The funnel (401) is connected to the top of the top cover (3). The bottom end of the funnel (401) penetrates the top of the top cover (3) and extends into the interior of the reaction tank (1). The bottom end of the funnel (401) is connected to a water distributor (402). The outer wall of the water distributor (402) is connected to several water distribution pipes (403). Alkali supply mechanism (5), which is used to supply alkali solution to the interior of the reaction tank (1); Filter screen one (12), the filter screen one (12) is fixedly installed on the inner wall of the reaction vessel (1); Drain pipe (14), the drain pipe (14) being connected to the bottom of the bottom cover (2); Filter screen two (13), the filter screen two (13) is fixedly installed on the inner wall of the drain pipe (14); Material collection troughs (15), both of which are located on one side of the reaction vessel (1); The two opening and closing plates (16) are fixedly installed on one side of the reaction vessel (1) by a rotating frame. The two opening and closing plates (16) are respectively adapted to the two material feeding troughs (15).

2. The water pollution treatment equipment according to claim 1, characterized in that, The alkali supply mechanism (5) is connected to the outer wall of the reaction tank (1). The alkali supply mechanism (5) includes an alkali supply pipe (501), which is connected to the outer wall of the reaction tank (1). One end of the alkali supply pipe (501) is connected to an alkali supply pump (502), and the input end of the alkali supply pump (502) is connected to an alkali supply tank (503) through a connecting pipe.

3. The water pollution treatment equipment according to claim 1, characterized in that, The end of the drain pipe (14) is connected to a transfer mechanism (6), which includes a transfer pump (601). The transfer pump (601) is connected to the end of the drain pipe (14), and the output end of the transfer pump (601) is connected to a transfer pipe (602).

4. The water pollution treatment equipment according to claim 3, characterized in that, The end of the transfer tube (602) is connected to an evaporator (17), which is mounted on the ground by a bracket, and an evaporator chamber (18) is fixedly installed on the top of the inner wall of the evaporator (17).

5. A water pollution treatment device according to claim 4, characterized in that, A stirring mechanism (7) is fixedly installed on the top of the evaporator (17). The stirring mechanism (7) includes a stirring motor (701). The stirring motor (701) is fixedly installed on the top of the evaporator (17) by a bracket. The output shaft of the stirring motor (701) is fixedly connected to a stirring shaft (702). The bottom end of the stirring shaft (702) passes through the top of the evaporator (17) and extends into the interior of the evaporator chamber (18). Several stirring blades (703) are fixedly installed on the surface of the stirring shaft (702).

6. A water pollution treatment device according to claim 4, characterized in that, Heating mechanisms (8) are fixedly installed on both sides of the inner wall of the evaporator (18). The heating mechanism (8) includes a fixing plate (801) and a rotary motor (802). The two fixing plates (801) are fixedly installed on both sides of the inner wall of the evaporator (18). Two active turntables (803) and two driven turntables (805) are rotatably installed on opposite sides of the two fixing plates (801). A connecting shaft (804) is fixedly installed inside each of the two active turntables (803). The two connecting shafts (804) are... 4) One end of each of them passes through one side of the fixed plate (801), the inner wall of the evaporating tank (18) and the inner wall of the evaporating tank (17) and extends to the outside. The two rotary motors (802) are both mounted on the ground by brackets. The output shafts of the two rotary motors (802) are respectively fixedly connected to the ends of the two connecting shafts (804) located outside the evaporating tank (17). Two sets of heating tubes (806) are fixedly installed between the two active turntables (803) and the two driven turntables (805).

7. A water pollution treatment device according to claim 6, characterized in that, A scraping mechanism (9) is slidably mounted on the surface of the two sets of heating tubes (806). The scraping mechanism (9) includes a scraper plate one (903), a scraper plate two (906), and a cylinder (901). The scraper plate one (903) and the scraper plate two (906) are slidably mounted on the surface of the two sets of heating tubes (806), respectively. The cylinder (901) is mounted on the ground by a bracket. One end of the cylinder (901) passes through the outer wall of the evaporator (17), the outer wall of the evaporator chamber (18), and the outer wall of the evaporator tube (17) in sequence. The fixed plate (801) extends to one side of the evaporator (18) and into the interior. The output end of the cylinder (901) is fixedly installed inside the scraper (903) via a bearing (902). The scraper (903) and the scraper (906) are both provided with annular grooves (904) on their peripheral surfaces. The scraper (903) and the scraper (906) are connected to a scraper (905) via the annular grooves (904). The scraper (905) is adapted to be installed in the evaporator (18).

8. A water pollution treatment device according to claim 4, characterized in that, One side of the evaporator (18) is connected to a discharge mechanism (11). The discharge mechanism (11) includes a discharge box (1101) and a second opening and closing plate (1102). The discharge box (1101) is connected to one side of the evaporator (18). One end of the discharge box (1101) penetrates the inner wall of the evaporator (17) and extends to the outside. The second opening and closing plate (1102) is fixedly installed on the inner wall of the evaporator (18) by a rotating frame. The second opening and closing plate (1102) is adapted to the discharge box (1101).

9. A water pollution treatment device according to claim 4, characterized in that, The inner wall of the evaporator (18) is connected to two one-way pipes (10), and the top of the evaporator (17) is connected to a steam pipe (19).

10. A process for recovering lithium, rubidium, and cesium from lepidolite leaching residue, requiring the use of a water pollution treatment device as described in any one of claims 1-9, characterized in that, Includes the following steps: S1: Pre-treatment crushing, crushing the lepidolite sulfuric acid roasting residue to 200 mesh, in the lepidolite sulfuric acid roasting residue It accounts for 0.5-1.2%. It accounts for 0.3-0.8%. The solid-liquid ratio is 1:

3. The solid-liquid ratio is 0.1-0.5%. The washing wastewater after washing with dilute sulfuric acid is sent to the water pollution treatment equipment for treatment and discharged in compliance with standards. S2: Lithium preferential leaching, prepared with 1 mol / L... +0.5mol / L A mixed solution with a solid-liquid ratio of 1:5 was reacted at 90℃ for 2 hours, with the final pH controlled at 2.

5. The solution was then filtered to obtain a lithium-containing leachate. The concentration is 8-12 g / L; Reaction formula: ； S3: Rubidium-cesium enhanced leaching, adding 2 mol / L of [unspecified substance] to the residue. +1mol / L The solution, with a solid-liquid ratio of 1:4, was subjected to high-pressure reaction at 120℃ for 3 hours. The pH was then adjusted to 1.0 to obtain a rubidium-cesium enriched solution. The concentration is 2-4 g / L. The concentration is 0.8-1.5 g / L; Reaction formula: ； S4: Stepwise precipitation separation, lithium precipitation: Add saturated sodium carbonate to the S2 leachate to pH=10 to form lithium carbonate; cesium preferential precipitation: Adjust the pH of the S3 solution to 3, add 0.1 mol / L sodium tetraphenylborate to form... Rubidium precipitation: Add 2 mol / L to the remaining solution Solution, formation ; Reaction formula: 。

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