Energy-saving boiler and spodumene brine thallium removal process

Abstract

The invention provides an energy-saving boiler and a thallium removal process for spodumene brine. Relates to the field of energy-saving boilers. The furnace body is fixedly mounted at the bottom of the inner wall of the isolation box through a bracket; and the top cover is fixedly mounted at the top of the furnace body. According to the energy-saving boiler and the spodumene brine thallium removal process provided by the invention, water is injected into the boiler body by arranging the water delivery pump, and external high-temperature flue gas sequentially flows through the plurality of heating pipes, so that layered and stepped uniform heating of the water body in the boiler body is realized, the heat energy utilization efficiency is remarkably improved, and the energy is saved; smoke flows step by step in the heating pipe and is finally discharged, the flow speed of the smoke is reduced, heat is fully exchanged, the smoke discharging temperature is reduced, meanwhile, the water suction pump continuously and stably outputs hot water at the constant temperature of 40 DEG C to the constant-temperature water bath, stability of the water supply temperature is guaranteed, operation is energy-saving, and the automation degree is high.

Description

Technical Field

[0001] This invention relates to the field of energy-saving boilers, and more particularly to an energy-saving boiler and a thallium removal process for spodumene brine. Background Technology

[0002] The technological development of energy-saving boilers is rooted in its rich history and engineering practice. In the process of industrialization, in order to ensure a stable and reliable supply of heat energy, a series of classic designs and technical paths were formed around the two core aspects of effective fuel combustion and efficient heat energy conversion. Limited by the material and process levels of a specific historical stage, the manufacturing technology, pressure-bearing components and heating surface design of boilers all prioritized safety and durability. Designs such as the drum-type natural circulation structure were widely used and continued for a long time. The technological evolution during this period was essentially to match the centralized energy supply system based on fossil fuels, aiming to meet the basic needs of ever-growing industrial capacity and urban centralized heating. Its technological paradigm was highly compatible with the energy structure, economic costs and industrialization stage at that time.

[0003] In existing energy-saving boilers, fuel is ignited in the furnace at the boiler base, and combustion air is provided by a blower. The flame and high-temperature flue gas heat the bottom of the heating vessel above. The water in the heating vessel absorbs heat and produces hot water or steam. The hot water can be output through specific pipelines. During the heating process, the cooling box wrapped around the outer wall of the heating vessel starts to work. A water pump pumps external cold water into the cooling box jacket through external water pipes and inlet water pipes for cooling and waste heat recovery.

[0004] However, existing energy-saving boilers only exchange heat at the bottom of the heating vessel during use. The water in the boiler is heated unevenly at the bottom and the heat is dissipated to both sides, resulting in a waste of heat energy.

[0005] Therefore, it is necessary to provide an energy-saving boiler and a thallium removal process for spodumene brine to solve the above-mentioned technical problems. Summary of the Invention

[0006] This invention provides an energy-saving boiler and a thallium removal process for spodumene brine, which solves the problem that heat exchange only occurs at the bottom of the heating vessel, resulting in uneven heating of the water in the boiler and heat loss to both sides.

[0007] To solve the above-mentioned technical problems, the present invention provides an energy-saving boiler, comprising: an isolation box placed on the ground;

[0008] The furnace body is fixedly installed on the bottom of the inner wall of the isolation box by a bracket;

[0009] Top cover, which is fixedly installed on the top of the furnace body;

[0010] A bottom cover, which is fixedly installed at the bottom of the furnace body;

[0011] A heating mechanism is provided, which extends through one side of the isolation box and into the interior. The heating mechanism includes a smoke supply pipe that extends through one side of the isolation box and into the interior. One end of the smoke supply pipe inside the isolation box is connected to a smoke inlet pipe via an intermediate gas box. The end of the smoke inlet pipe extends through the bottom of the bottom cover and into the interior of the furnace body. One end of the smoke inlet pipe inside the furnace body is connected to a heating pipe. The five heating pipes are connected to each other via riser pipes. The top of the heating pipe near the top cover is connected to an exhaust pipe. The exhaust pipe extends through the bottom of the top cover and the bottom of the isolation box in sequence and into the outside.

[0012] A water supply mechanism for supplying water to the interior of the furnace body;

[0013] A pumping mechanism is used to pump out the water that has been heated inside the furnace body.

[0014] Preferably, the water conveying mechanism is located on the ground. The water conveying mechanism includes a water tank, which is located on the ground. A water pump is fixedly installed on the top of the water tank. The pumping end of the water pump is connected to the inside of the water tank through a connecting pipe. The outlet end of the water pump is connected to a water valve through a water conveying pipe. One side of the water valve is connected to an inlet pipe through an intermediate water tank. The inlet pipe is connected to the bottom of the bottom cover.

[0015] Preferably, the water pumping mechanism is connected to one side of the furnace body. The water pumping mechanism includes a water pumping pipe connected to one side of the furnace body. The water pumping pipe passes through one side of the isolation box and extends to the outside. One end of the water pumping pipe located outside the isolation box is connected to a water pump. The water pump is located on the ground. The outlet end of the water pump is connected to a drain pipe.

[0016] Preferably, a vertical groove is formed on one side of the furnace body, and a sliding groove is formed on one side of the isolation box. An adjustment mechanism is fixedly installed on the top of the inner wall of the isolation box. The adjustment mechanism includes a float column and a piston. The float column is fixedly installed on the top of the inner wall of the isolation box. The bottom end of the float column penetrates the top of the top cover and extends into the interior of the furnace body. A float ball is slidably installed on the surface of the float column inside the furnace body. A drive plate is fixedly installed on one side of the float ball. The surface of the drive plate is slidably installed with the interior of the vertical groove and the sliding groove. Two right-angle plates are symmetrically fixedly installed on the bottom of the drive plate. The surface of the piston communicates with the top of the top cover. The piston penetrates the top of the inner wall of the isolation box and extends to the outside. A piston column is slidably installed inside the piston. The top of the piston column is fixedly installed on the top of the drive plate through a connecting rod.

[0017] Preferably, a disc is fixedly mounted on the surface of the water valve switch shaft, and a connecting plate is rotatably mounted on the surface of the disc via a convex shaft. The connecting plate is rotatably mounted between the two right-angled plates via a rotating shaft.

[0018] Preferably, a sealing plate is fixedly installed on the top of the drive plate, and the sealing plate is adapted to the vertical groove.

[0019] Preferably, a mixing mechanism is rotatably installed between the inner walls of the isolation box. The mixing mechanism includes a mixing shaft, which is rotatably installed between the inner walls of the isolation box. The mixing shaft passes through the intermediate water tank, the furnace body, and the intermediate gas box in sequence. Four mixing plates are fixedly installed on the surface of the mixing shaft inside the furnace body. Four fan blades are fixedly installed on the surface of the mixing plates inside the intermediate water tank. Two rotating plates are fixedly installed on the surface of the mixing plates inside the intermediate gas box.

[0020] Preferably, a wall scraping mechanism is fixedly installed on the top of the isolation box. The wall scraping mechanism includes a wall scraping motor, which is fixedly installed on the top of the isolation box. The output shaft of the wall scraping motor passes through the top of the isolation box and the top cover and extends into the furnace body. Four scrapers are fixedly installed at the bottom of the output shaft of the wall scraping motor through a circular sleeve.

[0021] Preferably, the bottom of the bottom cover is connected to a drain pipe via a drain valve, and the drain pipe passes through the bottom of the isolation box and extends to the outside.

[0022] A thallium removal process for spodumene brine includes the following steps:

[0023] S1: Pretreatment stage: The spodumene brine is introduced into a reaction vessel equipped with a high-efficiency stirring device. The pH value of the brine is precisely adjusted to 3-5 using dilute sulfuric acid or dilute sodium hydroxide solution. Within this pH range, thallium ions in the brine can exist in a form that is more conducive to subsequent removal. Under this pH condition, thallium that is originally bound to other substances is more likely to dissociate into ionic state, thereby significantly improving the effect of subsequent thallium removal operations.

[0024] S2: Preliminary filtration: A high-precision ceramic membrane filter is used to perform preliminary filtration on the brine after pH adjustment, effectively removing large particulate impurities in the brine, such as unreacted ore particles and silt. This operation can prevent large particulate impurities from clogging the subsequent thallium removal equipment and ensure the stable operation of the thallium removal process. Compared with traditional screen filtration, ceramic membrane filters have higher filtration accuracy and chemical stability and can better adapt to the complex environment of spodumene brine.

[0025] S3: Thallium Removal Stage: A specially formulated composite thallium removal agent is added to the pretreated brine. This composite thallium removal agent consists of ferrous sulfide, modified graphene quantum dot-supported mesoporous silica, and polyferric sulfate in a mass ratio of (3-5):(1-2):(0.5-1). Ferrous sulfide can chemically react with thallium ions in the brine to generate insoluble thallium sulfide precipitate. The modified graphene quantum dot-supported mesoporous silica has a unique structure. On the one hand, graphene quantum dots have excellent electron transport performance and high specific surface area, which can enhance... On the one hand, the mesoporous structure of the silica provides ample space for the adsorption of thallium ions. On the other hand, its surface is specially modified to contain a large number of functional groups that have specific adsorption effects on thallium ions, such as mercapto and amino groups, which can greatly improve the adsorption selectivity and adsorption capacity of thallium ions. The polynuclear hydroxy complexes generated by the hydrolysis of polyferric sulfate in brine can play a flocculation role, flocculating the generated thallium sulfide precipitate and the thallium and other impurities adsorbed by the modified graphene quantum dot-supported mesoporous silica together, which is convenient for subsequent separation.

[0026] S4: Reaction Condition Control: After adding the composite thallium removal agent, turn on the variable frequency stirring device and precisely control the stirring speed at 150-250 r / min to ensure that the composite thallium removal agent is in full contact with the brine and accelerate the reaction. At the same time, place the reaction vessel in a smart temperature-controlled constant temperature water bath to maintain the reaction temperature at 30-40℃. Within this temperature range, the chemical reaction and adsorption process can proceed under relatively ideal kinetic conditions. The reaction time is set to 1-2 hours to ensure that the thallium removal reaction is fully completed.

[0027] S5: Solid-liquid separation stage: After the reaction is completed, a new type of bio-flocculator is added to the brine. Its main components are a complex of microbial polysaccharides and proteins. The addition amount is 10-20 mg / L. Compared with traditional polyacrylamide flocculants, this bio-flocculator is biodegradable and will not cause secondary pollution to the environment. It can further promote the growth of the generated precipitate flocs, forming larger flocs, which facilitates sedimentation and separation.

[0028] S6: Sedimentation separation: The flocculated sediment is allowed to settle naturally in a sedimentation tank with an inclined tube sedimentation structure by gravity sedimentation. The sedimentation time is 2-3 hours. The inclined tube sedimentation structure can increase the sedimentation area and improve the sedimentation efficiency, so that the thallium and other impurities in the brine are quickly enriched at the bottom of the sedimentation tank, while the upper layer is the preliminarily purified brine.

[0029] S7: Filtration: The preliminarily purified brine is filtered through a plate and frame filter press using a cross-flow filtration method to further remove residual tiny particles and flocs in the brine, resulting in purer brine. The cross-flow filtration method can effectively reduce filter cake clogging and improve filtration efficiency and filtration quality.

[0030] S8: Deep purification stage: The brine after solid-liquid separation is passed through an ion exchange column equipped with a new type of chelating ion exchange resin. This chelating ion exchange resin has extremely high affinity and selectivity for trace amounts of thallium ions that may remain in the brine, which can further reduce the thallium content in the brine. The flow rate of the brine in the ion exchange column is controlled at 200-300 ml / h to ensure that the ion exchange reaction is fully carried out.

[0031] S9: Detection and Adjustment: The brine after adsorption by ion exchange resin is monitored in real time online. The thallium content in the brine is determined by advanced inductively coupled plasma mass spectrometry. This technology can achieve rapid and accurate detection of thallium content. If the detection results show that the thallium content in the brine still does not meet the expected standard, such as being lower than 1 μg / L, the brine is passed through the ion exchange column again for secondary adsorption, or the process parameters of the previous stages are adjusted according to the actual situation, such as increasing the amount of composite thallium removal agent or extending the reaction time, until the thallium content in the brine meets the requirements.

[0032] Compared with related technologies, the energy-saving boiler provided by the present invention has the following beneficial effects:

[0033] This invention provides an energy-saving boiler that injects water into the boiler body through a water pump and utilizes external high-temperature flue gas to flow sequentially through multiple heating tubes, achieving stratified and step-by-step uniform heating of the water inside the boiler. This significantly improves thermal efficiency and saves energy. The flue gas flows step by step within the heating tubes and is eventually discharged, slowing down the flue gas flow rate to allow for sufficient heat exchange and reducing the exhaust temperature. At the same time, the water pump continuously and stably outputs constant-temperature 40°C hot water to the constant-temperature water bath, ensuring stable water supply temperature. The boiler is energy-saving and highly automated. Attached Figure Description

[0034] Figure 1 This is a schematic diagram of a preferred embodiment of an energy-saving boiler provided by the present invention;

[0035] Figure 2 Another structural schematic diagram of a preferred embodiment of an energy-saving boiler;

[0036] Figure 3 for Figure 2 The diagram shows the structure of the heating mechanism.

[0037] Figure 4 for Figure 2 The diagram shows the structure of the water conveyance mechanism.

[0038] Figure 5 for Figure 2 The diagram shows the structure of the pumping mechanism.

[0039] Figure 6 This is a schematic diagram of the structure of a second embodiment of an energy-saving boiler;

[0040] Figure 7 This is another structural schematic diagram of a second embodiment of an energy-saving boiler;

[0041] Figure 8 for Figure 6 The diagram shows the structure of the adjustment mechanism.

[0042] Figure 9 for Figure 8 The diagram shows the installation of the piston rod;

[0043] Figure 10 for Figure 6 The diagram shows the structure of the mixing mechanism.

[0044] Figure 11 for Figure 6 The diagram shows the structure of the wall scraping mechanism.

[0045] Figure 12 This is a process flow diagram of a spodumene brine thallium removal process.

[0046] Numbered in the diagram: 1. Isolation box; 2. Furnace body; 3. Top cover; 4. Bottom cover; 5. Heating mechanism; 501. Smoke conveying pipe; 502. Intermediate gas box; 503. Smoke inlet pipe; 504. Heating pipe; 505. Riser pipe; 506. Exhaust pipe; 6. Water conveying mechanism; 601. Water tank; 602. Water pump; 603. Water conveying pipe; 604. Water valve; 605. Intermediate water tank; 606. Water inlet pipe; 7. Pumping mechanism; 701. Pumping pipe; 702. Pump; 703. Drainage pipe; 8. Regulator. 801. Float column, 802. Float, 803. Drive plate, 804. Right angle plate, 805. Piston, 806. Piston column, 807. Connecting rod, 9. Mixing mechanism, 901. Mixing shaft, 902. Mixing plate, 903. Fan blade, 904. Rotating plate, 10. Scraping mechanism, 1001. Scraping motor, 1002. Circular sleeve, 1003. Scraper, 11. Drain valve, 12. Drain pipe, 13. Connecting plate, 14. Sealing plate, 15. Vertical groove, 16. Disc, 17. Slide groove. Detailed Implementation

[0047] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0048] First Embodiment

[0049] Please refer to the following: Figure 1 , Figure 2 , Figure 3 , Figure 4 and Figure 5An energy-saving boiler includes: an isolation box 1 placed on the ground;

[0050] Furnace body 2, which is fixedly installed on the bottom of the inner wall of the isolation box 1 by a bracket;

[0051] Top cover 3, which is fixedly installed on the top of the furnace body 2;

[0052] Bottom cover 4, which is fixedly installed at the bottom of the furnace body 2;

[0053] Heating mechanism 5, which penetrates one side of the isolation box 1 and extends into the interior, includes a smoke supply pipe 501. The smoke supply pipe 501 penetrates one side of the isolation box 1 and extends into the interior. One end of the smoke supply pipe 501 inside the isolation box 1 is connected to a smoke inlet pipe 503 through an intermediate gas box 502. The end of the smoke inlet pipe 503 penetrates the bottom of the bottom cover 4 and extends into the interior of the furnace body 2. One end of the smoke inlet pipe 503 inside the furnace body 2 is connected to a heating pipe 504. The five heating pipes 504 are connected to each other through a riser pipe 505. The top of the heating pipe 504 near the top cover 3 is connected to an exhaust pipe 506. The exhaust pipe 506 penetrates the bottom of the top cover 3 and the bottom of the isolation box 1 in sequence and extends to the outside.

[0054] Water supply mechanism 6, which is used to supply water to the interior of the furnace body 2;

[0055] The water pumping mechanism 7 is used to pump out the water heated inside the furnace body 2.

[0056] The water conveying mechanism 6 is located on the ground and includes a water tank 601. The water tank 601 is located on the ground and a water pump 602 is fixedly installed on the top of the water tank 601. The water pump 602's pumping end is connected to the inside of the water tank 601 through a connecting pipe. The water pump 602's outlet end is connected to a water valve 604 through a water pipe 603. One side of the water valve 604 is connected to an inlet pipe 606 through an intermediate water tank 605. The inlet pipe 606 is connected to the bottom of the bottom cover 4.

[0057] The water pumping mechanism 7 is connected to one side of the furnace body 2. The water pumping mechanism 7 includes a water pumping pipe 701, which is connected to one side of the furnace body 2. The water pumping pipe 701 passes through one side of the isolation box 1 and extends to the outside. One end of the water pumping pipe 701 located outside the isolation box 1 is connected to a water pump 702. The water pump 702 is set on the ground, and the water outlet end of the water pump 702 is connected to a drain pipe 703.

[0058] In actual use, the heating tube 504 does not contact the inner wall of the furnace body 2.

[0059] The working principle of the energy-saving boiler provided by this invention is as follows:

[0060] First, the water pump 602 is started to pump water from the water tank 601 into the furnace body 2 through the water pipe 603, water valve 604, intermediate water tank 605 and inlet pipe 606. The flue pipe 501 is connected to the external high-temperature flue gas pipe. The high-temperature flue gas is discharged into the heating pipe 504 after passing through the intermediate gas box 502 and the inlet pipe 503. The heating pipe 504 heats the interior of the furnace body 2. The high-temperature flue gas inside the heating pipe 504 enters the next heating pipe 504 after passing through the riser pipe 505 to heat the water in the middle and upper layers. Finally, after the high-temperature flue gas is heated, it is discharged through the exhaust pipe 506.

[0061] Then, the water pump 702 is started to draw water from the inside of the furnace body 2 through the water pumping pipe 701, and the constant temperature 40℃ hot water is discharged into the constant temperature water bath through the drain pipe 703.

[0062] Compared with related technologies, the energy-saving boiler provided by the present invention has the following beneficial effects:

[0063] By setting up a water pump 602 to inject water into the interior of the furnace body 2, and utilizing the high-temperature flue gas from the outside to flow through multiple heating tubes 504 in sequence, the water in the furnace body 2 is heated in a layered, step-by-step, uniform manner, which significantly improves the thermal energy utilization efficiency and saves energy. The flue gas flows step by step in the heating tubes and is eventually discharged, which slows down the flue gas flow rate so that heat can be fully exchanged and the exhaust temperature is reduced. At the same time, the water pump 702 continuously and stably outputs constant-temperature 40℃ hot water to the constant-temperature water bath to ensure the stability of the water supply temperature. The operation is energy-saving and highly automated.

[0064] Second Embodiment

[0065] Please refer to the following: Figures 6-11 Based on the energy-saving boiler provided in the first embodiment of this application, the second embodiment of this application proposes another energy-saving boiler. 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.

[0066] Specifically, the second embodiment of this application provides an energy-saving boiler that differs in that a vertical groove 15 is provided on one side of the furnace body 2, a sliding groove 17 is provided on one side of the isolation box 1, and an adjustment mechanism 8 is fixedly installed on the top of the inner wall of the isolation box 1. The adjustment mechanism 8 includes a float column 801 and a piston 805. The float column 801 is fixedly installed on the top of the inner wall of the isolation box 1, and the bottom end of the float column 801 penetrates the top of the top cover 3 and extends into the interior of the furnace body 2. A float ball is slidably installed on the surface of the float column 801 inside the furnace body 2. 802, A drive plate 803 is fixedly installed on one side of the float 802. The surface of the drive plate 803 is slidably installed inside the vertical groove 15 and the sliding groove 17. Two right-angle plates 804 are symmetrically fixedly installed at the bottom of the drive plate 803. The surface of the piston 805 is connected to the top of the top cover 3. The piston 805 penetrates the top of the inner wall of the isolation box 1 and extends to the outside. A piston column 806 is slidably installed inside the piston 805. The top of the piston column 806 is fixedly installed on the top of the drive plate 803 through a connecting rod 807.

[0067] A disc 16 is fixedly mounted on the surface of the water valve 604 switch shaft. A connecting plate 13 is rotatably mounted on the surface of the disc 16 via a convex shaft. The connecting plate 13 is rotatably mounted between the two right-angle plates 804 via a rotating shaft.

[0068] A sealing plate 14 is fixedly installed on the top of the drive plate 803, and the sealing plate 14 is adapted to the vertical groove 15.

[0069] A mixing mechanism 9 is rotatably installed between the inner walls of the isolation box 1. The mixing mechanism 9 includes a mixing shaft 901, which is rotatably installed between the inner walls of the isolation box 1. The mixing shaft 901 passes through the intermediate water tank 605, the furnace body 2, and the intermediate gas box 502 in sequence. Four mixing plates 902 are fixedly installed on the surface of the mixing shaft 901 inside the furnace body 2. Four fan blades 903 are fixedly installed on the surface of the mixing plate 902 inside the intermediate water tank 605. Two rotating plates 904 are fixedly installed on the surface of the mixing plate 902 inside the intermediate gas box 502.

[0070] A wall scraping mechanism 10 is fixedly installed on the top of the isolation box 1. The wall scraping mechanism 10 includes a wall scraping motor 1001, which is fixedly installed on the top of the isolation box 1. The output shaft of the wall scraping motor 1001 passes through the top of the isolation box 1 and the top of the top cover 3 and extends into the interior of the furnace body 2. Four scraper blades 1003 are fixedly installed at the bottom of the output shaft of the wall scraping motor 1001 through a round sleeve 1002.

[0071] The bottom of the bottom cover 4 is connected to a drain pipe 12 via a drain valve 11. The drain pipe 12 passes through the bottom of the isolation box 1 and extends to the outside.

[0072] In actual use, the sealing plate 14 does not contact the isolation box 1 when it rises;

[0073] The scraper 1003 does not contact the heating tube 504.

[0074] The working principle of an energy-saving boiler provided in this embodiment is as follows:

[0075] First, during the process of water being pumped into the furnace body 2, when the water passes through the intermediate water tank 605, the water flows downward and impacts the fan blades 903, causing the mixing shaft 901 to rotate. The rotation of the mixing shaft 901 causes the mixing plate 902 to rotate and mix the water in different layers inside the furnace body 2 to avoid uneven heating and excessive local temperature, which would generate a large amount of steam. At the same time, the rotation of the mixing shaft 901 also causes the rotating plate 904 to rotate, opening the high-temperature flue gas passage multiple times and continuously to input high-temperature flue gas.

[0076] When high-temperature flue gas heats water to produce steam, it indicates that the water temperature is too high. At this time, a large amount of accumulated steam pushes up the piston column 806. The piston column 806 drives the drive plate 803 to rise through the connecting rod 807. The drive plate 803 drives the connecting plate 13 to move through the right-angle plate 804. The connecting plate 13 drives the disc 16 to rotate and turn the water valve 604 to reduce the water flow. At this time, after the water flow is reduced, the rate at which the water flow impacts the fan blade 903 becomes smaller. At the same time, the rotating plate 904 rotates slowly to reduce the input of flue gas and keep the water in the furnace body 2 stable.

[0077] Then, when the water level inside the furnace body 2 drops, the float ball 802 drives the drive plate 803 to drop, and the drive plate 803 drives the connecting plate 13 to rotate the disc 16 counterclockwise to increase the water flow of the water valve 604. At this time, the mixing plate 902 accelerates the mixing, and at the same time, the rotating plate 904 increases the rotation speed to increase the input of high-temperature flue gas, which quickly raises the water level inside the furnace body 2 and reaches the preset temperature. When the water level in the furnace body 2 rises too much, the water flow of the water valve 604 is reduced and the above process is repeated.

[0078] Finally, when scale forms on the inner wall of the furnace body 2 after long-term use, the scraper motor 1001 is started to drive the scraper 1003 to periodically and repeatedly scrape off the scale, and the drain valve 11 is opened to discharge wastewater through the drain pipe 12 for recycling.

[0079] Compared with related technologies, the energy-saving boiler provided in this embodiment has the following beneficial effects:

[0080] When the water temperature is too high and steam is generated, the steam pressure pushes the piston rod 806 upward. Through the cooperation of the right-angle plate 804 and the connecting plate 13, the water valve 604 is closed and the water flow and flue gas input are reduced simultaneously, realizing negative feedback regulation to prevent overheating. When the water level drops, the float ball 802 falls and opens the water valve 604, while accelerating the water flow and flue gas input rate, realizing positive feedback regulation for water replenishment and temperature increase. It can automatically respond to changes in operating conditions and maintain the water temperature and water level at the preset equilibrium point for a long time, ensuring the continuity and reliability of the constant 40℃ hot water output. Different steam generation states and water levels inside the furnace body 2 can drive the water flow of the water valve 604 to increase or decrease respectively. The water flow itself is used as a power source to drive the fan blade 903 to drive the mixing shaft 901 to rotate. The rotation of the mixing shaft 901 drives the rotating plate 904 to rotate, realizing the continuous operation of the mixing plate 902. The rotation breaks down the temperature stratification of the water inside the furnace body 2, ensuring uniform heat distribution and fundamentally reducing energy waste and steam ejection risks caused by local overheating. At the same time, the synchronous rotation of the rotating plate 904 mechanically and periodically opens the flue gas passage, making the high-temperature flue gas input appear as a high-frequency pulse, promoting the heat exchange efficiency between flue gas and water, and preventing the furnace body 2 from being too hot at any moment. This achieves refined and energy-saving heat input. The automatic adjustment of water flow and flue gas flow achieves efficient and uniform heating and dynamic optimization of energy consumption. By setting a wall scraping motor 1001 to drive the scraper 1003 to scrape off the scale attached to the furnace body 2, the problem of increased energy consumption and impure hot water output caused by scale buildup is avoided. After the drain valve 11 is opened, the wastewater is discharged through the drain pipe 12, and the scraped scale is discharged with the wastewater for treatment, which greatly reduces the labor intensity of manual cleaning, downtime and maintenance costs.

[0081] A process for thallium removal from spodumene brine

[0082] A thallium removal process for spodumene brine includes the following steps:

[0083] S1: Pretreatment stage: The spodumene brine is introduced into a reaction vessel equipped with a high-efficiency stirring device. The pH value of the brine is precisely adjusted to 3-5 using dilute sulfuric acid or dilute sodium hydroxide solution. Within this pH range, thallium ions in the brine can exist in a form that is more conducive to subsequent removal. Under this pH condition, thallium that is originally bound to other substances is more likely to dissociate into ionic state, thereby significantly improving the effect of subsequent thallium removal operations.

[0084] S2: Preliminary filtration: A high-precision ceramic membrane filter is used to perform preliminary filtration on the brine after pH adjustment, effectively removing large particulate impurities in the brine, such as unreacted ore particles and silt. This operation can prevent large particulate impurities from clogging the subsequent thallium removal equipment and ensure the stable operation of the thallium removal process. Compared with traditional screen filtration, ceramic membrane filters have higher filtration accuracy and chemical stability and can better adapt to the complex environment of spodumene brine.

[0085] S3: Thallium Removal Stage: A specially formulated composite thallium removal agent is added to the pretreated brine. This composite thallium removal agent consists of ferrous sulfide, modified graphene quantum dot-supported mesoporous silica, and polyferric sulfate in a mass ratio of (3-5):(1-2):(0.5-1). Ferrous sulfide can chemically react with thallium ions in the brine to generate insoluble thallium sulfide precipitate. The modified graphene quantum dot-supported mesoporous silica has a unique structure. On the one hand, graphene quantum dots have excellent electron transport performance and high specific surface area, which can enhance... On the one hand, the mesoporous structure of the silica provides ample space for the adsorption of thallium ions. On the other hand, its surface is specially modified to contain a large number of functional groups that have specific adsorption effects on thallium ions, such as mercapto and amino groups, which can greatly improve the adsorption selectivity and adsorption capacity of thallium ions. The polynuclear hydroxy complexes generated by the hydrolysis of polyferric sulfate in brine can play a flocculation role, flocculating the generated thallium sulfide precipitate and the thallium and other impurities adsorbed by the modified graphene quantum dot-supported mesoporous silica together, which is convenient for subsequent separation.

[0086] S4: Reaction Condition Control: After adding the composite thallium removal agent, turn on the variable frequency stirring device and precisely control the stirring speed at 150-250 r / min to ensure that the composite thallium removal agent is in full contact with the brine and accelerate the reaction. At the same time, place the reaction vessel in a smart temperature-controlled constant temperature water bath to maintain the reaction temperature at 30-40℃. Within this temperature range, the chemical reaction and adsorption process can proceed under relatively ideal kinetic conditions. The reaction time is set to 1-2 hours to ensure that the thallium removal reaction is fully completed.

[0087] S5: Solid-liquid separation stage: After the reaction is completed, a new type of bio-flocculator is added to the brine. Its main components are a complex of microbial polysaccharides and proteins. The addition amount is 10-20 mg / L. Compared with traditional polyacrylamide flocculants, this bio-flocculator is biodegradable and will not cause secondary pollution to the environment. It can further promote the growth of the generated precipitate flocs, forming larger flocs, which facilitates sedimentation and separation.

[0088] S6: Sedimentation separation: The flocculated sediment is allowed to settle naturally in a sedimentation tank with an inclined tube sedimentation structure by gravity sedimentation. The sedimentation time is 2-3 hours. The inclined tube sedimentation structure can increase the sedimentation area and improve the sedimentation efficiency, so that the thallium and other impurities in the brine are quickly enriched at the bottom of the sedimentation tank, while the upper layer is the preliminarily purified brine.

[0089] S7: Filtration: The preliminarily purified brine is filtered through a plate and frame filter press using a cross-flow filtration method to further remove residual tiny particles and flocs in the brine, resulting in purer brine. The cross-flow filtration method can effectively reduce filter cake clogging and improve filtration efficiency and filtration quality.

[0090] S8: Deep purification stage: The brine after solid-liquid separation is passed through an ion exchange column equipped with a new type of chelating ion exchange resin. This chelating ion exchange resin has extremely high affinity and selectivity for trace amounts of thallium ions that may remain in the brine, which can further reduce the thallium content in the brine. The flow rate of the brine in the ion exchange column is controlled at 200-300 ml / h to ensure that the ion exchange reaction is fully carried out.

[0091] S9: Detection and Adjustment: The brine after adsorption by ion exchange resin is monitored in real time online. The thallium content in the brine is determined by advanced inductively coupled plasma mass spectrometry. This technology can achieve rapid and accurate detection of thallium content. If the detection results show that the thallium content in the brine still does not meet the expected standard, such as being lower than 1 μg / L, the brine is passed through the ion exchange column again for secondary adsorption, or the process parameters of the previous stages are adjusted according to the actual situation, such as increasing the amount of composite thallium removal agent or extending the reaction time, until the thallium content in the brine meets the requirements.

[0092] First Embodiment

[0093] Pretreatment: Take 1L of spodumene brine with an initial pH of 6.5 and a thallium content of 80μg / L. Add the brine to a reaction vessel equipped with a frequency converter and slowly add dilute sulfuric acid. At the same time, monitor the pH value in real time using a high-precision pH sensor and adjust the pH value of the brine to 4.

[0094] Preliminary filtration: The brine after pH adjustment is filtered using a ceramic membrane filter with a pore size of 0.1μm to remove large particulate impurities and obtain clear brine.

[0095] Thallium removal reaction: Weigh 3g ferrous sulfide, 1.5g modified graphene quantum dot-supported mesoporous silica and 0.75g polyferric sulfate, mix them evenly and add them to the pretreated brine. Turn on the variable frequency stirrer and control the stirring speed to 200r / min. Place the reaction vessel in a constant temperature water bath and maintain the temperature at 35℃ for 1.5 hours.

[0096] Flocculation and sedimentation: After the reaction is complete, add 15mg of the new biological flocculant to the brine, stir evenly and let stand for 15 minutes to allow the precipitate to flocculate and grow.

[0097] Sedimentation separation: The brine is transferred to a sedimentation tank with an inclined tube sedimentation structure for gravity sedimentation. The sedimentation time is 2.5 hours. The sediment accumulates at the bottom of the sedimentation tank, and the upper layer is the pre-purified brine. The pre-purified brine is filtered through a plate and frame filter press using a cross-flow filtration method to obtain purer brine.

[0098] Deep purification: The brine after solid-liquid separation is passed through an ion exchange column packed with a novel chelating ion exchange resin at a flow rate of 250 ml / h.

[0099] Testing and Adjustment: The brine after adsorption by ion exchange resin was tested using ICP-MS. The results showed that the thallium content in the brine was 0.8 μg / L, which met the expected standard.

[0100] Second Embodiment

[0101] Pretreatment stage: Take 2L of spodumene brine with an initial pH of 7 and a thallium content of 120μg / L. Add the brine to the reaction vessel and adjust the pH to 3.5 with dilute sulfuric acid solution. The pH change is monitored in real time using a high-precision pH sensor.

[0102] Preliminary filtration: The brine is filtered through a ceramic membrane filter with a pore size of 0.1μm to remove large particulate impurities.

[0103] Thallium removal reaction stage: Add 5g ferrous sulfide, 2g modified graphene quantum dot-supported mesoporous silica and 1g polyferric sulfate to the pretreated brine. The stirring speed is controlled at 180r / min, the reaction temperature is maintained at 32℃, and the reaction time is 2 hours.

[0104] Flocculation and sedimentation: After the reaction is complete, add 20 mg of the new bio-flocculating agent, stir and let stand for 20 minutes.

[0105] Sedimentation separation: Settling is carried out in a sedimentation tank with an inclined tube sedimentation structure for 3 hours, followed by filtration using a plate and frame filter press with cross-flow filtration.

[0106] Deep purification: The brine is passed through an ion exchange column at a flow rate of 200 ml / h.

[0107] Testing and Adjustment: ICP-MS testing showed that the thallium content in the brine was 0.5 μg / L, which meets the requirements.

[0108] Compared with related technologies, the thallium removal process for spodumene brine provided by this invention has the following beneficial effects:

[0109] Highly Efficient Thallium Removal: By employing the specially formulated composite thallium removal agent, novel bio-flocculator, novel chelating ion exchange resin, and optimized process steps of this invention, the thallium removal process of this invention can reduce the thallium content in spodumene brine from tens or even hundreds of μg / L initially to below 1 μg / L, with a thallium removal efficiency of over 99%, far exceeding the thallium removal efficiency of traditional thallium removal processes. This meets the most stringent environmental emission standards and the brine quality requirements of subsequent lithium extraction processes. Low Cost: Ferrous sulfide and polyferric sulfate in the composite thallium removal agent are common and relatively inexpensive chemical reagents with wide availability. Although the preparation process of modified graphene quantum dot-supported mesoporous silica is relatively complex, it has extremely high adsorption performance, requires relatively small amounts, and has a controllable overall cost. The novel bio-flocculator has abundant raw material sources and low preparation costs. The entire process does not require expensive equipment or frequent replacement of consumables. Compared with traditional ion exchange methods, it reduces the frequent replacement of ion exchange resins. This invention effectively reduces the cost of thallium removal and is environmentally friendly: the precipitate generated during the reaction process is mainly insoluble substances such as thallium sulfide, which can be properly treated after solid-liquid separation, unlike the traditional sulfide precipitation method which is prone to secondary pollution. The novel bio-flocculator used is biodegradable and will not impose an additional burden on the environment. Furthermore, no other harmful substances that would have adverse effects on the environment are introduced during the entire process, which is in line with the concept of green and environmentally friendly development. It is also highly adaptable: considering the complex composition of spodumene brine, the process of this invention, through pretreatment to adjust the pH value and high-precision preliminary filtration, as well as the synergistic effect of the various components of the composite thallium removal agent in the thallium removal reaction stage, can effectively reduce the interference of other metal ions and impurities in the brine on the thallium removal effect. It has good adaptability to spodumene brine of different sources and compositions. At the same time, the advanced detection technology and flexible adjustment mechanism adopted in the deep purification stage can ensure the stability and reliability of the process.

[0110] 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. An energy-saving boiler, characterized in that, include: Isolation boxes placed on the ground; The furnace body is fixedly installed on the bottom of the inner wall of the isolation box by a bracket; Top cover, which is fixedly installed on the top of the furnace body; A bottom cover, which is fixedly installed at the bottom of the furnace body; A heating mechanism is provided, which extends through one side of the isolation box and into the interior. The heating mechanism includes a smoke supply pipe that extends through one side of the isolation box and into the interior. One end of the smoke supply pipe inside the isolation box is connected to a smoke inlet pipe via an intermediate gas box. The end of the smoke inlet pipe extends through the bottom of the bottom cover and into the interior of the furnace body. One end of the smoke inlet pipe inside the furnace body is connected to a heating pipe. The five heating pipes are connected to each other via riser pipes. The top of the heating pipe near the top cover is connected to an exhaust pipe. The exhaust pipe extends through the bottom of the top cover and the bottom of the isolation box in sequence and into the outside. A water supply mechanism for supplying water to the interior of the furnace body; A pumping mechanism is used to pump out the water that has been heated inside the furnace body.

2. The energy-saving boiler according to claim 1, characterized in that, The water conveying mechanism is set on the ground. The water conveying mechanism includes a water tank. The water tank is set on the ground. A water pump is fixedly installed on the top of the water tank. The water pump's pumping end is connected to the inside of the water tank through a connecting pipe. The water pump's outlet end is connected to a water valve through a water pipe. One side of the water valve is connected to an inlet pipe through an intermediate water tank. The inlet pipe is connected to the bottom of the bottom cover.

3. The energy-saving boiler according to claim 1, characterized in that, The water pumping mechanism is connected to one side of the furnace body. The water pumping mechanism includes a water pumping pipe connected to one side of the furnace body. The water pumping pipe passes through one side of the isolation box and extends to the outside. One end of the water pumping pipe located outside the isolation box is connected to a water pump. The water pump is located on the ground. The outlet end of the water pump is connected to a drain pipe.

4. An energy-saving boiler according to claim 2, characterized in that, A vertical groove is formed on one side of the furnace body, and a sliding groove is formed on one side of the isolation box. An adjustment mechanism is fixedly installed on the top of the inner wall of the isolation box. The adjustment mechanism includes a float column and a piston. The float column is fixedly installed on the top of the inner wall of the isolation box. The bottom end of the float column penetrates the top of the top cover and extends into the interior of the furnace body. A float ball is slidably installed on the surface of the float column inside the furnace body. A drive plate is fixedly installed on one side of the float ball. The surface of the drive plate is slidably installed with the interior of the vertical groove and the sliding groove. Two right-angle plates are symmetrically fixedly installed on the bottom of the drive plate. The surface of the piston communicates with the top of the top cover. The piston penetrates the top of the inner wall of the isolation box and extends to the outside. A piston column is slidably installed inside the piston. The top of the piston column is fixedly installed on the top of the drive plate through a connecting rod.

5. An energy-saving boiler according to claim 4, characterized in that, A disc is fixedly mounted on the surface of the water valve switch shaft, and a connecting plate is rotatably mounted on the surface of the disc via a convex shaft. The connecting plate is rotatably mounted between the two right-angled plates via a rotating shaft.

6. An energy-saving boiler according to claim 4, characterized in that, A sealing plate is fixedly installed on the top of the drive plate, and the sealing plate is adapted to the vertical groove.

7. An energy-saving boiler according to claim 2, characterized in that, A mixing mechanism is rotatably installed between the inner walls of the isolation box. The mixing mechanism includes a mixing shaft, which is rotatably installed between the inner walls of the isolation box. The mixing shaft passes through the intermediate water tank, the furnace body, and the intermediate gas box in sequence. Four mixing plates are fixedly installed on the surface of the mixing shaft inside the furnace body. Four fan blades are fixedly installed on the surface of the mixing plates inside the intermediate water tank. Two rotating plates are fixedly installed on the surface of the mixing plates inside the intermediate gas box.

8. An energy-saving boiler according to claim 1, characterized in that, A wall scraping mechanism is fixedly installed on the top of the isolation box. The wall scraping mechanism includes a wall scraping motor, which is fixedly installed on the top of the isolation box. The output shaft of the wall scraping motor passes through the top of the isolation box and the top cover and extends into the furnace body. Four scrapers are fixedly installed at the bottom of the output shaft of the wall scraping motor through a circular sleeve.

9. An energy-saving boiler according to claim 1, characterized in that, The bottom of the cover is connected to a drain pipe via a drain valve, and the drain pipe passes through the bottom of the isolation box and extends to the outside.

10. A thallium removal process for spodumene brine, requiring the use of an energy-saving boiler as described in any one of claims 1-9, characterized in that, Includes the following steps: S1: Pretreatment stage: The spodumene brine is introduced into a reaction vessel equipped with a high-efficiency stirring device. The pH value of the brine is precisely adjusted to 3-5 using dilute sulfuric acid or dilute sodium hydroxide solution. Within this pH range, thallium ions in the brine can exist in a form that is more conducive to subsequent removal. Under this pH condition, thallium that is originally bound to other substances is more likely to dissociate into ionic state, thereby significantly improving the effect of subsequent thallium removal operations. S2: Preliminary filtration: A high-precision ceramic membrane filter is used to perform preliminary filtration on the brine after pH adjustment, effectively removing large particulate impurities in the brine, such as unreacted ore particles and silt. This operation can prevent large particulate impurities from clogging the subsequent thallium removal equipment and ensure the stable operation of the thallium removal process. Compared with traditional screen filtration, ceramic membrane filters have higher filtration accuracy and chemical stability and can better adapt to the complex environment of spodumene brine. S3: Thallium Removal Stage: A specially formulated composite thallium removal agent is added to the pretreated brine. This composite thallium removal agent consists of ferrous sulfide, modified graphene quantum dot-supported mesoporous silica, and polyferric sulfate in a mass ratio of (3-5):(1-2):(0.5-1). Ferrous sulfide can chemically react with thallium ions in the brine to generate insoluble thallium sulfide precipitate. The modified graphene quantum dot-supported mesoporous silica has a unique structure. On the one hand, graphene quantum dots have excellent electron transport performance and high specific surface area, which can enhance... On the one hand, the mesoporous structure of the silica provides ample space for the adsorption of thallium ions. On the other hand, its surface is specially modified to contain a large number of functional groups that have specific adsorption effects on thallium ions, such as mercapto and amino groups, which can greatly improve the adsorption selectivity and adsorption capacity of thallium ions. The polynuclear hydroxy complexes generated by the hydrolysis of polyferric sulfate in brine can play a flocculation role, flocculating the generated thallium sulfide precipitate and the thallium and other impurities adsorbed by the modified graphene quantum dot-supported mesoporous silica together, which is convenient for subsequent separation. S4: Reaction Condition Control: After adding the composite thallium removal agent, turn on the variable frequency stirring device and precisely control the stirring speed at 150-250 r / min to ensure that the composite thallium removal agent is in full contact with the brine and accelerate the reaction. At the same time, place the reaction vessel in a smart temperature-controlled constant temperature water bath to maintain the reaction temperature at 30-40℃. Within this temperature range, the chemical reaction and adsorption process can proceed under relatively ideal kinetic conditions. The reaction time is set to 1-2 hours to ensure that the thallium removal reaction is fully completed. S5: Solid-liquid separation stage: After the reaction is completed, a new type of bio-flocculator is added to the brine. Its main components are a complex of microbial polysaccharides and proteins. The addition amount is 10-20 mg / L. Compared with traditional polyacrylamide flocculants, this bio-flocculator is biodegradable and will not cause secondary pollution to the environment. It can further promote the growth of the generated precipitate flocs, forming larger flocs, which facilitates sedimentation and separation. S6: Sedimentation separation: The flocculated sediment is allowed to settle naturally in a sedimentation tank with an inclined tube sedimentation structure by gravity sedimentation. The sedimentation time is 2-3 hours. The inclined tube sedimentation structure can increase the sedimentation area and improve the sedimentation efficiency, so that the thallium and other impurities in the brine are quickly enriched at the bottom of the sedimentation tank, while the upper layer is the preliminarily purified brine. S7: Filtration: The preliminarily purified brine is filtered through a plate and frame filter press using a cross-flow filtration method to further remove residual tiny particles and flocs in the brine, resulting in purer brine. The cross-flow filtration method can effectively reduce filter cake clogging and improve filtration efficiency and filtration quality. S8: Deep purification stage: The brine after solid-liquid separation is passed through an ion exchange column equipped with a new type of chelating ion exchange resin. This chelating ion exchange resin has extremely high affinity and selectivity for trace amounts of thallium ions that may remain in the brine, which can further reduce the thallium content in the brine. The flow rate of the brine in the ion exchange column is controlled at 200-300 ml / h to ensure that the ion exchange reaction is fully carried out. S9: Detection and Adjustment: The brine after adsorption by ion exchange resin is monitored in real time online. The thallium content in the brine is determined by advanced inductively coupled plasma mass spectrometry. This technology can achieve rapid and accurate detection of thallium content. If the detection results show that the thallium content in the brine still does not meet the expected standard, such as being lower than 1 μg / L, the brine is passed through the ion exchange column again for secondary adsorption, or the process parameters of the previous stages are adjusted according to the actual situation, such as increasing the amount of composite thallium removal agent or extending the reaction time, until the thallium content in the brine meets the requirements.

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