Automated production method for producing fluorine-containing crystalline products using hydrofluoric acid solution

Abstract

An automated production method is provided for producing fluorine-containing crystalline products using a hydrofluoric acid solution. [Solution] The method comprises sensing the concentration of the hydrofluoric acid solution and pre-setting the supply flow rate; an automatic control module outputting a predetermined flow rate of the reaction solution based on the concentration and flow rate of the hydrofluoric acid solution and the concentration of the reaction solution; supplying the reaction solution and the hydrofluoric acid solution to the reaction zone; sensing the fluoride ion concentration of the solution in the reaction zone in real time and controlling the supply flow rate of the reaction solution in real time by the automatic control module; and sensing the precipitation height of the fluorine-containing crystals in real time and controlling whether or not to discharge the fluorine-containing crystals by the automatic control module. The present invention makes it possible to obtain granular sodium fluoroaluminate crystals or sodium fluorosilicate crystals with low water content and high Na / Al molecular ratio by processing a high-concentration hydrofluoric acid solution in a simple manner.

Description

[Technical Field]

[0001] The present invention relates to a system and method for producing fluorine-containing crystalline products, and more particularly to an automated production system and method for producing fluorine-containing crystalline products (e.g., sodium fluoroaluminate or sodium fluorosilicate) using a hydrofluoric acid solution. [Background technology]

[0002] In high-tech industrial processing, hydrofluoric acid is typically used to remove inorganic metal ion impurities, thus providing cleaning applications. In particular, in the semiconductor manufacturing industry, hydrofluoric acid (HF) solutions are used for silicon dioxide etching during wet etching and cleaning processes of wafers. However, this process generates highly concentrated wastewater containing hydrofluoric acid components. If proper treatment or reuse is not possible, it inevitably has serious impacts on the environment and aquatic ecosystems, hindering sustainable environmental development.

[0003] Conventional treatment methods primarily involve chemical coagulation and precipitation, where slaked lime or calcium chloride is added to hydrofluoric acid wastewater to initiate a reaction, and polyaluminum chloride (PAC) coagulant is added midway through to cause precipitation. However, this treatment method generates a large amount of calcium fluoride sludge waste, preventing effective resource reuse and leading to resource loss and waste.

[0004] For this reason, in recent years, the industrial sector has been actively researching how to effectively reuse hydrofluoric acid wastewater and convert it into reusable fluorine-containing products. Conventional techniques involve reacting high-concentration hydrofluoric acid wastewater with sodium hydroxide or sodium carbonate. However, this reaction requires first generating sodium fluoride to lower the fluoride ion concentration, then adding sodium aluminate reagent, and finally adding sodium hydroxide to control the pH value of the reaction. This treatment method is complicated, and it is not easy to control the process conditions. Furthermore, the sodium fluoroaluminate powder obtained by the treatment has a high water content (over 30%), requiring solid-liquid separation in a plate filter press process, and the subsequent processing steps are also relatively complicated.

[0005] Another conventional technique involves reacting high-concentration hydrofluoric acid wastewater (40 g / L or more) with sodium carbonate to form sodium fluoride. After solid-liquid separation, a low-concentration hydrofluoric acid wastewater (approximately 10 g / L) is obtained, and sodium aluminate is added to initiate a second crystallization reaction to obtain sodium fluoroaluminate powder. However, this conventional technique also has drawbacks, including a complicated process, a relatively high water content in the sodium fluoroaluminate powder after the reaction, high energy consumption costs for dehydration and drying, a powdery final crystalline product, and a low sodium / aluminum molecular ratio. Therefore, the reuse value of this sodium fluoroaluminate is low, making it unsuitable for recovering and reusing fluorine-containing materials. [Overview of the project] [Problems that the invention aims to solve]

[0006] In light of the problems mentioned above, it is currently necessary to develop more effective automated sodium fluoroaluminate production technologies to address the many shortcomings of conventional technologies and to meet the current global expectations for sustainable development and highly efficient resource reuse. [Means for solving the problem]

[0007] One objective of the present invention is to effectively reuse high-concentration hydrofluoric acid solutions and obtain fluorine-containing crystalline products (e.g., sodium fluoroaluminate (crylite) or sodium fluorosilicate) with high economic value using a simple and easily controllable production technology.

[0008] To achieve the above-mentioned objectives, the present invention provides an automated production method for producing fluorine-containing crystalline products using a hydrofluoric acid solution. The method involves supplying a hydrofluoric acid solution and a reaction solution which is an aluminate solution or silicate solution having a predetermined concentration; sensing the fluoride ion concentration of the hydrofluoric acid solution and pre-setting the supply flow rate of the hydrofluoric acid solution; an automatic control module outputting a predetermined flow rate of the reaction solution based on the fluoride ion concentration and supply flow rate of the hydrofluoric acid solution and the predetermined concentration of the reaction solution; supplying the reaction solution to a reaction zone at the predetermined flow rate and supplying the hydrofluoric acid solution to the reaction zone at the supply flow rate to carry out a crystallization reaction in the reaction zone and form a mixed solution; and simultaneously supplying the reaction solution and the hydrofluoric acid solution, sensing the fluoride ion concentration of the mixed solution in the reaction zone in real time, the automatic control module receiving the fluoride ion concentration parameter of the mixed solution in the reaction zone, and controlling the supply flow rate of the reaction solution in real time. If the fluoride ion concentration received by the automatic control module falls within ±5% of the target crystal nucleation concentration, the automatic control module controls the supply flow rate of the reaction solution to be equal to a predetermined flow rate of the reaction solution. If the fluoride ion concentration received by the automatic control module is higher than 5% above the target crystal nucleation concentration, the automatic control module controls the supply flow rate of the reaction solution to be greater than a predetermined flow rate of the reaction solution. If the fluoride ion concentration received by the automatic control module is lower than 5% below the target crystal nucleation concentration, the automatic control module controls the supply flow rate of the reaction solution to be less than a predetermined flow rate of the reaction solution. The automatic control module also senses the fluorine-containing crystals that have reacted and precipitated in the crystal collection zone in real time, and controls whether to discharge the solution containing the fluorine-containing crystals based on whether the fluorine-containing crystals have reached a predetermined height. Finally, it collects and obtains fluorine-containing crystal products from the solution containing the fluorine-containing crystals.

[0009] According to a proposed technology that senses the fluoride ion concentration of the mixed solution in the reaction zone in real time and controls the supply flow rate of the reaction solution, it contributes to maintaining the target concentration of crystal nucleation in the mixed solution in the reaction zone within the most favorable range possible during the induced crystallization reaction process. Therefore, the present invention makes it possible to process a high-concentration hydrofluoric acid solution using a simple automated production method, regenerate fluorine-containing crystalline products, and obtain sodium fluoroaluminate crystalline products or sodium fluorosilicate crystalline products that are granular, have a low water content (20% or less), and a high sodium / aluminum molecular ratio (2.6 or more). Furthermore, compared to conventional processing methods, it is possible to eliminate complicated processes such as pH value control, plate filter press processing, and a two-stage crystallization step, thereby improving the economic value of recovering and reusing fluorine-containing materials.

[0010] Preferably, the concentration of the hydrofluoric acid solution is 10 g / L to 400 g / L, but is not limited thereto. The hydrofluoric acid solution may be hydrofluoric acid waste liquid, and by recovering and reusing the fluoride ions in the hydrofluoric acid waste liquid, economically valuable sodium fluoroaluminate crystal product or sodium fluorosilicate crystal product is produced. Here, the hydrofluoric acid solution may contain other components such as hydrochloric acid, nitric acid, sulfuric acid, etc., and the above-mentioned components may be present in the hydrofluoric acid solution individually or in combination, but is not limited thereto. Preferably, the concentration of hydrochloric acid in the hydrofluoric acid solution may be 0 to 20 vol%, the concentration of nitric acid in the hydrofluoric acid solution may be 0 to 50 vol%, and the concentration of sulfuric acid in the hydrofluoric acid solution may be 0 to 60 vol%, but is not limited thereto. In one embodiment, the hydrofluoric acid solution may contain 0.1 vol% to 15 vol% hydrochloric acid and 0.1 vol% to 30 vol% nitric acid. In another embodiment, the hydrofluoric acid solution may contain 0.1 vol% to 10 vol% hydrochloric acid, 0.1 vol% to 20 vol% nitric acid and 0.1 vol% to 30 vol% sulfuric acid. In yet another embodiment, the hydrofluoric acid solution may contain 0.1 vol% to 20 vol% hydrochloric acid.

[0011] Preferably, the aluminate solution as the reaction solution is, for example, a sodium aluminate solution, an aluminum sulfate solution containing a sodium source, a polyaluminum chloride solution containing a sodium source, or a combination thereof, wherein the sodium source is sodium hydroxide, sodium chloride, sodium nitrate, or a combination thereof, and the silicate solution as the reaction solution is, for example, a sodium silicate solution, but is not limited thereto.

[0012] Preferably, the automated production method senses the turbidity of the rectification zone in real time, and an automatic control module receives the turbidity parameter and adjusts the upward flow rate of the carrier-containing solution (solution containing carriers) in the rectification zone to the reaction zone in real time based on the turbidity parameter, thereby adjusting the upward flow rate of the carrier-containing solution in the rectification zone, and the rectification zone is located between the reaction zone and the crystal collection zone and communicates with each other. In the automated production method for sodium fluoroaluminate of the present invention, if the turbidity parameter received by the automatic control module is higher than 100 NTU, the automatic control module controls the upward flow rate of the carrier-containing solution in the rectification zone to be 0.4 cm / s to 0.6 cm / s, and if the turbidity parameter received by the automatic control module is lower than 100 NTU, the automatic control module controls the upward flow rate of the carrier-containing solution in the rectification zone to be 2.2 cm / s to 2.6 cm / s. Preferably, if the automatic control module wants to increase the upward flow rate of the carrier-containing solution in the rectification zone, it can be adjusted by increasing the upward flow rate of the carrier-containing solution in the rectification zone by 0.25 cm / s to 0.75 cm / s per minute. According to the present invention, the rectification zone contains a mixed solution and a carrier-containing solution derived from the reaction zone, and when the crystalline material becomes quicksand-like, the gravity-induced sedimentation of the granular solid is greater than the upward flow rate of the carrier-containing solution in the rectification zone. Therefore, the crystalline material in the rectification zone is settled by gravity-induced sedimentation through the sedimentation port along the sedimentation hopper to the crystalline material collection zone.

[0013] The automated production method for producing fluorine-containing crystalline products using the hydrofluoric acid solution of the present invention can be adjusted based on the following control conditions when controlling the supply flow rate of the reaction solution.For example, if the fluoride ion concentration parameter of the mixed solution in the reaction zone received by the automatic control module is 5% to 10% higher than the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be 1.5% to 2.5% higher than the predetermined flow rate. If the fluoride ion concentration parameter of the mixed solution in the reaction zone received by the automatic control module is 5% to 10% lower than the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be 1.5% to 2.5% lower than the predetermined flow rate. If the fluoride ion concentration parameter of the mixed solution in the reaction zone received by the automatic control module is 10% to 20% higher than the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be 3.5% to 4.5% higher than the predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter of the mixed solution in the reaction zone received by the automatic control module is 10% to 20% lower than the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be 3.5% to 4.5% lower than the predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter of the mixed solution in the reaction zone received by the automatic control module is 20% to 30% higher than the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be 7.5% to 8.5% higher than the predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter of the mixed solution in the reaction zone received by the automatic control module is 20% to 30% lower than the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be 7.5% to 8.5% lower than the predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter of the mixed solution in the reaction zone, as received by the dynamic control module, is higher than a 30% increase above the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be 14.5% to 15.5% higher than the predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter of the mixed solution in the reaction zone, as received by the automatic control module, is lower than a 30% decrease above the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be at least 14.5% to 15.5% lower than the predetermined flow rate of the reaction solution.

[0014] In one embodiment of the present invention, if the reaction solution is an aluminate solution and the fluorine-containing crystalline product is a sodium fluoroaluminate crystalline product, the automatic control module outputs a predetermined flow rate of the aluminate solution based on a ratio of aluminum ions in the aluminate solution to fluorine ions in the hydrofluoric acid solution of 1:6 to 1.20:6, calculated according to the aluminum-to-fluorine ratio of the sodium fluoroaluminate crystalline product. In another embodiment, the automatic control module outputs a predetermined flow rate of the aluminate solution based on a ratio of aluminum ions in the aluminate solution to fluorine ions in the hydrofluoric acid solution of 1:6 to 1.05:6, calculated according to the aluminum-to-fluorine ratio of the sodium fluoroaluminate crystalline product. In another embodiment, if the reaction solution is a silicate solution and the fluorine-containing crystalline product is a sodium fluorosilicate crystalline product, the automatic control module calculates the silicon-to-fluorine ratio of the sodium fluorosilicate crystalline product and outputs a predetermined flow rate of the silicate solution based on a ratio of 1:6 to 1.20:6 for silicon ion concentration in the silicate solution and fluorine ion concentration in the hydrofluoric acid solution.

[0015] Preferably, the target concentration for crystal nucleation is 1000 ppm to 12000 ppm. In one embodiment, the target concentration for crystal nucleation is 1000 ppm to 9500 ppm. In another embodiment, the target concentration for crystal nucleation is 1500 ppm to 12000 ppm.

[0016] In the automated production method for producing sodium fluoroaluminate crystals of the present invention, the target concentration for crystal nucleation to produce sodium fluoroaluminate by reacting hydrofluoric acid with an aluminate solution may be controlled so that the fluoride ion concentration is 1000 ppm to 9500 ppm, and more specifically, it may be controlled so that it is 1000 ppm to 2500 ppm, but is not limited thereto. Those skilled in the art will know the target particle size and solubility (5.6 g / L) of the sodium fluoroaluminate crystals based on its solubility product constant (Ksp: 1.98 × 10⁻¹⁰). -5 ) can be calculated, and appropriate adjustments can be made to the target concentration. For example, the aluminum ion concentration in the aluminate solution, the target concentration for crystal nucleation, and the Ksp ratio ([Al][F] 3 When the product (product and Ksp ratio) is approximately 200 to 600 times, the target particle size of the sodium fluoroaluminate crystal product can be controlled to 200 to 325 mesh, and the target concentration for crystal nucleation may be 1000 ppm to 4500 ppm. [Al][F] 3 When the product and Ksp ratio are approximately 1800 to 2200 times, the target particle size of the sodium fluoroaluminate crystal product can be controlled to 400 mesh, and the target concentration for crystal nucleation may be 3000 ppm to 7000 ppm. [Al][F] 3 When the product and Ksp ratio are approximately 4500 to 5500 times, the target particle size of the sodium fluoroaluminate crystal product can be controlled to 600 mesh, and the target concentration for crystal nucleation may be 3500 ppm to 9500 ppm. For ease of understanding, the aluminum ion concentrations of different aluminate solutions are listed below: [Al][F] 3 The following table lists, but is not limited to, the conditions under which the target concentration for crystal nucleation can be set based on the product, Ksp ratio, and target particle size.

[0017] [Table 0A] In the automatic production method for producing the sodium fluorosilicate crystal product of the present invention, the target concentration of crystal nucleus formation for generating sodium fluorosilicate by reacting hydrofluoric acid and a silicate solution may be controlled so that the fluoride ion concentration is 1500 ppm to 12000 ppm. Specifically, it may be controlled to be 1000 ppm to 2500 ppm, but it is not limited thereto. Those skilled in the art can calculate its solubility product constant (Ksp: 7.14×10 -5 ) based on the target particle size and solubility (7.8 g / L) of the sodium fluorosilicate crystal product, and make appropriate adjustments to the target concentration. For example, when the silicon ion concentration in the silicate solution, the product of [Si][F] 6 and the Ksp multiple ([Si][F] 6 product and Ksp multiple) is about 100 times to 400 times, the target particle size of the sodium fluorosilicate crystal product can be controlled to be 140 mesh to 200 mesh, and the target concentration of crystal nucleus formation may be 1500 ppm to 6000 ppm. When the product of [Si][F] 6 and the Ksp multiple is about 1000 times to 4000 times, the target particle size of the sodium fluorosilicate crystal product can be controlled to be 325 mesh to 400 mesh, and the target concentration of crystal nucleus formation may be 3000 ppm to 12000 ppm. For easier understanding, the conditions for setting the target concentration of crystal nucleus formation based on the silicon ion concentration, the product of [Si][F] 6 and the Ksp multiple, and the target particle size of different silicate solutions are listed in the following table, but it is not limited thereto.

[0018]

Table 0B

[0019] Preferably, the automatic production method may include supplying water or a recovered carrier-containing solution to the reaction zone in advance, further supplying the reaction solution to the reaction zone at the predetermined flow rate, and further supplying the hydrofluoric acid solution to the reaction zone at a preset supply flow rate.

[0020] The step of collecting and obtaining the fluorine-containing crystalline product from the solution containing the above-mentioned fluorine-containing crystals includes collecting and obtaining the fluorine-containing crystalline product by centrifuging the solution containing the fluorine-containing crystals.

[0021] Preferably, the reaction solution can be supplied to the reaction zone by the spray method, and the hydrofluoric acid solution can be supplied to the reaction zone by the spray method. The shapes of the reaction solution and the hydrofluoric acid solution sprayed are independently fan-shaped, hollow conical, solid conical, spiral or cylindrical, increasing the reaction area between the hydrofluoric acid solution and the reaction solution. Preferably, one of the reaction solution and the hydrofluoric acid solution forms a fan spray or a solid conical spray by the spray method and is supplied to the upper half of the reaction zone, and the other of the reaction solution and the hydrofluoric acid solution forms a hollow conical spray and a spiral spray by the spray method and is supplied to the lower half of the reaction zone. Also, the carrier-containing solution is guided to the reaction zone by the spray method, and the shape of the solution containing the carrier sprayed is fan-shaped, hollow conical, solid conical, spiral or cylindrical, but is not limited thereto.

[0022] Preferably, the automatic production method can stir the mixed solution in the reaction zone at a stirring speed of 40 rpm to 120 rpm.

[0023] To achieve the above object, the present invention provides an automatic production system for producing a fluorine-containing crystal product using a hydrofluoric acid solution. The automatic production system includes a crystal processing device, a first supply module, a second supply module, a crystal product processing module, and an automatic control module.

[0024] The crystal processing device has an outer tank body, an inner tank body, a precipitation hopper, a crystal product discharge port, a fluoride ion concentration sensor, and an optical fiber sensor. The inner tank body is installed inside the outer tank body. A circulation port is installed in the inner tank body. The precipitation hopper is installed below the inner tank body and inside the outer tank body. The crystal product discharge port is installed at the bottom of the outer tank body. The crystal processing device has a reaction zone, a rectification zone, and a crystal product collection zone that communicate with each other. The reaction zone is partitioned by the inner tank body. The rectification zone is located outside the inner tank body, inside the outer tank body, and above the precipitation hopper. The crystal product collection zone is located inside the outer tank body and below the precipitation hopper. The fluoride ion concentration sensor is installed on the outer tank body, and its sensing end extends into the reaction zone. The optical fiber sensor is installed below the precipitation hopper and above the crystal product discharge port.

[0025] The first supply module has a first supply tank, a first supply pipe, and a first pump. The first supply tank of the first supply module is connected to the inner tank body via the first supply pipe. The first pump is installed between the upstream side and the downstream side of the first supply pipe.

[0026] The second supply module comprises a second supply tank, a second supply pipe, and a second pump. The second supply tank of the second supply module is connected to the inner tank body via the second supply pipe. The second pump is installed between the upstream and downstream sides of the second supply pipe.

[0027] The crystal processing module includes a discharge pipe and a discharge pump. The upstream end of the discharge pipe is connected to the crystal discharge port. The discharge pump is installed between the upstream and downstream ends of the discharge pipe.

[0028] The automatic control module is electrically connected to the fluoride ion concentration sensor, the optical fiber sensor, the first pump, the second pump, and the discharge pump. The automatic control module receives the fluoride ion concentration parameter from the fluoride ion concentration sensor and controls the first pump or the second pump, and the automatic control module receives the sensing result from the optical fiber sensor and controls the opening and closing of the discharge pump.

[0029] The automatic control module is electrically connected to a fluoride ion concentration sensor, an optical fiber sensor, a first pump, a second pump, and a discharge pump. By technical means of controlling the first pump, the second pump, and the discharge pump based on the fluoride ion concentration parameter and the sensing result of the optical fiber sensor, the present invention can maintain the target concentration of crystal nucleation in the mixed solution in the reaction zone within the most favorable range possible in the process of the induced crystallization reaction. Therefore, the automated production system of the present invention can contribute to simplifying and controlling the reaction and flow of fluorine-containing crystalline products.

[0030] Preferably, the automated production system further comprises a carrier circulation module. The carrier circulation module comprises a guide pipe and a transport pump. The carrier circulation module is connected to the inner tank body of the crystallization apparatus via the guide pipe. The guide pipe has opposing suction and transport ends. The suction end extends into the rectification zone. The transport end extends into the reaction zone. The transport pump is installed between the suction and transport ends of the guide pipe. This allows the carrier circulation module to guide crystal nuclei in the rectification zone into the reaction zone of the inner tank body for reaction, which is advantageous for collecting fluorine-containing crystal products of a target particle size and uniformity.

[0031] Furthermore, the automated production system may include a turbidity sensor. The turbidity sensor is installed on the outer tank body, with its sensing end extending into the rectification zone. The automated control module is electrically connected to the transport pump and the turbidity sensor. The automated control module receives the turbidity parameter from the turbidity sensor and controls the transport pump of the carrier circulation module.

[0032] In one embodiment, the first supply module has a spray head. The spray head of the first supply module is installed downstream of the first supply pipe. The second supply module has a spray head. The spray head of the second supply module is installed downstream of the second supply pipe. The spray heads of the first supply module and the spray head of the second supply module are installed within the inner tank body. Here, the spray head of the second supply pipe is installed above the spray head of the first supply pipe, and the opening of the spray head of the second supply module faces the opening of the spray head of the first supply module. Preferably, the height of the spray head of the first supply module may be lower than the installation position of the flow port, and the spray material is installed on the transport end of the guide pipe.

[0033] Preferably, the sedimentation hopper is provided with a sedimentation port. The crystallization apparatus has a guide plate. The guide plate is installed below the sedimentation port. The guide plate is inclined from the side of the outer tank body closest to the crystal discharge port to the side opposite the crystal discharge port. The crystallization apparatus also has an overflow port. The overflow port is installed near the top of the outer tank body.

[0034] The automated production system may also include a stirring unit. This stirring unit is installed on the inner tank body, extends into the reaction zone, and uniformly stirs the mixed solution within the reaction zone.

[0035] Preferably, the crystalline processing module includes a centrifuge, which is connected downstream of the discharge pipe. The centrifuge may also be further connected to a product collection tank to receive the centrifuged product processed by the centrifuge.

[0036] Preferably, the automated production method for producing fluorine-containing crystalline products using the hydrofluoric acid solution of the present invention can be carried out in combination with any of the automated production equipment for producing fluorine-containing crystalline products using the hydrofluoric acid solution described above. [Brief explanation of the drawing]

[0037] [Figure 1] This is a schematic diagram of an automated production system that produces fluorine-containing crystalline products using hydrofluoric acid solution. [Figure 2] This is a flowchart illustrating an automated production method for producing fluorine-containing crystalline products using hydrofluoric acid solution. [Figure 3] This is a schematic diagram illustrating the automated production flow using an automated production system in the initial stages. [Figure 4] This is a schematic diagram showing the automated production flow after a certain period of time using an automated production system. [Figure 5A]This line graph shows the flow rate of sodium aluminate solution, controlled by the automatic control module based on the fluoride ion concentration parameter in the automated production method of Example 1, corresponding to the reaction time. [Figure 5B] This line graph shows the reaction time corresponding to the rising flow rate of the self-assembling carrier-containing solution, which was controlled by the automatic control module based on the turbidity parameter in the automated production method of Example 1. [Figure 6A] This line graph shows the flow rate of the aluminum sulfate solution containing sodium chloride, controlled by the automatic control module based on the fluoride ion concentration parameter in the automated production method of Example 2, corresponding to the reaction time. [Figure 6B] This line graph shows the reaction time corresponding to the rising flow rate of the self-assembling carrier-containing solution, which was controlled by the automatic control module based on the turbidity parameter in the automated production method of Example 2. [Figure 7A] This line graph shows the flow rate of sodium aluminate solution, controlled by the automatic control module based on the fluoride ion concentration parameter in the automated production method of Example 3, corresponding to the reaction time. [Figure 7B] This line graph shows the reaction time corresponding to the rising flow rate of the self-assembling carrier-containing solution, which was controlled by the automatic control module based on the turbidity parameter in the automated production method of Example 3. [Figures 8A-8B] This is an SEM image of the sodium fluoroaluminate crystalline product from Example 1. [Figure 8C-8D] This is an SEM image of the sodium fluoroaluminate crystalline product from Example 2. [Figures 8E-8F] This is an SEM image of the sodium fluoroaluminate crystalline product from Example 3. [Figure 9] These are XRD diagrams of the sodium fluoroaluminate crystalline products and sodium fluoroaluminate standards from Examples 1-3. [Figure 10A] This line graph shows the flow rate of sodium silicate solution, controlled by the automatic control module based on the fluoride ion concentration parameter in the automated production method of Example 4, corresponding to the reaction time. [Figure 10B] This line graph shows the reaction time corresponding to the rising flow rate of the self-assembling carrier-containing solution, which was controlled by the automatic control module based on the turbidity parameter in the automated production method of Example 4. [Figure 11A-11B] This is an SEM image of the sodium fluorosilicate crystalline product of Example 4. [Figure 12] This is an XRD diagram of the sodium fluorosilicate crystalline product and the sodium fluorosilicate standard from Example 4. [Modes for carrying out the invention]

[0038] Embodiments of an automated production system and automated production method for fluorine-containing crystalline products will be described below with reference to the drawings. Those skilled in the art will readily understand the advantages and effects of the present invention from this specification in order to carry out or apply the contents of the present invention, and various modifications and changes can be made without departing from the spirit of the invention.

[0039] Automated production system for producing fluorine-containing crystalline products using hydrofluoric acid solution As shown in Figure 1, the automated production system for fluorine-containing crystalline products of the present invention comprises a crystallization processing apparatus 10, a first supply module 20, a second supply module 30, a crystalline material processing module 40, a carrier circulation module 50, and an automatic control module 60.

[0040] The crystallization apparatus 10 comprises an outer tank body 11, an inner tank body 12, a sedimentation hopper 13, a crystal material discharge port 14, a guide plate 15, an overflow port 16, a fluoride ion concentration sensor 17, a turbidity sensor 18, and an optical fiber sensor 19. The inner tank body 12 is installed inside the outer tank body 11. The inner tank body 12 has a flow port 121 and a stirring unit 122. The sedimentation hopper 13 is installed inside the outer tank body 11 and is located below the inner tank body 12. The upper edge of the sedimentation hopper 13 is in close contact with the inner wall of the outer tank body 11. The lower edge of the sedimentation hopper 13 gradually narrows towards the center of the outer tank body 11, where a sedimentation port 131 is installed. The crystal material discharge port 14 is installed near the bottom of the outer tank body 11. The guide plate 15 is installed below the sedimentation port 131. The guide plate 15 slopes from the inner wall of the outer tank body 11, near the crystal material discharge port 14, to the side opposite the crystal material discharge port 14. The overflow port 16 is installed near the top of the outer tank body 11.

[0041] According to the structural design described above, the crystallization apparatus 10 can be divided into a reaction zone A1, a flow straightening zone A2, and a crystal collection zone A3. The reaction zone A1 is partitioned by the inner tank body 12 and is located inside the inner tank body 12. The flow straightening zone A2 is located outside the inner tank body 12, inside the outer tank body 11, and above the sedimentation hopper 13. The crystal collection zone A3 is located inside the outer tank body 11 and below the sedimentation hopper 13. The spaces of the reaction zone A1, the flow straightening zone A2, and the crystal collection zone A3 are in communication with each other.

[0042] Furthermore, in the crystallization apparatus 10, the fluoride ion concentration sensor 17 is installed on the inner tank body 12, and its sensing end extends into the reaction zone A1, thereby sensing the fluoride ion concentration of the mixed solution in the reaction zone A1 in real time. The turbidity sensor 18 is installed on the outer tank body 11, and its sensing end extends into the rectification zone A2, thereby sensing the turbidity of the liquid in the rectification zone A2 in real time. The optical fiber sensor 19 is installed on the outer tank body 11 and is located below the sedimentation hopper 13 and above the crystal discharge port 14, thereby sensing in real time whether the settled crystals in the crystal collection zone A3 have reached a corresponding predetermined level on the optical fiber sensor 19.

[0043] The first supply module 20 is connected to the crystallization apparatus 10 and is used to supply the inner tank body 12 of the crystallization apparatus 10. The first supply tank 21 can contain either a hydrofluoric acid solution or a reaction solution. The upstream side of the first supply pipe 22 is connected to the first supply tank 21. The downstream side of the first supply pipe 22 is installed inside the inner tank body 12 of the crystallization apparatus 10 and extends to the lower half of the inner tank body 12. The plurality of spray heads 23 are installed downstream of the first supply pipe 22 and communicate with the first supply pipe 22. The opening of each spray head 23 is installed so as to face the top of the inner tank body 12. The height of the spray heads 23 may be lower than the installation position of the flow port 121 of the inner tank body 12. The first pump 24 is connected to the first supply pipe 22 and is installed between the upstream and downstream sides of the first supply pipe 22.

[0044] The second supply module 30 is connected to the crystallization apparatus 10 and is used to supply the inner tank body 12 of the crystallization apparatus 10. The second supply module 30 includes a second supply tank 31, a second supply pipe 32, a plurality of spray heads 33, and a second pump 34. The second supply tank 31 can contain either a hydrofluoric acid solution or another reaction solution. The upstream end of the second supply pipe 32 is connected to the second supply tank 31. The downstream end of the second supply pipe 32 is installed inside the inner tank body 12 of the crystallization apparatus 10 and extends to the upper half of the inner tank body 12. The plurality of spray heads 33 are installed downstream of the second supply pipe 32 and communicate with the second supply pipe 32. The openings of the spray heads 33 of the second supply module 30 are positioned to face the bottom of the inner tank body 12. That is, the opening of the spray head 33 of the second supply module 30 can face the opening of the spray head 23 of the first supply module 20. The height of the spray head 33 may be higher and further away from the installation position of the flow port 121. The second pump 34 is connected to the second supply pipe 32 and is installed between the upstream and downstream sides of the second supply pipe 32. The stirring unit 122 installed in the inner tank body 12 described above has a plurality of blades 1221. These plurality of blades 1221 may be located between the spray head 23 of the first supply module and the spray head 33 of the second supply module 30.

[0045] The crystal processing module 40 is connected to the crystal processing apparatus 10 and is used to receive fluorine-containing crystals discharged from the crystal discharge port 14 of the crystal processing apparatus 10, and to obtain the desired fluorine-containing crystal product (for example, sodium fluoroaluminate crystal product or sodium fluorosilicate crystal product) through subsequent processing. The crystal processing module 40 includes a discharge pipe 41, a discharge pump 42, a centrifuge 43, and a product collection tank 44. The upstream side of the discharge pipe 41 of the crystal processing module 40 is connected to the crystal discharge port 14 of the crystal processing apparatus 10. The discharge pump 42 is installed on the discharge pipe 41 and is located between the upstream and downstream sides of the discharge pipe 41. The centrifuge 43 is connected to the downstream side of the discharge pipe 41. The product collection tank 44 is connected to the centrifuge 43 and collects and obtains the fluorine-containing crystal product from the centrifuge 43.

[0046] The carrier circulation module 50 is connected to the inner tank body 12 of the crystallization processing apparatus 10 and includes a guide pipe 51, a transport pump 52, and a spray material 53. The guide pipe 51 has opposing suction ends 511 and transport ends 512. The suction end 511 extends into the rectification zone A2. The transport end 512 extends into the reaction zone A1. The transport pump 52 is installed on the guide pipe 51 and is located between the suction end 511 and the transport end 512 of the guide pipe 51. The spray material 53 is installed on the transport end 512 of the guide pipe 51 and is in communication with the guide pipe 51. The opening of the spray material 53 is positioned to face the bottom of the inner tank body 12. The spray material 53 may also be located between the spray head 23 of the first supply module 20 and the spray head 33 of the second supply module 30.

[0047] The automatic control module 60 includes a programmable logic controller (PLC). The automatic control module 60 is electrically connected to a fluoride ion concentration sensor 17, a turbidity sensor 18, an optical fiber sensor 19, a first pump 24, a second pump 34, and a discharge pump 42. Specifically, the automatic control module 60 receives fluoride ion concentration data of the mixed solution sensed by the fluoride ion concentration sensor 17 by being electrically connected to the fluoride ion concentration sensor 17. Based on the sensed fluoride ion concentration data, the automatic control module 60 controls the supply flow rate of the reaction solution from the first supply tank 21 to the first supply pipe 22 and / or from the second supply tank 31 to the second supply pipe 32, respectively, by controlling the first pump 24 and / or the second pump 34. Furthermore, the automatic control module 60 receives turbidity data sensed by the turbidity sensor 18 by electrically connecting to the turbidity sensor 18, and controls the upward flow velocity of the self-organizing carrier-containing solution extracted from the rectification zone A2 as it flows through the guide pipe 51 to the reaction zone A1 by controlling the transport pump 52 of the carrier circulation module 50 based on the sensed turbidity data. The automatic control module 60 also receives whether the optical fiber sensor 19 has sensed fluorine-containing crystals by electrically connecting to the optical fiber sensor 19, that is, whether a certain amount of fluorine-containing crystals has accumulated in the crystal collection zone A3 and whether a predetermined height has been reached. Based on the sensing result, the automatic control module 60 controls whether or not to discharge the fluorine-containing crystals in the crystal collection zone A3 from the crystal outlet 14 to the centrifuge 43, and collects and obtains the fluorine-containing crystal product by performing subsequent processing or purification steps.

[0048] Automated production method for producing fluorine-containing crystalline products using hydrofluoric acid solution As shown in Figure 2, the automated production method for sodium fluoroaluminate according to the present invention comprises the following steps.

[0049] (1) A hydrofluoric acid solution (or hydrofluoric acid waste liquid awaiting reaction) and a reaction solution having a predetermined concentration are supplied. The reaction solution may be an aluminate solution such as a sodium aluminate solution, an aluminum sulfate solution, or a polyaluminum chloride solution, or a silicate solution such as a sodium silicate solution.

[0050] (2) The fluoride ion concentration of the hydrofluoric acid solution is sensed, and the supply flow rate of the hydrofluoric acid solution is set in advance.

[0051] (3) The automatic control module outputs a predetermined flow rate of the reaction solution based on the fluoride ion concentration and supply flow rate of the hydrofluoric acid solution and the predetermined concentration of the reaction solution.

[0052] (4) The reaction solution is supplied to the reaction zone at a predetermined flow rate, and the hydrofluoric acid solution is supplied to the reaction zone at a predetermined supply flow rate, thereby carrying out a crystallization reaction in the reaction zone and forming a mixed solution.

[0053] (5) The reaction solution and the hydrofluoric acid solution are supplied, and at the same time, the fluoride ion concentration of the mixed solution is sensed in real time. The automatic control module receives the fluoride ion concentration parameter and controls the supply flow rate of the reaction solution in real time based on the fluoride ion concentration parameter of the mixed solution. Specifically, if the fluoride ion concentration parameter received by the automatic control module falls within ±5% of the target concentration for crystal nucleation, the automatic control module maintains the supply flow rate of the reaction solution to be equal to a predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter received by the automatic control module is higher than a 5% increase above the target concentration for crystal nucleation, the automatic control module controls the supply flow rate of the reaction solution to be greater than a predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter received by the automatic control module is lower than a 5% decrease below the target concentration for crystal nucleation, the automatic control module controls the supply flow rate of the reaction solution to be less than a predetermined flow rate of the reaction solution.

[0054] (6) The automatic control module senses the fluorine-containing crystals that have reacted and precipitated in the crystal collection zone in real time, and controls whether to discharge the solution containing the fluorine-containing crystals based on whether the fluorine-containing crystals have reached a predetermined height.

[0055] (7) The fluorine-containing crystalline material is centrifuged to collect and obtain fluorine-containing crystalline products (for example, sodium fluoroaluminate crystalline products or sodium fluorosilicate crystalline products).

[0056] In one embodiment, when an aluminate solution is selected as the reaction solution to prepare the sodium fluoroaluminate crystalline product, the concentration of the hydrofluoric acid solution (or hydrofluoric acid waste liquid awaiting reaction) may be 10 g / L to 400 g / L, but is not limited thereto. The reaction solution may be prepared as an aluminate solution with an aluminum ion concentration of 25 g / L to 260 g / L, but is not limited thereto. In another embodiment, when a silicate solution is selected as the reaction solution to prepare the sodium fluorosilicate crystalline product, the concentration of the hydrofluoric acid solution (or hydrofluoric acid waste liquid awaiting reaction) may be 10 g / L to 400 g / L, but is not limited thereto. The reaction solution may be prepared as a silicate solution with a silicon ion concentration of 30 g / L to 320 g / L, but is not limited thereto. Preferably, the concentration of the hydrofluoric acid solution may be measured manually and input to the automatic control module, or the concentration of the hydrofluoric acid solution may be sensed using a concentration sensor and the sensed concentration parameter may be transmitted to the automatic control module. The automatic control module then sets and controls a predetermined flow rate of the reaction solution based on the concentration parameter of the hydrofluoric acid solution.

[0057] In another embodiment, if the aluminate solution is a sodium aluminate solution, the hydrofluoric acid solution and aluminate solution supplied to the reaction zone can undergo the following reaction: namely, 12HF + 3NaAlO2 → Na3AlF6 + 2AlF3 + 6H2O. In yet another embodiment, if the aluminate solution is an aluminum sulfate solution containing sodium chloride, the hydrofluoric acid solution and aluminate solution supplied to the reaction zone can undergo the following reaction: namely, 12HF + Al2(SO4)3 + 6NaCl → 2Na3AlF6 + 3H2SO4 + 6HCl. In yet another embodiment, if the aluminate solution is a polyaluminum chloride solution containing sodium chloride, the hydrofluoric acid solution and aluminate solution supplied to the reaction zone can undergo the following reaction: namely, 12HF + Al2(OH)Cl5 + 6NaCl → 2Na3AlF6 + 11HCl + H2O. The automatic control module determines the aluminum-to-fluorine ratio of sodium fluoroaluminate (Na3AlF6) according to the reaction equation and theoretical basis, thereby determining the aluminum ion concentration ([Al 3+ ]) is calculated, and the fluoride ion concentration ([F) in the hydrofluoric acid solution is calculated. - Based on a ratio of 1:6 to 1.05:6, the system calculates the predetermined flow rate of the aluminate solution based on the concentration and supply flow rate of the received hydrofluoric acid solution and the predetermined concentration of the aluminate solution, and outputs the predetermined flow rate of the aluminate solution. Alternatively, the hydrofluoric acid solution and silicate solution supplied to the reaction zone can carry out the following reaction: namely, 6HF + Na2SiO3 → Na2SiF6 + 3H2O. The automatic control module forms the silicon-to-fluorine ratio of sodium fluorosilicate (Na2SiF6) according to the above reaction equation and theoretical basis, and calculates the silicon ion concentration ([SiF6) in the silicate solution. 4+ ]) is calculated, and the fluoride ion concentration ([F) in the hydrofluoric acid solution is calculated. - Based on a ratio of 1:6 to 1.05:6, the system calculates the predetermined flow rate of the silicate solution based on the concentration and supply flow rate of the received hydrofluoric acid solution and the predetermined concentration of the silicate solution, and outputs the predetermined flow rate of the silicate solution.

[0058] In the automated process of the induced crystallization reaction, the automatic control module controls the flow rate of the reaction solution in real time based on the fluoride ion concentration parameter, and controls the fluoride ion concentration parameter, which is sensed and obtained in the reaction zone, to reach the target concentration corresponding to the metastable zone. The target concentration corresponding to the metastable zone may be between 1500 ppm and 12000 ppm.

[0059] Preferably, in a process for automating an induced crystallization reaction, if the fluoride ion concentration parameter of the mixed solution in the reaction zone received by the automatic control module is 5% to 10% higher than the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be 1.5% to 2.5% higher than the predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter of the mixed solution in the reaction zone received by the automatic control module is 5% to 10% lower than the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be 1.5% to 2.5% higher than the predetermined flow rate of the reaction solution. The automatic control module controls the flow rate of the reaction solution to be 3.5% to 4.5% higher than the predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter of the mixed solution in the reaction zone received by the automatic control module is 10% to 20% higher than the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be 3.5% to 4.5% higher than the predetermined flow rate of the reaction solution. The automatic control module controls the flow rate of the reaction solution to be reduced by %. If the fluoride ion concentration parameter of the mixed solution in the reaction zone received by the automatic control module is 20% to 30% higher than the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be 7.5% to 8.5% higher than the predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter of the mixed solution in the reaction zone received by the automatic control module is 20% to 30% lower than the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be 7.5% to 8.5% lower than the predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter of the mixed solution in the reaction zone, as received by the automatic control module, is higher than a 30% increase above the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be 14.5% to 15.5% higher than the predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter of the mixed solution in the reaction zone, as received by the automatic control module, is lower than a 30% decrease above the target concentration for crystal nucleation, the automatic control module controls the flow rate of the reaction solution to be 14.5% to 15.5% lower than the predetermined flow rate of the reaction solution.If the fluoride ion concentration parameter of the mixed solution in the reaction zone, as received by the automatic control module, is lower than the limit concentration, the automatic control module controls the flow rate of the reaction solution to zero. This limit concentration may be between 500 ppm and 1000 ppm.

[0060] Preferably, before initiating the injection of hydrofluoric acid solution and reaction solution, water or recovered carrier-containing solution (which can be obtained by recovering the carrier-containing solution through the production process of the previous batch) is supplied to the reaction zone, and the hydrofluoric acid solution and reaction solution are continuously supplied to the reaction zone at the set supply flow rate of the hydrofluoric acid solution and the predetermined flow rate of the reaction solution. In addition, in the process of automating the induced crystallization reaction, the mixed solution in the reaction zone can also be stirred at a stirring speed of 40 rpm to 120 rpm, depending on the situation.

[0061] Preferably, the reaction contact area can be increased by continuously supplying the reaction solution and / or the hydrofluoric acid solution to the reaction zone by a spray method. The sprayed shape may be, but is not limited to, a fan shape, a hollow cone shape, a solid cone shape, a spiral shape, or a cylindrical shape. In one embodiment, the hydrofluoric acid solution may be continuously supplied from the upper half of the reaction zone, and the reaction solution may be continuously supplied from the lower half of the reaction zone. In another embodiment, the hydrofluoric acid solution may be continuously supplied from the lower half of the reaction zone, and the reaction solution may be continuously supplied from the upper half of the reaction zone. Preferably, one of the reaction solution and the hydrofluoric acid solution is supplied to the upper half of the reaction zone by a spray method forming a fan-shaped spray or a solid cone-shaped spray, and the other of the reaction solution and the hydrofluoric acid solution is supplied to the lower half of the reaction zone by a spray method forming a hollow cone-shaped spray and a spiral-shaped spray.

[0062] Preferably, the fluoride ion concentration of the mixed solution in the reaction zone is sensed in real time, and the turbidity of the rectification zone is sensed in real time simultaneously with the supply of the reaction solution and the hydrofluoric acid solution. The automatic control module receives the turbidity parameter and controls the upward flow velocity of the carrier-containing solution in the rectification zone by controlling the flow rate that guides the carrier-containing solution from the rectification zone to the reaction zone based on the turbidity parameter. The rectification zone is located between the reaction zone and the crystal collection zone and communicates with each other. If the turbidity parameter received by the automatic control module is higher than 100 NTU, the automatic control module controls the upward flow velocity of the carrier-containing solution in the rectification zone to be between 0.4 cm / s and 0.6 cm / s. If the turbidity parameter received by the automatic control module is lower than 100 NTU, the automatic control module controls the upward flow velocity of the carrier-containing solution in the rectification zone to be between 2.2 cm / s and 2.6 cm / s. When the automatic control module increases the upward flow velocity in the rectification zone based on the turbidity parameter, it adjusts the upward flow velocity in the rectification zone by an increase of 0.25 cm / s to 0.75 cm / s per minute. Preferably, the self-organizing carrier-containing solution can be guided into the reaction zone by a spray method, thereby increasing the contact area for the reaction. The sprayed shape may be a fan, a hollow cone, a solid cone, a spiral, or a cylinder, with fan and solid cone shapes being more preferable, but not limited to these.

[0063] The following describes, with reference to several examples, how to carry out an automated production method using an automated production system to produce fluorine-containing crystalline products using a hydrofluoric acid solution. Those skilled in the art will readily understand the advantages and effects of the present invention from the contents of this specification and can implement or apply the contents of the invention by making various modifications and changes to the embodiments of the listed examples without departing from the spirit of the invention.

[0064] Example 1: Automated production of sodium fluoroaluminate crystals using hydrofluoric acid solution In this embodiment, hydrofluoric acid waste liquid recovered by manufacturer A is selected and used as the raw material. The hydrofluoric acid waste liquid is continuously supplied to the upper half of the inner tank body 12 of the crystallization treatment apparatus 10, and sodium aluminate solution (i.e., aluminate solution as a reaction solution) is continuously supplied to the lower half of the inner tank body 12 of the crystallization treatment apparatus 10. Sodium fluoroaluminate crystal product is obtained in a simple process by the following automated production method. The specific implementation method will be explained below with reference to Figures 2 to 4.

[0065] First, the hydrofluoric acid waste liquid stored in the second supply tank 31 of the second supply module 30 is supplied, and the concentration of the hydrofluoric acid waste liquid in the second supply module 30 is detected as 112.1 g / L via the concentration sensor 171. This concentration parameter is transmitted to the automatic control module 60, and the supply flow rate of the hydrofluoric acid waste liquid to reaction zone A1 is pre-set to 40 liters / minute (liters per minute, lpm).

[0066] Meanwhile, a sodium aluminate solution is prepared and stored in the first supply tank 21 of the first supply module 20. The predetermined concentration of the sodium aluminate solution is 82.0 g / L for aluminum ions and 210.0 g / L for sodium ions. These predetermined concentration parameters are input to the automatic control module 60, which calculates and outputs predetermined flow rate parameters for the sodium aluminate solution according to the reaction equation and theoretical basis, thereby completing the preparation work before the induced crystal reaction. Here, the automatic control module 60 receives the concentration parameter of the hydrofluoric acid waste liquid sensed by the concentration sensor 171, and calculates a predetermined flow rate of the sodium aluminate solution using 112.1 * 40 ÷ 19 ÷ 6 × 27 ÷ 82 × 1.04 = 13.5 based on the concentration parameter of the hydrofluoric acid waste liquid, the supply flow rate, and the predetermined concentration of the sodium aluminate solution, and outputs this to the second pump 34, thereby controlling the supply of the sodium aluminate solution to the reaction zone A1 at a predetermined flow rate of 13.5 lpm in the initial stage.

[0067] Before continuously supplying the hydrofluoric acid waste liquid and sodium aluminate solution, clean water may be injected into the inner tank body 12 of the crystallization treatment device 10 to raise the liquid level of the clean water to a position 5 centimeters higher than the first supply pipe 22. Then, the automatic control module 60 controls the first pump 24 according to the predetermined flow rate parameters of the output sodium aluminate solution, first causing the sodium aluminate solution in the first supply tank 21 to flow into the first supply pipe 22 and spray head 23, and continuously supplying it to the lower half of reaction zone A1 by spraying at a predetermined flow rate of 13.5 lpm for 30 seconds. After that, the automatic control module 60 controls the second pump 34 to cause the hydrofluoric acid waste liquid in the second supply tank 31 to flow into the second supply pipe 32 and spray head 33, and continuously supplying it to the upper half of reaction zone A1 by spraying at a supply flow rate of 40 lpm, thereby forming a mixed solution containing sodium aluminate solution and hydrofluoric acid waste liquid in reaction zone A1. During the supply process, the stirring unit 122 continuously and uniformly stirs the mixed solution in reaction zone A1, maintaining a stirring speed of 120 revolutions per minute (rpm) throughout the entire process.

[0068] After continuously supplying sodium aluminate solution and hydrofluoric acid waste liquid to reaction zone A1 of the inner tank body 12 of the crystallization treatment apparatus 10 for a certain period of time, as shown in Figure 3, the mixed solution in reaction zone A1 flows through the flow port 121 to the rectification zone A2, and then flows downwards through the sedimentation port 131 to collect in the crystal material collection zone A3, causing the liquid level to gradually rise from the bottom of the outer tank body 11 and gradually approach the horizontal height of the suction end 511 of the guide pipe 51. As shown in Figure 4, after continuous supply, the liquid level gradually rises to a position higher than the horizontal height of the suction end 511 of the guide pipe 51. At this time, the mixed solution can flow in reaction zone A1, rectification zone A2, and crystal material collection zone A3.

[0069] After the sodium aluminate solution and hydrofluoric acid waste liquid are continuously supplied to reaction zone A1 of the inner tank body 12 of the crystallization treatment apparatus 10, the fluoride ion concentration sensor 17 begins to sense the fluoride ion concentration parameter of the mixed solution in reaction zone A1 and transmits this fluoride ion concentration parameter to the automatic control module 60 in real time. The automatic control module 60 receives the fluoride ion concentration parameter from the fluoride ion concentration sensor 17 and controls the second pump 34 according to the sensed fluoride ion concentration parameter to adjust the supply flow rate of the sodium aluminate solution in real time, thereby controlling the fluoride ion concentration of the mixed solution in reaction zone A1 to be as close as possible to the crystal nucleation target concentration (abbreviated as target concentration in Table 1 below) corresponding to the metastable zone, thereby favorably advancing the induced crystallization reaction. In this embodiment, when the induced crystallization reaction proceeds, the target concentration for crystal nucleation corresponding to the metastable zone is 2000 ppm. The automatic control module 60 receives the sensed fluoride ion concentration parameter in real time and controls the supply flow rate of the sodium aluminate solution in real time according to the relationship between the fluoride ion concentration and the supply flow rate of the sodium aluminate solution shown in Table 1 below, thereby controlling the fluoride ion concentration of the mixed solution to be as low as possible in the automated production process, up to 2000 ppm.

[0070] Specifically, in this embodiment, the results of controlling the supply flow rate of the sodium aluminate solution based on the fluoride ion concentration parameter actually sensed in the induced crystal reaction are shown in Figure 5A. At 5 minutes of continuous supply of sodium aluminate (4.5 minutes of continuous supply of hydrofluoric acid waste liquid), the sensed fluoride ion concentration was 1850 ppm (corresponding to a 5% to 10% reduction from the target concentration), and therefore the automatic control module 60 controls the supply flow rate of the sodium aluminate solution to approximately 13.2 lpm. At 10 minutes of continuous supply of sodium aluminate, the sensed fluoride ion concentration was 2310 ppm (corresponding to a 10% to 20% increase from the target concentration), and therefore the automatic control module 60 controls the supply flow rate of the sodium aluminate solution to approximately 14.0 lpm. After 40 minutes of continuous supply of sodium aluminate, the fluoride ion concentration falls below 1000 ppm, and the automatic control module 60 automatically stops the supply of the sodium aluminate solution. The results of controlling the fluoride ion concentration parameters sensed at other times and the supply flow rate of sodium aluminate are shown in Figure 5A.

[0071] Table 1: Relationship in which the automatic control module of Example 1 controls the supply flow rate of sodium aluminate solution according to the fluoride ion concentration parameter of the mixed liquid in the reaction zone. [Table 1]

[0072] Five minutes after supplying sodium aluminate, the liquid level reaches a position higher than the horizontal height of the suction end 511 of the guide pipe 51 and the sensing end of the turbidity sensor 18. At this time, in addition to sensing the fluoride ion concentration of the mixed solution in the reaction zone A1 in real time using the fluoride ion concentration sensor 17, the system continues to supply the sodium aluminate solution and the hydrofluoric acid solution to carry out the induced crystal reaction. Simultaneously, the system also senses the turbidity of the carrier-containing solution in the rectification zone A2 in real time. The automatic control module 60 receives the turbidity parameter sensed by the turbidity sensor 18 and controls the transport pump 52 of the carrier circulation module 50 according to the turbidity parameter. This controls the flow rate in real time that draws the carrier-containing solution from the rectification zone A2 through the suction end 511 and guides it to the reaction zone A1, thereby promoting the progress of the induced crystal reaction.

[0073] Specifically, during the first 5 minutes after the sodium aluminate solution is supplied, the liquid level has not yet reached the sensing end of the turbidity sensor 18, the automatic control module 60 has not yet received the turbidity parameter, and has not yet controlled the transport pump 52. At this time, the upward flow velocity of the self-organizing carrier-containing solution in the rectification zone A2 is 0.151 cm / s. At the 5th minute after the sodium aluminate solution is supplied, the actual sensed turbidity parameter received by the automatic control module 60 is higher than 100 NTU. The automatic control module 60 controls the transport pump 52 to control the flow rate that guides the carrier-containing solution in the rectification zone A2 back to the reaction zone A1 to 9.96 cubic meters / hour (CMH), thereby reducing the upward flow velocity of the self-organizing carrier-containing solution in the rectification zone A2 to 0.47 cm / s. By employing a low flow rate, the suspended seed crystals are lifted, guided back to the reaction zone, and allowed to grow continuously. On the other hand, if the turbidity parameter received by the automatic control module 60 is lower than 100 NTU, it means that the particle size has grown to a certain extent, and the automatic control module 60 adjusts the upward flow velocity of the self-organized carrier-containing solution in the rectification zone A2 at a rate of increasing by 0.5 cm / s per minute, controlling it to increase the upward flow velocity to 2.33 cm / s. This causes the crystals that have grown to the target particle size to gradually precipitate in the crystal collection zone A3, and subsequently promotes the deposition of sodium fluoroaluminate crystals in the quicksand-like sediment in the crystal collection zone A3. The result of the automatic control module 60 controlling the upward flow velocity of the self-organized carrier-containing solution in the rectification zone A2 according to the received turbidity parameter is shown in Figure 5B.In this embodiment, when the automatic control module 60 controls the guide flow rate of the transport pump 52 to 9.96 CMH, the upward flow velocity in the straightening zone A2 becomes 0.47 cm / s; when the automatic control module 60 controls the guide flow rate of the transport pump 52 to 10.62 CMH, the upward flow velocity in the straightening zone A2 becomes 0.50 cm / s; and when the automatic control module 60 controls the guide flow rate of the transport pump 52 to 21.18 CMH, the upward flow velocity in the straightening zone A2 becomes 1.00 cm / s. Furthermore, the automatic control module 60 controls the guide flow rate of the transport pump 52 to 31.86 CMH, resulting in an upward flow velocity of 1.50 cm / s in the straightening zone A2. When the automatic control module 60 controls the guide flow rate of the transport pump 52 to 42.48 CMH, the upward flow velocity of 2.00 cm / s in the straightening zone A2. When the automatic control module 60 controls the guide flow rate of the transport pump 52 to 49.49 CMH, the upward flow velocity of 2.33 cm / s in the straightening zone A2. In addition, a fiber optic sensor 19, installed below the sedimentation hopper 13 and at a specific distance above the crystal discharge port 14, senses the sodium fluoroaluminate crystals that have precipitated on the guide plate 15 of the crystal collection zone A3 after the reaction in real time. The automatic control module 60 controls whether to discharge the solution containing the sodium fluoroaluminate crystals based on whether the sodium fluoroaluminate crystals have reached a predetermined height.

[0074] Here, Figures 5A and 5B show data for adjusting the supply flow rate of the sodium aluminate solution based on a fluoride ion concentration parameter sensed every 5 minutes, and data for adjusting the rising flow velocity in the rectification zone based on a turbidity parameter sensed every 5 minutes. The frequency of this sensing and control is not particularly limited. Those skilled in the art can adjust the frequency of sensing the fluoride ion concentration and controlling the supply flow rate as needed.

[0075] In Example 1, the total reaction time was 90 min. During the reaction process, the supply flow rate of hydrofluoric acid waste liquid was fixed, and the automatic control module 60 controlled the supply flow rate of the sodium aluminate solution in real time based on the sensed fluoride ion concentration parameter. It also controlled the upward flow rate of the self-organizing carrier-containing solution in the rectification zone based on the sensed turbidity parameter. In this example, at 22 minutes after supply, the optical fiber sensor 19 first detected that the sodium fluoroaluminate crystals had accumulated to a predetermined height on the guide plate 15. At 1 atmosphere (atm), the automatic control module 60 controlled the discharge pump 42 of the crystal processing module 40 to activate, causing the solution containing the sodium fluoroaluminate crystals (fluoride ion concentration of 1450 ppm, turbidity of 36 NTU) to be discharged from the crystal outlet 14 through the discharge pipe 41 to the centrifuge 43. The centrifuge 43 performs centrifugal dehydration on a solution containing sodium fluoroaluminate crystals, yielding approximately 750 kg of sodium fluoroaluminate crystal product (crylcite). This sodium fluoroaluminate crystal product can be stored in the product collection tank 44. After drying, 695 kg of dried product can be obtained from the 750 kg of sodium fluoroaluminate crystal product, with a moisture content of approximately 7.3%.

[0076] The dried products were analyzed using a particle size sieve, with approximately 82% to 85% of the products having a particle size exceeding 200 mesh. Furthermore, the content of aluminum (CNS 10116), fluorine (CNS 10113), and sodium (CNS 10115) in natural and artificial cryolite was measured using the National Standard Analytical Method of the Republic of China (CNS). The specific experimental results are shown in Table 2. The sodium fluoroaluminate crystal product was subjected to compositional analysis using the CNS method, and after three random samplings and analysis, the average percentages of fluorine, sodium, and aluminum were found to be 53.65 wt%, 30.79 wt%, and 12.80 wt%, respectively, and the average sodium / aluminum molecular ratio (molar ratio of sodium element to aluminum element) was found to be 2.82. From the experimental results, it was confirmed that in Example 1, it is indeed possible to produce high-quality sodium fluoroaluminate crystal product with a high molecular weight in a granular form. Those skilled in the art may also use other standard analytical methods (e.g., GB-4291-2007) in addition to the CNS analytical method described above to analyze the content of each component in the sodium fluoroaluminate crystal product.

[0077] Table 2: Component analysis results of fluorine, sodium, and aluminum in the sodium fluoroaluminate crystal product of Example 1 [Table 2]

[0078] From the experimental results above, it was confirmed that the automated production method for sodium fluoroaluminate using the automated production system of Example 1 can indeed recover high-concentration hydrofluoric acid wastewater and regenerate it into cryolite, which has high economic value. Specifically, in Example 1, high-concentration hydrofluoric acid wastewater (112.1 g / L) was treated by the automated production method to produce a solution with a fluoride ion concentration of approximately 1450 ppm, and the removal rate was high at 98.7%.

[0079] Example 2: Automated production of sodium fluoroaluminate crystals using hydrofluoric acid solution In this embodiment as well, hydrofluoric acid waste liquid recovered by manufacturer A is selected and used as the raw material, and sodium fluoroaluminate products are produced using an automated sodium fluoroaluminate production system that is almost the same as that shown in Figures 1, 3, and 4. The difference from Embodiment 1 is that in Embodiment 2, hydrofluoric acid waste liquid is continuously supplied to the lower half of the inner tank body 12 of the crystallization processing apparatus 10, and an aluminum sulfate solution containing sodium chloride (i.e., an aluminate solution as a reaction solution) is continuously supplied to the upper half of the inner tank body 12 of the crystallization processing apparatus 10. Furthermore, the concentration sensor (not shown) of the automated production system is not installed in the position of the concentration sensor 171 as shown in Figures 3 and 4, but rather in the first supply tank 21 in Figure 1.

[0080] To facilitate understanding of the present invention, the parts of the automated production method in Example 2 that are common to Example 1 will not be described in detail. The following description will focus on the control methods and conditions that differ from those in Example 1.

[0081] In this embodiment, hydrofluoric acid waste liquid is stored in the first supply tank 21 of the first supply module 20, and a pre-prepared aluminum sulfate solution containing sodium chloride at a predetermined concentration is stored in the second supply tank 32 of the second supply module 30. The concentration and predetermined flow rate of the hydrofluoric acid waste liquid are the same as in Example 1, and the predetermined concentration of the aluminum sulfate solution containing sodium chloride in Example 2 is 82.0 g / L of aluminum ions and 210.0 g / L of sodium ions.

[0082] Before continuously supplying the hydrofluoric acid waste liquid and the aluminum sulfate solution containing sodium chloride, clean water may be injected into the inner tank body 12 of the crystallization treatment device 10 to raise the liquid level of the clean water to 5 centimeters higher than the first supply pipe 22. Then, the automatic control module 60 controls the second pump 34 according to a predetermined flow rate parameter (13.5 lpm) of the output aluminum sulfate solution containing sodium chloride (hereinafter abbreviated as aluminate solution) to cause the aluminate solution to flow into the second supply pipe 32 and continuously supply it to the upper half of reaction zone A1 by spraying for 30 seconds. After that, the automatic control module 60 controls the first pump 24 to cause the hydrofluoric acid waste liquid to flow into the first supply pipe 22 at a supply flow rate of 40 lpm and continuously supply it to the lower half of reaction zone A1 by spraying, thereby forming a mixed solution containing the aluminate solution and the hydrofluoric acid waste liquid in reaction zone A1. During the supply process, the stirring unit 122 maintains continuous and uniform stirring of the mixed solution in reaction zone A1 at a rotational speed of 120 rpm.

[0083] When the aluminate solution is continuously supplied for 5 minutes (or 4.5 minutes after the hydrofluoric acid waste liquid has been continuously supplied), the automatic control module 60 begins to receive the fluoride ion concentration parameter and controls the supply flow rate of the aluminate solution by controlling the second pump 34. At the same time, the automatic control module 60 also receives the turbidity parameter and adjusts the upward flow rate of the self-organizing carrier-containing solution in the rectification zone A2 by controlling the transport pump 52.

[0084] In this embodiment, when the induced crystallization reaction proceeds, the target concentration for crystal nucleation corresponding to the metastable zone is 1500 ppm. The automatic control module 60 receives the sensed fluoride ion concentration parameter in real time and controls the supply flow rate of the aluminate solution in real time according to the relationship between the fluoride ion concentration and the supply flow rate of the aluminate solution shown in Table 3 below, thereby controlling the fluoride ion concentration of the mixed solution to be as low as possible in the automated production process, up to 1500 ppm.

[0085] Specifically, in this embodiment, the results of controlling the supply flow rate of the aluminum sulfate solution containing sodium chloride based on the fluoride ion concentration parameter actually sensed in the induced crystal reaction are shown in Figure 6A. At 5 minutes of continuous supply of the aluminate solution (4.5 minutes of continuous supply of hydrofluoric acid waste liquid), the sensed fluoride ion concentration was 1550 ppm (corresponding to within 5% of the target concentration), and therefore the automatic control module 60 controls the supply flow rate of the aluminate solution to be equal to a predetermined flow rate (13.5 lpm). At 10 minutes of continuous supply of the aluminate solution, the sensed fluoride ion concentration was 1330 ppm (corresponding to a 10% to 20% decrease from the target concentration), and therefore the automatic control module 60 controls the supply flow rate of the aluminate solution to be approximately 13.0 lpm. At 50 minutes of continuous supply of sodium aluminate, the fluoride ion concentration falls below 500 ppm, and the automatic control module 60 automatically stops the supply of the aluminate solution. The fluoride ion concentration parameters sensed at other times, along with the results of controlling the supply flow rate of the aluminate solution, are shown in Figure 6A.

[0086] Table 3: Relationship in which the automatic control module of Example 2 controls the supply flow rate of the aluminum sulfate solution containing sodium chloride according to the fluoride ion concentration parameter of the mixed liquid in the reaction zone. [Table 3]

[0087] For the first 5 minutes after the aluminate solution is supplied, the upward flow rate of the self-assembling carrier-containing solution in the rectification zone A2 is 0.151 cm / s. At the 5th minute after the aluminate solution is supplied, the turbidity parameter actually sensed by the automatic control module 60 is 180 NTU. Based on this turbidity parameter, the automatic control module 60 controls the upward flow rate of the self-assembling carrier-containing solution in the rectification zone A2 to 0.50 cm / s, guiding the minute, suspended self-assembling carriers and the seed crystals in the rectification zone A2 to the reaction zone A1. Subsequently, if the turbidity parameter received by the automatic control module 60 is higher than 100 NTU, the automatic control module 60 controls the upward flow rate of the self-assembling carrier-containing solution in the rectification zone A2 to 0.50 cm / s. On the other hand, if the turbidity parameter received by the automatic control module 60 is lower than 100 NTU, the automatic control module 60 adjusts the upward flow velocity of the self-organizing carrier-containing solution in the rectification zone A2 at a rate of increasing 0.5 cm / s per minute, controlling it to increase the upward flow velocity to 2.50 cm / s. This causes the crystals that have grown to the target particle size to gradually precipitate in the crystal collection zone A3, promoting the deposition of sodium fluoroaluminate crystals in the quicksand-like sediment within the crystal collection zone A3. The result of the automatic control module 60 controlling the upward flow velocity of the self-organizing carrier-containing solution in the rectification zone A2 according to the received turbidity parameter is shown in Figure 6B.

[0088] In Example 1, the total reaction time was 90 minutes. During the reaction process, the supply flow rate of hydrofluoric acid waste liquid was fixed, and the automatic control module 60 controlled the supply flow rate of the aluminate solution in real time based on the sensed fluoride ion concentration parameter. It also controlled the upward flow rate of the self-organizing carrier-containing solution in the rectification zone A2 based on the sensed turbidity parameter. In this example, 18 minutes after supply, the optical fiber sensor 19 first detected that the sodium fluoroaluminate crystals had accumulated to a predetermined height on the guide plate 15. Based on this, the automatic control module 60 controlled the discharge pump 42 of the crystal processing module 40 to activate, causing the solution containing the sodium fluoroaluminate crystals (fluoride ion concentration of 1320 ppm, turbidity of 33 NTU) to be discharged from the crystal outlet 14 through the discharge pipe 41 to the centrifuge 43. The centrifuge 43 performs centrifugal dehydration on a solution containing sodium fluoroaluminate crystals, yielding approximately 730 kg of sodium fluoroaluminate crystal product (crylcite). This sodium fluoroaluminate crystal product can be stored in the product collection tank 44. After drying, 690 kg of dried product can be obtained from the 730 kg of sodium fluoroaluminate crystal product, with a moisture content of approximately 5.5%.

[0089] The dried product was analyzed using a particle size sieve, and approximately 86% to 89% of the product had a particle size exceeding 200 mesh. Analysis was performed using the same method as in Example 1, and the proportions of fluorine, sodium, and aluminum were found to be 53.60 wt%, 33.15 wt%, and 13.14 wt%, respectively, with an average sodium / aluminum molecular ratio of 2.96. Specific experimental results are shown in Table 4. From the experimental results, it was confirmed that Example 2 can indeed produce high-quality sodium fluoroaluminate crystalline products in a granular form with a high molecular ratio.

[0090] Table 4: Component analysis results of fluorine, sodium, and aluminum in the sodium fluoroaluminate crystal product of Example 2 [Table 4]

[0091] From the experimental results above, it was confirmed that the automated production method for sodium fluoroaluminate using the automated production system of Example 2 can indeed recover high-concentration hydrofluoric acid wastewater and regenerate it into cryolite, which has high economic value. Specifically, in Example 2, high-concentration hydrofluoric acid wastewater (112.1 g / L) was treated by the automated production method to produce a solution with a fluoride ion concentration of approximately 1320 ppm, and the removal rate was high at 98.8%.

[0092] Example 3: Automated production of sodium fluoroaluminate crystals using hydrofluoric acid solution In this embodiment, hydrofluoric acid waste liquid recovered by manufacturer B is selected as the raw material, and sodium fluoroaluminate products are produced using an automated sodium fluoroaluminate production system similar to that in Figure 1. The difference from Embodiment 1 is that in Embodiment 3, hydrofluoric acid waste liquid is continuously supplied to the lower half of the inner tank body 12 of the crystallization processing apparatus 10, and sodium aluminate solution (i.e., aluminate solution as a reaction solution) is continuously supplied to the upper half of the inner tank body 12 of the crystallization processing apparatus 10. Furthermore, the concentration sensor (not shown) of the automated production system is not installed in the position of the concentration sensor 171 as shown in Figures 3 and 4, but rather in the first supply tank 21 in Figure 1.

[0093] To facilitate understanding of the present invention, the parts of the automated production method in Example 3 that are common to Example 1 will not be described in detail. The following description will focus on the control methods and conditions that differ from those in Example 1.

[0094] First, hydrofluoric acid waste liquid is supplied and stored in the first supply tank 21 of the first supply module 20. A concentration sensor (not shown in Figure 1) detects that the concentration of the hydrofluoric acid waste liquid in the first supply tank 21 of the first supply module 20 is 235.6 g / L. This concentration parameter is transmitted to the automatic control module 60, and the supply flow rate of the hydrofluoric acid waste liquid to reaction zone A1 is preset to 30 lpm. Meanwhile, a sodium aluminate solution is prepared and stored in the second supply tank 31 of the second supply module 30. The predetermined concentration of the sodium aluminate solution is an aluminum ion concentration of 82.0 g / L and a sodium ion concentration of 210.0 g / L. These predetermined concentration parameters are input to the automatic control module 60. The automatic control module 60 receives the concentration parameter of the hydrofluoric acid waste liquid sensed by the concentration sensor, and calculates a predetermined flow rate of the sodium aluminate solution using 235.6 * 30 ÷ 19 ÷ 6 × 27 ÷ 82 × 1.05 = 21.4 based on the concentration parameter of the hydrofluoric acid waste liquid, the supply flow rate, and a predetermined concentration of the sodium aluminate solution, and outputs this to the second pump 34, thereby controlling the supply of the sodium aluminate solution to the reaction zone A1 at a predetermined flow rate of 21.4 lpm in the initial stages.

[0095] Before continuously supplying the hydrofluoric acid waste liquid and sodium aluminate solution, clean water may be injected into the inner tank body 12 of the crystallization treatment device 10 to raise the liquid level of the clean water to a position 5 centimeters higher than the first supply pipe 22. Then, the automatic control module 60 controls the second pump 34 according to a predetermined flow rate parameter (21.4 lpm) of the output sodium aluminate solution, causing the sodium aluminate solution to flow into the second supply pipe 32 and continuously supply it to the upper half of reaction zone A1 by spraying for 30 seconds. After that, the automatic control module 60 controls the first pump 24 to cause the hydrofluoric acid waste liquid to flow into the first supply pipe 22 at a supply flow rate of 30 lpm and continuously supply it to the lower half of reaction zone A1 by spraying, thereby forming a mixed solution containing the sodium aluminate solution and hydrofluoric acid waste liquid in reaction zone A1. During the supply process, the stirring unit 122 maintains continuous and uniform stirring of the mixed solution in reaction zone A1 at a rotational speed of 120 rpm.

[0096] When the sodium aluminate solution is continuously supplied for 5 minutes (or 4.5 minutes after the hydrofluoric acid waste liquid has been continuously supplied), the automatic control module 60 begins to receive the fluoride ion concentration parameter and controls the supply flow rate of the sodium aluminate solution by controlling the second pump 34. At the same time, the automatic control module 60 also receives the turbidity parameter and adjusts the upward flow rate of the self-organizing carrier-containing solution in the rectification zone A2 by controlling the transport pump 52.

[0097] In this embodiment, when the induced crystal reaction proceeds, the target concentration for crystal nucleation corresponding to the metastable zone is 1200 ppm. The automatic control module 60 receives the sensed fluoride ion concentration parameter in real time and controls the supply flow rate of the sodium aluminate solution in real time according to the relationship between the fluoride ion concentration and the supply flow rate of the sodium aluminate solution shown in Table 5 below, thereby controlling the fluoride ion concentration of the mixed solution to be as low as possible in the automated production process, up to 1200 ppm.

[0098] Specifically, in this embodiment, the results of controlling the supply flow rate of the sodium aluminate solution based on the fluoride ion concentration parameter actually sensed in the induced crystal reaction are shown in Figure 7A. At 5 minutes of continuous supply of sodium aluminate solution (4.5 minutes of continuous supply of hydrofluoric acid waste liquid), the sensed fluoride ion concentration was 1100 ppm (corresponding to a 5% to 10% reduction from the target concentration), and therefore the automatic control module 60 controls the supply flow rate of the sodium aluminate solution to 21.0 lpm. At 10 minutes of continuous supply of sodium aluminate solution, the sensed fluoride ion concentration was 800 ppm (corresponding to a level lower than a 30% reduction from the target concentration), and therefore the automatic control module 60 controls the supply flow rate of the sodium aluminate solution to approximately 18.2 lpm. After 30 minutes of continuous supply of sodium aluminate solution, the fluoride ion concentration falls below 500 ppm (which is lower than a 30% reduction from the target concentration, but still higher than the limit concentration). Therefore, the automatic control module 60 controls the supply flow rate of the sodium aluminate solution to approximately 18.2 lpm. The results of controlling the supply flow rate of the sodium aluminate solution in relation to the fluoride ion concentration parameters sensed at other times are shown in Figure 7A.

[0099] Table 5: Relationship in which the automatic control module of Example 3 controls the supply flow rate of sodium aluminate solution according to the fluoride ion concentration parameter of the mixed liquid in the reaction zone. [Table 5]

[0100] For the first 5 minutes after the sodium aluminate solution is supplied, the upward flow rate of the self-assembling carrier-containing solution in the rectification zone A2 is 0.144 cm / s. At the 5th minute after the sodium aluminate solution is supplied, the turbidity parameter actually sensed by the automatic control module 60 is 160 NTU. Based on this turbidity parameter, the automatic control module 60 controls the upward flow rate of the self-assembling carrier-containing solution in the rectification zone A2 to 0.50 cm / s via the guide pipe 51 to the reaction zone A1, and begins guiding the seed crystals in the rectification zone A2 to the reaction zone A1. If the turbidity parameter received by the automatic control module 60 is lower than 100 NTU, the automatic control module 60 adjusts the upward flow rate at a rate of increasing 0.5 cm / s per minute, controlling it to increase the upward flow rate up to 2.50 cm / s. This causes the crystals that have grown to the target particle size to gradually precipitate in the crystal collection zone A3, promoting the deposition of sodium fluoroaluminate crystals in the quicksand-like sediment within the crystal collection zone A3. The result of the automatic control module 60 controlling the upward flow rate of the self-organized carrier-containing solution in the rectification zone A2 according to the received turbidity parameter is shown in Figure 7B.

[0101] In Example 3, the total reaction time was 90 minutes. During the reaction process, the supply flow rate of hydrofluoric acid waste liquid was fixed, and the automatic control module 60 controlled the supply flow rate of the sodium aluminate solution in real time based on the sensed fluoride ion concentration parameter. It also controlled the upward flow rate of the self-organizing carrier-containing solution in the rectification zone A2 based on the sensed turbidity parameter. In this example, 10 minutes after supply, the optical fiber sensor 19 first detected that the sodium fluoroaluminate crystals had accumulated to a predetermined height on the guide plate 15. Based on this, the automatic control module 60 controlled the discharge pump 42 of the crystal processing module 40 to activate, causing the solution containing the sodium fluoroaluminate crystals (fluoride ion concentration of 980 ppm, turbidity of 26 NTU) to be discharged from the crystal outlet 14 through the discharge pipe 41 to the centrifuge 43. The centrifuge 43 performs centrifugal dehydration on a solution containing sodium fluoroaluminate crystals, yielding approximately 1150 kg of sodium fluoroaluminate crystal product (crylcite). This sodium fluoroaluminate crystal product can be stored in the product collection tank 44. After drying, 1084 kg of dried product can be obtained from the 1150 kg of sodium fluoroaluminate crystal product, with a moisture content of approximately 5.7%.

[0102] The dried product was analyzed using a particle size sieve, and approximately 79% to 83% of the product had a particle size exceeding 200 mesh. Analysis was performed using the same method as in Example 1, and the proportions of fluorine, sodium, and aluminum were found to be 51.66 wt%, 31.66 wt%, and 12.79 wt%, respectively, with an average sodium / aluminum molecular ratio of 2.91. Specific experimental results are shown in Table 6. From the experimental results, it was confirmed that Example 3 can indeed produce high-quality sodium fluoroaluminate crystalline products.

[0103] Table 6: Component analysis results of fluorine, sodium, and aluminum in the sodium fluoroaluminate crystal product of Example 3 [Table 6]

[0104] From the experimental results above, it was confirmed that the automated production method for sodium fluoroaluminate using the automated production system of Example 3 can indeed recover high-concentration hydrofluoric acid wastewater and regenerate it into cryolite, which has high economic value. Specifically, in Example 3, high-concentration hydrofluoric acid wastewater (235.6 g / L) was treated by the automated production method to produce a solution with a fluoride ion concentration of approximately 980 ppm, and the removal rate was high at 99.6%.

[0105] To summarize the above Examples 1 to 3, the automated production method for sodium aluminate using the automated production system of the present invention can efficiently recover fluoride ions from high-concentration hydrofluoric acid waste liquid through the automated production method, achieving a removal rate of 98% or more. Furthermore, the final dried product consists of 80% or more sodium fluoroaluminate crystal products with a particle size of 200 mesh or larger (74 μm or larger).

[0106] Experimental Example 1 The sodium fluoroaluminate crystal products of Examples 1 to 3 were observed using a scanning electron microscope (SEM), and the results are shown in Figures 8A to 8F. As can be seen from Figures 8A to 8F, the microstructure of the sodium fluoroaluminate crystal products of Examples 1 to 3 all has a high-purity crystalline phase.

[0107] Furthermore, the crystal structure of the sodium fluoroaluminate crystal products of Examples 1 to 3 was analyzed by X-ray diffractometer (XRD), and the results are shown in Figure 9. As shown in Figure 9, when the XRD analysis results of the sodium fluoroaluminate crystal products of Examples 1 to 3 were compared with the XRD diagram of the sodium fluoroaluminate (NA3ALF6) standard product (PDF25-0772), it was confirmed that the sodium fluoroaluminate crystal products of Examples 1 to 3 have a monoclinic crystal structure.

[0108] From the above SEM and XRD analysis results, it was confirmed that the XRD analysis results were the same as the SEM microstructure results, and that the present invention can be implemented as an automated production method for sodium fluoroaluminate using an automated production system. It was confirmed that hydrofluoric acid waste liquid can be reused with high efficiency and that it can be produced as a high-purity sodium fluoroaluminate crystalline product.

[0109] Example 4: Automated production of sodium fluorosilicate crystals using hydrofluoric acid solution In this embodiment, hydrofluoric acid waste liquid recovered by manufacturer C is selected and used as the raw material. The hydrofluoric acid waste liquid is continuously supplied to the lower half of the inner tank body 12 of the crystallization treatment apparatus 10, and sodium silicate solution is continuously supplied to the upper half of the inner tank body 12 of the crystallization treatment apparatus 10. Sodium fluorosilicate crystals are obtained in a simple process by the following automated production method. The specific implementation method will be explained below with reference to Figures 2 to 4.

[0110] First, the hydrofluoric acid waste liquid stored in the second supply tank 31 of the second supply module 30 is supplied, and concentration analysis is performed to determine that the concentration of the hydrofluoric acid waste liquid in the second supply module 30 is 160.4 g / L. This concentration parameter is then transmitted to the automatic control module 60, and the supply flow rate of the hydrofluoric acid waste liquid to reaction zone A1 is pre-set to 30 lpm.

[0111] Meanwhile, a sodium silicate solution is prepared and stored in the first supply tank 21 of the first supply module 20. The predetermined concentration of the sodium silicate solution is 160.0 g / L of silicon ions and 270.0 g / L of sodium ions. These predetermined concentration parameters are input to the automatic control module 60, which calculates and outputs predetermined flow rate parameters for the sodium silicate solution according to the reaction equation and theoretical basis, thereby completing the preparation work before the induced crystal reaction. Here, the automatic control module 60 receives the concentration parameters of the hydrofluoric acid waste liquid that we have analyzed and measured, and calculates a predetermined flow rate of the sodium silicate solution using 160.4 * 30 ÷ 19 ÷ 6 × 28 ÷ 160 × 1.03 = 7.6 based on the concentration parameters of the hydrofluoric acid waste liquid, the supply flow rate, and the predetermined concentration of the sodium silicate solution, and outputs this to the second pump 34, thereby controlling the supply of the sodium silicate solution to the reaction zone A1 at a predetermined flow rate of 7.6 lpm in the initial stage.

[0112] Before continuously supplying the hydrofluoric acid waste liquid and sodium silicate solution, clean water may be injected into the inner tank body 12 of the crystallization treatment device 10 to raise the liquid level of the clean water to a position 5 centimeters higher than the first supply pipe 22. Then, the automatic control module 60 controls the first pump 24 according to the predetermined flow rate parameters of the output sodium silicate solution, first causing the sodium silicate solution in the first supply tank 21 to flow into the first supply pipe 22 and spray head 23, and continuously supplying it to the upper half of reaction zone A1 by spraying at a predetermined flow rate of 7.6 lpm for 30 seconds. After that, the automatic control module 60 controls the second pump 34 to cause the hydrofluoric acid waste liquid in the second supply tank 31 to flow into the second supply pipe 32 and spray head 33, and continuously supplying it to the lower half of reaction zone A1 by spraying at a supply flow rate of 30 lpm, thereby forming a mixed solution containing sodium silicate solution and hydrofluoric acid waste liquid in reaction zone A1. During the supply process, the stirring unit 122 continuously and uniformly stirs the mixed solution in reaction zone A1, and the stirring speed is maintained at 120 rpm per minute throughout the entire process.

[0113] After continuously supplying sodium silicate solution and hydrofluoric acid waste liquid to reaction zone A1 of the inner tank body 12 of the crystallization treatment apparatus 10 for a certain period of time, as shown in Figure 3, after supplying hydrofluoric acid waste liquid and sodium silicate solution, the mixed solution in reaction zone A1 flows through the flow port 121 to the rectification zone A2, and then flows downwards through the sedimentation port 131 to collect in the crystal material collection zone A3, causing the liquid level to gradually rise from the bottom of the outer tank body 11 and gradually approach the horizontal height of the suction end 511 of the guide pipe 51. As shown in Figure 4, after continuous supply, the liquid level gradually rises to a position higher than the horizontal height of the suction end 511 of the guide pipe 51. At this time, the mixed solution can flow in reaction zone A1, rectification zone A2, and crystal material collection zone A3.

[0114] After continuously supplying sodium silicate solution and hydrofluoric acid waste liquid to reaction zone A1 of the inner tank body 12 of the crystallization treatment apparatus 10, the fluoride ion concentration sensor 17 begins to sense the fluoride ion concentration parameter of the mixed solution in reaction zone A1 and transmits this fluoride ion concentration parameter to the automatic control module 60 in real time. The automatic control module 60 receives the fluoride ion concentration parameter from the fluoride ion concentration sensor 17 and controls the second pump 34 according to the sensed fluoride ion concentration parameter to adjust the supply flow rate of the sodium silicate solution in real time, thereby controlling the fluoride ion concentration of the mixed solution in reaction zone A1 to be as close as possible to the crystal nucleation target concentration (abbreviated as target concentration in Table 1 below) corresponding to the metastable zone, thereby favorably advancing the induced crystallization reaction. In this embodiment, when the induced crystal reaction proceeds, the target concentration for crystal nucleation corresponding to the metastable zone is 2000 ppm. The automatic control module 60 receives the sensed fluoride ion concentration parameter in real time and controls the supply flow rate of the sodium silicate solution in real time according to the relationship between the fluoride ion concentration and the supply flow rate of the sodium silicate solution shown in Table 7 below, thereby controlling the fluoride ion concentration of the mixed solution to be as low as possible in the automated production process, up to 2000 ppm.

[0115] Specifically, in this embodiment, the results of controlling the supply flow rate of the sodium silicate solution based on the fluoride ion concentration parameter actually sensed in the induced crystal reaction are shown in Figure 10A. At 5 minutes of continuous supply of sodium silicate (4.5 minutes of continuous supply of hydrofluoric acid waste liquid), the sensed fluoride ion concentration was 4800 ppm (corresponding to a 30% increase above the target concentration), and therefore the automatic control module 60 controls the supply flow rate of the sodium silicate solution to approximately 8.7 lpm. At 10 minutes of continuous supply of sodium silicate, the sensed fluoride ion concentration was 2510 ppm (corresponding to a 20% to 30% increase above the target concentration), and therefore the automatic control module 60 controls the supply flow rate of the sodium silicate solution to approximately 8.2 lpm. The results of controlling the supply flow rate of sodium silicate in relation to the fluoride ion concentration parameter sensed at other times are shown in Figure 10A.

[0116] Table 7: Relationship of the automatic control module in Example 4 in controlling the supply flow rate of sodium silicate solution according to the fluoride ion concentration parameter of the mixed liquid in the reaction zone. [Table 7]

[0117] Five minutes after supplying sodium silicate, the liquid level reaches a position higher than the horizontal height of the suction end 511 of the guide pipe 51 and the sensing end of the turbidity sensor 18. At this time, in addition to sensing the fluoride ion concentration of the mixed solution in the reaction zone A1 in real time using the fluoride ion concentration sensor 17, the automatic control module 60 also senses the turbidity of the carrier-containing solution in the rectification zone A2 in real time while continuing to supply the sodium silicate solution and the hydrofluoric acid solution to carry out the induced crystal reaction. The automatic control module 60 receives the turbidity parameter sensed by the turbidity sensor 18 and controls the transport pump 52 of the carrier circulation module 50 according to the turbidity parameter, thereby controlling the flow rate in real time of the carrier-containing solution drawn from the suction end 511 into the rectification zone A2 and guided into the reaction zone A1. This controls the upward flow rate of the carrier-containing solution in the rectification zone A2 and promotes the progress of the induced crystal reaction.

[0118] Specifically, during the first five minutes after the sodium silicate solution is supplied, the liquid level has not yet reached the sensing end of the turbidity sensor 18, the automatic control module 60 has not yet received the turbidity parameter, and has not yet controlled the transport pump 52. At this time, the upward flow velocity of the self-organizing carrier-containing solution in the rectification zone is 0.11 cm / s. At the fifth minute after the sodium silicate solution is supplied, the actual turbidity parameter received by the automatic control module 60 is higher than 100 NTU, so the automatic control module 60 controls the upward flow velocity in the rectification zone to 0.50 cm / s, employing a low flow rate to lift the suspended seed crystals, guide them back to the reaction zone, and allow them to grow continuously. On the other hand, if the turbidity parameter received by the automatic control module 60 is lower than 100 NTU, it means that the particle size has grown to a certain extent, and the automatic control module 60 adjusts the upward flow velocity in the straightening zone at a rate of increasing 0.5 cm / s per minute, controlling it to increase the upward flow velocity in the straightening zone to 2.50 cm / s. This causes the crystals that have grown to the target particle size to gradually precipitate in the crystal collection zone A3, and subsequently promotes the deposition of sodium fluorosilicate crystals in the quicksand-like sediment within the crystal collection zone A3. The result of the automatic control module 60 controlling the upward flow velocity in the straightening zone according to the received turbidity parameter is shown in Figure 10B.

[0119] Furthermore, a fiber optic sensor 19, installed below the sedimentation hopper 13 and at a specific distance above the crystal discharge port 14, senses the sodium fluorosilicate crystals that have settled on the guide plate 15 of the crystal collection zone A3 after the reaction in real time, and the automatic control module 60 controls whether or not to discharge the solution containing the sodium fluorosilicate crystals based on whether the sodium fluorosilicate crystals have reached a predetermined height.

[0120] Here, Figures 10A and 10B show data for adjusting the supply flow rate of the sodium silicate solution based on a fluoride ion concentration parameter sensed every 5 minutes, and data for adjusting the rising flow velocity in the rectification zone based on a turbidity parameter sensed every 5 minutes. The frequency of this sensing and control is not particularly limited. Those skilled in the art can adjust the frequency of sensing the fluoride ion concentration and controlling the supply flow rate as needed.

[0121] In Example 4, the total reaction time was 90 minutes. During the reaction process, the supply flow rate of hydrofluoric acid waste liquid was fixed, and the automatic control module 60 controlled the supply flow rate of the sodium silicate solution in real time based on the sensed fluoride ion concentration parameter. It also controlled the upward flow rate of the self-organizing carrier-containing solution in the rectification zone A2 based on the sensed turbidity parameter. In this example, 40 minutes after supply, the optical fiber sensor 19 first detected that the sodium fluorosilicate crystals had accumulated to a predetermined height on the guide plate 15. At 1 atmosphere, the automatic control module 60 controlled the discharge pump 42 of the crystal processing module 40 to activate, causing the solution containing the sodium fluorosilicate crystals (fluoride ion concentration of 2040 ppm, turbidity of 24 NTU) to be discharged from the crystal outlet 14 through the discharge pipe 41 to the centrifuge 43. The centrifuge 43 performed centrifugal dehydration on the solution containing the sodium fluorosilicate crystals, yielding approximately 705 kg of sodium fluorosilicate crystal product. The sodium fluorosilicate crystal product can be stored in the product collection tank 44. After drying, 705 kg of sodium fluorosilicate crystal product yields 672 kg of dried product with a moisture content of approximately 4.7%.

[0122] The dried product was analyzed using a particle size sieve, and approximately 76% to 81% of the product had a particle size exceeding 140 mesh. Furthermore, purity measurements were performed using the American Water Treatment Association (AWWA) B702:2018. The sodium fluorosilicate crystal product was subjected to compositional analysis using the AWWA method, and after three random samplings and analysis, the average purity values ​​were 99.89 wt%, 99.95 wt%, and 99.88 wt%, respectively, with an average purity of 99.91%. From the experimental results, it was confirmed that in Example 4, it is indeed possible to produce and obtain a high-purity, high-quality sodium fluorosilicate crystal product in a granular form.

[0123] From the experimental results above, it was confirmed that the automated production method for sodium fluorosilicate using the automated production system of Example 4 can indeed recover high-concentration hydrofluoric acid wastewater and regenerate it into a highly economically valuable sodium fluorosilicate crystalline product. Specifically, in Example 4, high-concentration hydrofluoric acid wastewater (160.4 g / L) was treated by the automated production method to produce a solution with a fluoride ion concentration of approximately 2040 ppm, achieving a high removal rate of 98.7%.

[0124] Experimental Example 2 The sodium fluorosilicate crystal product of Example 4 was observed using a scanning electron microscope (SEM), and the results are shown in Figures 11A to 11B. As can be seen from Figures 11A to 11B, the microstructure of the sodium fluorosilicate crystal product of Example 4 all has a high-purity crystalline phase.

[0125] Furthermore, the crystal structure of the sodium fluorosilicate crystal product of Example 4 was analyzed by XRD, and the results are shown in Figure 12. As shown in Figure 12, when the XRD analysis results of the sodium fluorosilicate crystal product of Example 4 were compared with the XRD diagram of the sodium fluorosilicate (Na2SiF6) standard product (PDF33-1280), it was confirmed that the sodium fluorosilicate crystal product of Example 4 has a hexagonal crystal structure.

[0126] From the above SEM and XRD analysis results, it was confirmed that the XRD analysis results were the same as the SEM microstructure results, and that the present invention can be implemented as an automated production method for sodium fluorosilicate using an automated production system. It was confirmed that hydrofluoric acid waste liquid can be reused with high efficiency and that it can be produced as a high-purity sodium fluorosilicate crystalline product.

[0127] In summary, the present invention enables the effective reuse of high-concentration hydrofluoric acid solutions and allows for the production of economically valuable fluorine-containing crystalline products through a simple and easily controllable automated production technology. Furthermore, the present invention contributes to the smooth production of granular sodium fluoroaluminate or sodium fluorosilicate crystalline products with low water content and a high sodium / aluminum molecular ratio, eliminating the complex processes of the prior art.

[0128] (Explanation of symbols) 10: Crystallization Processing Equipment 11: Outer tank body 12: Inner tank body 121: Distribution port 122: Stirring Unit 1221: Feather 13: Sedimentation hopper 131: Sedimentation port 14: Crystal discharge port 15: Information board 16: Overflow port 17: Fluoride ion concentration sensor 171: Concentration sensor 18: Turbidity sensor 19: Fiber optic sensor 20: First supply module 21: First supply tank 22: First supply pipe 23: Spray head 24: The first pump 30: Second supply module 31: Second supply tank 32: Second supply pipe 33: Spray head 34: The second pump 40: Crystallized material processing module 41: Discharge pipe 42: Discharge pump 43: Centrifuge 44: Product collection tank 50: Carrier circulation module 51: Guide pipe 511: Inlet end 512: Transport end 52: Transport pump 53: Spray material 60: Automatic control module A1: Reaction Zone A2: Rectification Zone A3: Crystal Collection Zone

[0129] (Biological deposit)

Claims

1. The process involves supplying a hydrofluoric acid solution and a reaction solution which is an aluminate solution or silicate solution having a predetermined concentration. The system senses the fluoride ion concentration of the hydrofluoric acid solution and pre-sets the supply flow rate of the hydrofluoric acid solution. The automatic control module outputs a predetermined flow rate of the reaction solution based on the fluoride ion concentration of the hydrofluoric acid solution, the supply flow rate, and the predetermined concentration of the reaction solution. By supplying the reaction solution to the reaction zone at the predetermined flow rate and supplying the hydrofluoric acid solution to the reaction zone at the predetermined supply flow rate, a crystallization reaction is carried out in the reaction zone to form a mixed solution. The system supplies the reaction solution and the hydrofluoric acid solution, simultaneously sensing the fluoride ion concentration of the mixed solution in the reaction zone in real time. The automatic control module receives the fluoride ion concentration parameter of the mixed solution in the reaction zone and controls the flow rate of the reaction solution in real time. If the fluoride ion concentration parameter received by the automatic control module falls within ±5% of the target crystal nucleation concentration, the automatic control module controls the flow rate of the reaction solution to be equal to the predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter received by the automatic control module is higher than a 5% increase above the target crystal nucleation concentration, the automatic control module controls the flow rate of the reaction solution to be greater than the predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter received by the automatic control module is lower than a 5% decrease below the target crystal nucleation concentration, the automatic control module controls the flow rate of the reaction solution to be less than the predetermined flow rate of the reaction solution. The automatic control module senses the fluorine-containing crystals that have reacted and precipitated in the crystal collection zone in real time, and controls whether or not to discharge the solution containing the fluorine-containing crystals based on whether or not the fluorine-containing crystals have reached a predetermined height. An automated production method for producing fluorine-containing crystalline products using a hydrofluoric acid solution, characterized by comprising collecting a fluorine-containing crystalline product from the solution containing fluorine-containing crystals.

2. The automated production method according to claim 1, characterized in that the turbidity of the rectification zone is sensed in real time, the automatic control module receives the turbidity parameter, the upward flow rate of the carrier-containing solution in the rectification zone is controlled in real time based on the turbidity parameter, and the rectification zone is located between the reaction zone and the crystal collection zone and is in communication with each other.

3. The automated production method according to claim 2, characterized in that, if the turbidity parameter received by the automated control module is higher than 100 NTU, the automated control module controls the upward flow velocity of the carrier-containing solution in the straightening zone to be between 0.4 cm / s and 0.6 cm / s, and if the turbidity parameter received by the automated control module is lower than 100 NTU, the automated control module controls the upward flow velocity of the carrier-containing solution in the straightening zone to be between 2.2 cm / s and 2.6 cm / s.

4. If the fluoride ion concentration parameter of the mixed solution in the reaction zone, as received by the automatic control module, is 5% to 10% higher than the target concentration for crystal nucleation, the automatic control module controls the supply flow rate of the reaction solution to be 1.5% to 2.5% higher than the predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter of the mixed solution in the reaction zone, as received by the automatic control module, is 5% to 10% lower than the target concentration for crystal nucleation, the automatic control module controls the supply flow rate of the reaction solution to be The automatic control module controls the flow rate of the reaction solution to be 1.5% to 2.5% less than the predetermined flow rate, and when the fluoride ion concentration parameter of the mixed solution in the reaction zone, as received by the automatic control module, is 10% to 20% higher than the target concentration for crystal nucleation, the automatic control module controls the supply flow rate of the reaction solution to be 3.5% to 4.5% higher than the predetermined flow rate, and when the fluoride ion concentration parameter of the mixed solution in the reaction zone, as received by the automatic control module, is 10% to 2 If the decrease is 0%, the automatic control module controls the supply flow rate of the reaction solution to be 3.5% to 4.5% less than the predetermined flow rate of the reaction solution; if the fluoride ion concentration parameter of the mixed solution in the reaction zone received by the automatic control module is 20% to 30% higher than the target concentration for crystal nucleation, the automatic control module controls the supply flow rate of the reaction solution to be 7.5% to 8.5% higher than the predetermined flow rate of the reaction solution; and the automatic control module controls the supply flow rate of the mixed solution in the reaction zone received by the automatic control module to be 3.5% to 4.5% less than the predetermined flow rate of the reaction solution. If the fluoride ion concentration parameter of the solution is 20% to 30% less than the target concentration for crystal nucleation, the automatic control module controls the supply flow rate of the reaction solution to be 7.5% to 8.5% less than the predetermined flow rate of the reaction solution; if the fluoride ion concentration parameter of the mixed solution in the reaction zone received by the automatic control module is higher than 30% more than the target concentration for crystal nucleation, the automatic control module controls the supply flow rate of the reaction solution to be 14.5% to 15.5% more than the predetermined flow rate of the reaction solution.The automated production method according to claim 1, characterized in that, if the fluoride ion concentration parameter of the mixed solution in the reaction zone received by the automatic control module is lower than 30% less than the target concentration for crystal nucleation, the automatic control module controls the supply flow rate of the reaction solution to be at least 14.5% to 15.5% less than the predetermined flow rate of the reaction solution.

5. The automated production method according to claim 1, characterized in that the aluminate solution includes a sodium aluminate solution, an aluminum sulfate solution containing a sodium source, a polyaluminum chloride solution containing a sodium source, or a combination thereof, and the sodium source includes sodium hydroxide, sodium chloride, sodium nitrate, or a combination thereof.

6. The automated production method according to claim 1, characterized in that the silicate solution includes a sodium silicate solution.

7. The automated production method according to claim 1, characterized in that the hydrofluoric acid solution includes hydrochloric acid, nitric acid, sulfuric acid, or a combination thereof.

8. The automated production method according to claim 1, characterized in that the target concentration for crystal nucleation is 1,000 ppm to 12,000 ppm.

9. The automated production method according to claim 1, further comprising supplying water or a recovered carrier-containing solution to the reaction zone, supplying the reaction solution to the reaction zone at a predetermined flow rate, and supplying the hydrofluoric acid solution to the reaction zone at a preset supply flow rate.

10. The automated production method according to claim 1, characterized in that collecting and obtaining the fluorine-containing crystalline product from the solution containing the fluorine-containing crystals includes collecting and obtaining the fluorine-containing crystalline product by centrifuging the solution containing the fluorine-containing crystals.

11. The automated production method according to claim 1, comprising supplying the reaction solution to the reaction zone by a spray method and supplying the hydrofluoric acid solution to the reaction zone by a spray method, wherein the sprayed shapes of the reaction solution and the hydrofluoric acid solution are independently a fan shape, a hollow cone shape, a solid cone shape, a spiral shape, or a cylindrical shape.

12. The automated production method according to claim 11, characterized in that one of the reaction solution and the hydrofluoric acid solution is supplied to the upper half of the reaction zone by a spraying method to form a fan-shaped spray or a solid cone-shaped spray, and the other of the reaction solution and the hydrofluoric acid solution is supplied to the lower half of the reaction zone by a spraying method to form a hollow cone-shaped spray and a spiral-shaped spray.

13. The automated production method according to claim 1, characterized in that the concentration of the hydrofluoric acid solution is 10 g / L to 400 g / L.

14. The automatic production method according to any one of claims 1 to 13, wherein, when the reaction solution is the aluminate solution and the fluorine-containing crystalline product is a sodium fluoroaluminate crystalline product, the automatic control module outputs a predetermined flow rate of the aluminate solution based on the aluminum-to-fluorine ratio of the sodium fluoroaluminate crystalline product, with the ratio of aluminum ions in the aluminate solution to fluorine ions in the hydrofluoric acid solution being 1:6 to 1.20:

6.

15. The automated production method according to any one of claims 1 to 13, characterized in that, when the reaction solution is the silicate solution and the fluorine-containing crystalline product is a sodium fluorosilicate crystalline product, the automatic control module outputs a predetermined flow rate of the sodium silicate solution, calculated according to the silicon-to-fluorine ratio of the sodium fluorosilicate crystalline product, based on a ratio of 1:6 to 1.20:6 for the silicon ion concentration in the sodium silicate solution and the fluorine ion concentration in the hydrofluoric acid solution.

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