A kind of phosphorus removal and fluorine removal agent and preparation method thereof

Abstract

The present invention relates to the field of phosphorus-containing and fluorine-containing wastewater treatment technology, a kind of phosphorus removal and fluorine removal agent and preparation method thereof are provided, solve existing phosphorus reduction and fluorine removal agent and there is manufacturing and use cost higher, defluorination effect is poor, is greatly affected by pH, and may cause the problem of secondary pollution;Phosphorus removal and fluorine removal agent is made up of calcium chloride, calcium oxide and activated magnesium oxide;Preparation method includes according to purity and particle size, prepares calcium chloride, calcium oxide and activated magnesium oxide;According to the molar ratio of calcium chloride, calcium oxide and activated magnesium oxide, mix;In premixed calcium chloride and calcium oxide, press calcium oxide, calcium chloride and activated magnesium oxide mass 1:2:7 12 ratio add activated magnesium oxide;Mixed powder is carried out refinement process by fine grinding machine, the powder after refinement process secondary screening;The powder after refinement process is sealed and packaged and stored.The present invention is simple to use condition, only needs activated magnesium oxide and calcium oxide, calcium chloride to be mixed in proportion.

Description

Technical Field

[0001] The present invention relates to the technical field of phosphorus- and fluorine-containing wastewater treatment, specifically to a phosphorus- and fluorine-containing wastewater simultaneous removal agent in high, medium, and low concentration ranges and pH ranges; and particularly to a phosphorus- and fluorine-removing agent and a preparation method thereof. Background Art

[0002] The phosphorus chemical industry holds a significant position in my country and globally, but it also produces a significant byproduct: phosphogypsum. Phosphogypsum is a solid waste generated during the wet-process phosphoric acid process. Every ton of phosphoric acid produced generates approximately 4.5-5 tons of phosphogypsum. The most common method for disposing of phosphogypsum is temporary storage. However, this not only consumes significant land resources, but leakage from the slag dump can lead to excessive levels of total phosphorus and other substances in waterways, posing serious environmental risks. Currently, Guizhou alone has 120 million tons or more of these phosphogypsum, with approximately 8 to 12 million tons added annually. Due to the lack of anti-seepage measures or ineffective anti-seepage measures in some early slag dumps, phosphorus pollution has occurred in large karst springs in Guizhou, such as the Jiaoyishan slag dump-No. 34 Spring in Xifeng County and the Baiji slag dump-Facai Cave in Fuquan City, impacting the water quality of the Wujiang and Yangtze Rivers. Phosphogypsum has a very complex chemical composition. Besides calcium sulfate, it also contains numerous impurities, including incompletely decomposed phosphate rock, residual phosphoric acid, fluoride, acid-insoluble matter, organic matter, alkali metal salts, silicon, iron, magnesium, and aluminum. Among the various impurities in phosphogypsum, phosphorus and fluorine have the greatest impact on its properties. Furthermore, the acidic nature of phosphogypsum leachate (pH 2-6) limits its handling and disposal. While phosphogypsum has been widely utilized as a cement retarder, a building material, for sulfuric acid co-production of cement, and as a soil conditioner, the presence of impurities such as phosphorus and fluorine, which continue to accumulate in phosphogypsum storage yards, not only limits its comprehensive utilization but also significantly increases the risks associated with its storage.

[0003] Leachate from phosphogypsum reservoirs is acidic wastewater with high phosphorus and fluoride content. Currently, the main treatment methods for pollutants such as phosphorus, fluoride and organic matter in water include chemical methods, ion exchange methods, membrane separation methods, biological treatment methods and adsorption methods. Chemical precipitation and magnesium ammonium phosphate precipitation methods are generally used for phosphorus removal in phosphogypsum leachate. Calcium-magnesium phosphorus removal in chemical phosphorus removal uses calcium ions and magnesium ions to form insoluble substances with phosphate groups, and removes phosphate groups from the wastewater through precipitation. It is difficult to meet the requirements of emission standards by relying solely on calcium-magnesium chemical phosphorus removal. In actual engineering projects, other chemical agents need to be added for phosphorus removal reactions to ensure that the total phosphorus meets the effluent water quality indicators. Chemical phosphorus removal agents mainly include calcium salts, iron salts and aluminum salts.

[0004] Fluoride removal processes are similar to those for phosphate removal, and in many cases compete with phosphorus removal. For wastewater containing high concentrations of fluoride, calcium ions are typically added to precipitate the fluoride, even though Ca reacts with F to form CaF2 for precipitated removal. However, the limits of calcium-based fluoride removal are limited by the solubility of CaF2. The theoretical minimum residual fluoride concentration for calcium-based fluoride removal at room temperature is approximately 6.93 mg / L-7.9 mg / L. In phosphogypsum slag storage, the continuous accumulation of impurities can easily cause the leachate to exceed the fluoride discharge standard of 10 mg / L. Furthermore, due to inadequate anti-seepage measures, leachate from phosphogypsum storage yards or treated wastewater containing phosphorus and fluoride may need to be discharged to surface and groundwater bodies. Therefore, given the high phosphorus, high fluoride, and low pH characteristics of wastewater from the phosphorus chemical industry, the development of safe and efficient phosphorus and fluoride removal agents is crucial for pollution prevention and control in the phosphorus chemical industry.

[0005] Prior art one, Chinese patent, application number: 202410457271.3 discloses a fluorine-fixing and phosphorus-locking system and method for phosphogypsum slag storage and wastewater deep treatment, including a fluorine-fixing and phosphorus-locking subsystem for the phosphogypsum slag storage, that is, the supporting facilities of the existing phosphogypsum slag storage and the continued construction of the phosphogypsum slag storage, and also includes: a mineral material dam subsystem is set at the valley mouth downstream of the storage body, and the wastewater deep treatment subsystem for combined treatment of the storage body leachate and the wastewater discharged from the phosphogypsum factory is composed of a wastewater deep treatment unit, namely a comprehensive regulating tank, a neutralization reaction tank, a mixing reaction tank, a first sedimentation tank, a hydrolysis acidification tank, a biological contact oxidation tank, a second sedimentation tank, a multi-media filter, a clear water tank, a sludge concentration tank, The system is composed of a filter press, etc., which uses the technology of fluorine-fixing and phosphorus-locking to fix fluorine and phosphorus in the phosphogypsum slag, and uses the technology of mineral material reaction dam to carry out ecological interception treatment on the leachate. Although the leachate and the wastewater discharged from the phosphogypsum factory are combined for deep treatment using comprehensive treatment technology, the treatment is comprehensive, the treatment cost is low, and there is no secondary pollution. However, although the agent used in this scheme can greatly reduce the phosphorus and fluorine content, the agent needs to use lanthanum, and the reserves of rare earth materials are scarce and non-renewable, and the separation, purification and processing are difficult, resulting in high prices. In addition, Guizhou has a large reserve of phosphogypsum, but scarce rare earth resources. If this agent is used as an in-situ remediation agent for the phosphogypsum slag depot in Guizhou Province, the economic cost will be huge.

[0006] Prior art 2, Chinese patent application number: 202410262793.8, discloses a deep defluoridation agent and its preparation method. The preparation method comprises: adding ferric chloride and aluminum chloride to an acetic acid solution of chitosan to obtain a mixed solution, adjusting the pH of the mixed solution to 4.5-5.0 with ammonia water, and stirring for a set time to obtain a first dispersion; dispersing polyacrylamide in an aqueous dispersion of nano-calcium carbonate to obtain a second dispersion; adding the second dispersion to the first dispersion to obtain a third dispersion, adjusting the pH of the third dispersion to 7-7.5 with ammonia water, and then standing to obtain a precipitate as the defluoridation agent. Although this effectively solves the problem of current defluoridation agents having high defluoridation effects but high costs, and low costs but unsatisfactory defluoridation effects, the agent can stably control the fluoride ion concentration below 1 mg / L. However, the initial fluoride ion concentration is low and the pH value requirement is high.

[0007] Prior art three, Chinese patent, application number: 202110466372.3 discloses a method for synthesizing a calcium iron magnesium ternary nanocomposite defluoridant, the method is as follows: (1) using industrial grade CaC l2 , FeCl3·6H2O, MgCl2·6H2O as calcium salt, iron salt and magnesium salt raw materials; (2) determine the addition mass of calcium salt, iron salt and magnesium salt according to the molar ratio of calcium, iron and magnesium of 1:2:1; (3) add the weighed calcium salt, iron salt and magnesium salt to an appropriate amount of water in turn, stir and mix thoroughly and then add to the reactor; (4) add 2 molL-1 NaOH solution dropwise to the reactor while stirring until the pH value of the mixed solution reaches 7-9; (5) continue stirring at room temperature and pressure for 1 hour and age for 12 hours; (6) take out the product, filter and wash until the filtrate is neutral; (7) place the filter cake in a constant temperature drying oven at 100℃ and dry for 24 hours; (8) cool the product to room temperature and crush to obtain a calcium iron magnesium ternary nanocomposite defluoridant. Advantages: The preparation process is simple and easy to operate at room temperature and pressure, and can be produced and applied on a large scale. Although the defluoridation method of the agent used is relatively single. However, the defluorination effect is difficult to meet emission standards.

[0008] Currently, existing technologies 1, 2, and 3 have the following problems: the existing phosphorus removal and fluoride removal agents have high manufacturing and use costs, poor defluorination effect, are greatly affected by pH, and may cause secondary pollution. Therefore, the present invention provides a phosphorus removal and fluoride removal agent and a preparation method thereof. Summary of the Invention

[0009] In order to achieve the above object, the present invention adopts the following technical solutions:

[0010] In one aspect of the present invention, a phosphorus and fluorine removal agent is provided, which is composed of calcium chloride, calcium oxide and activated magnesium oxide; the mass ratio of calcium oxide, calcium chloride and activated magnesium oxide is 1:2:7-12.

[0011] In an alternative embodiment, the activated magnesium oxide is replaced by activated aluminum oxide or hydroxyapatite.

[0012] In an optional embodiment, more than 0.6 g of active magnesium oxide is added per 10 g; and the amount of active magnesium oxide added is not less than 0.5 g / 10 g of phosphogypsum slag.

[0013] Another aspect of the present invention provides a method for preparing a dephosphorus and defluoridation agent, which is used to prepare the dephosphorus and defluoridation agent, comprising:

[0014] Prepare calcium chloride, calcium oxide, and activated magnesium oxide according to purity and particle size;

[0015] Calcium chloride, calcium oxide, and activated magnesium oxide are mixed according to a molar ratio; calcium chloride and calcium oxide are weighed in proportion and placed in a dry mixer respectively; low-speed stirring is used for pre-mixing to ensure that the two powders are evenly distributed; the activated magnesium oxide is placed in a dryer for drying; the dried activated magnesium oxide is screened through a sieve to remove lumps and impurities;

[0016] Add active magnesium oxide to the premixed calcium chloride and calcium oxide in a molar ratio; mix them by high-speed stirring;

[0017] The mixed powder is refined by a fine grinder, and the refined powder is screened for a second time by a sieve; the refined powder is sealed and packaged.

[0018] In an optional embodiment, the low-speed stirring speed is ≤50 rpm; the drying process is carried out at a temperature of 95°C-100°C for not less than 2 hours; and the mesh size of the dried sieve is ≤0.05 mm;

[0019] The speed of high-speed stirring is ≥300rpm, and the stirring time is 10-15 minutes.

[0020] In an optional embodiment, the process of placing the activated magnesium oxide in a dryer comprises the following steps:

[0021] Deploy multi-dimensional intelligent sensors in drying and screening equipment, including temperature sensors, humidity sensors, and particle size sensors, to achieve comprehensive data collection. Connect the drying equipment, screening equipment, temperature controllers, and screen inspection equipment through the Internet of Things, and transmit sensor-collected data to the controller in real time.

[0022] Among them, the particle size distribution equation is used to describe the distribution of active magnesium oxide particle size, and its form is:

[0023]

[0024] Where f(r,t) represents the particle size distribution function, which indicates the number or concentration of active magnesium oxide particles with a particle size of r at time t; D p It represents the particle size diffusion coefficient, which indicates the diffusion ability of particle size distribution in space. The diffusion term represents the particle size distribution, which describes the diffusion process of the particle size distribution in space; represents the nonlinear effect term; v represents the particle size change rate, which represents the rate of change of the active magnesium oxide particle size with time; vf(r,t) represents the convection term of the particle size distribution, which describes the movement process of the particle size distribution with the particle size change rate v;

[0025]

[0026] Represents the diffusion process of particle size distribution in space;

[0027] Intelligent control is used to predict the changing trend of activated magnesium oxide at different temperatures and screen apertures, and to optimize the control strategy; based on the prediction results, the drying temperature and screen aperture are automatically adjusted;

[0028] The intelligent control system includes a generative adversarial network model. The generator of the generative adversarial network model creates a simulated activated magnesium oxide production environment, including different parameter combinations such as temperature, humidity, and screen aperture. The discriminator determines whether the generated environment is realistic and continuously optimizes the generator's simulation capabilities by comparing it with real data.

[0029] A large amount of simulated data was generated using a generative adversarial network model to expand the historical data set; multiple simulation experiments were conducted in a virtual environment to explore the effects of different parameter combinations on the activity and particle size of activated magnesium oxide and find the optimal parameter combination.

[0030] In an optional embodiment, a reinforcement learning model for adaptive reinforcement learning is established to define a state space, including key parameters such as real-time temperature, humidity, particle size distribution, and screen aperture; an action space is defined, including operations such as adjusting the drying temperature and changing the screen aperture; a reward function is designed to give the agent corresponding rewards or penalties based on the activity and particle size consistency of the activated magnesium oxide; the agent continuously learns new control strategies during the production process and dynamically adjusts the control strategies based on simulated data and real-time data generated by a generative adversarial network; offline training is performed using historical data, while online learning is performed during the production process to continuously optimize the agent's decision-making strategy; and the simulated data generated by the generative adversarial network is used to detect abnormal conditions in the production process, such as temperature fluctuations and screen damage, and to issue timely warnings.

[0031] Among them, the expression of the reward function is:

[0032]

[0033] In the formula, R(s,a) represents the reward function, which represents the reward obtained by performing action a in state s, and α i represents the activity consistency weight, which indicates the contribution of the activity consistency of the i-th batch to the reward, β i represents the particle size consistency weight, which indicates the contribution of the particle size consistency of the i-th batch to the reward, γ i represents the anomaly detection weight, which indicates the contribution of the anomaly detection of the i-th batch to the reward, δ i represents the energy consumption optimization weight, which indicates the contribution of the energy consumption optimization of the i-th batch to the reward, ∈ i represents the production efficiency weight, which indicates the contribution of the i-th batch production efficiency to the reward, ζ i Represents the equipment life weight, indicating the contribution of the equipment life of the i-th batch to the reward, η i Represents the environmental impact weight, which indicates the contribution of the environmental impact of the i-th batch to the reward, θ i Represents the quality control weight, which indicates the contribution of the quality control of the i-th batch to the reward.

[0034] In an optional implementation manner, the specific calculation method is:

[0035]

[0036] Among them, the activity standard deviation is the standard deviation of the activity of the i-th batch of active magnesium oxide, and the maximum activity standard deviation is the preset maximum allowable standard deviation;

[0037]

[0038] Among them, the particle size standard deviation is the standard deviation of the particle size of the i-th batch of activated magnesium oxide, and the maximum particle size standard deviation is the preset maximum allowable standard deviation;

[0039]

[0040] Energy consumption optimization = current energy consumption / target energy consumption

[0041] Production efficiency = current production volume / target production volume;

[0042] Equipment life = current equipment life / target equipment life;

[0043] Environmental impact = current environmental impact / target environmental impact;

[0044] Quality control = current quality control index / target quality control index.

[0045] In an optional embodiment, the control process of mixing by high-speed stirring comprises the following steps:

[0046] During the initial mixing stage, the stirring speed does not exceed 50 rpm; the initial mixing time is set to 5 minutes; after the initial mixing, the stirring speed is kept below 50 rpm; the time for the uniform distribution stage is set to 3 minutes;

[0047] After the low-speed stirring stage is completed, switch to the high-speed stirring stage, and the stirring speed should be no less than 300 rpm; the time of the intensive mixing stage is set to 5 minutes; after the intensive mixing, the stirring speed is maintained at 300 rpm; the time of the final mixing stage is set to 5-10 minutes;

[0048] During the mixing process, sampling and testing should be carried out every 2 minutes. The sampling points should be evenly distributed in different positions of the mixing container. The uniformity of the mixture should be tested by microscopic observation or chemical analysis methods. The stirring speed should be adjusted according to the sampling and testing results.

[0049] In an optional embodiment, if the test results show uneven mixing, the stirring speed is increased or the stirring time is extended; if the test results show excessive mixing, the stirring speed is reduced or the stirring time is shortened; and the stirring time is adjusted according to the sampling test results.

[0050] The dephosphorus and defluoridation agent of the present invention is simple to use and does not require complex preparation. It simply requires a proper mixture of activated magnesium oxide, calcium oxide, and calcium chloride. Most defluoridation agents currently available on the market require a neutral pH, but phosphogypsum leachate is acidic, requiring the solution to be adjusted to neutral before use. This agent has no pH requirements and can effectively remove fluoride in acidic conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation of the present invention. In the accompanying drawings:

[0052] Figure 1 This is a flow chart of the preparation method of the dephosphorization and defluorination agent provided in Example 1 of the present invention;

[0053] Figure 2 The fluorine removal effect of phosphogypsum leachate under different calcium oxide addition amounts provided in Example 5 of the present invention;

[0054] Figure 3 This is a diagram showing the phosphorus removal effect of phosphogypsum leachate at different calcium oxide addition amounts provided in Example 5 of the present invention;

[0055] Figure 4 This is a schematic diagram of the chloride ion removal rate provided in Example 5 of the present invention;

[0056] Figure 5 This is a schematic diagram of the total phosphorus removal rate provided in Example 5 of the present invention;

[0057] Figure 6 This is a schematic diagram comparing the defluorination effects of different agents provided in Example 5 of the present invention;

[0058] Figure 7 This is a schematic diagram of the simulated adsorption first-order kinetic equation provided in Example 5 of the present invention;

[0059] Figure 8 This is a schematic diagram of the simulated adsorption second-order kinetic equation provided in Example 5 of the present invention;

[0060] Figure 9 Schematic diagram of treating simulated phosphogypsum leachate using a mixed calcium agent of calcium oxide + calcium chloride in different ratios provided in Example 5 of the present invention;

[0061] Figure 10 The change in the removal rate of P and F by active magnesium oxide in the first 1470 minutes provided in Example 5 of the present invention;

[0062] Figure 11 This is a graph showing changes in the removal rates of P and F by active magnesium oxide in the first 150 minutes provided in Example 5 of the present invention;

[0063] Figure 12 This is a diagram showing the fluoride ion removal effect at various reagent ratios provided in Example 5 of the present invention;

[0064] Figure 13 This is a diagram showing the total phosphorus removal effect at various reagent ratios provided in Example 5 of the present invention. DETAILED DESCRIPTION

[0065] The technical solutions in the embodiments of the present invention will be described below with reference to the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0066] In the following, the terms "first," "second," etc., are used for descriptive convenience only and should not be construed as indicating or implying relative importance or implicitly specifying the number of the technical features being referred to. Thus, a feature identified with "first," "second," etc., may explicitly or implicitly include one or more of such features. In the description of the present invention, unless otherwise specified, "plurality" means two or more.

[0067] The embodiments of the present invention can be used to control fixed pollutants containing phosphorus and fluorine, and can also be used to control pollution in wastewater containing phosphorus and fluorine. The treated wastewater containing phosphorus and fluorine is not affected by the initial pH and is applicable to various pH ranges. It is used for the simultaneous removal of pollutants in wastewater containing phosphorus and fluorine, and can also be used to treat wastewater containing phosphorus or fluorine alone. It is applicable to the treatment of wastewater or solid waste containing phosphorus and fluorine in various concentration ranges, from high to low. By compounding different reagents and following the ratio of the reagents, the optimal use of the reagents can be achieved. The calcium oxide, calcium chloride, and activated magnesium oxide used in the reagents are all common industrial reagents, which are easy to obtain, inexpensive, and highly operable. Moreover, through the development of compounding control, no new pollution will be caused to groundwater or surface water.

[0068] The key technical features of the embodiments of the present invention are as follows: calcium oxide, calcium chloride and activated magnesium oxide or activated aluminum oxide or hydroxyapatite, the mass ratio between the different components ensures the synergistic effect of each component in the reaction, and improves the effect of phosphorus removal and fluorine removal; activated magnesium oxide can be replaced by activated aluminum oxide or hydroxyapatite, which increases the applicability and flexibility of the agent. An appropriate amount of activated magnesium oxide can effectively adsorb and remove fluoride ions to ensure the defluorination effect; the added amount is not less than 0.5g / 10g phosphogypsum slag to ensure a stable defluorination effect under acidic conditions. It is only necessary to mix the activated magnesium oxide with calcium oxide and calcium chloride in proportion, without the need for complex configuration; the agent has no special requirements for the environmental pH value and can play a good defluorination role under acidic conditions; the configuration and use process of the agent is simplified, and the difficulty of operation is reduced; there is no need to adjust the pH value of the solution, and it is suitable for the treatment of acidic phosphogypsum leachate, which expands the application range of the agent. Compared with the existing technology, most existing defluoridation agents require a neutral pH range, while phosphogypsum leachate is acidic, so the solution must be adjusted to neutral before use; there is no need to adjust the pH value, which reduces additional processing steps and costs; and reduces the chemical consumption and environmental pollution caused by adjusting the pH value. The dephosphorization and defluoridation agent of this embodiment achieves efficient, simple, and environmentally friendly dephosphorization and defluoridation effects through a reasonable component ratio, an appropriate amount of activated magnesium oxide addition, and adaptability to the pH value; the key technical features not only improve the defluoridation efficiency of the agent, but also simplify the operation process and reduce the cost of use, with significant technical advantages and application value.

[0069] Example 1:

[0070] like Figure 1 As shown, the embodiment of the present invention provides a dephosphorization and defluorination agent composed of calcium oxide, calcium chloride and activated magnesium oxide; according to the mass ratio of 1:2:7-12;

[0071] The active magnesium oxide may also be active alumina or hydroxyapatite; more than 0.6 g of active magnesium oxide is added per 10 g; and the amount of active magnesium oxide added is not less than 0.5 g / 10 g of phosphogypsum slag.

[0072] In the above-mentioned embodiment, the defluorination agent of this embodiment is simple to use and does not require complex configuration. It only requires a proper mixture of activated magnesium oxide, calcium oxide, and calcium chloride. Most defluorination agents currently available on the market require a neutral pH range, but phosphogypsum leachate is acidic, requiring the solution to be adjusted to neutral before use. This agent has no pH requirements and can effectively remove fluoride in acidic conditions.

[0073] Example 2:

[0074] like Figure 2 As shown, based on Example 1, the preparation method of the dephosphorization and defluorination agent provided in the embodiment of the present invention comprises the following steps:

[0075] Step S100: Prepare calcium chloride, calcium oxide and activated magnesium oxide according to purity and particle size;

[0076] Among them, the purity of calcium chloride is ≥98%, and the particle size is ≤0.1mm; the purity of calcium oxide is ≥95%, and the particle size is ≤0.2mm; the purity of activated magnesium oxide is ≥99%, and the particle size is ≤0.05mm;

[0077] Step S200: Calcium chloride, calcium oxide, and activated magnesium oxide are mixed according to a mass ratio; calcium chloride and calcium oxide are weighed in proportion and placed in a dry mixer; low-speed stirring (speed ≤ 50 rpm) is used for pre-mixing to ensure that the two powders are evenly distributed; the activated magnesium oxide is placed in a dryer for drying at a temperature of 95° C.-100° C. for at least 2 hours; the dried activated magnesium oxide is screened through a sieve (mesh size ≤ 0.05 mm) to remove lumps and impurities;

[0078] Step S300: Adding activated magnesium oxide to the premixed calcium chloride and calcium oxide in a mass ratio of calcium oxide, calcium chloride, and activated magnesium oxide of 1:2:7-12; mixing with high-speed stirring (speed ≥ 300 rpm); controlling the high-speed stirring time to 10-15 minutes to ensure that all components are fully mixed to form a uniform powder mixture;

[0079] Step S400: The mixed powder is refined by a fine grinder, and the particle size is controlled to be ≤0.05 mm; the refined powder is screened again by a sieve (sieve hole size ≤0.05 mm); the refined powder is sealed and packaged and stored in a dry and cool environment.

[0080] In the above embodiment, step S100 involves raw material preparation to ensure high raw material purity and improve the reaction efficiency and stability of the reagent. The raw material particle size is controlled to ensure mixing uniformity and reactivity. Significance: Providing high-quality raw materials for mixing and reaction, ensuring the overall performance of the reagent. Step S200 involves setting the mixing ratio and premixing. Pre-mixing is performed using low-speed stirring to ensure uniform distribution of calcium chloride and calcium oxide. The activated magnesium oxide is dried to remove moisture and impurities and enhance its activity. Significance: Premixing and drying improve the uniformity and stability of the mixture. Drying and screening the activated magnesium oxide enhances its reactivity in acidic environments. Step S300 involves adding the activated magnesium oxide and high-speed mixing. The activated magnesium oxide is added at a molar ratio of 0.5 to ensure uniform distribution throughout the mixture. High-speed stirring is used to ensure thorough mixing of the activated magnesium oxide with the other components. Significance: High-speed mixing increases the contact area and reaction efficiency of the components. It ensures uniform dispersion of the activated magnesium oxide throughout the mixture, enhancing the overall performance of the reagent. Step S400: Refining, packaging, and storage: Refining the powder using a fine grinder increases its reactivity. Secondary screening with a screen removes lumps and impurities, ensuring uniformity and fineness. The refined powder is then sealed and packaged to prevent moisture and oxidation. Significance: Refining increases the powder's reactivity and enhances its ability to remove fluoride in acidic environments. Sealed packaging and storage conditions ensure the long-term stability and effectiveness of the agent.

[0081] In summary, the dephosphorization and defluorination agent of this embodiment not only simplifies the conditions of use, but also significantly improves the defluorination effect in an acidic environment. The specific significance is as follows: simplified conditions of use, no complicated configuration process is required, and only mixing in proportion is required; adaptability to acidic environments, it can still effectively play a defluorination role under acidic conditions, without the need to adjust the solution to neutrality; by precisely controlling the amount of active magnesium oxide added and refined treatment, the reaction efficiency and stability of the agent are improved, and it has high innovation and practicality. The dephosphorization and defluorination agent of this embodiment has significant advantages and potential in practical applications. Through the above-mentioned preparation process, the dephosphorization and defluorination agent of this embodiment not only simplifies the conditions of use, but also significantly improves the defluorination effect in an acidic environment, and it has high innovation and practicality.

[0082] Example 3:

[0083] Based on Example 2, the process of placing the activated magnesium oxide in the dryer in step S200 provided in the embodiment of the present invention includes the following steps:

[0084] Step S201: Deploy multi-dimensional intelligent sensors in the drying equipment and screening equipment, including temperature sensors, humidity sensors, and particle size sensors, to achieve all-round data collection; interconnect the drying equipment, screening equipment, temperature controller, and screen inspection equipment through the Internet of Things technology, and transmit the data collected by the sensors to the controller in real time;

[0085] Among them, the particle size distribution equation is used to describe the distribution of active magnesium oxide particle size, and its form is:

[0086]

[0087] Where f(r,t) represents the particle size distribution function, which indicates the number or concentration of active magnesium oxide particles with a particle size of r at time t; D p It represents the particle size diffusion coefficient, which indicates the diffusion ability of particle size distribution in space. The diffusion term represents the particle size distribution, which describes the diffusion process of the particle size distribution in space; represents the nonlinear effect term; v represents the particle size change rate, which represents the rate of change of the active magnesium oxide particle size with time; vf(r,t) represents the convection term of the particle size distribution, which describes the movement process of the particle size distribution with the particle size change rate v;

[0088]

[0089] Represents the diffusion process of particle size distribution in space;

[0090] Step S202: Using intelligent control to predict the changing trend of activated magnesium oxide at different temperatures and screen apertures, and optimizing the control strategy; automatically adjusting the drying temperature and screen aperture according to the prediction results;

[0091] The intelligent control system includes a generative adversarial network model. The generator of the generative adversarial network model creates a simulated activated magnesium oxide production environment, including different parameter combinations such as temperature, humidity, and screen aperture. The discriminator determines whether the generated environment is realistic and continuously optimizes the generator's simulation capabilities by comparing it with real data.

[0092] Step S203: Generate a large amount of simulation data using a generative adversarial network model to expand the historical data set; conduct multiple simulation experiments in a virtual environment to explore the effects of different parameter combinations on the activity and particle size of activated magnesium oxide and find the optimal parameter combination;

[0093] A reinforcement learning model for adaptive reinforcement learning was established, defining the state space, including key parameters such as real-time temperature, humidity, particle size distribution, and screen aperture; the action space, including operations such as adjusting the drying temperature and changing the screen aperture; a reward function was designed to reward or penalize the agent based on the activity and particle size consistency of the activated magnesium oxide; the agent continuously learned new control strategies during the production process and dynamically adjusted the control strategies based on simulated data and real-time data generated by the generative adversarial network; offline training was conducted using historical data, while online learning was conducted during the production process to continuously optimize the agent's decision-making strategy; and the simulated data generated by the generative adversarial network was used to detect anomalies in the production process, such as temperature fluctuations and screen damage, and to issue timely warnings.

[0094] Among them, the expression of the reward function is:

[0095]

[0096] In the formula, R(s,a) represents the reward function, which represents the reward obtained by performing action a in state s, and α i represents the activity consistency weight, which indicates the contribution of the activity consistency of the i-th batch to the reward, β i represents the particle size consistency weight, which indicates the contribution of the particle size consistency of the i-th batch to the reward, γ i represents the anomaly detection weight, which indicates the contribution of the anomaly detection of the i-th batch to the reward, δ i represents the energy consumption optimization weight, which indicates the contribution of the energy consumption optimization of the i-th batch to the reward, ∈ i represents the production efficiency weight, which indicates the contribution of the i-th batch production efficiency to the reward, ζ i Represents the equipment life weight, indicating the contribution of the equipment life of the i-th batch to the reward, η i Represents the environmental impact weight, which indicates the contribution of the environmental impact of the i-th batch to the reward, θ i represents the quality control weight, which indicates the contribution of the quality control of the i-th batch to the reward;

[0097] Specific calculation method:

[0098]

[0099] Among them, the activity standard deviation is the standard deviation of the activity of the i-th batch of active magnesium oxide, and the maximum activity standard deviation is the preset maximum allowable standard deviation;

[0100]

[0101] Among them, the particle size standard deviation is the standard deviation of the particle size of the i-th batch of activated magnesium oxide, and the maximum particle size standard deviation is the preset maximum allowable standard deviation;

[0102]

[0103] Energy consumption optimization = current energy consumption / target energy consumption

[0104] Production efficiency = current production volume / target production volume;

[0105] Equipment life = current equipment life / target equipment life;

[0106] Environmental impact = current environmental impact / target environmental impact;

[0107] Quality control = current quality control index / target quality control index;

[0108] The advantages of the reward function comprehensively consider the activity consistency, particle size consistency, anomaly detection, energy consumption optimization, production efficiency, equipment life, environmental impact and quality control of activated magnesium oxide to ensure the comprehensive optimization of the production process; by adjusting the weights, the focus of the reward function can be flexibly adjusted according to actual production needs; the anomaly detection mechanism ensures the safety and stability of the production process, and timely warns of abnormal situations to avoid production accidents; energy consumption optimization, equipment life and environmental impact considerations ensure the sustainability and long-term benefits of the production process; the introduction of quality control indicators ensures product quality in the production process and improves customer satisfaction; through this complex reward function design, the intelligent agent can continuously optimize the control strategy during the production process and improve the production quality and efficiency of activated magnesium oxide.

[0109] In the above embodiment, step S201 involves multi-dimensional intelligent sensor deployment and data acquisition. By deploying multi-dimensional intelligent sensors such as temperature sensors, humidity sensors, and particle size sensors, comprehensive monitoring of the activated magnesium oxide production environment is achieved. Leveraging Internet of Things technology, the drying equipment, screening equipment, temperature controller, and screen inspection equipment are interconnected to ensure that sensor-collected data can be transmitted to the controller in real time, enabling immediate data processing and analysis. Significance: Comprehensive data acquisition and real-time transmission ensure data accuracy and timeliness, providing a solid foundation for intelligent control and optimization. Real-time monitoring and data recording enhance transparency in the production process, helping to promptly identify and resolve problems and improve production efficiency. Step S202 involves intelligent control and optimization strategies. Intelligent control is used to predict the changing trends of activated magnesium oxide at different temperatures and screen apertures, optimizing the control strategy to ensure stability and efficiency of the production process. Based on the predicted results, the drying temperature and screen aperture are automatically adjusted, reducing human intervention and improving production consistency and controllability. Significance: Through intelligent control and automatic parameter adjustment, manual operation time and costs are reduced, production efficiency is improved, and precise control of production parameters ensures the stable quality of activated magnesium oxide, meeting high-standard production requirements. Step S203 uses a generative adversarial network model and adaptive reinforcement learning. This model generates a large amount of simulated data, expanding the historical dataset and providing rich data support for virtual experiments. Multiple simulation experiments are conducted in a virtual environment to explore the effects of different parameter combinations on the activity and particle size of activated magnesium oxide and identify the optimal parameter combination. A reinforcement learning model for adaptive reinforcement learning is established. By defining the state space and action space and designing a reward function, the agent continuously learns new control strategies and dynamically adjusts them during the production process. Significance: Through generative adversarial networks and adaptive reinforcement learning, the agent can dynamically adjust control strategies based on simulated and real-time data, improving the intelligence and flexibility of decision-making. The simulated data generated by the generative adversarial network is used to detect abnormalities in the production process, such as temperature fluctuations and screen damage, and to issue timely warnings, enhancing the robustness and safety of the system.

[0110] In summary, the production process of activated magnesium oxide in this embodiment has achieved intelligence, automation and efficiency, which not only improves production efficiency and product quality, but also enhances the safety and controllability of the production process. The production of activated magnesium oxide is made more scientific, accurate and sustainable, in line with the high standards of modern industrial production. For the first time, generative adversarial networks (GANs) are applied to the simulation and data enhancement of the activated magnesium oxide production process to improve the diversity and training effect of the data set; combined with the adaptive reinforcement learning mechanism, the dynamic adjustment and optimization of the intelligent agent in the production process are realized, and the flexibility and accuracy of the control strategy are improved; through GAN anomaly detection and reinforcement learning anomaly handling, intelligent early warning and real-time decision support are realized, and the stability and safety of the production process are improved. Through this innovative solution, intelligent and adaptive control of the activated magnesium oxide production process can be achieved, product quality and production efficiency can be improved, while reducing human intervention and reducing production costs. Not only is the latest AI technology combined, but also a higher level of intelligent and adaptive control is achieved through the combination of GAN and adaptive reinforcement learning.

[0111] Example 4:

[0112] Based on Example 2, the control process of high-speed stirring for mixing provided in the embodiment of the present invention includes the following steps:

[0113] S301: During the initial mixing stage, the stirring speed does not exceed 50 rpm; the initial mixing time is set to 5 minutes; after the initial mixing, the stirring speed is maintained below 50 rpm; the time for the uniform distribution stage is set to 3 minutes;

[0114] Step S302: After the low-speed stirring stage is completed, switch to the high-speed stirring stage, and the stirring speed should be no less than 300 rpm; the time of the intensive mixing stage is set to 5 minutes; after the intensive mixing, the stirring speed is maintained at 300 rpm; the time of the final mixing stage is set to 5-10 minutes;

[0115] Step S303: During the mixing process, sampling and testing are performed every 2 minutes, and the sampling points should be evenly distributed at different positions of the mixing container; the uniformity of the mixture is tested by microscopic observation or chemical analysis methods; the stirring speed is adjusted according to the sampling and testing results; if the test results show uneven mixing, the stirring speed is increased or the stirring time is extended; if the test results show excessive mixing, the stirring speed is reduced or the stirring time is shortened; and the stirring time is adjusted according to the sampling and testing results.

[0116] In the above embodiment, in step S301, the initial mixing stage, low-speed stirring helps prevent particles in the mixture from breaking or generating excessive bubbles due to high-speed stirring, thereby maintaining the integrity of the particles and the stability of the mixture. The initial mixing time is set to 5 minutes, which is sufficient for the mixture to be initially mixed without causing excessive mixing or particle breakage. The uniform distribution stage is set to 3 minutes. After the initial mixing, low-speed stirring is continued to ensure that the mixture is evenly distributed in the container and avoid local concentration differences. The significance of the achievement is: to ensure the initial uniformity of the mixture. Through low-speed stirring and an appropriate initial mixing time, the mixture is guaranteed to achieve basic uniformity in the initial stage, laying a good foundation for subsequent high-speed stirring. In step S302, the high-speed stirring stage is carried out, with high-speed stirring (not less than 300 rpm). High-speed stirring can significantly improve the mixing efficiency, allowing the particles in the mixture to be dispersed and mixed more quickly. The intensive mixing stage is set to 5 minutes, which is sufficient for the mixture to reach a more uniform state under high-speed stirring, thereby enhancing the mixing effect. The final mixing stage is set to 5-10 minutes. Mixing is continued under high-speed stirring to ensure that the mixture reaches a final uniform state. The time range setting can be adjusted according to actual conditions. Significance achieved: High-speed stirring significantly improves mixing efficiency, allowing the mixture to achieve high uniformity in a shorter period of time; ensuring the uniformity of the final mixture. By setting a reasonable final mixing time, the mixture is guaranteed to reach a final uniform state under high-speed stirring, meeting production requirements. Step S303: Sampling, testing, and adjustment: Sampling and testing are performed every 2 minutes. Regular sampling and testing can monitor the uniformity of the mixture in real time and promptly identify problems in the mixing process; sampling points are evenly distributed to ensure a uniform distribution of sampling points and avoid inaccurate test results due to sampling point deviations; testing the uniformity of the mixture through microscopic observation or chemical analysis methods can accurately assess the uniformity of the mixture and provide a basis for adjustment; adjusting the stirring speed and time based on the test results. Based on the test results, the stirring speed and time are dynamically adjusted to ensure the mixture reaches the optimal uniformity. Significance achieved: Regular sampling and dynamic adjustment ensure that the mixing process is always in the optimal state, avoiding problems such as over-mixing or under-mixing; through real-time monitoring and adjustment, the uniformity of the final mixture is significantly improved, meeting high-standard production requirements. During the high-speed stirring process, sampling and testing are performed every 2 minutes. Suppose that during a sample taken at the fourth minute, microscopic observation reveals uneven distribution of powder particles in certain areas. At this point, the test results indicate uneven mixing, so the decision is made to increase the stirring speed to 380 rpm and extend the stirring time to 10 minutes to ensure uniform mixing. At the sixth minute, a sample is taken: chemical analysis reveals that the chemical composition of the mixture is still uneven in certain areas.At this point, the stirring speed was increased to 400 rpm, and the final mixing phase was extended to 12 minutes. Samples were taken at the 8th minute: microscopic observation and chemical analysis showed that the mixing uniformity had significantly improved, but slight unevenness still existed. At this point, the stirring speed was maintained at 400 rpm, and the final mixing phase was extended to 15 minutes. Samples were taken at the 10th minute: final testing showed that the mixture had met the expected uniformity, and the stirring process was terminated.

[0117] In summary, this embodiment ensures that the mixture can reach the best uniform state at different stages through reasonable speed and time settings, as well as real-time monitoring and adjustment. Not only is the mixing efficiency improved, but the quality of the final product is also guaranteed, which has important technical significance and economic value. This embodiment can ensure the uniformity of the agent during the mixing process through a hierarchical stirring speed and time control process, thereby improving the effect of phosphorus removal and fluorine removal. The specific control process includes four stages: initial mixing, uniform distribution, intensive mixing and final mixing. Each stage has a clear stirring speed and time setting, and the mixing uniformity is guaranteed by sampling detection and adjustment control.

[0118] Example 5:

[0119] like Figure 3 As shown, based on Example 1, the test process of the dephosphorization and defluorination agent provided in the embodiment of the present invention includes:

[0120] 1. Component Description:

[0121] 1. Calcium oxide: The pollutants in phosphogypsum leachate are mainly soluble phosphorus and fluorine, among which soluble phosphorus is mainly in the form of H2PO4 - 、HPO4 2- PO4 3- Soluble fluoride exists in the form of fluoride ions. When calcium ions are added, soluble phosphorus combines with calcium ions to form calcium phosphate precipitation, thereby reducing the concentration of soluble phosphorus in the system. - With the addition of calcium oxide, it can be 2+ A reaction occurs, producing CaF2 precipitate, as shown in the following reaction equation. Furthermore, phosphogypsum often contains residual sulfuric acid and other acidic substances from the phosphoric acid production process. Because phosphogypsum leachate is significantly acidic, with a pH typically ranging from 2-5, the addition of calcium oxide can effectively adjust the leachate pH, facilitating the precipitation and removal of phosphorus and fluoride.

[0122] Ca 2+ +2H2PO4 - →Ca(H2PO4)2

[0123] Ca 2+ +HPO4 2- →CaHPO4

[0124] 3Ca 2+ +2PO4 3- →Ca3(PO4)2

[0125] H + +F - →HF

[0126] Ca 2+ +2F - →CaF2

[0127] The removal of soluble phosphorus and soluble fluoride from phosphogypsum leachate is closely related to the amount of calcium oxide added. A higher calcium oxide addition increases the calcium ion concentration, which in turn increases the binding rate of soluble phosphorus and soluble fluoride with calcium in the leachate, leading to higher removal rates. However, excessive calcium oxide addition can lead to an excessively high leachate pH, which not only increases economic costs but also, when used in the field, can impact the surrounding surface and groundwater environments. To determine the optimal calcium oxide addition amount, a leachate was prepared from phosphogypsum stored for more than three years. The fluoride ion concentration was 57.23 mg / L, the total phosphorus concentration was 6.544 mg / L, and the pH was 4.68. Because the reaction between phosphorus and fluoride and calcium ions is closely related to pH, under acidic conditions, hydrogen ions in the system compete with fluoride ions, forming hydrofluoric acid, which impairs fluoride precipitation. Therefore, in this experiment, the leachate pH was adjusted to 9 with NaOH before dosing. Then, the leachate was added at a concentration of 0.2% to 4% by weight of phosphogypsum. The results are shown in Table 1. The addition of calcium oxide has a good effect on the removal of total phosphorus (see Appendix Figure 2 and attached Figure 3 ), the total phosphorus concentration can be stably maintained below 0.1 mg / L, and the removal rate is stably above 98%. With increasing calcium oxide addition, the total phosphorus removal effect no longer significantly increases. Regarding fluoride ions, calcium oxide's fluoride removal effect is weaker than its phosphorus removal effect. Although the fluoride ion removal rate significantly increases with increasing calcium oxide addition, when the addition amount reaches 4%, the fluoride ion concentration is 10.09 mg / L, and the removal rate is only 82.37%. This indicates that the addition of calcium oxide can fully achieve the required removal of soluble phosphorus, but cannot completely achieve the removal of fluoride ions.

[0128] Table 1 Phosphorus and fluorine removal effect of phosphogypsum leachate at different calcium oxide addition amounts

[0129]

[0130]

[0131] 2. Calcium Chloride: While the addition of calcium oxide facilitates the removal of phosphate and fluoride ions, excessive addition can lead to excessively high system pH. Therefore, utilizing the common ion effect, calcium chloride is used as a calcium supplement in the mixed reagent to promote the precipitation reaction of soluble phosphorus and soluble fluoride with calcium ions. To determine the effectiveness of calcium chloride in removing phosphorus and fluoride, the test also used a phosphogypsum slag leachate with a fluoride ion concentration of 57.23 mg / L, a total phosphorus concentration of 6.544 mg / L, and a pH of 4.68. Prior to dosing, the leachate pH was adjusted to 9 with NaOH. Then, dosing was performed at a phosphogypsum mass ratio of 0.4% to 8%. The results are shown in Table 2. As can be seen from the chart, when calcium chloride is added alone, the total phosphorus concentration can be stably reduced to below 0.08 mg / L, and the removal rate can be stably increased to more than 98%. This shows that the addition of calcium chloride can achieve the desired phosphorus removal effect. However, the fluoride ion removal effect is not as good as that of calcium oxide. When the addition amount reaches 8%, the removal rate is only 70.23%, and the concentration is 17.04 mg / L (see attached). Figure 4 and attached Figure 5 ).

[0132] Table 2 Phosphorus and fluorine removal effect of phosphogypsum leachate under different calcium chloride addition amounts

[0133]

[0134] 3. Activated magnesium oxide: Activated magnesium oxide is a high-performance metal-based adsorbent with a high specific surface area, large adsorption capacity, non-toxic and harmless, green and safe. It has a strong chemical adsorption effect on fluoride ions in fluoride-containing wastewater to form insoluble magnesium fluoride. Although calcium oxide and calcium chloride can effectively remove soluble phosphorus in leachate, the fluoride removal effect is not good. In order to solve the problem of fluoride removal by chemicals, the test used activated alumina, activated magnesium oxide, hydroxyapatite, magnesium oxide, and alumina to compare the fluoride removal effects. The fluoride ion concentration of the leachate was 24.71 mg / L, the amount of chemical added was 0.3 g / 100 ml, and the pH of the leachate was not adjusted. The results are shown in the following chart. It can be seen from the chart that activated magnesium oxide has the best fluoride removal effect among several chemicals. The fluoride removal rates of the two activated magnesium oxides are both above 95%, and the fluoride ion concentration is no more than 1 mg / L (see attached Figure 6 ).

[0135] Table 3 Comparison of fluoride removal effects of different agents

[0136]

[0137]

[0138] In order to further study the adsorption mechanism of active magnesium oxide, isothermal adsorption tests and adsorption kinetics studies were carried out on active magnesium oxide. After testing, the P of the 1:20 leachate of fresh phosphogypsum produced by the factory was 105 mg / L, the fluorine was 55 mg / L, the pH was 3.01, the sulfate was 1520 mg / L, and the chloride ion was not detected. Sodium fluoride, potassium dihydrogen phosphate, and anhydrous sodium sulfate were used to prepare a solution to simulate fresh phosphogypsum leachate to carry out isothermal adsorption experiments. The amount of active magnesium oxide added was 0.5 g / 100 mL, stirred for 30 minutes, and filtered and monitored after standing for 20 hours. The experimental data were fitted with Langmuir and Freundlich equations, respectively. The results are as follows:

[0139] Table 4 Activated magnesium oxide isothermal adsorption fitting results (total phosphorus)

[0140]

[0141] Table 5 Isothermal adsorption fitting results of activated magnesium oxide (fluoride ion)

[0142]

[0143] Analysis of the fitting results shows that the Freundlich adsorption isotherm model fitting correlation coefficient R2 for activated magnesium oxide for phosphorus and fluorine is greater than the Langmuir adsorption isotherm model fitting correlation coefficient, indicating that the adsorption of phosphorus and fluorine by activated magnesium oxide is more inclined to heterogeneous surface and multilayer adsorption. In the Freundlich adsorption isotherm model, the value of 1 / n indicates the degree of adsorption favorability: 0 < 1 / n < 1 is favorable for adsorption, 1 / n = 1 is irreversible adsorption, and 1 / n > 1 is unfavorable for adsorption. As can be seen from the table, the 1 / n values ​​of activated magnesium oxide for phosphorus and fluorine are 0.57 and 0.65, respectively. In the range of greater than 0 and less than 1, it shows that activated magnesium oxide has good adsorption strength for both phosphorus and fluorine.

[0144] Sodium fluoride, potassium dihydrogen phosphate, and anhydrous sodium sulfate were used to prepare a solution with a fluoride ion concentration of 100 mg / L, a total phosphorus concentration of 100 mg / L, and a sulfate ion concentration of 1500 mg / L. The amount of active magnesium oxide added was 0.5 g / 100 ml. The solution was stirred for 30 minutes, allowed to stand for different periods of time, and then filtered. The total phosphorus and fluoride ion concentrations were monitored, and the adsorption kinetics equation was simulated. The results are as follows: Figure 7 and Figure 8 shown.

[0145] In the initial stage of adsorption, the adsorption rate is fast, and then the adsorption rate gradually decreases until the adsorption reaches equilibrium. Comparing the two figures, it can be seen that the linear relationship of the second-order kinetic model has a higher correlation coefficient than the first-order kinetic model. The R2 fitting of fluoride ion and total phosphorus is greater than 0.99, indicating that the adsorption of fluorine and phosphorus by activated magnesium oxide is more suitable for the second-order kinetic model.

[0146] 2. Research on drug ratio

[0147] (1) Mixed calcium agent for phosphorus and fluoride removal

[0148] The solubility of CaF2 in solution, expressed as F ions, is 7.9 mg / L, which can be understood as the minimum theoretical value for calcium-based fluoride removal. Removing F and P requires the provision of as much free calcium ions as possible. Therefore, calcium oxide, which is relatively inexpensive and can increase the system pH but has relatively low solubility, and calcium chloride, which has good solubility and can enhance the common ion effect of calcium, were used as the basis for this agent.

[0149] During the study, the total amount of calcium oxide required to completely react with the calcium in calcium oxide (assuming the calcium in calcium oxide is completely dissolved) and the soluble phosphorus and phosphorus in the phosphogypsum leachate was 1. The total amount of calcium chloride required to completely react with the calcium in calcium chloride and the soluble phosphorus and phosphorus in the phosphogypsum leachate was 1.

[0150] The simulated phosphogypsum leachate was treated with a mixture of calcium oxide and calcium chloride in different ratios. Figure 9 Experimental results show that either too high or too low a ratio of calcium oxide to calcium chloride is detrimental to the simultaneous removal of phosphorus and fluoride. Excessive calcium chloride levels can easily lead to excessive chloride ion levels in groundwater, while excessive calcium oxide levels can also lead to excessively high pH. Therefore, a mixed calcium oxide:calcium chloride ratio of 1:2 by mass is used.

[0151] (2) Removal of phosphorus and fluorine by activated magnesium oxide

[0152] Active magnesium oxide was used alone to adsorb new phosphogypsum slag and old slag stored in the slag storage. The solid-liquid ratio of the leachate was 1:20. The adsorption results are shown in Table 6:

[0153] Table 6 Adsorption results

[0154]

[0155] Adsorption tests were conducted using activated magnesium oxide on the old slag from the Da'ao slag yard and the new slag from Kailin Company. The results showed that the removal rate of phosphorus by activated magnesium oxide reached over 99%, and the removal rate of fluorine increased with the increase of the added amount.

[0156] (3) Study the reaction time of calcium and active magnesium oxide.

[0157] By studying the different reaction times of calcium and magnesium, the feasibility of combining a mixed calcium agent with activated magnesium oxide was explored. This approach allows the mixed calcium agent to remove high-concentration phosphorus and fluorine, and then activated magnesium oxide to adsorb low-concentration phosphorus and fluorine, achieving overall efficient removal. Figure 10Using fresh slag leachate and a 1:2 ratio of calcium oxide to calcium chloride, the researchers studied the effects of the mixed agent on phosphorus and fluorine removal in a simulated mixed solution at different reaction times. The first 30 minutes involved magnetic stirring, followed by a period of stagnant standing. The experiments verified the influence of reaction time on the removal of phosphorus and fluorine. The chemically reactive calcium oxide + calcium chloride agent removed most phosphorus within one minute (over 99% removal rate), while fluorine removal was primarily achieved within the first 10 minutes. Activated magnesium oxide, on the other hand, primarily removed phosphorus through adsorption within the first five minutes, while fluorine removal significantly improved after 30 minutes.

[0158] Figure 11 It can be seen from the removal rate that the adsorption and removal of phosphorus by activated magnesium oxide is mainly in the first 5 minutes, and the adsorption and removal of fluorine is significantly improved from 30 minutes.

[0159] Therefore, by utilizing the different removal efficiencies of calcium and activated magnesium oxide for phosphorus and fluoride removal, it is possible to quickly remove high-concentration phosphorus and fluoride using calcium, and then use activated magnesium oxide to adsorb low-concentration phosphorus and low-concentration fluoride, thereby achieving the goal of overall efficient removal while saving the amount of activated magnesium oxide.

[0160] (4) Research on different proportions of mixed agents

[0161] The active magnesium oxide multiple is determined based on the fluorine concentration of the phosphogypsum leachate. The corresponding concentration range is found on the adsorption isotherm of the simulated mixed solution, and the amount of magnesium oxide required for complete adsorption of F ions is determined as 1 according to its saturated adsorption capacity.

[0162] To explore the optimal ratio of several reagents, we conducted a ratio test. We weighed 10g of fresh phosphogypsum slag, added it to 200ml of water, and stirred it rapidly with a magnetic stirrer for 30 minutes. The mixture was then filtered through filter paper to obtain a phosphogypsum leachate. The supernatant was measured to reveal a fluoride ion concentration of 105mg / L, a total phosphorus concentration of 55.3mg / L, a sulfate ion concentration of 1520mg / L, and a pH of 3.01. Calcium oxide, calcium chloride, and activated magnesium oxide powder were weighed and mixed in varying proportions. The mixture was then added to the phosphogypsum leachate, stirred rapidly with a magnetic stirrer for 30 minutes, and allowed to rest for 24 hours. The supernatant was then measured for fluoride and total phosphorus concentrations. The results are shown in Table 7.

[0163] Table 7 Phosphorus and fluorine removal effects under different reagent ratios

[0164]

[0165] Depend on Figure 12 and Figure 13It can be seen that under different reagent ratios, the total phosphorus removal rate can stably reach more than 99%. In terms of fluoride removal, when the reagent mass ratio is 1:2:27, the fluoride removal effect is the best, the fluoride ion concentration is only 1.62 mg / L, and the removal rate is 96.77%. When the reagent mass ratio is 1:2:18, the fluoride ion concentration is higher than the former, at 2.64 mg / L, and the removal rate is 94.74%.

[0166] Different proportions of slag were added to the new phosphogypsum slag leachate to test pH, chloride ion, and sulfate ion content. The pH of the new slag leachate was 3.08, the chloride ion content was undetectable, and the sulfate ion content was 1520 mg / L. The results after adding different proportions of the reagent are shown in Table 8. The sulfate ion content relative to the original slag decreased in each group, and the pH value was higher than 9.0. The chloride ion content slightly exceeded the standard in the reagent ratio of 1:2:18 by mass, while the chloride ion content in the ratio of 1:2:9 by mass was below the groundwater requirement of 250 mg / L. However, this reagent can reduce the amount of activated magnesium oxide used, lowering the trial cost. Therefore, this reagent was used in a ratio of CaO, CaCl2, and activated magnesium oxide of 1:1.1:0.5.

[0167] Table 8

[0168]

[0169] (5) Verification of the applicability of reagents and proportions to phosphogypsum slag

[0170] We selected phosphogypsum slag from the Da'ao slag field and measured a fluoride content of 32.3 mg / L and a total phosphorus concentration of 3.81 mg / L. We treated the phosphogypsum slag using a ratio of calcium oxide to calcium chloride of 1:2 and adding different amounts of activated magnesium oxide. The results are as follows, as shown in Table 9:

[0171] Table 9

[0172]

[0173] The effects of varying additions of calcium oxide, calcium chloride, and activated magnesium oxide on new slag from Kailin Company and old slag from the Da'ao slag field were studied. Data showed that all mixed reagents had good P removal rates, with lower additions of calcium oxide actually having a better effect on F removal. This is likely due to the increased pH of the solution caused by the excess calcium oxide, which is detrimental to fluoride removal. It is recommended to add at least 0.6g of activated magnesium oxide per 10g of phosphogypsum. Based on the results of chloride ion dissolution in calcium chloride, to avoid excessive chloride ion levels, a reagent mass ratio of calcium oxide: calcium chloride: activated magnesium oxide = 2:1:7-12 is recommended, with an active magnesium oxide addition of no less than 0.5g / 10g of phosphogypsum slag.

[0174] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A dephosphorization and defluorination agent, characterized in that: Used for the treatment of phosphogypsum leachate containing phosphogypsum slag, the agent is composed of calcium chloride, calcium oxide and activated magnesium oxide; the mass ratio of calcium oxide, calcium chloride and activated magnesium oxide is 1:2:7-12; The amount of active magnesium oxide added is not less than 0.5g / 10g of phosphogypsum slag.

2. The dephosphorization and defluorination agent according to claim 1, wherein: Add more than 0.6g of active magnesium oxide for every 10g of phosphogypsum slag.

3. A method for preparing a dephosphorization and defluorination agent, for producing the dephosphorization and defluorination agent according to any one of claims 1 to 2, characterized in that: Include: Prepare calcium chloride, calcium oxide, and activated magnesium oxide according to purity and particle size; Calcium chloride, calcium oxide, and activated magnesium oxide are mixed according to a mass ratio; calcium chloride and calcium oxide are weighed in proportion and placed in a dry mixer respectively; low-speed stirring is used for pre-mixing to ensure that the two powders are evenly distributed; the activated magnesium oxide is placed in a dryer for drying; the dried activated magnesium oxide is screened through a sieve to remove lumps and impurities; Add active magnesium oxide to the premixed calcium chloride and calcium oxide in a molar ratio; mix them by high-speed stirring; The mixed powder is refined by a fine grinder, and the refined powder is screened for a second time by a sieve; the refined powder is sealed and packaged; The process of placing activated magnesium oxide in a desiccator includes the following steps: Deploy multi-dimensional intelligent sensors in drying and screening equipment, including temperature sensors, humidity sensors, and particle size sensors, to achieve comprehensive data collection. Connect the drying equipment, screening equipment, temperature controllers, and screen inspection equipment through the Internet of Things, and transmit the data collected by the sensors to the controller in real time. Among them, the particle size distribution equation is used to describe the distribution of active magnesium oxide particle size, and its form is: Where f(r,t) represents the particle size distribution function, which indicates the number or concentration of active magnesium oxide particles with a particle size of r at time t; D p It represents the particle size diffusion coefficient, which indicates the diffusion ability of particle size distribution in space. The diffusion term represents the particle size distribution, which describes the diffusion process of the particle size distribution in space; represents the nonlinear effect term; v represents the particle size change rate, which represents the rate of change of the active magnesium oxide particle size with time; vf(r,t) represents the convection term of the particle size distribution, which describes the movement process of the particle size distribution with the particle size change rate v; Represents the diffusion process of particle size distribution in space; Intelligent control is used to predict the changing trend of activated magnesium oxide at different temperatures and screen apertures, and to optimize the control strategy; based on the prediction results, the drying temperature and screen aperture are automatically adjusted; The intelligent control system includes a generative adversarial network model. The generator of the generative adversarial network model creates a simulated activated magnesium oxide production environment, including different combinations of temperature, humidity, and screen aperture parameters. The discriminator determines whether the generated environment is realistic and continuously optimizes the generator's simulation capabilities by comparing it with real data. A large amount of simulated data was generated using a generative adversarial network model to expand the historical data set; multiple simulation experiments were conducted in a virtual environment to explore the effects of different parameter combinations on the activity and particle size of activated magnesium oxide and find the optimal parameter combination.

4. The method for preparing the dephosphorization and defluorination agent according to claim 3, wherein: The speed of low-speed stirring is ≤50rpm; the drying temperature is 95℃-100℃, and the time is not less than 2 hours; the mesh size of the sieve after drying is ≤0.05mm; The speed of high-speed stirring is ≥300rpm, and the stirring time is 10-15 minutes.

5. The method for preparing the dephosphorization and defluorination agent according to claim 3, wherein: Establish a reinforcement learning model for adaptive reinforcement learning, define the state space, including key parameters such as real-time temperature, humidity, particle size distribution, and screen aperture; define the action space, including operations such as adjusting the drying temperature and changing the screen aperture; A reward function was designed to reward or penalize the agent based on the activity and particle size consistency of the activated magnesium oxide. The agent continuously learned new control strategies during the production process and dynamically adjusted them based on simulated and real-time data generated by the generative adversarial network. Offline training was conducted using historical data, while online learning was conducted during the production process to continuously optimize the agent's decision-making strategy. Using simulated data generated by generative adversarial networks, we can detect abnormalities in the production process, including temperature fluctuations and screen damage, and issue timely warnings. Among them, the expression of the reward function is: In the formula, R(s,a) represents the reward function, which represents the reward obtained by performing action a in state s, and α i represents the activity consistency weight, which indicates the contribution of the activity consistency of the i-th batch to the reward, β i represents the particle size consistency weight, which indicates the contribution of the particle size consistency of the i-th batch to the reward, γ i represents the anomaly detection weight, which indicates the contribution of the anomaly detection of the i-th batch to the reward, δ i Represents the energy consumption optimization weight, which represents the contribution of the energy consumption optimization of the i-th batch to the reward, ∈ i represents the production efficiency weight, which indicates the contribution of the i-th batch production efficiency to the reward, ζ i Represents the equipment life weight, indicating the contribution of the equipment life of the i-th batch to the reward, η i Represents the environmental impact weight, which indicates the contribution of the environmental impact of the i-th batch to the reward, θ i Represents the quality control weight, which indicates the contribution of the quality control of the i-th batch to the reward.

6. The method for preparing the dephosphorization and defluorination agent according to claim 5, wherein: Specific calculation method: Among them, the activity standard deviation is the standard deviation of the activity of the i-th batch of active magnesium oxide, and the maximum activity standard deviation is the preset maximum allowable standard deviation; Among them, the particle size standard deviation is the standard deviation of the particle size of the i-th batch of activated magnesium oxide, and the maximum particle size standard deviation is the preset maximum allowable standard deviation; Energy consumption optimization = current energy consumption / target energy consumption; Production efficiency = current production volume / target production volume; Equipment life = current equipment life / target equipment life; Environmental impact = current environmental impact / target environmental impact; Quality control = current quality control index / target quality control index.

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