Chloride ion-free defluorination agent and preparation process thereof

Abstract

The invention discloses a chlorine ion-free defluorination agent and a preparation process, and particularly relates to the field of defluorination agents.The preparation process comprises the steps that when a dispersion medium system and a skeleton structure enhancing component are mixed, fluid pressure is detected in real time through a fluid pressure-sensitive element, and when a detection value is inconsistent with a first preset threshold value, the defluorination agent is defluorination agent; adjusting the stirring speed until the detection value is adjusted to a preset threshold value I, so as to obtain a mixture I; when the magnetic core-shell structure carrier component is added into the first mixture, the instantaneous pressure is continuously monitored, if the detection value is not consistent with a second preset threshold value, the raw material adding rate is adjusted until the detection value is adjusted to the second preset threshold value, and a second mixture is obtained on the basis of the adjustment. A fluid pressure-sensitive element is introduced in each stage, and dynamic comparison and control response of a pressure threshold are combined, so that the forming condition of each step is operated in an optimal pressure window, and particularly, structural distortion and collapse are effectively inhibited in the pore channel construction and drying forming stages.

Description

Technical Field

[0001] The present invention relates to the technical field of defluorination agents, and more specifically, to a defluorination agent without chloride ions and a preparation process thereof. Background Art

[0002] In the current water treatment field, defluorination technologies mainly rely on adsorbents based on metal oxides or porous materials. Most of these adsorbents rely on a single adsorption mechanism, have insufficient structural design, and low regeneration efficiency. Especially in engineering applications, problems such as particle structure damage, adsorption attenuation, and interfacial shedding are likely to occur. The existing technologies lack a dynamic response mechanism, resulting in unstable performance of existing defluorination materials in complex water environments and short cycle life, which is not conducive to meeting the defluorination requirements under high-load and complex working conditions. Under this background, although some studies have attempted to improve the reusability through composite structures or particle size control, there are still deficiencies such as insufficient control of the pore structure forming process, serious degradation of the interfacial structure, and structural collapse during the drying process. Moreover, there is a lack of real-time regulation means during the processing. In particular, the formation of the pore structure often depends on empirically set parameters and cannot respond to the actual flow state, resulting in poor batch stability of the products and difficulty in popularizing and applying them in actual projects. Summary of the Invention

[0003] In order to overcome the above-mentioned defects of the prior art, an embodiment of the present invention provides a defluorination agent without chloride ions and a preparation process thereof. By constructing a whole-process pressure-sensitive feedback control mechanism and combining preset pressure thresholds at each stage, key parameters such as mixing, forming, pore formation, and drying are dynamically adjusted to solve the problems proposed in the above background art.

[0004] To achieve the above object, the present invention provides the following technical solution: A defluorination agent without chloride ions, comprising: The total mass of the agent is 100 parts by mass and is composed of the following components: Magnetic core-shell structure carrier component: 5 - 30 parts, and the magnetic core-shell structure carrier component includes magnetic particles with Fe3O4 as the core and SiO2 or activated carbon as the shell; Skeleton structure strengthening component: 20 - 40 parts, and the skeleton structure strengthening component is composed of silica and / or porous activated carbon, and the skeleton structure strengthening component is used to provide an adsorption and support skeleton; Defluorination active component: 5 - 15 parts, and the defluorination active component includes one or more of alumina, iron oxide, zirconia, and / or the complex state of trivalent metal ions; Functional structure regulation component: 3 - 10 parts, and the functional structure regulation component includes polymer grafts and / or dispersion stabilizers, which are used to improve the adhesion, dispersibility, and formability between particles; Pore structure construction component: 3 - 8 parts, the pore structure construction component includes a pore former and / or a bubble inducer, which is used to form multi-level pores during the curing or heat treatment stage; Interface stability enhancement component: 2 - 6 parts, the interface stability enhancement component includes a silane coupling agent, an organic small molecule modifier, or other surface modifiers that can form a firm bond at the core-shell interface and the framework surface; Dispersion medium system: the remaining number of parts, the dispersion medium system includes water and / or alcohols and / or a pH regulator.

[0005] A preparation process of a defluorination agent without chloride ions, comprising the following steps: When mixing the dispersion medium system and the framework structure enhancement component, use a fluid pressure sensitive element to detect the fluid pressure in real time. When the detected value is inconsistent with the first preset threshold, adjust the stirring speed until the detected value is adjusted to the first preset threshold, and based on this, obtain mixture one; When adding the magnetic core-shell structure carrier component to mixture one, continuously monitor the instantaneous pressure. If the detected value is inconsistent with the second preset threshold, adjust the raw material addition rate until the detected value is adjusted to the second preset threshold, and based on this, obtain mixture two; During the process of adding the defluorination active component to mixture two, detect the mixture pressure in real time. If the detected value is inconsistent with the third preset threshold, adjust the raw material supply rate until the detected value is adjusted to the third preset threshold, and based on this, obtain mixture three; When adding the functional structure regulation component to mixture three, make a determination according to the fluid pressure monitored in real time. If the detected value is inconsistent with the fourth preset threshold, adjust the mixing parameters until the detected value is adjusted to the fourth preset threshold, and based on this, obtain the functional complex; When adding the pore structure construction component during the curing or heat treatment stage of the functional complex, monitor the quasi-stable pressure. If the detected value is inconsistent with the fifth preset threshold, adjust the injection rate of the pore former and the bubble inducer and the treatment temperature until the detected value is adjusted to the fifth preset threshold, and based on this, obtain the functional multi-level pore complex; When adding the interface stability enhancement component during the drying stage of the functional multi-level pore complex, make a determination according to the fluid pressure monitored in real time. If the detected value is inconsistent with the sixth preset threshold, adjust the drying conditions according to the environmental model until the detected value is adjusted to the sixth preset threshold, and finally obtain the defluorination agent without chloride ions.

[0006] In a preferred embodiment, during the acquisition stage of mixture one, control the dispersion medium system and the framework structure enhancement component to form a stable initial slurry under shear peak conditions, and to represent the moment the stirring response coefficient at, dynamically adjust the stirring speed based on the stirring response coefficient; and set the first preset threshold as , through to refer to the pressure required for the target slurry state; Based on the ratio model composed of viscosity resistance, mixing efficiency, and pressure feedback, judge the deviation between the mixing resistance and the target state through real-time feedback, and form feedback control with the stirring speed as the adjustment means; It is expressed as: ; where is the mass of the skeleton structure reinforcing component; is the dynamic viscosity of the dispersion medium; is the volume of the mixing system; is the slurry mixing non-uniformity factor; is the system pressure monitored in real time by the fluid pressure-sensitive element; is the anti-oscillation perturbation term.

[0007] In a preferred embodiment, when obtaining the mixture II, magnetic core-shell structure particles composed of magnetic core-shell structure carrier components are distributed in the slurry to avoid agglomeration and structural deviation; through to represent the instantaneous addition rate of the magnetic core-shell structure carrier component at time Based on construct a response model for the diffusion of magnetic core-shell structure particles in the flow field, and adjust the feeding rate through the coupling of pressure deviation and perturbation term to avoid non-linear agglomeration behavior; based on this, construct : ; where represents the mass of the cumulative added components; is the initial recommended addition rate; is the current pressure value; is the preset threshold II; is the particle magnetic response ratio; is the slurry perturbation index.

[0008] In a preferred embodiment, for the mixture III formed by adding the defluorination active component, the inverse cube root control of the active site complexation efficiency and the pressure deviation is used to achieve non-linear response, so as to still stably form available sites under pressure fluctuations, and form the generation of chemical coordination or physical adsorption sites in contact with the slurry. Based on this, represents the feeding rate of the defluorination active component, refers to the preset threshold III; the feeding rate of the defluorination active component is expressed as: ; where represents the feeding rate of the defluorination active component; is the standard complexation rate constant; instantaneous complexation site formation efficiency function; is the deviation disturbance resistance factor, which is used to adjust the sensitivity of the acceleration rate to the pressure deviation.

[0009] In a preferred embodiment, in the functional complex formed by adding the functional structure regulation component, the pressure error is adjusted by the cohesive logarithmic response function to release the regulation component under the structural consistency, improve the integrity of the three-dimensional structure, and formulate Preset threshold four, the structural regulation ability index is used to guide the supply of the regulation component, and is expressed as: ; where is the cohesive density coefficient; is the structural integrity target value; is the particle flow field distortion function; When adding the pore structure construction component in the curing or heat treatment stage of the functional complex, in the stage of forming the pore structure component, the temperature, gas release rate and pressure error are used as the driving factors for forming the pore structure. Based on this, the pore formation ability is modeled, and the injection rhythm and heat treatment curve are feedback adjusted to form the functional multi-stage pore channel complex, and formulate represents the pore structure generation intensity; ; where is the pore expansion ability caused by the unit gas release; is the instantaneous gas release amount for pore formation; is the heat treatment temperature; is the pore nucleation coefficient; is the preset threshold five.

[0010] In a preferred embodiment, when adding the interface stability enhancement component in the drying stage of the functional multi-stage pore channel complex, the defluorination agent without chlorine ions is finally obtained; in this stage, a feedback mechanism between the water evaporation rate and the interface structure strength is established, and a regulation relationship is constructed by using the square term of the real-time concentration of the interface enhancement component and the pressure deviation, so as to dynamically control the interface formation rate and the drying environment parameters, and finally make the material form a stable core-shell combined interface and overall structural integrity; ; where is the drying stability enhancement effect; is the interface adhesion efficiency constant; is the surfactant concentration; is the system water evaporation rate; is the system disturbance response coefficient; is the preset threshold six.

[0011] In a preferred embodiment, an environmental model is constructed. The environmental model is based on the combination of hyperbolic tangent, Gaussian distribution, and logarithmic function to construct a non-linear response and a convergence path, and a target matching interval comparison structure and a deviation penalty mechanism are introduced into the environmental model; the environmental model is used in conjunction with the control equations of each stage to form a closed-loop control mechanism. The environmental model is constructed by to describe the system's drying environment fitness index, and is used to determine whether the current drying conditions are suitable for enhancing the component effect and interface formation;

[0012] where represents the drying curve activity factor within a time period; is the moisture evaporation dynamic matching term; is the time the instantaneous moisture evaporation rate of the material per unit mass within the system; is the evaporation rate reference value; is the evaporation rate adjustment coefficient; is the surfactant concentration coupling term; is the real-time concentration of the interface-stabilizing component; is the central value of the concentration interval; is the concentration deviation tolerance, and the concentration deviation tolerance is used to control the influence of the concentration deviation on the structural stability; A Gaussian function is used to construct the peak effect between the interface concentration and the structural stability; is the interface concentration regulation weight coefficient; is the pressure deviation suppression term; is the pressure deviation penalty coefficient; is used to perform logarithmic convergence processing on the pressure error.

[0013] The technical effects and advantages of the present invention: By introducing fluid pressure-sensitive elements at each stage and combining dynamic comparison of pressure thresholds with control responses, the forming conditions of each step are operated within the optimal pressure window, effectively suppressing structural distortion and collapse especially in the pore channel construction and drying forming stages; Particles with Fe3O4 as the core and SiO2 or carbon as the shell are used, and combined with polymer grafting and interface stabilizers to enhance the forming force between particles on the basis of realizing magnetic separation, ensuring that the structure is not easily detached during repeated regeneration; During the heat treatment or curing process, pore-forming agents and bubble-inducing agents are introduced, and their release rhythm is adjusted through real-time pressure detection to ensure the formation of multi-scale pore channels, effectively increasing the specific surface area and improving the fluoride ion migration efficiency; During the drying stage, a non-linear environmental model is used to coordinately regulate the temperature, humidity, and structural reaction process, preventing cracking or bonding failure at the interface due to unbalanced drying rates and enhancing the overall mechanical and chemical stability of the material. A mathematical control mechanism including perturbation response, ratio function, non-linear fitting, and regulation threshold is established to maintain structural uniformity and functional consistency under multi-factor intervention, providing an implementable path for industrial continuous preparation. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 It is a process flow chart of the preparation method of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0016] Referring to Tables 1-6 in the detailed description of the invention, a defluorination agent without chlorine ions of the present invention includes: The agent is calculated by mass fraction, and the total mass fraction is 100 parts, and is composed of the following components: Magnetic core-shell structure carrier component: 5-30 parts, and the magnetic core-shell structure carrier component includes magnetic particles with Fe3O4 as the core and SiO2 or activated carbon as the shell; Skeleton structure strengthening component: 20-40 parts, and the skeleton structure strengthening component includes silica and / or porous activated carbon, and the skeleton structure strengthening component is used to provide an adsorption and support skeleton; Defluorination active component: 5-15 parts, and the defluorination active component includes one or more of alumina, iron oxide, and zirconium oxide, and / or the complex state of the corresponding trivalent metal ions; Functional structure regulation component: 3-10 parts, and the functional structure regulation component includes polymer grafts and / or dispersion stabilizers, and is used to improve the adhesion, dispersibility, and formability between particles; Pore structure construction component: 3-8 parts, and the pore structure construction component includes pore-forming agents and / or bubble inducing agents, and is used to form hierarchical pore channels during the curing or heat treatment stage; Interface stability enhancement component: 2-6 parts, and the interface stability enhancement component includes silane coupling agents, organic small molecule modifiers, or other surface modifiers that can form a firm bond at the core-shell interface and the skeleton surface; Dispersion medium system: the remaining parts, and the dispersion medium system includes water and / or alcohols and / or pH regulators.

[0017] Example 1 included in a fluoride removal agent without chloride ions: Magnetic core-shell structure carrier component: 5 parts; Skeleton structure strengthening component: 20 parts; Fluoride removal active component: 5 parts; Functional structure regulation component: 3 parts; Pore structure construction component: 3 parts; Interface stability enhancement component: 2 parts; Dispersion medium system: 62 parts; Regarding Example 1, it should be noted that: In this example, by maintaining relatively low ratios in aspects such as the magnetic core-shell structure carrier component, the skeleton structure strengthening component, and the fluoride removal active component, and maximizing the dispersion medium, a magnetically recyclable fluoride removal material is initially constructed while ensuring high fluidity and easy formability; Example 2 included in a fluoride removal agent without chloride ions: Magnetic core-shell structure carrier component: 10 parts; Skeleton structure strengthening component: 25 parts; Fluoride removal active component: 6 parts; Functional structure regulation component: 4 parts; Pore structure construction component: 5 parts; Interface stability enhancement component: 2 parts; Dispersion medium system: 48 parts; Regarding Example 2, it should be noted that: In this example, a slightly increased magnetic core-shell structure carrier component and a medium proportion of skeleton structure strengthening component are adopted to balance the fluoride removal activity while taking into account the magnetic recovery efficiency and overall mechanical stability; Example 3 included in a fluoride removal agent without chloride ions: Magnetic core-shell structure carrier component: 15 parts; Skeleton structure strengthening component: 30 parts; Fluoride removal active component: 10 parts; Functional structure regulation component: 7 parts; Pore structure construction component: 3 parts; Interface stability enhancement component: 3 parts; Dispersion medium system: 32 parts; Regarding Example 3, it should be noted that: In this example, a moderate increase is made in the magnetic core-shell structure carrier component and the fluoride removal active component, and a relatively high proportion of functional structure regulation component and interface stability enhancement component are added to enhance the particle formability and regeneration and recycling performance; Example 4 included in a fluoride removal agent without chloride ions: Magnetic core-shell structure carrier component: 20 parts; Skeleton structure strengthening component: 25 parts; Fluoride removal active component: 8 parts; Functional structure regulation component: 5 parts; Pore structure construction component: 6 parts; Interface stability enhancement component: 2 parts; Dispersion medium system: 34 parts; Regarding Example 4, it should be noted that: In this example, the dosages of the magnetic core-shell structure carrier component and the pore structure construction component are increased, aiming to construct hierarchical pores while significantly enhancing the magnetic separation efficiency and the stability of the pore structure; Example 5 of a fluoride removal agent without chloride ions includes: Magnetic core-shell structure carrier component: 30 parts; Skeleton structure strengthening component: 20 parts; Fluoride removal active component: 5 parts; Functional structure regulation component: 3 parts; Pore structure construction component: 3 parts; Interface stability enhancement component: 2 parts; Dispersion medium system: 37 parts; Regarding Example 5, it should be noted that: In this example, the dosage of the magnetic core-shell structure carrier component reaches the highest upper limit, and the skeleton structure strengthening component and other components are reduced to the lowest values to fully embody the magnetic recovery characteristics and maintain the basic adsorption skeleton; Example 6 of a fluoride removal agent without chloride ions includes: Magnetic core-shell structure carrier component: 8 parts; Skeleton structure strengthening component: 40 parts; Fluoride removal active component: 15 parts; Functional structure regulation component: 10 parts; Pore structure construction component: 8 parts; Interface stability enhancement component: 6 parts; Dispersion medium system: 13 parts; Regarding Example 6, it should be noted that: In this example, the dosages of the skeleton structure strengthening component and the fluoride removal active component are increased as much as possible, and the functional structure regulation component and the interface stability enhancement component are correspondingly increased to enhance the adsorption capacity and the overall strength of the particles; Example 7 of a fluoride removal agent without chloride ions includes: Magnetic core-shell structure carrier component: 25 parts; Skeleton structure strengthening component: 30 parts; Fluoride removal active component: 10 parts; Functional structure regulation component: 3 parts; Pore structure construction component: 8 parts; Interface stability enhancement component: 6 parts; Dispersion medium system: 18 parts; Regarding Example 7, it should be noted that: In this example, the magnetic core-shell structure carrier and the skeleton structure enhancement component are maintained at a relatively high level, while the pore structure construction component and the interface stability enhancement component are improved to obtain a better pore distribution and core-shell interface adhesion; Example 8 included in a fluoride-removing agent without chloride ions: Magnetic core-shell structure carrier component: 5 parts; Skeleton structure enhancement component: 40 parts; Fluoride-removing active component: 15 parts; Functional structure regulation component: 10 parts; Pore structure construction component: 8 parts; Interface stability enhancement component: 6 parts; Dispersion medium system: 16 parts; Regarding Example 8, it should be noted that: In this example, the lowest proportion of the magnetic core-shell structure carrier component and the highest proportions of the skeleton structure enhancement component, the functional structure regulation component, the pore structure construction component, and the interface stability enhancement component are adopted to create ultra-high skeleton stability and porous characteristics; Example 9 included in a fluoride-removing agent without chloride ions: Magnetic core-shell structure carrier component: 5 parts; Skeleton structure enhancement component: 40 parts; Fluoride-removing active component: 10 parts; Functional structure regulation component: 10 parts; Pore structure construction component: 8 parts; Interface stability enhancement component: 6 parts; Dispersion medium system: 21 parts; Regarding Example 9, it should be noted that: In this example, the dosage of the fluoride-removing active component is increased compared with Example 8 to further enhance the adsorption capacity and regeneration efficiency under the combined action of a high skeleton content and the functional regulation component; Example 10 included in a fluoride-removing agent without chloride ions: Magnetic core-shell structure carrier component: 5 parts; Skeleton structure enhancement component: 20 parts; Fluoride-removing active component: 15 parts; Functional structure regulation component: 10 parts; Pore structure construction component: 8 parts; Interface stability enhancement component: 6 parts; Dispersion medium system: 36 parts; Regarding Implementation 10, it should be noted that: while maintaining the minimum magnetic core-shell structured carrier components in this embodiment, the defluorination active components and functional structure regulation components are significantly increased, so as to have both basic magnetic separation ability and high-efficiency adsorption characteristics; Based on Embodiment 11 included in a defluorination agent without chlorine ions: Magnetic core-shell structured carrier components: 28 parts; Skeleton structure strengthening components: 35 parts; Defluorination active components: 12 parts; Functional structure regulation components: 8 parts; Pore structure construction components: 5 parts; Interface stability enhancement components: 5 parts; Dispersion medium system: 7 parts; Regarding Implementation 11, it should be noted that: in this embodiment, when the magnetic core-shell structured carrier components, skeleton structure strengthening components, and defluorination active components are all at relatively high levels, supplemented with appropriate functional structure regulation components and pore structure construction components, the material has both strong adsorption performance and good recycling and regeneration properties; Based on Embodiment 12 included in a defluorination agent without chlorine ions: Magnetic core-shell structured carrier components: 29 parts; Skeleton structure strengthening components: 21 parts; Defluorination active components: 14 parts; Functional structure regulation components: 9 parts; Pore structure construction components: 4 parts; Interface stability enhancement components: 4 parts; Dispersion medium system: 19 parts; Regarding Implementation 12, it should be noted that: in this embodiment, while maintaining high values of the magnetic core-shell structured carrier components and defluorination active components, the skeleton structure strengthening components and pore structure construction components are balanced, and an appropriate amount of interface stability enhancement components is added to comprehensively improve the magnetic recovery efficiency, defluorination ability, and long-term stability of the material; Based on Embodiments 1 - 12, a defluorination performance comparison experiment was constructed, and its experimental data table 1 is shown as follows:

[0018] Based on Embodiments 1 - 12, a renewable and cyclic stability experiment was constructed, and its experimental data table 2 is shown as follows:

[0019] Based on Embodiments 1 - 12, a magnetic recovery efficiency and response speed experiment was constructed, and its experimental data table 3 is shown as follows:

[0020] Based on Examples 1 - 12, the molding structure and mechanical strength analysis were constructed, and the experimental data table 4 is as follows:

[0021] Based on Examples 1 - 12, the interface action and component compatibility verification experiment were constructed, and the experimental data table 5 is as follows:

[0022] Based on Examples 1 - 12, the multi - factor orthogonal experimental design was constructed, and the experimental data table 6 is as follows:

[0023] Regarding the above - mentioned scheme, it should be noted that Fluoride removal performance results: Table 1 shows that there are obvious differences among the examples in terms of adsorption capacity, adsorption rate, and final fluoride concentration control. Among them, the high - proportion skeleton - enhanced and fluoride - removing active components show higher adsorption capacity and faster reaction rate, such as Examples 8 and 12, indicating that reasonable component matching can significantly improve the fluoride - removing efficiency; Renewability and cycle stability results: The data in Table 2 show that after multiple rounds of cycle tests, some examples can maintain an adsorption capacity of up to 86%. The low particle breakage rate proves the key role of the skeleton structure - enhancing and pore - structure - constructing components in stabilizing the structure and extending the service life, thus verifying the excellent stability of the material during repeated regeneration; Magnetic recovery efficiency and response speed results: In the experiments of Table 3, the examples with higher magnetic core - shell structure carrier components show shorter recovery time and higher recovery efficiency in magnetic recovery tests, such as Examples 8 and 12, proving the necessity of magnetic design in achieving rapid and effective recovery and reducing the operation cost in subsequent processes; Molding structure and mechanical strength results: The compressive strength, BET specific surface area, and average pore diameter data in Table 4 show that appropriately increasing the functional structure regulation and pore - structure - constructing components can effectively improve the mechanical stability of the particles and the porous structure distribution, thus providing stable physical support and higher adsorption activity for the fluoride - removing agent; Interface action and component compatibility results: In Table 5, the higher interface bonding strength, lower thermal weight - loss rate, and obvious displacement of the FTIR characteristic peaks prove the importance of the interface - stabilizing and enhancing components in ensuring the formation of strong chemical bonds between the magnetic core - shell structure and the skeleton and fluoride - removing active components, thus ensuring the long - term chemical stability of the overall material; Optimization results of multi-factor orthogonal experiments: Table 6 confirmed the comprehensive effects of the proportions of key components on the defluorination efficiency and cycle retention rate through orthogonal experimental design. The results showed that the best combination had significant advantages in improving adsorption performance and regeneration stability, further verifying the synergistic effect between components and the importance of optimized ratios.

[0024] Refer to the attached instructions Figure 1 , the preparation process of a defluorination agent without chloride ions according to the present invention includes the following steps: When mixing and dispersing the medium system and the skeleton structure enhancing component, use a fluid pressure sensitive element to detect the fluid pressure in real time. When the detected value is inconsistent with the preset threshold one, adjust the stirring speed until the detected value is adjusted to the preset threshold one, and based on this, obtain mixture one; When adding the magnetic core-shell structure carrier component to mixture one, continuously monitor the instantaneous pressure. If the detected value is inconsistent with the preset threshold two, adjust the raw material addition rate until the detected value is adjusted to the preset threshold two, and based on this, obtain mixture two; During the process of adding the defluorination active component to mixture two, detect the mixture pressure in real time. If the detected value is inconsistent with the preset threshold three, adjust the raw material supply rate until the detected value is adjusted to the preset threshold three, and based on this, obtain mixture three; When adding the functional structure regulating component to mixture three, make a determination according to the fluid pressure monitored in real time. If the detected value is inconsistent with the preset threshold four, adjust the mixing parameters until the detected value is adjusted to the preset threshold four, and based on this, obtain the functional complex; When adding the pore structure constructing component during the curing or heat treatment stage of the functional complex, monitor the quasi-stable pressure. If the detected value is inconsistent with the preset threshold five, adjust the injection rates of the pore-forming agent and the bubble inducing agent and the treatment temperature until the detected value is adjusted to the preset threshold five, and based on this, obtain the functional multi-channel complex; When adding the interface stability enhancing component during the drying stage of the functional multi-channel complex, make a determination according to the fluid pressure monitored in real time. If the detected value is inconsistent with the preset threshold six, adjust the drying conditions according to the environmental model until the detected value is adjusted to the preset threshold six, and finally obtain the defluorination agent without chloride ions.

[0025] During the acquisition stage of mixture one, control the dispersion medium system and the skeleton structure enhancing component to form a stable initial slurry under the shear peak condition, through to represent the stirring response coefficient at time , and dynamically adjust the stirring speed based on the stirring response coefficient; and set the preset threshold one as , and through to refer to the pressure required for the target slurry state; Based on the ratio model composed of viscosity resistance, mixing efficiency, and pressure feedback, the deviation between the mixing resistance and the target state is judged through real-time feedback, and feedback control is formed by taking the stirring speed as the adjustment means; It is expressed as: ; Where is the mass of the skeleton structure enhancing component; is the dynamic viscosity of the dispersion medium, and the dynamic viscosity of the dispersion medium changes in real time with temperature and shear conditions; is the volume of the mixing system; is the non-uniformity factor of the slurry mixing, which depends on the degree of flow field disturbance in actual applications; is the system pressure monitored in real time by the fluid pressure-sensitive element; is the anti-oscillation perturbation term. During the actual preparation process, takes a positive real number and can be selected as 0.01 - 0.1 times the value.

[0026] When obtaining the second mixture, magnetic core-shell structure particles composed of magnetic core-shell structure carrier components are uniformly distributed in the slurry to avoid agglomeration and structural deviation; by is used to represent the instantaneous addition rate of the magnetic core-shell structure carrier component at time . Based on , a response model for the diffusion of magnetic core-shell structure particles in the flow field is constructed, and the feeding rate is adjusted by coupling the pressure deviation and the perturbation term to avoid non-linear agglomeration behavior; based on this, is constructed: ; Where represents the cumulative mass of the added components; is the initial recommended addition rate; is the current pressure value; is the preset threshold two; is the particle magnetic response ratio, and the particle magnetic response ratio is used to reflect the coupling characteristics of the particle response to the magnetic force field and the shear force field; is the slurry perturbation index, and the slurry perturbation index represents the degree of disorder of the internal flow or the degree of particle gyration; in the above formula, is the differential operator, represents the infinitesimal change of the relative time .

[0027] For the third mixture formed by adding the defluorination active component, the inverse cube root of the active site complexation efficiency and the pressure deviation is used for control to achieve non-linear response, so as to still stably form available sites under pressure fluctuations, and form the generation of chemical coordination or physical adsorption sites in contact with the slurry. Based on this, represents the feeding rate of the defluorination active component, Denote the preset threshold three; the dosing rate of the defluorination active component is expressed as: ; Where represents the dosing rate of the defluorination active component; is the standard complexation rate constant; the instantaneous complexation site formation efficiency function; is the deviation anti-interference factor, which is used to adjust the sensitivity of the dosing rate to the pressure deviation.

[0028] For the functional complex formed by adding the functional structure regulating component, the pressure error is adjusted by the cohesive logarithmic response function to enable the reasonable release of the regulating component under high structural consistency and improve the integrity of the three-dimensional structure. It is proposed that the preset threshold four, the structure regulation ability index is used to guide the supply of the regulating component, and it is expressed as: ; where is the cohesive density coefficient; is the target value of the structure integrity; is the particle flow field distortion function, where the larger the value of the more difficult it is to form the structure; When adding the pore structure construction component during the curing or heat treatment stage of the functional complex, during the stage of forming the pore structure component, the temperature, gas release rate and pressure error are used as the driving factors for forming the pore structure. Based on this, the pore formation ability is modeled, and the injection rhythm and heat treatment curve are feedback-adjusted to form the functional multi-level pore channel complex. It is proposed that represents the pore structure generation intensity; ; Where is the pore expansion ability caused by the unit gas release amount; is the instantaneous gas release amount of the pore-forming gas; is the heat treatment temperature; is the pore channel nucleation coefficient; is the preset threshold five.

[0029] When adding the interface stability enhancing component during the drying stage of the functional multi-level pore channel complex, the defluorination agent without chloride ions is finally obtained; during this stage, a feedback mechanism between the water evaporation rate and the interface structure strength is established, and the regulation relationship is constructed using the square term of the real-time concentration of the interface enhancing component and the pressure deviation, so as to dynamically control the interface formation rate and the drying environment parameters, and finally make the material form a stable core-shell combined interface and overall structure integrity; ; Where is the drying stability enhancement effect; is the interface adhesion efficiency constant; is the surfactant concentration; is the system moisture evaporation rate; is the system disturbance response coefficient; is the preset threshold six.

[0030] Construct an environmental model. The environmental model is based on the combination of hyperbolic tangent, Gaussian distribution, and logarithmic function to construct a non-linear response and a convergence path, and introduce a target matching interval comparison structure and a deviation penalty mechanism into the environmental model; The environmental model is used in conjunction with the control equations of each stage to form a closed-loop control mechanism. The environmental model is constructed by to describe the system dry environment fitness index, which is used to determine whether the current drying conditions are suitable for enhancing the component effect and interface formation; The environmental model is used to keep the system pressure stable at the preset threshold six, achieve the synchronization of the best moisture evaporation rate and the interface structure setting rate, and automatically adapt to the influence of external disturbances on the drying efficiency, such as environmental temperature and humidity fluctuations, and finally ensure the structural integrity and core-shell bonding strength of the formed material;

[0031] where represents the drying curve activity factor within a time period, which depends on the current heat source power, wind speed setting, and cavity volume; is the moisture evaporation dynamic matching term; is the moment The instantaneous moisture evaporation rate of the material per unit mass within the system; is the evaporation rate reference value, which is used to correspond to the dehydration speed required to form a stable surface structure; is the evaporation rate adjustment coefficient, and the evaporation rate adjustment coefficient is used to reflect the tolerance degree of the system to dehydration deviation; Adopt the hyperbolic tangent function to form a response critical region, which changes rapidly before and after the critical speed and is sensitive to response; is the moisture evaporation control weight coefficient; is the surfactant concentration coupling term; is the real-time concentration of the interface stability enhancing component; is the center value of the concentration interval, and the center value of the concentration interval corresponds to the maximum interface bonding efficiency; is the concentration deviation tolerance, and the concentration deviation tolerance is used to control the influence of the concentration deviation degree on the structural stability; Adopt the Gaussian function to construct the peak effect between the interface concentration and the structural stability; is the interface concentration control weight coefficient; is the pressure deviation suppression term; is the pressure deviation penalty coefficient, The larger the value, the more sensitive the system is to deviations; used for logarithmic convergence processing of pressure error to enhance the control accuracy of micro-perturbations; In practical applications, it should be noted that when is greater than the threshold set by this model in the preparation process it can be considered that the current environment is suitable for drying and curing the interface enhancement component, and the preparation process can continue; If the system executes this set of actions; The actions include: adjusting the hot air temperature, wind speed or cavity ventilation ratio; reducing or delaying the release rate of the interface enhancement component; adjusting the drying curve to make converge to or adjusting close to

[0032] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A fluoride-removing agent without chloride ions, characterized in that, Comprising: The medicament is calculated by mass parts, and the total mass parts is 100 parts, which is composed of the following components: Magnetic core-shell structure carrier component: 5 - 30 parts, the magnetic core-shell structure carrier component includes magnetic particles with Fe3O4 as the core and SiO2 or activated carbon as the shell; Skeleton structure strengthening component: 20 - 40 parts, the skeleton structure strengthening component includes silica and / or porous activated carbon, and the skeleton structure strengthening component is used to provide an adsorption and support skeleton; Fluoride removal active component: 5 - 15 parts, the fluoride removal active component includes one or more of alumina, iron oxide, zirconia, and / or the complex state of trivalent metal ions; Functional structure regulating component: 3 - 10 parts, the functional structure regulating component includes polymer grafts and / or dispersion stabilizers, which are used to improve the adhesion, dispersibility, and formability between particles; Pore structure construction component: 3 - 8 parts, the pore structure construction component includes pore-forming agents and / or bubble inducing agents, which are used to form hierarchical pore channels during the curing or heat treatment stage; Interface stability enhancing component: 2 - 6 parts, the interface stability enhancing component includes silane coupling agents, organic small molecule modifiers, or other surface modifiers that can form a firm bond at the core-shell interface and the surface of the skeleton; Dispersion medium system: the remaining parts, the dispersion medium system includes water and / or alcohols and / or pH regulators.

2. A preparation process of a defluorination agent without chloride ions, characterized in that, Including the following steps: When mixing the dispersion medium system and the skeleton structure strengthening component, use a fluid pressure sensor to detect the fluid pressure in real time. When the detected value is inconsistent with the preset threshold one, adjust the stirring speed until the detected value is adjusted to the preset threshold one, and based on this, obtain mixture one; When adding the magnetic core-shell structure carrier component to mixture one, continuously monitor the instantaneous pressure. If the detected value is inconsistent with the preset threshold two, adjust the raw material addition rate until the detected value is adjusted to the preset threshold two, and based on this, obtain mixture two; During the process of adding the fluoride removal active component to mixture two, detect the mixture pressure in real time. If the detected value is inconsistent with the preset threshold three, adjust the raw material supply rate until the detected value is adjusted to the preset threshold three, and based on this, obtain mixture three; When adding the functional structure regulating component to mixture three, make a determination according to the fluid pressure monitored in real time. If the detected value is inconsistent with the preset threshold four, adjust the mixing parameters until the detected value is adjusted to the preset threshold four, and based on this, obtain the functional complex; When adding the pore structure construction component during the curing or heat treatment stage of the functional complex, monitor the quasi-steady pressure. If the detected value is inconsistent with the preset threshold five, adjust the injection rate of the pore-forming agent and the bubble inducing agent and the treatment temperature until the detected value is adjusted to the preset threshold five, and based on this, obtain the functional hierarchical pore channel complex; When adding the interface stability enhancing component during the drying stage of the functional hierarchical pore channel complex, make a determination according to the fluid pressure monitored in real time. If the detected value is inconsistent with the preset threshold six, adjust the drying conditions according to the environmental model until the detected value is adjusted to the preset threshold six, and finally obtain a fluoride removal medicament without chloride ions.

3. The preparation process of a fluoride removal medicament without chloride ions according to claim 2, wherein: During the acquisition stage of Mixture 1, control the dispersion medium system and the skeleton structure reinforcing component to form a stable initial slurry under the shear peak condition. By to represent the moment the stirring response coefficient at, dynamically adjust the stirring speed based on the stirring response coefficient; And set the first preset threshold as , and through to represent the pressure required for the target slurry state; Based on the ratio model composed of viscosity resistance, mixing efficiency, and pressure feedback, judge the deviation between the mixing resistance and the target state through real-time feedback, and form a feedback control with the stirring speed as the adjustment means; It is expressed as: ; where is the mass of the skeleton structure reinforcing component; is the dynamic viscosity of the dispersion medium; is the volume of the mixed system; is the non-uniformity factor of the slurry mixture; is the system pressure monitored in real time by the fluid pressure-sensitive element; is the anti-oscillation perturbation term.

4. The preparation process of a defluorination agent without chloride ions according to claim 3, characterized in that: When obtaining the second mixture, magnetic core-shell structure particles composed of magnetic core-shell structure carrier components are distributed in the slurry to avoid agglomeration and structural deviation; by to represent the time the instantaneous addition rate of the magnetic core-shell structure carrier component below, based on construct a response model for the diffusion of magnetic core-shell structure particles in the flow field, and adjust the feeding rate by coupling the pressure deviation and the disturbance term to avoid non-linear agglomeration behavior; based on this, construct : ; wherein represents the cumulative mass of the added components; is the initial recommended addition rate; is the current pressure value; is the preset threshold two; is the particle magnetic response ratio; is the slurry disturbance index.

5. The preparation process of a defluorination agent without chloride ions according to claim 4, characterized in that: For the mixture three formed by adding defluorination active components, it is controlled by the inverse ratio of the cube root of the active site complexation efficiency to the pressure deviation to achieve non-linear response, which is used to stably form available sites under pressure fluctuations, and to form the generation of chemical coordination or physical adsorption sites in contact with the slurry. Based on this, represents the defluorination active component addition rate, refers to the preset threshold three; the defluorination active component addition rate is expressed as: ; wherein represents the addition rate of the defluorination active component; is the standard complexation rate constant; instantaneous complexation site formation efficiency function; is the deviation disturbance resistance factor, and the deviation disturbance resistance factor is used to adjust the sensitivity of the addition rate to the pressure deviation.

6. The preparation process of a defluorination agent without chloride ions according to claim 5, characterized in that: In the functional complex formed by adding functional structure control components, the pressure error is adjusted with the cohesive logarithmic response function to release the control components under the same structure consistency, improve the integrity of the three-dimensional structure, and formulate Preset threshold four, structure control ability index Used to guide the supply of control components, which is expressed as: ; where Is the cohesive density coefficient; Is the target value of structure integrity; Is the particle flow field distortion function; When adding pore structure construction components during the curing or heat treatment stage of the functional complex, a pore structure component formation stage is formed. The temperature, gas release rate, and pressure error are used as driving factors for forming the pore structure. Based on this, the pore formation ability is modeled, and the injection rhythm and heat treatment curve are feedback-adjusted to form a functional multi-level pore complex, and it is proposed that represents the pore structure generation intensity; ； wherein is the pore expansion ability triggered by the unit gas release amount; is the instantaneous gas release amount for pore formation; is the heat treatment temperature; is the pore nucleation coefficient; is the preset threshold value five.

7. The preparation process of a defluorination agent without chloride ions according to claim 6, characterized in that: When adding an interface stability enhancement component during the drying stage of the functional multi - pore complex, a defluorination agent without chloride ions is finally obtained; a feedback mechanism between the water evaporation rate and the interface structure strength is established at this stage, and a regulation relationship is constructed using the square term of the real - time concentration and pressure deviation of the interface enhancement component, so as to dynamically control the interface formation rate and the drying environment parameters, and finally enable the material to form a stable core - shell combined interface and overall structural integrity; ； Among them is the drying stability enhancement effect; is the interfacial adhesion efficiency constant; is the surfactant concentration; is the system moisture evaporation rate; is the system disturbance response coefficient; is the preset threshold six.

8. The preparation process of a defluorination agent without chloride ions according to claim 7, characterized in that: Build an environmental model. The environmental model is based on the combination of hyperbolic tangent, Gaussian distribution, and logarithmic function to construct a non-linear response and a convergence path, and introduce a target matching interval comparison structure and a deviation penalty mechanism into the environmental model. The environmental model is used in conjunction with the control equations of each stage to form a closed-loop control mechanism. The environmental model is constructed by describing the system's dry environment fitness index, and is used to determine whether the current drying conditions are suitable for enhancing the component effect and interface formation. wherein represents the drying curve activity factor within a time period; is the moisture volatilization dynamic matching term; is the moment the instantaneous moisture volatilization rate of the material per unit mass within the system; is the reference value of the volatilization rate; is the volatilization rate adjustment coefficient; is the surfactant concentration coupling term; is the real-time concentration of the interface stability enhancement component; is the central value of the concentration range; is the concentration deviation tolerance, and the concentration deviation tolerance is used to control the influence of the concentration deviation degree on the structural stability; The peak effect between the interface concentration and the structural stability is constructed by using a Gaussian function; is the interface concentration regulation weight coefficient; is the pressure deviation suppression term; is the pressure deviation penalty coefficient; is used to perform logarithmic convergence processing on the pressure error.

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