Artificial intelligence dosing method for Fenton reaction

Abstract

Aiming at the characteristics of high salinity, high COD (Chemical Oxygen Demand), high complexation, strong alkalinity, high viscosity and particulate matter content of reactive dye dyeing raffinate in the printing and dyeing industry, the artificial intelligence dosing method for the Fenton reaction realizes efficient treatment through the following steps: pretreating and pre-collecting characteristic parameters of the raffinate; adding an anti-complexing carrier and a liquid-phase catalyst to activate a catalytic site; aI, hydrogen peroxide is added in stages, and the fluidized bed is regulated and controlled to generate micro-vortex enhanced mass transfer; and alkali is added to adjust the pH value, and then solid-liquid separation is performed to obtain purified effluent and a recyclable carrier. Through cooperation of the anti-complexing carrier, AI precise dosing and the fluidized bed technology, the problems of catalyst deactivation, insufficient mass transfer and the like of traditional Fenton in complex wastewater treatment are solved, the catalytic efficiency is improved, the sludge yield is reduced, and advanced wastewater treatment and carrier recycling are achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of sewage treatment, and in particular to an artificial intelligence dosing method for Fenton reaction. Background Art

[0002] With the rapid development of industrialization, the composition of industrial wastewater has become increasingly complex, especially wastewater containing difficult-to-degrade organic matter, which has become a major challenge in the field of wastewater treatment. Traditional biological treatment methods are inefficient for such pollutants because microorganisms have difficulty metabolizing highly toxic or inert substances; physical adsorption methods have saturation regeneration problems, and membrane technology is susceptible to pollution and is costly. Advanced oxidation technology has attracted much attention because it can produce strong oxidizing free radicals to degrade stubborn organic matter. Among them, the Fenton reaction has become the mainstream choice because of its simple operation and easy availability of reagents. However, the traditional Fenton process relies on homogeneous iron catalysis, requires a strictly acidic environment, and produces a large amount of iron-containing sludge, causing secondary pollution and high disposal costs. In addition, complexing agents, high salt content or suspended solids in complex wastewater can easily deactivate the catalyst, resulting in unstable oxidation efficiency, which restricts its large-scale application.

[0003] The current optimization of the Fenton process focuses on adjusting the reagent ratio or improving the reactor, but there are still fundamental bottlenecks: 1. Limited catalytic efficiency: homogeneous iron ions easily form precipitation or chelates with phosphates, humic acid, etc. in wastewater, losing catalytic activity; 2. Strong pH dependence: Iron precipitates rapidly under neutral or alkaline conditions, requiring continuous acid addition, increasing operational complexity and cost; 3. Prominent sludge problems: Fe 3+ The amount of sludge converted into Fe(OH)3 is high, making dehydration and disposal difficult; 4. Weak anti-interference ability: high chloride ions quench free radicals, high salt content inhibits reaction kinetics, resulting in ineffective decomposition of H2O2.

[0004] Although the introduction of auxiliary means such as light and electrocatalysis can partially alleviate the problem, the equipment investment increases dramatically and cannot solve the core defects such as sludge and salt resistance.

[0005] Therefore, it is necessary to improve an artificial intelligence dosing method for Fenton reaction in the existing technology to solve the above problems. Summary of the Invention

[0006] The present invention overcomes the shortcomings of the existing technology and provides an artificial intelligence dosing method for the Fenton reaction, aiming to solve the difficult problems of treating the high salt, high viscosity and high complexing properties of reactive dye residual liquid in the printing and dyeing industry.

[0007] To achieve the above-mentioned purpose, the technical solution adopted by the present invention is: an artificial intelligence dosing method for Fenton reaction, comprising: S1, pre-treating the reactive dye dyeing residual liquid and conveying it to a fluidized bed, and pre-collecting a first characteristic parameter of the reactive dye dyeing residual liquid; wherein the first characteristic parameter is the complexing agent concentration and the residual liquid volume; S2, adding anti-complexation carrier to the fluidized bed based on the first characteristic parameter, monitoring the second characteristic parameter in real time, and adding liquid phase catalyst; wherein the second characteristic parameter is COD concentration, Fe 3+ concentration and Fe 3+ and Fe 2+ molar ratio, liquid phase catalyst is used to activate the active sites on the surface of the anti-complexation support; S3. After the liquid catalyst is added, the AI ​​control system adds hydrogen peroxide in stages, simultaneously increases the flow rate of the fluidized bed in steps, and combines microwaves to carry out the Fenton reaction; S4. After the Fenton reaction is completed, AI controls the addition of alkali to adjust the pH, separate the solid and liquid, and obtain purified water.

[0008] In a preferred embodiment of the present invention, in step S1, the preprocessing includes: The reactive dyeing residual liquid is mechanically sheared at a speed of 3000-5000 rpm for 2-5 minutes to break up the fiber fragment agglomerates and reduce the residual liquid viscosity to 8-10 cP; Then add sulfuric acid to the residual liquid to adjust the pH, the amount of acid used is 3-5kg / m 3 , react for 10-15 minutes, reduce the pH to 2-3, and destroy the chelate bond between EDTA and metal ions by pH adjustment, releasing free Fe 3+ , among which the released free Fe 3+ It is subsequently used as a catalyst for the Fenton reaction.

[0009] In a preferred embodiment of the present invention, in step S2, the preparation of the anti-complexation carrier comprises: In an ammonia solution with a pH of 10-11, ZrOCl2 and Fe3O4 were co-precipitated at a mass ratio of 4-5:1 and reacted at 180°C for 12 hours to form ZrO2@Fe3O4 composite microspheres with a diameter of 0.5-1 mm, forming a magnetic core layer. The microspheres were immersed in a 0.5-0.6 mol / L Fe(NO3)3 solution and ultrasonically treated at 60°C for 30-40 minutes. They were then calcined at 500-550°C for 2 hours under a nitrogen atmosphere to form α-Fe2O3 microaggregates with a particle size of 10-20 nm on the surface of the microspheres, forming a catalytically active layer. The microspheres are immersed in an EDTA-Fe complex solution with a pH of 4-5 and a concentration of 0.1-0.2 mol / L, and reacted at 60°C for 3-5 hours with stirring to form a competitive binding layer on the catalytic active layer; ZrO2-SiO2 sol is spin-coated on the surface of the microspheres, wherein the molar ratio of Zr to Si is 3-4:1. After spin-coating, the microspheres are first dried at 60-80°C for 15-20 minutes and then sintered at 500-550°C for 1-1.5 hours to form a ZrO2-SiO2 coating film with a thickness of 50-100nm and a lattice spacing of 0.28-0.31nm on the competitive binding layer to form a shielding protective layer, and finally an anti-complexation carrier is obtained.

[0010] In a preferred embodiment of the present invention, the spin coating process parameters are: sol solid content 8-12wt%, spin coating is carried out in two stages, the first stage is spin coating at a speed of 300-500 rpm for 15-20 seconds, and the second stage is spin coating at a speed of 1000-1500 rpm for 40-60 seconds; the spin coating environment is controlled at a temperature of 20-25°C and a relative humidity of 40-60%.

[0011] In a preferred embodiment of the present invention, the liquid catalyst in step S2 is a ferrous sulfate solution, the ferrous sulfate particle size is 20-50 nm, and the concentration is 50-100 mg / L.

[0012] In a preferred embodiment of the present invention, the step of adding hydrogen peroxide in step S3 is as follows: The first stage lasts for 10-15 minutes, with 30% of the total amount added, a flow rate of 5-8L / h, and the target ORP rises to 300-350mV; the second stage lasts for 15-20 minutes, with 50% of the total amount added, a flow rate of 10-15L / h, and the target ORP rises to 450-500mV; the third stage lasts for 10-15 minutes, with the remaining 20% ​​added, a flow rate of 5-8L / h, and the ORP maintained at 500-550mV; if the target ORP is not reached in a certain stage, the AI ​​system dynamically extends the time of that stage.

[0013] In a preferred embodiment of the present invention, in step S3, the fluidization control of the fluidized bed includes increasing the rising flow rate from the initial flow rate to 0.025 m / s, controlling the bed expansion ratio to 1.5-1.8 times, and maintaining the shear rate greater than 500s -1 , generating 50-100μm micro-vortices, and the shear stress at the bottom of the bed is greater than 8Pa.

[0014] In a preferred embodiment of the present invention, in step S4, the alkali addition callback comprises: Use 10wt% NaOH solution or waste alkali solution to monitor the pH value in real time. If the pH is less than 6.0, add NaOH; if the pH exceeds 7.5, stop adding. The target pH is controlled at 6.5-7.5, and the reaction time is 5-10 minutes. When the content of micron-sized fiber fragments is greater than 1g / L or Fe 3+When the concentration is lower than 10 mg / L, add 10-20 mg / L of polyaluminium chloride and 1-2 mg / L of anionic polyacrylamide, mix quickly first and then stir slowly.

[0015] In a preferred embodiment of the present invention, in step S3, when the UV270 detection value is greater than 0.6 AU, a microwave source is started along the side wall of the fluidized bed with a power of 2 kW for 10 minutes. The microwave adopts an intermittent operation mode, which is turned on for 2 minutes and turned off for 1 minute.

[0016] In a preferred embodiment of the present invention, in step S4, the magnetic components are initially separated by magnetic separation, and then deep dehydration is performed. The filter cloth is made of polyester with a pore size of 5-10 μm, and the filtration pressure is controlled at 0.4-0.6 MPa.

[0017] The present invention solves the defects existing in the background technology and has the following beneficial effects: (1) The present invention provides a fluidized bed Fenton treatment system and method for reactive dye residues in the printing and dyeing industry. By constructing a magnetic ZrO2@Fe3O4 carrier with anti-complexation function, combined with AI-controlled precise dosing and a fluidized bed reactor, it achieves deep treatment of complex wastewater with high salt, high COD, high complexation strength, strong alkalinity, high viscosity and particulate matter. This technology reduces the viscosity of the residual liquid and destroys the EDTA complex through mechanical shearing and pH adjustment pretreatment, and then adds an anti-complexation carrier with a surface-loaded α-Fe2O3 catalytic active layer and an EDTA-Fe competitive binding layer. Under AI control, hydrogen peroxide is added in stages and the fluidization state is optimized. Micro-vortex is used to enhance mass transfer. Finally, through intelligent neutralization and solid-liquid separation, qualified effluent and recyclable carriers are obtained, effectively solving the problem of complete failure of traditional Fenton in the treatment of such wastewater.

[0018] (2) The present invention adopts an anti-complexation carrier composed of a magnetic ZrO2 microsphere core, micro-aggregates of α-Fe2O3, EDTA-Fe competition and a ZrO2-SiO2 coating film, wherein the magnetic ZrO2 microspheres provide mechanical strength and magnetic recyclability, the micro-aggregates of α-Fe2O3 serve as catalytic active sites, the EDTA-Fe competition layer blocks the chelation of the chelating agent in the wastewater to the catalytic sites through competitive binding, and the ZrO2-SiO2 coating film shields the penetration of the chelating agent to ensure the stability of the internal active sites; this composite structure avoids the active sites being blocked by the chelating agent, ensuring the continuous catalytic cycle. Compared with the problem that homogeneous iron ions in traditional Fenton reactions easily form stable complexes with EDTA, resulting in loss of activity, the catalytic stability is significantly improved, and the efficient operation of the Fenton reaction in highly complexed printing and dyeing wastewater is achieved.

[0019] (3) The present invention adds a liquid catalyst according to real-time monitoring parameters while adding the anti-complexation carrier, and adds the liquid catalyst to activate the active sites on the carrier surface, wherein the liquid Fe2+ As an electron bridge to the carrier surface α-Fe 2 O 3 Micro-aggregates undergo electron transfer to generate highly active ≡Fe 2+ The site initiates the Fenton chain reaction, and the free Fe 2+ It preferentially combines with the chelating agent to form a soluble complex; this synergistic effect quickly activates the active sites of the carrier and blocks the blockade of the carrier by EDTA. Compared with the traditional Fenton catalysis that relies on homogeneous iron catalysis and has difficulty in dealing with the problem of catalyst deactivation caused by highly complex wastewater, it enhances the catalytic efficiency, reduces the waste of reagents, and ensures that the reaction continues to proceed efficiently.

[0020] (4) The present invention uses an AI control system to add hydrogen peroxide in stages and simultaneously activates fluidized bed fluidization control to generate 50-100 μm micro-scale vortices. The staged addition is dynamically adjusted according to the ORP target to avoid local excessive self-decomposition of hydrogen peroxide. The fluidized bed enhances mass transfer by adjusting the rising flow rate and shear rate to prevent the deposition of micron-sized fiber fragments. This improves the utilization efficiency of hydrogen peroxide and promotes sufficient contact between H2O2 and pollutants such as reactive dye polymerization products. Compared with the traditional Fenton hydrogen peroxide addition method, which is prone to incomplete oxidation due to insufficient mass transfer or high-salt environment, the reaction efficiency is significantly improved, and the deep degradation of pollutants in high-salt, high-viscosity dye residues is achieved.

[0021] (5) After the Fenton reaction is completed, the present invention controls the addition of alkali by AI to adjust the pH to neutral, and uses a magnetic separator, plate and frame filter press or centrifuge to separate the solid and liquid to recover the magnetic anti-complexation carrier. At the same time, the pH is controlled to promote the free Fe 3+ The sludge volume is reduced by converting it into flocs and combining it with a flocculant. The efficient recovery and regeneration of the carrier reduces carrier loss, and the sludge production is controlled at a low level. Compared with the traditional Fenton process, which produces a large amount of iron-containing sludge and has high dehydration and disposal costs, the present invention effectively reduces operating costs, further reduces secondary pollution, and meets environmental protection requirements. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments described in the present invention. Those skilled in the art can also derive other drawings based on these drawings without inventive efforts. Figure 1 This is a flow chart of the artificial intelligence dosing method according to a preferred embodiment of the present invention; Figure 2 It is a main process flow chart of a preferred embodiment of the present invention; Figure 3It is a structure-function diagram of the anti-complexation carrier of a preferred embodiment of the present invention. DETAILED DESCRIPTION

[0023] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0024] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Therefore, the scope of protection of the present invention is not limited to the specific embodiments disclosed below.

[0025] Application Overview: The present invention targets reactive dye residual liquid in the printing and dyeing industry, especially the high-concentration intermediate wastewater remaining after primary filtration and evaporation concentration in the printing and dyeing process; such wastewater has the characteristics of high COD, high complexing strength and containing particulate matter.

[0026] Traditional Fenton technology is completely ineffective in this scenario. The complexing agent strongly chelates the free Fe in the residual liquid of the reactive dye. 2+ / Fe 3+ , forming a stable complex, blocking the catalytic cycle; the heterocyclic structure in the reactive dye polymerization product has high chemical bond energy, and conventional hydroxyl radicals are difficult to effectively break, resulting in the difficulty of degrading the core pollutants. In order to solve the above problems, the present invention proposes to establish an anti-complexation catalysis, enhanced mass transfer, and salt-resistant environment. The present invention is based on the deep integration of heterogeneous catalysis and reactor dynamics, by combining the Fenton reaction with fluidized bed technology: first, a magnetic ZrO2@Fe2O4 carrier with anti-complexation function is prepared to effectively block the chelation effect of the complexing agent on the catalytic site; secondly, the AI ​​control system is used to accurately control the staged addition of hydrogen peroxide to avoid catalyst deactivation and ensure that the reaction is fully carried out; thirdly, the mass transfer process is enhanced by the fluidized bed reactor to improve the reaction efficiency; finally, a magnetic separator, plate and frame filter press or centrifuge is used for solid-liquid separation to achieve efficient recovery and regeneration of wastewater.

[0027] Exemplary methods: like Figure 1 and Figure 2 As shown, an artificial intelligence dosing method for Fenton reaction includes the following steps: S1, pre-treating the reactive dye dyeing residual liquid and conveying it to a fluidized bed, and pre-collecting a first characteristic parameter of the reactive dye dyeing residual liquid; wherein the first characteristic parameter is the complexing agent concentration and the residual liquid volume; S2, adding anti-complexation carrier to the fluidized bed based on the first characteristic parameter, monitoring the second characteristic parameter in real time, and adding liquid phase catalyst; wherein the second characteristic parameter is COD concentration, Fe 3+ concentration and Fe 3+ and Fe 2+ molar ratio, liquid phase catalyst is used to activate the active sites on the surface of the anti-complexation support; S3. After the liquid catalyst is added, the AI ​​control system adds hydrogen peroxide in stages, simultaneously increases the flow rate of the fluidized bed in steps, and combines microwaves to carry out the Fenton reaction; S4. After the Fenton reaction is completed, AI controls the addition of alkali to adjust the pH, separate the solid and liquid, and obtain purified water.

[0028] The residual liquid of reactive dye dyeing is enriched with complex components that cannot be removed by primary filtration and evaporation concentration, including: reactive dye polymerization products, dyeing auxiliary residues, metal ions, micron-sized fiber fragments and high-salt matrix; Specifically, reactive dye polymerization products include: azo dye dimers, trimers and other heterocyclic structure substances; reactive dye polymerization products account for 15-20wt% and the concentration is >150,000mg / L, forming high COD core pollutants; Dyeing auxiliary residues, mainly ethylenediaminetetraacetic acid (EDTA) and sodium tripolyphosphate, with a concentration of 8,000–12,000 mg / L, have strong chelating properties; Metal ions, including Fe 2+ 、Fe 3+ 、Cu 2+ Cr 3+ , the total concentration is 200–500 mg / L, combining with EDTA to form a stable complex; Micron-sized fiber fragments are cotton / polyester fiber fragments with a particle size of 1–5 μm and a concentration of 1–3 g / L, which results in high viscosity of the reactive dye dyeing residual solution; High salt matrices, including: Na + 、SO4 2- 、Cl - , ion concentration>5wt%, quenching free radicals and interfering with reaction mass transfer.

[0029] In step S1, the first characteristic parameters include: complexing agent concentration and residual liquid volume; In step S1, characteristic parameters of the reactive dye dyeing residual liquid include: COD concentration, complexing agent concentration, total metal ion amount, fiber fragment concentration and particle size, salt ion concentration, pH value and viscosity; Among them, COD concentration is detected using an online COD monitor to measure core pollutants in real time; the chelating agent concentration is analyzed using a high-performance liquid chromatography online detector or an ion chromatograph; the total amount of metal ions is determined with the help of an atomic absorption spectrometer or an inductively coupled plasma emission spectrometer; the fiber fragment concentration and particle size are measured by a UV-visible spectrophotometer, a turbidity meter, and a laser particle size analyzer, respectively; the salt ion concentration is detected by an ion chromatograph or an online conductivity meter; the pH value is measured using an online pH meter; and the viscosity is determined by an online rotational viscometer or a capillary viscometer.

[0030] In step S1, pretreatment of reactive dye dyeing residual liquid includes: The residual liquid is treated with a high-speed shearing machine, which performs mechanical shearing at a speed of 3000-5000 rpm for 2-5 minutes to break up the fiber fragment agglomerates and reduce the residual liquid viscosity to 8-10 cP; Then add sulfuric acid to the residual liquid through the acid pump to adjust the pH, the amount of acid used is 3-5kg / m 3 , react for 10-15 minutes, reduce the pH to 2-3, and destroy the chelate bond between EDTA and metal ions by pH adjustment, releasing free Fe 3+ , among which the released free Fe 3+ It can be used as a Fenton reaction catalyst later.

[0031] S1 pretreatment converts the highly complex residual liquid into a low-viscosity, acidic, homogeneous reaction matrix through precise acid control and controllable shear, laying the foundation for the anti-complexation of S2 carrier and efficient oxidation of S3.

[0032] The fluidized bed of the present application is a liquid-solid fluidized bed reactor for treating reactive dye dyeing residual liquid. The reactive dye dyeing residual liquid is used as the liquid medium, and the residual liquid is made to flow through the anti-complexing magnetic carrier in the bed. Through fluidization control, the carrier is suspended and flowed in the liquid, which greatly increases the contact area and collision frequency between the carrier and the pollutants, liquid catalyst and hydrogen peroxide in the residual liquid, strengthens the mass transfer process, and thus improves the efficiency of the Fenton reaction.

[0033] The fluidized bed is made of acid- and alkali-resistant 316L stainless steel or fiberglass. The bed height-to-diameter ratio is designed to be 3-5:1, ensuring ample fluidization space for the carrier. A tapered transition section is provided at the bottom of the bed to reduce dead zones for liquid retention, and an expansion section is provided at the top to reduce local flow velocity, thereby minimizing spillage of carrier particles with the liquid and preventing micron-sized fiber fragments from agglomerating and accumulating at the top. A liquid catalyst addition port is provided in the middle and upper part of the bed, and a hydrogen peroxide water stage addition port is provided in the middle and lower part to ensure that the reagent directly enters the intense fluidization area and disperses quickly. A pH adjustment alkali addition port is provided at the top to adjust the pH after the reaction is completed. A liquid outlet is provided at the bottom of the fluidized bed to discharge the purified wastewater, as well as a carrier recovery port.

[0034] In step S2, the initial fluidization flow rate of the fluidized bed is 0.005-0.02 m / s to break through the viscous stagnation zone and reach a turbulent state. This range can not only ensure that the carrier is fully fluidized to avoid deposition, but also prevent the carrier from being carried out of the reactor by the high-speed fluid; the filling rate of the anti-complexing carrier is controlled at 30-40%. If the filling rate is lower than 30%, the active sites on the carrier surface are insufficient and the catalytic efficiency will decrease; if it is higher than 40%, the fluidization dead zone will expand, affecting the mass transfer efficiency; the bed height is set to 1.2-1.8 m, the distribution plate opening rate is 0.8-1.2%, and the opening diameter is 0.6-0.8 mm. This can avoid the blockage of incompletely dispersed agglomerates in step S1 and ensure the good operation of the fluidized bed.

[0035] In step S2, the anti-complexing support is the core material for capturing EDTA-metal complexes and activating catalytic sites in the Fenton reaction; like Figure 3 As shown, the anti-complexation carriers include: The magnetic core layer, namely the magnetic ZrO2 microspheres, is used to provide mechanical strength and magnetic recovery, resist high shear wear in the fluidized bed, and avoid carrier breakage leading to loss of active components; The catalytic active layer is the catalytic active particles loaded on the surface of the microspheres. Specifically, it is a small aggregate of α-Fe2O3 with a particle size of 10-20nm and a specific surface area of ​​>120m 2 / g, providing a large number of catalytic reaction sites for the Fenton reaction; the catalytically active particles in the catalytic active layer serve as the core catalytic sites of the Fenton reaction, starting a chain reaction under the activation of the liquid phase catalyst, efficiently decomposing hydrogen peroxide to produce hydroxyl radicals and degrading pollutants.

[0036] The competitive binding layer prevents the strong complexing agent in the residual liquid from destroying the catalytic active sites inside the carrier by actively occupying the residual liquid. The strong complexing agent contained in the residual liquid has a strong chelating ability and is easy to combine with the iron element in the catalytic active layer of the carrier to form a stable complex, resulting in the catalytic sites being blocked and losing their activity. The competitive binding layer is pre-combined with EDTA and Fe on the surface of the carrier. 3+ The formed complexes occupy the binding sites on the surface of the carrier, which is equivalent to building a barrier on the outer layer of the carrier.

[0037] When the strong complexing agent in the residual solution flows through the carrier, it competes with the EDTA-Fe that has occupied the site in the binding layer. 3+ Will compete with strong complexing agents: since these sites are already occupied by EDTA-Fe 3+ Occupied, it is difficult for the strong chelating agent to combine with the iron element in the catalytic active layer inside the carrier, thereby blocking the chelation of the strong chelating agent to the catalytic site.

[0038] The shielding protective layer is a ZrO2-SiO2 coating film with a thickness of 50-100nm and a lattice spacing of 0.28-0.31nm, which is smaller than the size of strong complexing agent molecules, thereby preventing large molecular complexing agents from directly contacting the interior, shielding the penetration of strong complexing agents, and ensuring the stability of internal active sites; the coating film is not completely closed, but selectively allows small molecular reactants and products such as H2O2 and OH to pass through through nanoscale pores, forming a selective channel where "reactant molecules can enter but complexing agent molecules are rejected."

[0039] The shielding protective layer and the competitive binding layer form a dual protection: the competitive binding layer consumes the free complexing agent through chemical competition, while the shielding protective layer blocks the unconsumed complexing agent from further penetration. The two work together to reduce the deactivation rate of the catalytic active layer, thus achieving the recyclable use of the anti-complexing carrier.

[0040] Preparation of anti-complexation carrier: To synthesize magnetic ZrO2 microspheres, ZrOCl2 and Fe3O4 were co-precipitated in an ammonia solution with a pH of 10-11 at a mass ratio of 4-5:1. The mixture was reacted at 180°C for 12 hours to form ZrO2@Fe3O4 composite microspheres with a diameter of 0.5-1mm, which is in the hundreds of micrometers level. The spin coating method is fully applicable to this size.

[0041] The magnetic ZrO2 microspheres were immersed in a 0.5-0.6 mol / L Fe(NO3)3 solution and ultrasonically treated at 60°C for 30-40 minutes. The microspheres were then calcined at 500-550°C for 2 hours under a nitrogen atmosphere to form tiny aggregates of α-Fe2O3 with a particle size of 10-20 nm on the surface of the microspheres. The carrier loaded with α-Fe2O3 micro-aggregates is immersed in an EDTA-Fe complex solution with a pH of 4-5 and a concentration of 0.1-0.2 mol / L. The solution is stirred at 60°C for 3-5 hours to allow the carboxyl groups of EDTA to react with the hydroxyl groups on the surface of ZrO2 to form a -Zr-OOC- bond, thus completing the construction of the competitive binding layer. A spin coating process is used to spin-coat ZrO2-SiO2 sol on the surface of the microspheres, wherein the molar ratio of Zr to Si is 3-4:1; the spin coating process parameters are: sol solid content 8-12wt%, spin coating is carried out in two stages, the first stage is spin coating at a speed of 300-500rpm for 15-20 seconds, and the second stage is spin coating at a speed of 1000-1500rpm for 40-60 seconds; the spin coating environment is controlled at a temperature of 20-25℃ and a relative humidity of 40-60%; after spin coating, it is first dried at 60-80℃ for 15-20 minutes, and then sintered at a temperature of 500-550℃ for 1-1.5 hours to form a dense ZrO2-SiO2 coating with a thickness in the range of 50-100nm and a lattice spacing of 0.28-0.31nm, thereby shielding TMEDA penetration and ensuring the stability of the active sites inside the carrier.

[0042] Regeneration of the anti-complexation carrier: after every 50-70 cycles, the carrier needs to be soaked in 5-8% oxalic acid solution for 1-1.5 hours to remove the surface Fe 3+ After precipitation, the product was calcined at 300-350℃ for 2 hours to restore its activity.

[0043] In step S2, the concentration of the complexing agent directly determines the adsorption requirement of the anti-complexing carrier. The residual liquid volume refers to the total volume of the reactive dye residual liquid after pretreatment and transported to the fluidized bed for Fenton reaction treatment. The AI ​​system calculates the carrier dosage using the following logic: ,in, is the complexing agent concentration, is the residual liquid volume, is the equilibrium adsorption capacity of the carrier for EDTA.

[0044] Through the key parameters of carrier preparation, its anti-complexation ability (EDTA retention rate), catalytic activity (COD removal rate), and stability (activity retention rate after 50 cycles) were verified. Preparation variables: The mass ratio of ZrOCl2 to Fe3O4 is set into three groups: 4:1, 4.5:1, and 5:1; The concentration of Fe(NO3)3 solution was set into three groups: 0.5mol / L, 0.55mol / L, and 0.6mol / L; Comparative Example 1: The mass ratio of ZrOCl2 to Fe3O4 is 3:1, and the concentration of Fe(NO3)3 solution is 0.4 mol / L; Comparative Example 2: The mass ratio of ZrOCl2 to Fe3O4 is 6:1, and the concentration of Fe(NO3)3 solution is 0.7 mol / L;

[0045] The performance of the anti-complexation support depends on the coordinated optimization of the magnetic core layer, catalytically active layer, and dual protective layer. In the magnetic core layer, the mass ratio of ZrOCl2 to Fe3O4 (4-5:1) directly affects the core's mechanical strength and magnetic recovery ability. A too low ratio (such as 3:1 in Comparative Example 1) results in poor core wear resistance due to insufficient ZrO2. A too high ratio (such as 6:1 in Comparative Example 2) reduces the Fe3O4 content and affects magnetic stability. An intermediate value of 4.5:1 balances the two, providing a stable framework for the support. In the catalytically active layer, the Fe(NO3)3 solution concentration (0.5-0.6 mol / L) determines the particle size and dispersion of the α-Fe2O3 microaggregates. A too low concentration (0.4 mol / L) reduces catalytic efficiency due to insufficient active particles, while a too high concentration (0.7 mol / L) leads to particle agglomeration and reduces active sites. An intermediate value of 0. 55mol / L can form high specific surface area particles of 10-20nm, maximizing catalytic activity; the effectiveness of the double protective layer (competitive binding layer and shielding protection layer) also depends on parameter matching. When the base-core ratio of 4.5:1 is combined with the Fe(NO3)3 concentration of 0.55mol / L, the competitive binding layer can fully occupy the coordination site, and the shielding protection layer (50-100nm film thickness, 0.28-0.31nm lattice spacing) can effectively block the penetration of the chelating agent, so that the EDTA retention rate, COD removal rate and cycle stability are all optimized (90.2%, 97.7%, 92.5%). Parameter deviation will destroy this synergy, resulting in a significant decline in performance, which fully confirms the decisive role of carrier preparation parameters on structural integrity and functional efficiency.

[0046] In step S2, according to the second characteristic parameter, a liquid phase catalyst is added to activate the active sites on the surface of the anti-complexation support; Liquid-phase catalysts refer to catalytically active substances that exist in a dissolved or nano-dispersed state in the Fenton reaction system and are used to synergistically enhance the surface reaction of the anti-complexation support; This application uses ferrous sulfate solution as a liquid phase catalyst, the particle size of ferrous sulfate is 20-50nm, the concentration of ferrous sulfate is 50-100mg / L, and free Fe 2+ Ions act as an electronic bridge to activate the micro-aggregates of α-Fe2O3 on the surface of the carrier; the reaction time is 5-15 minutes; Fe 2+ α-Fe2O3 surface ≡Fe 3+ Electron transfer occurs, generating highly active ≡Fe 2+ site, initiating the Fenton chain reaction , thereby activating the catalytic active sites of the microaggregates and greatly improving the decomposition efficiency of H2O2; free Fe 2+ Preferentially competes with EDTA-Fe for binding to EDTA, forming soluble [Fe(EDTA)3] 2+, blocking complexation and protecting the active sites of the carrier from being blocked; liquid phase Fe 2+ Concentration and free Fe 3+ The molar ratio of concentration is 1:4-6; Fe 2+ Concentration range is 5–10 mg / L; The Fe content of the residual liquid after pretreatment is obtained in real time through online sensors 3+ and Fe 2+ content, pH value and COD concentration, the AI ​​system calculates the liquid phase Fe based on the following formula 2+ Dosage ,in, is the COD concentration, Fe 3+ concentration, M is Fe 3+ and Fe 2+ molar ratio; The steps of adding liquid catalyst are as follows: a ferrous sulfate solution tank is configured in the liquid storage unit with a concentration of 50–100 mg / L and a particle size of 20–50 nm, and nitrogen is used to seal the solution to prevent Fe 2+ Oxidation; the dosing unit uses an electromagnetic metering pump with an accuracy of ±1%. The pump head is made of polytetrafluoroethylene, with a flow range of 0-10L / h and a suitable reactor processing capacity of 1-10m 3 / h; a static mixer is set at the inlet pipe of the fluidized bed reactor, with a mixing length of 3-5 times the pipe diameter to ensure that Fe 2+ The solution is quickly and evenly mixed with the residual liquid after pretreatment, and the mixing time is less than 1 minute.

[0047] After pretreatment to convert the residual liquid from reactive dyeing into a low-viscosity, acidic, homogeneous matrix, S2 completes the catalytic activation of the reaction system through two-dimensional addition: on the one hand, based on the pre-collected characteristic parameters such as the complexing agent concentration and the total amount of metal ions, the anti-complexing carrier is accurately added, and its composite structure realizes anti-complexing adsorption and catalytic site protection; on the other hand, the total amount of metal ions, pH and COD concentration of the residual liquid after pretreatment are monitored in real time through online sensors, and the AI ​​system dynamically calculates the amount of liquid-phase catalyst added. After the fluidization of the carrier is stabilized, it is evenly added through a metering pump and a static mixer. The active site activation of the α-Fe2O3 micro-aggregates on the carrier surface and the EDTA complexation blocking are completed within 5-15 minutes, laying the catalytic foundation for the Fenton reaction.

[0048] After the anti-complexing carrier and the liquid-phase catalyst are synergistically activated, the system enters the key step S3, where hydrogen peroxide is added in stages through AI and the fluidization state of the fluidized bed is regulated. Microscale vortexes are used to enhance mass transfer, initiate an efficient Fenton reaction, and achieve deep degradation of high-salt, high-complexing active dye residues.

[0049] In step S3, AI starts the staged addition of hydrogen peroxide, including: The first stage lasts for 10-15 minutes, with a total dosage of 30%, a flow rate of 5-8 L / h, and a target ORP of 300-350 mV; The second stage lasts for 15-20 minutes, with a total dosage of 50%, a flow rate of 10-15 L / h, and a target ORP of 450-500 mV; The third stage lasts for 10-15 minutes, during which the remaining 20% ​​is added at a flow rate of 5-8 L / h to maintain ORP at 500-550 mV. If the target ORP is not reached in a certain stage, the AI ​​system will dynamically extend the duration of that stage; Hydrogen peroxide is stored in a hydrogen peroxide storage tank with a concentration of 25-30% hydrogen peroxide solution, equipped with a cooling jacket to maintain the temperature at 15-20°C; 4-6 fan-shaped nozzles with an aperture of 0.5-0.6mm are arranged in the lower part of the fluidized bed for multi-point spraying to avoid local excess of H2O2 leading to self-decomposition.

[0050] The fluidized bed adopts variable frequency circulation pump with head of 15-20m and flow rate of 0-30m 3 / h, with AI dynamic adjustment; at the same time, a distribution plate is set with an opening rate of 0.8-1.2%, an opening diameter of 0.6-0.8mm, and a hole spacing of 10-15mm.

[0051] Increase the rising velocity from the initial velocity to 0.025 m / s, control the bed expansion ratio at 1.5-1.8 times, and maintain the shear rate greater than 500 s -1 .

[0052] Ultimately, 50-100μm micro-vortices are generated, which strengthen the contact between H2O2 and pollutants, improve the mass transfer coefficient, prevent the deposition of micron-sized fiber fragments (cotton / polyester fiber debris), and ensure that the shear stress at the bottom of the bed is greater than 8Pa.

[0053] Furthermore, a microwave source with a frequency of 2.45 GHz and an adjustable power of 1-5 kW is placed along the sidewalls of the bed. When the UV270 value detected exceeds 0.6 AU, the microwave is activated at 2 kW for 10 minutes. UV270 refers to the absorbance at a wavelength of 270 nm. The microwave operates in an intermittent mode, on for 2 minutes and off for 1 minute, to prevent local overheating and thus improve the efficiency of cleaving the azo rings in the reactive dye polymers.

[0054] In step S3, when the UV270 detection value is greater than 0.6AU, the microwave source is activated along the side wall of the fluidized bed. This is to improve the cleavage efficiency of the azo ring in the reactive dye polymerization product through the action of microwaves, reflect the concentration change of the reactive dye polymerization product in the Fenton reaction system and the reaction progress, and provide a judgment basis for whether to start the microwave-assisted reaction.

[0055] In step S3, the AI ​​control system adds hydrogen peroxide in stages and regulates the fluidization state of the fluidized bed, utilizing micro-scale vortices to enhance mass transfer and initiate a highly efficient Fenton reaction. Hydrogen peroxide addition is divided into three stages, with the total dosage, flow rate, and target ORP increasing in sequence. If the target ORP is not reached, the AI ​​system dynamically extends the duration of each stage. The hydrogen peroxide storage tank is equipped with a cooling jacket to maintain the temperature at 15-20°C, and multi-point spraying is performed through fan-shaped nozzles at the bottom of the fluidized bed. The fluidized bed utilizes a variable frequency circulating pump with AI dynamic regulation. The fluidization state is controlled by a guide tube and distribution plate, generating 50-100μm micro-vortices to enhance the contact between H2O2 and pollutants and prevent the deposition of micron-sized fiber fragments (cotton / polyester fiber debris).

[0056] In step S4, the AI ​​controls the addition of alkali to adjust the pH, and the purified water and recyclable carrier are obtained through solid-liquid separation; Alkali callback includes: The alkali solution preferably uses 10wt% NaOH solution or waste alkali solution, and an intelligent metering pump with an alkali-resistant PTFE pump head is used, with a flow accuracy of ±1% and a response time of less than 2 seconds.

[0057] The pH control logic is: real-time monitoring of pH value, if pH is less than 6.0, then add NaOH; if pH exceeds 7.5, then stop adding. The goal is to control the end pH in the range of 6.5-7.5 to avoid Fe 3+ Redissolve or generate Fe(OH)3 colloid, the reaction time is about 5-10 minutes, and the ORP drops to less than 100mV, indicating that the neutralization is complete. This operation can neutralize the acidic effluent to near neutrality, meeting the requirements of subsequent biochemical treatment or discharge, and promoting the free Fe 3+ Converted into Fe(OH)3 flocs to facilitate solid-liquid separation.

[0058] When the content of micron-sized fiber fragments (cotton / polyester fiber fragments) in the residual liquid is greater than 1g / L or Fe 3+ When the concentration is lower than 10 mg / L, add flocculants, including: Polyaluminium chloride, concentration 10-20mg / L; Anionic polyacrylamide, concentration is 1-2 mg / L.

[0059] Mixing conditions: quick mixing first, G=300-350s -1 , 1-2 minutes, then stir slowly, (G = 50-60s -1 , 5-6 minutes.

[0060] The separation device is: Magnetic separator, for magnetic carriers, field strength 0.3-0.5T; Plate and frame filter press, filtration pressure 0.4-0.6MPa, filter cloth pore size 5-10μm; Or centrifuge, speed 3000-5000rpm, suitable for high-salt wastewater.

[0061] The separation parameters require that the carrier recovery moisture content is less than 5%, and it can be directly returned to the fluidized bed for recycling; the sludge output is 0.5-1.0kg / m 3 Wastewater.

[0062] The final product: The purified effluent, with COD < 5000mg / L, Fe < 0.1mg / L, and pH = 6.5-7.5, enters the plant's biochemical system or meets discharge standards; The recovered carrier, mainly ZrO2@Fe3O4 microspheres, can be returned to step S2 for recycling.

[0063] This application targets the wastewater treatment of reactive dye residues from the printing and dyeing industry. The materials involved can be procured through a combination of purchase and in-house preparation. The core components of the anti-complexing carrier (such as ZrOCl2, Fe3O4, Fe(NO3)3, and EDTA) can be purchased as industrial-grade or analytical-grade reagents, while the composite structure (magnetic core layer, catalytically active layer, competitive binding layer, and shielding protective layer) is in-house prepared using a specific process. The raw material for the liquid-phase catalyst (ferrous sulfate solution) is industrial-grade ferrous sulfate, which is nano-milled and then used. Reagents such as hydrogen peroxide, sulfuric acid, and NaOH, as well as flocculants such as polyaluminum chloride and polyacrylamide, are all purchased from industrial sources. The materials used for fluidized bed equipment (316L stainless steel and fiberglass reinforced plastics) can be custom-made. Through the appropriate selection and preparation of these materials, efficient treatment of high-salt, high-complexation, and high-COD printing and dyeing residues can be achieved.

[0064] Example 1:

[0065] Select 1m of reactive dye residual liquid 3 Its characteristic parameters are: COD concentration 180000mg / L, complexing agent (EDTA) concentration 10000mg / L, metal ion (Fe 2+ 、Fe 3+ 、Cu 2+ Cr 3+ ) total amount 350mg / L, micron-grade cotton fiber fragment concentration 2g / L, particle size 3μm, salt ions (Na + 、Cl - 、SO4 2- )Total concentration 6wt%, pH=12.

[0066] S1. The above characteristic parameters are collected through online detection equipment and transmitted to the AI ​​control system. The dyeing residual liquid is sent to the pretreatment system: a high-speed shearing machine is used to shear at a speed of 4000 rpm for 3.5 minutes to reduce the viscosity to 9 cP; then, waste acid from the factory is added to adjust the pH to 2.5. The reaction time is 12 minutes. The residual liquid after pretreatment is transported to the fluidized bed.

[0067] S2. Based on the pre-collected complexing agent concentration, the AI ​​system calculates the dosage of the anti-complexing carrier as 2 kg (the equilibrium adsorption capacity of the carrier for EDTA is 5000 mg / g), and adds it to the fluidized bed reactor; at the same time, the parameters of the residual liquid after pretreatment are monitored in real time, and a ferrous sulfate solution with a concentration of 75 mg / L and a particle size of 35 nm is added as a liquid-phase catalyst. It is injected at a flow rate of 5 L / h through an electromagnetic metering pump, mixed with the residual liquid through a static mixer (mixing length 4 times the pipe diameter), and reacted for 10 minutes to control the liquid-phase Fe 2+ Concentration 7.5mg / L, with free Fe 3+ The concentration molar ratio is 1:5.

[0068] After the addition of S3 and liquid catalyst is completed, the AI ​​control system starts the staged addition of hydrogen peroxide: the first stage lasts for 12 minutes, with 30% of the total amount of 27.5% hydrogen peroxide solution added at a flow rate of 6.5 L / h, and the target ORP is raised to 325 mV; the second stage lasts for 17 minutes, with 50% of the total amount added at a flow rate of 12.5 L / h, and the target ORP is raised to 475 mV; the third stage lasts for 12 minutes, with the remaining 20% ​​added at a flow rate of 6.5 L / h, maintaining the ORP at 525 mV. The fluidized bed fluidization control is started simultaneously, increasing the rising flow rate from the initial 0.012 m / s to 0.025 m / s, controlling the bed expansion ratio to 1.65, and the shear rate to 600 s -1 , generating 75 μm micro-vortices and a shear stress of 9 Pa at the bottom of the bed. When the UV270 detection value reached 0.7 AU, the 2.45 GHz microwave source was started with a power of 2 kW and operated for 10 min in a 2 min on, 1 min off mode.

[0069] After the completion of S4 and Fenton reaction, the AI ​​control system starts to add 10wt% NaOH solution, and adjusts the pH back to 7.0 through the alkali-resistant intelligent metering pump (flow accuracy ±1%). The reaction time is 7 minutes, and the ORP drops to 80mV. Because the concentration of fiber fragments in the residual liquid is 2g / L, 15mg / L polyaluminum chloride and 1.5mg / L anionic polyacrylamide are added. First, G=325s -1 Mix quickly for 1.5 minutes, then mix at G=55 seconds -1 Stir slowly for 5.5 minutes. Use a plate and frame filter press (filtration pressure 0.5 MPa, filter cloth pore size 7.5 μm) for solid-liquid separation to obtain purified effluent and recovered carrier.

[0070] Example 2:

[0071] An artificial intelligence dosing method for Fenton reaction, the similarities with Example 1 are not repeated here, and the differences from Example 1 are: The dosage of the anti-complexing carrier is 1.5 kg.

[0072] Example 3:

[0073] An artificial intelligence dosing method for Fenton reaction, the similarities with Example 1 are not repeated here, and the differences from Example 1 are: The dosage of the anti-complexing carrier is 2.5 kg.

[0074] Example 4:

[0075] An artificial intelligence dosing method for Fenton reaction, the similarities with Example 1 are not repeated here, and the differences from Example 1 are: The concentration of ferrous sulfate is 50 mg / L.

[0076] Example 5:

[0077] An artificial intelligence dosing method for Fenton reaction, the similarities with Example 1 are not repeated here, and the differences from Example 1 are: The concentration of ferrous sulfate is 100 mg / L.

[0078] Example 6:

[0079] An artificial intelligence dosing method for Fenton reaction, the similarities with Example 2 are not repeated here, and the differences from Example 2 are: The concentration of ferrous sulfate is 50 mg / L.

[0080] Example 7:

[0081] An artificial intelligence dosing method for Fenton reaction, the similarities with Example 2 are not repeated here, and the differences from Example 2 are: The concentration of ferrous sulfate is 100 mg / L.

[0082] Example 8:

[0083] An artificial intelligence dosing method for Fenton reaction, the same as Example 3 is not repeated here, and the difference from Example 3 is: The concentration of ferrous sulfate is 50 mg / L.

[0084] Example 9:

[0085] An artificial intelligence dosing method for Fenton reaction, the same as Example 3 is not repeated here, and the difference from Example 3 is: The concentration of ferrous sulfate is 100 mg / L.

[0086] Example 10: An artificial intelligence dosing method for Fenton reaction, the similarities with Example 1 are not repeated here, and the differences from Example 1 are: The rising velocity of the fluidized bed is 0.02 m / s.

[0087] Example 11: An artificial intelligence dosing method for Fenton reaction, the similarities with Example 1 are not repeated here, and the differences from Example 1 are: The rising velocity of the fluidized bed is 0.03 m / s.

[0088] Experimental Example 1: This experimental example selected Examples 1-9 for testing: the dosage of the anti-complexing carrier directly determines the blocking ability of the strong chelating agent (EDTA), which is the core of achieving anti-complexing catalysis; the concentration of the liquid phase catalyst affects the activation efficiency of the carrier active sites and is related to the catalytic reaction rate; Table 1 Anti-complexation carrier dosage and liquid catalyst concentration change test

[0089] The data in Table 1 show that the synergistic effect of the dosage of anti-complexing carrier and the concentration of ferrous sulfate significantly affects the treatment effect: when the carrier dosage is insufficient, the complexing blocking ability of EDTA is weakened, resulting in the blocking of catalytic sites and a decrease in COD removal rate; if the concentration of ferrous sulfate is too low, it is difficult to fully activate the active sites on the carrier surface. Although too high a concentration can improve the reaction efficiency, it may increase the risk of Fe residual. The intermediate concentration combination (2kg carrier + 75mg / L catalyst) has the best effect due to the balance between complexing blocking and activity activation.

[0090] Experimental Example 2: This experimental example selected Examples 1, 10, and 11 for testing: The rising flow rate of the fluidized bed affects the contact efficiency between the pollutants and the oxidant and catalyst by regulating the mass transfer process, and is the key to enhancing mass transfer.

[0091] Table 2 Fluidized bed rising velocity variable experiment

[0092] The data in Table 2 show that the rising flow rate of the fluidized bed affects the reaction by regulating the mass transfer efficiency: when the flow rate is too low (0.02 m / s), the micro-vortex intensity is insufficient, the contact between the pollutants and the catalyst is insufficient, and the COD removal rate is slightly reduced; although the flow rate is too high (0.03 m / s) to enhance the mass transfer, the energy consumption increases and the carrier is easily carried out, while the intermediate flow rate (0.025 m / s) takes into account both the mass transfer efficiency and the system stability, and the overall effect is better.

[0093] The above description is based on the ideal embodiment of the present invention. Based on the above description, relevant personnel can make various changes and modifications without departing from the technical scope of this invention. The technical scope of this invention is not limited to the content of the specification and must be determined according to the scope of the claims.

Claims

1. An artificial intelligence dosing method for Fenton reaction, characterized in that: Including steps: S1, pre-treating the reactive dye dyeing residual liquid and conveying it to a fluidized bed, and pre-collecting a first characteristic parameter of the reactive dye dyeing residual liquid; wherein the first characteristic parameter is the complexing agent concentration and the residual liquid volume; S2, adding anti-complexation carrier to the fluidized bed based on the first characteristic parameter, monitoring the second characteristic parameter in real time, and adding liquid phase catalyst; wherein the second characteristic parameter is COD concentration, Fe 3+ concentration and Fe 3+ and Fe 2+ molar ratio, liquid phase catalyst is used to activate the active sites on the surface of the anti-complexation support; S3. After the liquid catalyst is added, the AI ​​control system adds hydrogen peroxide in stages, simultaneously increases the flow rate of the fluidized bed in steps, and combines microwaves to carry out the Fenton reaction; S4. After the Fenton reaction is completed, AI controls the addition of alkali to adjust the pH, separate the solid and liquid, and obtain purified water.

2. The artificial intelligence dosing method for Fenton reaction according to claim 1, characterized in that: In step S1, preprocessing includes: The reactive dyeing residual liquid is mechanically sheared at a speed of 3000-5000 rpm for 2-5 minutes to break up the fiber fragment agglomerates and reduce the residual liquid viscosity to 8-10 cP; Then add sulfuric acid to the residual liquid to adjust the pH, the amount of acid used is 3-5kg / m 3 , react for 10-15 minutes, reduce the pH to 2-3, and destroy the chelate bond between EDTA and metal ions by pH adjustment, releasing free Fe 3+ , among which the released free Fe 3+ It is subsequently used as a catalyst for the Fenton reaction.

3. The artificial intelligence dosing method for Fenton reaction according to claim 1, characterized in that: In step S2, the preparation of the anti-complexation carrier includes: In an ammonia solution with a pH of 10-11, ZrOCl2 and Fe3O4 were co-precipitated at a mass ratio of 4-5:1 and reacted at 180°C for 12 hours to form ZrO2@Fe3O4 composite microspheres with a diameter of 0.5-1 mm, forming a magnetic core layer. The microspheres were immersed in a 0.5-0.6 mol / L Fe(NO3)3 solution and ultrasonically treated at 60°C for 30-40 minutes. They were then calcined at 500-550°C for 2 hours under a nitrogen atmosphere to form α-Fe2O3 microaggregates with a particle size of 10-20 nm on the surface of the microspheres, forming a catalytically active layer. The microspheres are immersed in an EDTA-Fe complex solution with a pH of 4-5 and a concentration of 0.1-0.2 mol / L, and reacted at 60°C for 3-5 hours with stirring to form a competitive binding layer on the catalytic active layer; ZrO2-SiO2 sol is spin-coated on the surface of the microspheres, wherein the molar ratio of Zr to Si is 3-4:

1. After spin-coating, the microspheres are first dried at 60-80°C for 15-20 minutes and then sintered at 500-550°C for 1-1.5 hours to form a ZrO2-SiO2 coating film with a thickness of 50-100nm and a lattice spacing of 0.28-0.31nm on the competitive binding layer to form a shielding protective layer, and finally an anti-complexation carrier is obtained.

4. The artificial intelligence dosing method for Fenton reaction according to claim 3, characterized in that: The spin coating process parameters are: sol solid content 8-12wt%, spin coating is carried out in two stages, the first stage is spin coating at 300-500 rpm for 15-20 seconds, and the second stage is spin coating at 1000-1500 rpm for 40-60 seconds; the spin coating environment is controlled at a temperature of 20-25°C and a relative humidity of 40-60%.

5. The artificial intelligence dosing method for Fenton reaction according to claim 1, characterized in that: The liquid phase catalyst in step S2 is a ferrous sulfate solution with a ferrous sulfate particle size of 20-50 nm and a concentration of 50-100 mg / L.

6. The artificial intelligence dosing method for Fenton reaction according to claim 1, characterized in that: The specific steps of adding hydrogen peroxide in step S3 are as follows: The first stage lasts for 10-15 minutes, with 30% of the total amount added, a flow rate of 5-8L / h, and the target ORP rises to 300-350mV; the second stage lasts for 15-20 minutes, with 50% of the total amount added, a flow rate of 10-15L / h, and the target ORP rises to 450-500mV; the third stage lasts for 10-15 minutes, with the remaining 20% ​​added, a flow rate of 5-8L / h, and the ORP maintained at 500-550mV; if the target ORP is not reached in a certain stage, the AI ​​system dynamically extends the time of that stage.

7. The artificial intelligence dosing method for Fenton reaction according to claim 1, characterized in that: In step S3, the fluidized bed control includes increasing the rising flow rate from the initial flow rate to 0.025 m / s, controlling the bed expansion ratio at 1.5-1.8 times, and maintaining the shear rate greater than 500 s -1 , generating 50-100μm micro-vortices, and the shear stress at the bottom of the bed is greater than 8Pa.

8. The artificial intelligence dosing method for Fenton reaction according to claim 1, characterized in that: In step S4, the alkali addition callback includes: Use 10wt% NaOH solution or waste alkali solution to monitor the pH value in real time. If the pH is less than 6.0, add NaOH; if the pH exceeds 7.5, stop adding. The target pH is controlled at 6.5-7.5, and the reaction time is 5-10 minutes. When the content of micron-sized fiber fragments is greater than 1g / L or Fe 3+ When the concentration is lower than 10 mg / L, add 10-20 mg / L of polyaluminium chloride and 1-2 mg / L of anionic polyacrylamide, mix quickly first and then stir slowly.

9. The artificial intelligence dosing method for Fenton reaction according to claim 1, characterized in that: In step S3, when the UV270 detection value is greater than 0.6AU, the microwave source is started along the side wall of the fluidized bed with a power of 2kW for 10 minutes. The microwave adopts an intermittent operation mode, which is turned on for 2 minutes and turned off for 1 minute.

10. The artificial intelligence dosing method for Fenton reaction according to claim 1, characterized in that: In step S4, the magnetic components are initially separated by magnetic separation, and then deeply dehydrated. The filter cloth is made of polyester with a pore size of 5-10 μm, and the filtration pressure is controlled at 0.4-0.6 MPa.

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