An artificial intelligence dosing method for fenton reaction

Abstract

The application discloses a Fenton reaction artificial intelligence dosing method, aiming at the high salt, high COD, high complex, strong alkalinity, high viscosity and particle-containing characteristics of residual liquid of reactive dye dyeing in the printing and dyeing industry, and realizes efficient treatment through the following steps: pretreatment and pre-collection of residual liquid characteristic parameters; adding an anti-complex carrier and activating the catalytic site of the liquid phase catalyst; AI stages adding hydrogen peroxide and regulating the fluidized bed to generate micro-vortex to strengthen mass transfer; after adding alkali to adjust the pH, solid-liquid separation is carried out to obtain purified effluent and recyclable carrier. Through the synergy of the anti-complex carrier, AI precise dosing and fluidized bed technology, the application solves the problems of catalyst deactivation and insufficient mass transfer of traditional Fenton in complex wastewater treatment, improves the catalytic efficiency, reduces the sludge yield, and realizes the deep treatment of wastewater and the recycling of the carrier.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of sewage treatment, and particularly relates to an artificial intelligence dosing method for Fenton reaction. BACKGROUND

[0002] With the rapid development of industrialization, the composition of industrial wastewater is becoming increasingly complex, and especially the wastewater containing refractory organic matter has become a major challenge in the field of sewage treatment. The traditional biological treatment method has low efficiency for such pollutants because microorganisms are difficult to metabolize highly toxic or inert substances; the physical adsorption method has the problem of saturation and regeneration, and the membrane technology is easily contaminated and has high cost. The advanced oxidation technology has attracted much attention because it can produce strong oxidizing free radicals to degrade stubborn organic matter, and the Fenton reaction has become the mainstream choice because of its simple operation and easy-to-obtain reagents. However, the traditional Fenton process relies on homogeneous iron catalysis, requires a strict acidic environment, and produces a large amount of iron-containing sludge, causing secondary pollution and high disposal cost. In addition, complex wastewater such as complexing agents, high salt content or suspended solids can easily deactivate the catalyst, resulting in unstable oxidation efficiency, which restricts its large-scale application.

[0003] The existing technology, the optimization of the current Fenton process is mostly focused on adjusting the ratio of reagents or improving the reactor, but there are still some fundamental bottlenecks: 1. Limited catalytic efficiency: homogeneous iron ions are easy to form precipitates or chelates with phosphates, humic acids and other substances in wastewater, losing catalytic activity; 2. Strong pH dependence: iron rapidly precipitates under neutral or alkaline conditions, requiring continuous acid addition for adjustment, increasing the complexity and cost of operation; 3. Sludge problem is prominent: Fe 3+ is converted into Fe(OH)3 sludge in large quantities, which is difficult to dewater and dispose; 4. Weak anti-interference ability: high chloride ions quench free radicals, and 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 the core defects such as sludge and salt resistance cannot be solved.

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

[0006] The present application overcomes the shortcomings of the prior art and provides an artificial intelligence dosing method for Fenton reaction, aiming to solve the problem of high salt, high viscosity and high complexing characteristics of the residual liquid of reactive dyeing in the dyeing industry.

[0007] To achieve the above purpose, the technical scheme adopted by the present application is as follows: an artificial intelligence dosing method for Fenton reaction, comprising:

[0008] S1. After pretreatment, the reactive dye dyeing residue is transported to a fluidized bed, and the first characteristic parameters of the reactive dye dyeing residue are pre-collected; wherein, the first characteristic parameters are the complexing agent concentration and the residue volume;

[0009] S2. Based on the first characteristic parameter, an anti-complexation carrier is added to the fluidized bed, the second characteristic parameter is monitored in real time, and a liquid-phase catalyst is added; 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 active sites on the surface of anti-complexing support;

[0010] S3. After the liquid-phase catalyst is added, the AI ​​control system adds hydrogen peroxide in stages, simultaneously increasing the fluidized bed flow rate in steps, and combining it with microwaves to carry out the Fenton reaction.

[0011] S4. After the Fenton reaction is completed, the AI ​​controls the addition of alkali to adjust the pH, and the solid and liquid are separated to obtain purified water.

[0012] In a preferred embodiment of the present invention, step S1 includes preprocessing:

[0013] Mechanical shearing is applied to the residual dyeing liquor of reactive dyes at a speed of 3000-5000 rpm for 2-5 minutes to break up fiber fragments and reduce the viscosity of the residual liquor to 8-10 cP.

[0014] Then add sulfuric acid to the residual liquid to adjust the pH, using 3-5 kg / m³ of acid. 3 After reacting for 10-15 minutes, the pH is lowered to 2-3. This pH adjustment breaks the chelate bond between EDTA and metal ions, releasing free Fe. 3+ Among them, the released free Fe 3+ It was subsequently used as a catalyst for the Fenton reaction.

[0015] In a preferred embodiment of the present invention, step S2, the preparation of the anti-complexing carrier includes:

[0016] In an ammonia solution with pH=10-11, ZrOCl2 and Fe3O4 were co-precipitated at a mass ratio of 4-5:1 and reacted at 180℃ for 12 hours to form ZrO2@Fe3O4 composite microspheres with a diameter of 0.5-1 mm, forming a magnetic core layer.

[0017] Microspheres were immersed in a Fe(NO3)3 solution with a concentration of 0.5-0.6 mol / L and subjected to ultrasonic treatment at 60°C for 30-40 minutes. Then, under nitrogen protection, they were calcined at 500-550°C for 2 hours to form α-Fe2O3 micro-aggregates with a particle size of 10-20 nm on the surface of the microspheres, forming a catalytic active layer.

[0018] The microspheres are immersed in an EDTA-Fe complex solution with pH=4-5 and concentration of 0.1-0.2 mol / L, and stirred and reacted at 60°C for 3-5 hours to form a competitive binding layer on the catalytically active layer;

[0019] The ZrO2-SiO2 sol is spin-coated on the surface of the microspheres, the molar ratio of Zr and Si is 3-4:1, and after spin-coating, the microspheres are first dried at 60-80°C for 15-20 minutes, and then sintered at a temperature of 500-550°C for 1-1.5 hours to form a ZrO2-SiO2 coating film with a thickness of 50-100 nm and a lattice spacing of 0.28-0.31 nm on the competitive binding layer, thereby forming a shielding protective layer, and finally obtaining a complexing-resistant carrier.

[0020] In a preferred embodiment of the present application, the spin-coating process parameters are as follows: the solid content of the sol is 8-12 wt%, the spin-coating is carried out in two stages, the first stage is spin-coated at a speed of 300-500 rpm for 15-20 seconds, and the second stage is spin-coated 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%.

[0021] In a preferred embodiment of the present application, the liquid phase catalyst in step S2 is a ferrous sulfate solution, the particle size of the ferrous sulfate is 20-50 nm, and the concentration is 50-100 mg / L.

[0022] In a preferred embodiment of the present application, the phased addition of hydrogen peroxide in step S3 is as follows:

[0023] The first stage lasts for 10-15 minutes, the total amount of hydrogen peroxide added is 30%, the flow rate is 5-8 L / h, and the target ORP is raised to 300-350 mV; the second stage lasts for 15-20 minutes, the total amount of hydrogen peroxide added is 50%, the flow rate is 10-15 L / h, and the target ORP is raised to 450-500 mV; the third stage lasts for 10-15 minutes, the remaining 20% of hydrogen peroxide is added, the flow rate is 5-8 L / h, and the ORP is maintained at 500-550 mV; if the target ORP is not reached in a certain stage, the AI system dynamically extends the time of that stage.

[0024] In a preferred embodiment of the present application, in step S3, the fluidized bed fluidization control includes stepwise increasing the upward flow rate from the initial flow rate to 0.025 m / s, controlling the bed expansion ratio to be 1.5-1.8 times, maintaining the shear rate to be greater than 500 s -1 , generating 50-100 μm micro-vortices, and the shear stress at the bottom of the bed is greater than 8 Pa.

[0025] In a preferred embodiment of the present application, in step S4, the alkali addition and adjustment include:

[0026] Using 10wt% NaOH solution or waste lye, monitoring pH value in real time, if pH is less than 6.0, adding NaOH; if pH exceeds 7.5, stopping adding, target pH control is 6.5-7.5, reaction time is 5-10 minutes; when the content of micro-fiber fragments is greater than 1g / L or Fe 3+ When the concentration of Fe is less than 10mg / L, 10-20mg / L of polyaluminum chloride and 1-2mg / L of anionic polyacrylamide are added, and then fast mixing and slow stirring are carried out.

[0027] In one preferred embodiment of the application, 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, the power is 2kW, and the duration is 10 minutes, the microwave adopts intermittent operation mode, and is opened for 2 minutes and closed for 1 minute.

[0028] In one preferred embodiment of the application, in step S4, the magnetic components are preliminarily separated by magnetic separation, and then deep dehydration is carried out, the filter cloth is selected to be polyester material with a pore size of 5-10um, and the filtration pressure is controlled to be 0.4-0.6MPa.

[0029] The application solves the defects in the background art, and has the following beneficial effects:

[0030] (1) The application provides a fluidized bed Fenton treatment system and method for reactive dyeing residual liquid in the printing and dyeing industry, by constructing a magnetic ZrO2@Fe3O4 carrier with complexing resistance function, combining AI-controlled precise dosing and a fluidized bed reactor, deep treatment of complex wastewater with high salt, high COD, high complexing strength, strong alkalinity, high viscosity and particles is realized. The technology reduces the viscosity of the residual liquid and destroys the EDTA complex through mechanical shearing and pH adjustment pretreatment, then adds an anti-complexing carrier with a surface loaded alpha-Fe2O3 catalytic active layer and an EDTA-Fe competitive binding layer, under the control of AI, hydrogen peroxide is added in stages and the fluidization state is optimized, mass transfer is intensified by micro-vortex, and finally standard effluent and recyclable carrier are obtained through intelligent neutralization and solid-liquid separation, effectively solving the problem that traditional Fenton completely fails in the treatment of such wastewater.

[0031] (2) The anti-complexing carrier is composed of a magnetic ZrO2 microsphere base core, a small aggregate of alpha-Fe2O3, EDTA-Fe competition and a ZrO2-SiO2 coating film, wherein the magnetic ZrO2 microsphere provides mechanical strength and magnetic recovery, the small aggregate of alpha-Fe2O3 serves as a catalytic active site, the EDTA-Fe competition layer blocks the chelation of the complexing agent in the wastewater to the catalytic site through competitive binding, and the ZrO2-SiO2 coating film shields the penetration of the complexing agent to protect the internal active site; this composite structure avoids the blocking of the active site by the complexing agent, ensures the continuous catalytic cycle, and significantly improves the catalytic stability compared with the traditional Fenton, which is prone to form stable complexes with EDTA, resulting in loss of activity, thereby realizing efficient operation of the Fenton reaction in high-complexity printing and dyeing wastewater.

[0032] (3) The anti-complexing carrier is added at the same time, and a liquid phase catalyst is added according to real-time monitoring parameters, which activates the active sites on the surface of the carrier, wherein the liquid phase Fe 2+ acts as an electronic bridge and transfers electrons to the alpha-Fe 2 O 3 small aggregate to generate high-activity ≡Fe 2+ sites to start the Fenton chain reaction, and the free Fe 2+ preferentially combines with the complexing agent to form a soluble complex; this synergistic effect rapidly activates the active sites of the carrier and blocks the blocking of the carrier by EDTA, thereby strengthening the catalytic efficiency, reducing the waste of reagents, and ensuring the continuous and efficient reaction compared with the traditional Fenton which relies on homogeneous iron catalysis and is difficult to deal with high-complexity wastewater, resulting in catalyst deactivation.

[0033] (4) The AI control system is used to add hydrogen peroxide in stages, and a fluidized bed flow control is started at the same time to generate 50-100 mu m micro-scale vortices, and the stage addition is dynamically adjusted according to the ORP target to avoid local excess self-decomposition of hydrogen peroxide; the fluidized bed adjusts the upward flow rate and shear rate to strengthen mass transfer and prevent micron-sized fiber fragments from depositing. This improves the utilization efficiency of hydrogen peroxide, promotes the sufficient contact between H2O2 and pollutants such as active dye polymerization products, and significantly improves the reaction efficiency compared with the traditional Fenton, which has a single hydrogen peroxide addition and is prone to incomplete oxidation due to insufficient mass transfer or high-salt environment, thereby realizing the deep degradation of pollutants in high-salt and high-viscosity dyeing residual liquid.

[0034] (5) After the Fenton reaction is completed, the AI control is used to add alkali to adjust the pH to neutral, and a magnetic separator, plate and frame filter press or centrifuge is used for solid-liquid separation to recover the magnetic anti-complexing carrier, and the pH is controlled to promote the free Fe 3+The transformation into floc and the combination of flocculants reduce the sludge amount; the efficient recovery and regeneration of the carrier reduce the carrier loss, and the sludge production is controlled at a low level; compared with the defects of the traditional Fenton process that produces a large amount of iron-containing sludge and has high dewatering disposal cost, the application effectively reduces the operation cost, further reduces the secondary pollution, and meets the environmental protection requirements. BRIEF DESCRIPTION OF DRAWINGS

[0035] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0036] Figure 1 is a preferred embodiment of the present application.

[0037] Figure 2 is a preferred embodiment of the present application.

[0038] Figure 3 is a preferred embodiment of the present application. DETAILED DESCRIPTION

[0039] The technical solutions in the embodiments of the present application will be described clearly and completely in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the present application.

[0040] In the following description, many specific details are set forth in order to provide a thorough understanding of the present application, but the present application can also be implemented in other ways different from those described herein, therefore, the protection scope of the present application is not limited by the specific embodiments disclosed below.

[0041] SUMMARY

[0042] The present application is aimed at the active dyeing 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 particle content.

[0043] The traditional Fenton technology is completely ineffective in this scenario, and the complexing agent strongly chelates the free Fe 2+ / Fe 3+, forming a stable complex, blocking the catalytic cycle; the chemical bond of the heterocyclic structure in the reactive dye polymerization product is high, and the conventional hydroxyl radical is difficult to effectively break, making it difficult to degrade the core pollutants. In order to solve the above problems, the application proposes to establish an anti-complexation catalysis, mass transfer enhancement, and salt-resistant environment. The application is based on the deep integration of heterogeneous catalysis and reactor kinetics, by combining Fenton reaction and fluidized bed technology: first, a magnetic ZrO2@Fe2O4 carrier with anti-complexation function is prepared, which effectively blocks the chelation of complexing agents to the catalytic site; second, the AI control system is used to accurately control the staged addition of hydrogen peroxide, avoiding catalyst deactivation and ensuring that the reaction proceeds fully; third, the mass transfer process is enhanced by using a fluidized bed reactor to improve reaction efficiency; finally, a magnetic separator, plate and frame filter or centrifuge is used for solid-liquid separation to achieve efficient recovery and regeneration of wastewater.

[0044] An exemplary method:

[0045] As shown in Figure 1 and Figure 2 , an artificial intelligence dosing method for Fenton reaction, comprising the steps of:

[0046] S1, the reactive dye dyeing residual liquid is pretreated and delivered to the fluidized bed, and the first characteristic parameter of the reactive dye dyeing residual liquid is collected; wherein the first characteristic parameter is the concentration of the complexing agent and the residual liquid volume;

[0047] S2, based on the first characteristic parameter, the anti-complexing carrier is added to the fluidized bed, the second characteristic parameter is monitored in real time, and the liquid phase catalyst is added; wherein the second characteristic parameter is the COD concentration, the Fe 3+ concentration and the Fe 3+ and Fe 2+ molar ratio, and the liquid phase catalyst is used to activate the active sites on the surface of the anti-complexing carrier;

[0048] S3, after the liquid phase catalyst is added, the AI control system adds hydrogen peroxide in stages, synchronously increases the flow rate of the fluidized bed in steps, and combines microwave to perform Fenton reaction;

[0049] S4, after the Fenton reaction is completed, the AI control adds alkali to adjust the pH, solid-liquid separation is performed, and purified effluent is obtained.

[0050] The reactive dye dyeing residual liquid is enriched by primary filtration and evaporation concentration, which cannot remove complex components, including: reactive dye polymerization products, dyeing auxiliary residues, metal ions, micron-sized fiber fragments, and high-salt substrates;

[0051] Specifically, the reactive dye polymerization product includes: azo dye dimers, trimers and other heterocyclic structure-containing substances; the proportion of the reactive dye polymerization product is 15-20wt%, the concentration is >150,000mg / L, and a high-COD core pollutant is formed;

[0052] Chromophore residues, mainly ethylenediaminetetraacetic acid (EDTA) and sodium tripolyphosphate, with a concentration of 8,000-12,000 mg / L, have strong chelating properties;

[0053] Metal ions, including: Fe 2+ , Fe 3+ , Cu 2+ , Cr 3+ , with a total concentration of 200-500 mg / L, form stable complexes with EDTA;

[0054] Micro-sized fiber fragments are cotton / polyester fiber debris with a particle size of 1-5 μm and a concentration of 1-3 g / L, resulting in high viscosity of the reactive dyeing residual solution;

[0055] High salt matrix, including: Na + , SO4 2- , Cl - , with an ionic concentration >5 wt%, quenching free radicals and interfering with reaction mass transfer.

[0056] In step S1, the first characteristic parameters include: complexing agent concentration and residual solution volume;

[0057] In step S1, the characteristic parameters of the reactive dyeing residual solution include: COD concentration, complexing agent concentration, total metal ion concentration, fiber fragment concentration and particle size, salt ion concentration, pH value, and viscosity;

[0058] Among them, the COD concentration is detected by an online COD monitor for real-time measurement of core pollutants; the complexing agent concentration is analyzed by a high-performance liquid chromatograph online detector or an ion chromatograph; the total metal ion concentration is determined by an atomic absorption spectrometer or an inductively coupled plasma emission spectrometer; the fiber fragment concentration and particle size are measured by an ultraviolet-visible spectrophotometer, a turbidimeter, 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 by an online pH meter; and the viscosity is determined by an online rotary viscometer or a capillary viscometer.

[0059] In step S1, the reactive dyeing residual solution pretreatment includes:

[0060] A high-speed shearing machine is used to treat the residual solution at a speed of 3000-5000 rpm for mechanical shearing for 2-5 min, with the purpose of breaking the fiber fragment agglomerates and reducing the residual solution viscosity to 8-10 cP;

[0061] Then, sulfuric acid is added to the residual solution through an acid pump to adjust the pH, with an acid amount of 3-5 kg / m 3 , and the reaction is carried out for 10-15 min to reduce the pH to 2-3, thereby destroying the chelating bond between EDTA and metal ions and releasing free Fe3+ wherein the released free Fe 3+ Subsequently, it can be used as a Fenton reaction catalyst.

[0062] S1 pretreatment converts high-complexity residual liquid into low-viscosity, acidic, and homogeneous reaction matrix through precise acid control and controllable shearing, laying a foundation for S2 carrier anti-complexation and S3 efficient oxidation.

[0063] The fluidized bed of the present application is a liquid-solid fluidized bed reactor for treating reactive dye dyeing residual liquid, taking the reactive dye dyeing residual liquid as the liquid medium, making the residual liquid flow through the anti-complexation magnetic carrier in the bed, and controlling the carrier to be in a suspended and flowing state in the liquid through fluidization, greatly increasing the contact area and collision frequency of the carrier and the pollutants in the residual liquid, liquid catalyst and hydrogen peroxide, and strengthening the mass transfer process, thereby improving the Fenton reaction efficiency.

[0064] The fluidized bed material is selected from 316L stainless steel or glass steel that is resistant to acid and alkali corrosion, and the height-to-diameter ratio of the bed body is designed to be 3-5:1 to ensure that the carrier has sufficient fluidization space; a conical transition section is arranged at the bottom of the bed body to reduce liquid stagnation dead zones, and an enlarged section is arranged at the top to reduce the carrier particles from overflowing with the liquid by reducing the local flow rate, while avoiding the accumulation of micron-sized fiber fragments at the top;

[0065] Liquid catalyst feeding ports are arranged in the upper part of the bed body, and hydrogen peroxide is fed in stages through the lower part of the bed body to ensure that the reagents directly enter the fluidization area, quickly disperse, and the top is provided with a pH adjustment alkali feeding port for adjusting the pH after the reaction is completed; the bottom of the fluidized bed is provided with a liquid outlet for discharging the purified wastewater, and a carrier recovery port.

[0066] In step S2, the initial fluidization flow rate of the fluidized bed is 0.005-0.02 m / s to break through the viscous stagnant flow zone and achieve turbulent flow state, which can ensure that the carrier is fully fluidized and avoid deposition, and can also prevent the carrier from being carried out of the reactor by high-speed fluid; the filling rate of the anti-complexation carrier is controlled at 30-40%, if the filling rate is lower than 30%, the surface active sites of the carrier are insufficient, and the catalytic efficiency will decrease; if it is higher than 40%, it will cause the expansion of the fluidization dead zone, 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, which can avoid the blockage of the agglomerates that are not completely dispersed in step S1, and can also ensure the good running state of the fluidized bed.

[0067] In step S2, the anti-complexation carrier is the core material for capturing EDTA-metal complexes and activating catalytic sites in the Fenton reaction;

[0068] As shown in Figure 3 the anti-complexation carrier includes:

[0069] Magnetic core layer, i.e. magnetic ZrO2 microspheres, is used to provide mechanical strength and magnetic recovery, resist high shear force abrasion of fluidized bed, and avoid carrier breakage leading to active component loss;

[0070] Catalytically active layer, i.e. catalytically active particles supported on the surface of microspheres, specifically, micro-aggregates of α-Fe2O3 with particle size of 10-20 nm and specific surface area > 120 m 2 / g, provides a large number of catalytic reaction sites for Fenton reaction; the catalytically active particles of the catalytically active layer act as core catalytic sites for Fenton reaction, and initiate chain reaction under liquid-phase catalyst activation to efficiently decompose hydrogen peroxide to generate hydroxyl radicals and degrade pollutants.

[0071] Competitive binding layer prevents strong complexing agents in residual liquid from destroying the catalytically active sites inside the carrier by means of active occupation; the strong complexing agents contained in the residual liquid have strong chelating ability and are easy to combine with iron elements in the catalytically active layer of the carrier to form stable complexes, resulting in blocked catalytic sites and loss of activity. The complexing agents in the competitive binding layer are pre-bound with Fe 3+ to form complexes, which occupy the binding sites on the surface of the carrier, equivalent to building a barrier on the outer layer of the carrier.

[0072] When the strong complexing agents in the residual liquid flow through the carrier, the EDTA-Fe 3+ complexes that have occupied the sites in the competitive binding layer will compete with the strong complexing agents; since these sites have been occupied by EDTA-Fe 3+ , it is difficult for the strong complexing agents to combine with the iron elements in the catalytically active layer inside the carrier, thereby blocking the chelation of the strong complexing agents to the catalytic sites.

[0073] Shielding protection layer, i.e. ZrO2-SiO2 coating film with a thickness of 50-100 nm and a lattice spacing of 0.28-0.31 nm, which is smaller than the size of the strong complexing agent molecules, thereby preventing direct contact of the macromolecular complexing agents with the inside and shielding the penetration of the strong complexing agents to ensure the stability of the active sites inside; the coating film is not completely closed, but selectively allows small molecules such as H2O2 and OH to pass through through the nanoscale pores, forming a selective channel that allows reaction molecules to enter but rejects complexing agent molecules.

[0074] The shielding protection layer and the competitive binding layer form a double protection: the competitive binding layer consumes free complexing agents through chemical competition, while the shielding protection layer blocks the penetration of the un-consumed complexing agents, and the two work together to reduce the deactivation rate of the catalytically active layer, realizing the recyclable use of the anti-complexing carrier.

[0075] Preparation of the anti-complexing carrier:

[0076] Synthetic magnetic ZrO2 microspheres, in the ammonia solution of pH = 10-11, ZrOCl2 and Fe3O4 are co-precipitated according to the mass ratio of 4-5:1, and ZrO2@Fe3O4 composite microspheres are formed under the condition of 180℃ for 12 hours, the diameter of the microspheres is in the range of 0.5-1mm, which belongs to the hundred-micron level, and the spin coating method is completely applicable to this size.

[0077] First, the magnetic ZrO2 microspheres are immersed in a Fe(NO3)3 solution with a concentration of 0.5-0.6mol / L, and ultrasonic treatment is carried out at 60℃ for 30-40 minutes; then, the microspheres are calcined at a temperature of 500-550℃ for 2 hours in a nitrogen atmosphere, so as to form a small aggregate of α-Fe2O3 with a particle size of 10-20nm on the surface of the microspheres;

[0078] The carrier loaded with the small aggregate of α-Fe2O3 is immersed in an EDTA-Fe complex solution with a pH of 4-5 and a concentration of 0.1-0.2mol / L, and stirred at 60℃ for 3-5 hours, so that the carboxyl group of EDTA and the hydroxyl group on the surface of ZrO2 undergo condensation reaction to form —Zr—OOC— bond, and the construction of the competitive binding layer is completed;

[0079] The ZrO2-SiO2 sol is spin-coated on the surface of the microspheres, wherein the molar ratio of Zr to Si is 3-4:1; the spin-coating process parameters are as follows: the solid content of the sol is 8-12wt%, the spin-coating is carried out in two stages, the first stage is spin-coated at a speed of 300-500rpm for 15-20 seconds, and the second stage is spin-coated 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, the microspheres are first dried at 60-80℃ for 15-20 minutes, and then sintered at a temperature of 500-550℃ for 1-1.5 hours, so as to form a dense ZrO2-SiO2 coating film with a thickness in the range of 50-100nm and a lattice spacing of 0.28-0.31nm, which can shield the penetration of TMEDA and protect the stability of the active sites in the carrier.

[0080] The regeneration of the anti-complexation carrier, after 50-70 cycles of operation, the carrier needs to be soaked in a 5-8% oxalic acid solution for 1-1.5 hours to remove the surface Fe 3+ precipitate, and then calcined at 300-350℃ for 2 hours to restore the activity.

[0081] In step S2, the concentration of the complexing agent directly determines the adsorption requirement of the anti-complexation carrier, and the residual liquid volume refers to the total volume of the active dye dyeing residual liquid after pretreatment and transported to the fluidized bed for Fenton reaction treatment, and the AI system calculates the carrier dosage through the following logic: , wherein, is the concentration of the complexing agent, For residual liquid volume, For the equilibrium adsorption capacity of the carrier to EDTA.

[0082] Through the carrier preparation key parameters, verify its anti complexing ability (EDTA interception rate), catalytic activity (COD removal rate), stability (after 50 times of activity retention rate),

[0083] Preparation variables:

[0084] ZrOCl2 and Fe3O4 mass ratio, set 3 groups: 4:1, 4.5:1, 5:1;

[0085] Fe(NO3)3 solution concentration, set 3 groups: 0.5mol / L, 0.55mol / L, 0.6mol / L;

[0086] Comparative example 1:

[0087] ZrOCl2 and Fe3O4 mass ratio is 3:1, Fe(NO3)3 solution concentration 0.4mol / L;

[0088] Comparative example 2:

[0089] ZrOCl2 and Fe3O4 mass ratio is 6:1, Fe(NO3)3 solution concentration 0.7mol / L;

[0090]

[0091] The performance of the anti-complexing carrier depends on the synergistic optimization of the magnetic base core layer, the catalytically active layer and the double protective layer. In the magnetic base core layer, the mass ratio (4-5:1) of ZrOCl2 to Fe3O4 directly affects the mechanical strength and magnetic recovery capacity of the base core. A low ratio (such as 3:1 in Comparative Example 1) will result in poor anti-wear resistance of the base core due to insufficient ZrO2, and a high ratio (such as 6:1 in Comparative Example 2) will affect the magnetic stability due to the decrease of the proportion of Fe3O4, while the intermediate value 4.5:1 can balance the two, providing a stable skeleton for the carrier. In the catalytically active layer, the concentration (0.5-0.6 mol / L) of Fe(NO3)3 solution determines the particle size and dispersity of the α-Fe2O3 micro-aggregates. A low concentration (0.4 mol / L) will reduce the catalytic efficiency due to insufficient active particles, and a high concentration (0.7 mol / L) will result in particle agglomeration and reduce active sites. The intermediate value 0.55 mol / L can form 10-20 nm particles with high specific surface area, maximizing the catalytic activity. The performance of the double protective layer (competitive binding layer and shielding protective layer) also depends on parameter matching. When the base core ratio is 4.5:1 and the Fe(NO3)3 concentration is 0.55 mol / L, the competitive binding layer can fully occupy the coordination sites, and the shielding protective layer (50-100 nm film thickness, 0.28-0.31 nm lattice spacing) can effectively block the penetration of complexing agents, making the EDTA interception rate, COD removal rate and cycle stability all optimal (90.2%, 97.7%, 92.5%), while deviation of the parameters will destroy this synergy, resulting in a significant decrease in performance, fully demonstrating the decisive role of carrier preparation parameters on the structural integrity and functional efficiency.

[0092] In step S2, according to the second characteristic parameter, the liquid phase catalyst is added to activate the active sites on the surface of the anti-complexing carrier;

[0093] The liquid phase catalyst refers to a catalytically active substance existing in a dissolved or nano-dispersed state in a Fenton reaction system, which is used to synergistically enhance the surface reaction of the anti-complexing carrier;

[0094] In this application, ferrous sulfate solution is used as the liquid phase catalyst, the particle size of ferrous sulfate is 20-50 nm, and the concentration of ferrous sulfate is 50-100 mg / L, providing free Fe 2+ ions as an electronic bridge to activate the α-Fe2O3 micro-aggregates on the surface of the carrier; the reaction time is 5-15 minutes;

[0095] Fe 2+ and the α-Fe2O3 surface ≡Fe 3+ occurs electron transfer to generate high-activity ≡Fe 2+ sites, starting the Fenton chain reaction , thereby activating the catalytically active sites of the micro-aggregates and greatly improving the H2O2 decomposition efficiency; free Fe 2+It preferentially competes with EDTA-Fe to bind with EDTA, forming soluble [Fe(EDTA)3] 2+ Blocking complexation and protecting the active sites of the carrier from blockage; liquid phase Fe 2+ Concentration and free Fe 3+ The molar ratio of the concentrations is 1:4-6; Fe 2+ The concentration range is 5–10 mg / L;

[0096] Fe in the pretreated residual liquid was acquired in real time using online sensors. 3+ and Fe 2+ Based on the content, pH value, and COD concentration, the AI ​​system calculates the liquid phase Fe content using the following formula. 2+ Dosage ,in, COD concentration, For Fe 3+ Concentration, M is Fe 3+ and Fe 2+ molar ratio;

[0097] The steps for adding the liquid-phase catalyst are as follows: A ferrous sulfate solution storage tank with a concentration of 50–100 mg / L and a particle size of 20–50 nm is prepared in the storage unit, and nitrogen gas is used for sealing 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, the flow rate range is 0–10 L / h, and it is suitable for reactors with a capacity of 1–10 m³ / h. 3 / h; A static mixer is installed in the inlet pipe of the fluidized bed reactor, with a mixing length of 3–5 times the pipe diameter, to ensure Fe... 2+ The solution and the pretreated residue are mixed quickly and evenly, with a mixing time of less than 1 minute.

[0098] After pretreatment to transform the reactive dye dyeing residue into a low-viscosity, acidic homogeneous matrix, S2 completes the catalytic activation of the reaction system through a two-dimensional addition: on the one hand, based on pre-collected characteristic parameters such as complexing agent concentration and total metal ion content, an anti-complexing carrier is precisely added, whose composite structure achieves anti-complexing adsorption and catalytic site protection; on the other hand, the total metal ion content, pH, and COD concentration of the pretreated residue are monitored in real time by online sensors, and the AI ​​system dynamically calculates the amount of liquid-phase catalyst to be added. After the carrier is fluidized and stabilized, it is uniformly added through a metering pump and a static mixer. Within 5–15 minutes, the active sites of the α-Fe2O3 micro-aggregates on the carrier surface are activated and EDTA complexation is blocked, laying the catalytic foundation for the Fenton reaction.

[0099] After the anti-complexing carrier is activated in cooperation with the liquid phase catalyst, the system enters the S3 key step, the AI adds hydrogen peroxide in stages and regulates the fluidized bed fluidization state, the micro-scale vortex is used to strengthen the mass transfer, the high-efficiency Fenton reaction is started, and the deep degradation of the high-salt and high-complexing active dye dyeing residual liquid is realized.

[0100] In step S3, the AI starts the hydrogen peroxide addition in stages, including:

[0101] In the first stage, the duration is 10-15 min, the total amount of hydrogen peroxide is 30%, the flow rate is 5-8 L / h, and the target ORP is increased to 300-350 mV.

[0102] In the second stage, the duration is 15-20 min, the total amount of hydrogen peroxide is 50%, the flow rate is 10-15 L / h, and the target ORP is 450-500 mV.

[0103] In the third stage, the duration is 10-15 min, the total amount of hydrogen peroxide is 20%, the flow rate is 5-8 L / h, and the ORP is maintained at 500-550 mV.

[0104] If the target ORP is not reached in a certain stage, the AI system will dynamically extend the stage time.

[0105] The hydrogen peroxide is stored in a hydrogen peroxide storage tank, the concentration of the hydrogen peroxide solution is 25-30%, a cooling jacket is provided to maintain the temperature at 15-20°C, 4-6 fan-shaped nozzles with a hole diameter of 0.5-0.6 mm are arranged in the lower part of the fluidized bed for multi-point injection, and local excess of H2O2 is avoided to cause self-decomposition.

[0106] The fluidized bed fluidization adopts a variable frequency circulating pump, the head is 15-20 m, the flow rate is 0-30 m 3 / h, and the AI is dynamically adjusted; at the same time, a distribution plate is provided, the opening rate of the distribution plate is 0.8-1.2%, the opening hole diameter is 0.6-0.8 mm, and the hole spacing is 10-15 mm.

[0107] The upward flow rate is increased from the initial flow rate to 0.025 m / s, the bed expansion ratio is controlled at 1.5-1.8 times, and the shear rate is maintained greater than 500 s -1 .

[0108] Finally, 50-100 μm micro-vortices are generated, the contact between H2O2 and pollutants is strengthened, the mass transfer coefficient is improved, micron-sized fiber fragments (cotton / polyester fiber debris) are prevented from depositing, and the shear stress at the bottom of the bed is ensured to be greater than 8 Pa.

[0109] Further, a microwave source is arranged along the side wall of the bed, with a frequency of 2.45 GHz and a power of 1-5 kW, which can be adjusted. When the UV270 detection value is greater than 0.6 AU, the microwave is started with a power of 2 kW and lasts for 10 minutes. UV270 refers to the absorbance at a wavelength of 270 nm. The microwave adopts an intermittent operation mode, which is turned on for 2 minutes and turned off for 1 minute to prevent local overheating, thereby improving the efficiency of breaking the azo ring in the active dye polymer product.

[0110] In step S3, when the UV270 detection value is greater than 0.6 AU, the microwave source is started along the side wall of the fluidized bed to improve the efficiency of breaking the azo ring in the active dye polymer product by the action of the microwave. This reflects the change in the concentration of the active dye polymer product in the Fenton reaction system and the progress of the reaction, and provides a basis for determining whether to start the microwave-assisted reaction.

[0111] In step S3, the AI control system adds hydrogen peroxide in stages and controls the fluidization state of the fluidized bed, uses micro-scale vortexes to strengthen mass transfer, and starts the high-efficiency Fenton reaction. The addition of hydrogen peroxide is divided into three stages, and the total amount, flow rate, and target ORP of each stage are progressively increased. If the target ORP is not reached, the AI system dynamically extends the time of the stage. The hydrogen peroxide storage tank is equipped with a cooling jacket to maintain a temperature of 15-20°C, and is injected through multiple points of fan-shaped nozzles at the bottom of the fluidized bed. The fluidized bed uses a variable frequency circulating pump in combination with AI dynamic adjustment to control the fluidization state through a draft tube and a distribution plate to generate 50-100 μm micro-vortices to strengthen the contact between H2O2 and pollutants, and to prevent micron-sized fiber fragments (cotton / polyester fiber debris) from depositing.

[0112] In step S4, the AI controls the addition of alkali to adjust the pH, and the purified effluent and recyclable carrier are obtained after solid-liquid separation;

[0113] The addition of alkali includes:

[0114] The alkali solution preferably selects 10 wt% 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.

[0115] The pH control logic is as follows: real-time monitoring of pH value, if pH is less than 6.0, add NaOH; if pH exceeds 7.5, stop adding. The goal is to control the end-point pH in the range of 6.5-7.5 to avoid Fe 3+ re-dissolution or the generation of Fe(OH)3 colloid, and the reaction time is about 5-10 minutes. When the ORP drops to less than 100 mV, it indicates that the neutralization is complete. This operation can neutralize the acidic effluent to near neutral, meeting the subsequent biochemical treatment or discharge requirements, and promoting the conversion of free Fe 3+ to Fe(OH)3 flocs for solid-liquid separation.

[0116] When the content of micron-sized fiber fragments (cotton / polyester fiber debris) in the raffinate is greater than 1 g / L or the Fe 3+ concentration is less than 10 mg / L, flocculants are added, including:

[0117] Polyaluminum chloride, concentration 10-20 mg / L;

[0118] Anionic polyacrylamide, concentration 1-2 mg / L.

[0119] The mixing conditions are first rapid mixing, G = 300-350 s -1 , 1-2 minutes, and then slow stirring (G = 50-60 s -1 , 5-6 minutes.

[0120] The separation device is:

[0121] Magnetic separator, for magnetic carriers, field strength 0.3-0.5 T;

[0122] Plate and frame filter press, filtration pressure 0.4-0.6 MPa, filter cloth pore size 5-10 μm;

[0123] Or centrifuge, speed 3000-5000 rpm, suitable for high-salinity wastewater.

[0124] The separation parameters require that the carrier recovery moisture content be less than 5%, which can be directly returned to the fluidized bed for recycling; sludge production is 0.5-1.0 kg / m 3 wastewater.

[0125] In the final product:

[0126] Purified effluent, COD <5000 mg / L, Fe <0.1 mg / L, pH = 6.5-7.5, into the plant biochemical system or discharged up to standard;

[0127] Recovered carriers, mainly ZrO2@Fe3O4 microspheres, can be returned to step S2 for recycling.

[0128] The application is directed to the wastewater treatment of reactive dyeing residual liquid in the printing and dyeing industry. The materials involved can be obtained by a combination of purchase and self-preparation: the core components of the anti-complexing carrier (such as ZrOCl2, Fe3O4, Fe(NO3)3, EDTA, etc.) can be purchased as industrial grade or analytical pure reagents, and the composite structure (magnetic base core layer, catalytically active layer, competitive binding layer, shielding protection layer) is self-prepared by a specific process; the raw material ferrous sulfate for liquid phase catalyst (ferrous sulfate solution) is industrial grade, which is processed by nano-grinding and then used; hydrogen peroxide, sulfuric acid, NaOH and other reaction reagents, as well as polyaluminum chloride and polyacrylamide flocculants are all industrial grade outsourcing products; the materials of fluidized bed and other equipment (316L stainless steel, glass steel) can be customized and processed. Through the reasonable selection and preparation of the above materials, the high-salt, high-complexing and high-COD printing and dyeing residual liquid can be efficiently treated.

[0129] Example 1:

[0130] The reactive dyeing residual liquid 1m 3 , and its characteristic parameters are: COD concentration 180000 mg / L, complexing agent (EDTA) concentration 10000 mg / L, total amount of metal ions (Fe 2+ , Fe 3+ , Cu 2+ , Cr 3+ ) 350 mg / L, micron-sized cotton fiber fragment concentration 2 g / L, particle size 3 μm, total salt ion (Na + , Cl - , SO4 2- ) concentration 6 wt%, pH = 12.

[0131] S1, the above characteristic parameters are collected by online detection equipment and transmitted to the AI control system, and 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 min, and the viscosity is reduced to 9 cP; then, the factory waste acid is added to adjust the pH to 2.5, and the reaction time is 12 min, and the residual liquid after pretreatment is transported to the fluidized bed.

[0132] S2, based on the pre-collected complexing agent concentration, the AI system calculates the anti-complexing carrier dosage as 2 kg (the equilibrium adsorption capacity of the carrier to EDTA is 5000 mg / g), which is added to the fluidized bed reactor; at the same time, the parameters of the residual liquid after pretreatment are monitored in real time, and the ferrous sulfate solution with a concentration of 75 mg / L and a particle size of 35 nm is added as a liquid phase catalyst, which is injected by an electromagnetic metering pump at a flow rate of 5 L / h, mixed with the residual liquid by a static mixer (mixing length 4 times pipe diameter), and reacted for 10 min, the liquid phase Fe 2+ concentration is controlled at 7.5 mg / L, and the molar ratio of free Fe 3+ concentration is 1:5.

[0133] S3, after the liquid phase catalyst is added, the AI control system starts to add hydrogen peroxide in stages: the first stage lasts for 12 min, the total amount of 30% 27.5% hydrogen peroxide solution is added, the flow rate is 6.5 L / h, and the target ORP rises to 325 mV; the second stage lasts for 17 min, the total amount of 50% is added, the flow rate is 12.5 L / h, and the target ORP rises to 475 mV; the third stage lasts for 12 min, the remaining 20% is added, the flow rate is 6.5 L / h, and the ORP is maintained at 525 mV. Synchronously start the fluidized bed fluidization control, and ladder the upward flow rate from the initial 0.012 m / s to 0.025 m / s, control the bed expansion ratio to be 1.65, and the shear rate to be 600 s -1 , generate 75 μm micro-vortex, and the shear stress at the bottom of the bed is 9 Pa. When the UV270 detection value is 0.7 AU, start the 2.45 GHz microwave source, the power is 2 kW, and the operation mode is 2 min on and 1 min off for 10 min.

[0134] S4, after the Fenton reaction is completed, the AI control system starts to add 10 wt% NaOH solution, and the pH is adjusted to 7.0 by means of an alkali-resistant intelligent metering pump (flow accuracy ±1%), the reaction time is 7 min, and the ORP is reduced to 80 mV. Because the concentration of fiber fragments in the residual liquid is 2 g / L, 15 mg / L of polyaluminum chloride and 1.5 mg / L of anionic polyacrylamide are added, first mixed at G=325 s -1 for 1.5 min, and then stirred at G=55 s -1 for 5.5 min. A plate and frame filter press (filtration pressure 0.5 MPa, filter cloth aperture 7.5 μm) is used for solid-liquid separation, and purified water and recovered carriers are obtained.

[0135] Example 2:

[0136] An AI dosing method for Fenton reaction, the same as in example 1, and the difference from example 1 is that:

[0137] The anti-complexing carrier is added in an amount of 1.5 kg.

[0138] Example 3:

[0139] An AI dosing method for Fenton reaction, the same as in example 1, and the difference from example 1 is that:

[0140] The anti-complexing carrier is added in an amount of 2.5 kg.

[0141] Example 4:

[0142] An AI dosing method for Fenton reaction, the same as in example 1, and the difference from example 1 is that:

[0143] The concentration of ferrous sulfate is 50 mg / L.

[0144] Example 5:

[0145] An artificial intelligence dosing method for Fenton reaction, the same as example 1, the different from example 1 is that:

[0146] The concentration of ferrous sulfate is 100 mg / L.

[0147] Example 6:

[0148] An artificial intelligence dosing method for Fenton reaction, the same as example 2, the different from example 2 is that:

[0149] The concentration of ferrous sulfate is 50 mg / L.

[0150] Example 7:

[0151] An artificial intelligence dosing method for Fenton reaction, the same as example 2, the different from example 2 is that:

[0152] The concentration of ferrous sulfate is 100 mg / L.

[0153] Example 8:

[0154] An artificial intelligence dosing method for Fenton reaction, the same as example 3, the different from example 3 is that:

[0155] The concentration of ferrous sulfate is 50 mg / L.

[0156] Example 9:

[0157] An artificial intelligence dosing method for Fenton reaction, the same as example 3, the different from example 3 is that:

[0158] The concentration of ferrous sulfate is 100 mg / L.

[0159] Example 10:

[0160] An artificial intelligence dosing method for Fenton reaction, the same as example 1, the different from example 1 is that:

[0161] The upflow velocity of the fluidized bed is 0.02 m / s.

[0162] Example 11:

[0163] An artificial intelligence dosing method for Fenton reaction, the same as example 1, the different from example 1 is that:

[0164] The fluidized bed upflow velocity is 0.03 m / s.

[0165] Experimental Example 1:

[0166] In this experimental example, Examples 1-9 are selected for testing: the anti-complexing carrier dosage directly determines the blocking ability to strong chelating agents (EDTA), which is the core of realizing anti-complexing catalysis; the liquid phase catalyst concentration affects the activation efficiency of the carrier active site, and is related to the catalytic reaction rate;

[0167] Table 1 Anti-complexing carrier dosage and liquid phase catalyst concentration change test

[0168]

[0169] The data in Table 1 shows that the synergistic effect of the anti-complexing carrier dosage and the concentration of ferrous sulfate significantly affects the treatment effect: when the carrier dosage is insufficient, the complex blocking ability to EDTA is weakened, resulting in the blocking of the catalytic site, and the COD removal rate decreases; when the concentration of ferrous sulfate is too low, it is difficult to fully activate the active sites on the surface of the carrier, and when it is too high, it can increase the risk of Fe residue, and the combination of intermediate concentration (2 kg of carrier + 75 mg / L of catalyst) has the optimal effect due to the balance between complex blocking and active activation.

[0170] Experimental Example 2:

[0171] In this experimental example, Examples 1, 10, and 11 are selected for testing: the fluidized bed upflow velocity affects the mass transfer process, and affects the contact efficiency of pollutants and oxidants and catalysts, which is the key to strengthening mass transfer.

[0172] Table 2 Fluidized bed upflow velocity variable experiment

[0173]

[0174] The data in Table 2 shows that the fluidized bed upflow velocity 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 pollutants do not fully contact with the catalyst, and the COD removal rate decreases slightly; when the flow rate is too high (0.03 m / s), the mass transfer is strengthened, but the energy consumption increases and the carrier is easily carried out, and the intermediate flow rate (0.025 m / s) takes into account the mass transfer efficiency and system stability, and has a better overall effect.

[0175] Based on the ideal embodiments of the present application, through the above description, relevant personnel can make various changes and modifications without deviating from the technical concept of the present application. The technical scope of the present application is not limited to the contents in the specification, and the technical scope must be determined according to the scope of claims.

Claims

1. An artificial intelligence dosing method for Fenton reaction, characterized in that, The method comprises the steps of: S1, the active dye dyeing residual liquid is pretreated and delivered to the fluidized bed, and the first characteristic parameter of the active dye dyeing residual liquid is collected; wherein the first characteristic parameter is the complexing agent concentration and the residual liquid volume; S2, based on the first characteristic parameter to the fluidized bed adding anti-complexing carrier, real-time monitoring of the second characteristic parameter, 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 for activating anti-complexing carrier surface active site; S3, after the liquid phase catalyst is added, the AI control system adds hydrogen peroxide in stages, synchronously increases the fluidized bed flow rate in stages, and combines the microwave to perform the Fenton reaction; S4, after the Fenton reaction is completed, the AI control adds alkali to adjust the pH, and solid-liquid separation is performed to obtain purified effluent water; In step S2, the preparation of the anti-complexing carrier comprises: In an ammonia solution with pH=10-11, ZrOCl2 and Fe3O4 are co-precipitated at a mass ratio of 4-5:1, and a ZrO2@Fe3O4 composite microsphere is formed under the condition of 180℃ for 12 hours, with a diameter of 0.5-1mm, forming a magnetic base layer; The microsphere is immersed in a Fe(NO3)3 solution with a concentration of 0.5-0.6mol / L, and ultrasonic treatment is performed at 60℃ for 30-40 minutes; then, under the protection of a nitrogen environment, the microsphere is calcined at a temperature of 500-550℃ for 2 hours, forming α-Fe2O3 micro-aggregates with a particle size of 10-20nm on the surface of the microsphere, forming a catalytically active layer; The microsphere is immersed in an EDTA-Fe complex solution with pH=4-5 and a concentration of 0.1-0.2mol / L, and stirring reaction is performed at 60℃ for 3-5 hours, forming a competitive binding layer on the catalytically active layer; A ZrO2-SiO2 sol is spin-coated on the surface of the microsphere, wherein the molar ratio of Zr to Si is 3-4:1, and after spin-coating, the microsphere is first dried at 60-80℃ for 15-20 minutes, and then calcined at a temperature of 500-550℃ for 1-1.5 hours, forming 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, forming a shielding protection layer, and finally obtaining an anti-complexing carrier.

2. The artificial intelligence dosing method for Fenton reaction according to claim 1, characterized in that: In step S1, the pretreatment comprises: The active dye dyeing residual liquid is subjected to mechanical shearing at a speed of 3000-5000rpm for 2-5min, the fiber fragment aggregates are broken, and the residual liquid viscosity is reduced to 8-10cP; Then add sulfuric acid to adjust pH, with acid amount of 3-5 kg / m 3 , reaction 10-15 min, reduce pH to 2-3, destroy the chelate bond of EDTA and metal ions through pH adjustment, release free Fe 3+ , where the released free Fe 3+ subsequently acts as a Fenton reaction catalyst.

3. The artificial intelligence dosing method for Fenton reaction according to claim 1, characterized in that: The spin-coating process parameters are as follows: the sol solid content is 8-12wt%, the spin-coating is performed in two stages, the first stage is spin-coated at a speed of 300-500rpm for 15-20 seconds, and the second stage is spin-coated 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%.

4. 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, the ferrous sulfate particle size is 20-50nm, and the concentration is 50-100mg / L.

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

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

7. The artificial intelligence dosing method for Fenton reaction according to claim 1, characterized in that: In step S4, the alkali addition back adjustment comprises: Using 10wt% NaOH solution or waste lye, monitoring pH value in real time, if pH is less than 6.0, adding NaOH; if pH exceeds 7.5, stopping adding, target pH control in 6.5-7.5, reaction time 5-10 minutes; when the content of micron-sized fiber fragments is greater than 1g / L or Fe 3+ When the concentration is less than 10mg / L, adding 10-20mg / L of polymeric aluminum chloride and 1-2mg / L of anionic polyacrylamide, first fast mixing and then slow stirring.

8. 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 0.6 AU, the microwave source is started along the fluidized bed side wall, the power is 2 kW, and the duration is 10 minutes; the microwave adopts an intermittent operation mode, is turned on for 2 minutes, and is turned off for 1 minute.

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

Images