Modified memory light-responsive material and modular dual reaction system

Abstract

This invention discloses a modified photoresponse material for memory and a modular dual-reaction system. The modified photoresponse material for memory is (BiVO4). y / Ag z / Fe x In 2‑x S3, where x is 0.18–1, y is 0.66–1.5, and z is 0.15–0.45, exhibits a memory effect, high charge separation and transfer efficiency, and good photocatalytic activity. This modular dual-reaction integrated treatment system employs multi-layer, multi-stage reaction tanks and utilizes the modified memory photoresponse material described in this invention to treat naphthalene-containing industrial wastewater. The operation process is simple, efficient, and effectively saves costs. Its tail gas absorption device avoids secondary pollution, making it environmentally friendly. Using this modified memory photoresponse material and the matching modular dual-reaction integrated treatment system to treat naphthalene-containing industrial wastewater, the primary COD degradation rate is over 65%.

Description

Technical Field

[0001] This invention relates to a modified memory photoresponsive material for effectively degrading naphthalene-containing industrial wastewater, its preparation method, application, and modular dual-reaction integrated treatment system and method, belonging to the field of photocatalyst treatment of naphthalene-containing wastewater technology. Background Technology

[0002] Naphthalene is a type of polycyclic aromatic hydrocarbon and an important raw material in the organic chemical industry, widely used in chemicals, pesticides, dyes, and other fields. Naphthalene in the aquatic environment has serious negative impacts on both the environment and humans. On October 27, 2017, the International Agency for Research on Cancer (IARC) of the World Health Organization listed naphthalene as a Group 2B carcinogen. The 10 carbon atoms on the naphthalene ring form a delocalized conjugated structure with high bond energy, making it difficult to degrade and exhibiting high chemical stability in the environment. Therefore, degrading naphthalene-containing wastewater pollutants is a significant challenge.

[0003] Currently, the main methods for treating naphthalene-containing industrial wastewater include biological treatment, physical treatment, and chemical treatment. Naphthalene-containing wastewater often has high COD and large pH fluctuations, which are unfavorable for biodegradation. Therefore, physical and chemical pretreatment methods are required to bring it to a level suitable for biological treatment, which is not economical or efficient. The most common physical method for treating naphthalene-containing wastewater is adsorption, but adsorption does not fundamentally eliminate pollutants and can easily cause secondary pollution if not handled properly. Advanced oxidation technologies, as one of the most important organic chemical treatment technologies, mainly include Fenton oxidation, Fenton-like oxidation, ozone oxidation, photocatalytic oxidation, and electrochemical oxidation. Currently, introducing light energy into the Fenton process has received widespread attention because it can promote the production of more active substances from hydrogen peroxide. However, traditional photocatalysts are limited by the presence of a light source; when the light source is turned off, the catalyst stops working. Photocatalysts with memory effects can maintain a certain level of photocatalytic activity in the absence of light, which can improve efficiency and reduce costs, thus having important significance in the industrial degradation of antibiotic wastewater. Summary of the Invention

[0004] Objectives of this invention: The first objective is to provide a modified memory photoresponsive material that efficiently catalyzes naphthalene-containing industrial wastewater under visible light; the second objective is to provide a method for preparing the modified memory photoresponsive material; the third objective is to provide the application of the modified memory photoresponsive material in treating naphthalene-containing industrial wastewater; the fourth objective is to provide a modular dual-reaction integrated treatment system for treating naphthalene-containing industrial wastewater using the modified memory photoresponsive material; and the fifth objective is to provide a method for treating naphthalene-containing industrial wastewater using the modular dual-reaction integrated treatment system.

[0005] Technical solution: The present invention discloses a modified photoresponse material for memory, wherein the modified photoresponse material is (BiVO4).y / Ag z / Fe x In 2-x S3, where x is 0.18-1, y is 0.66-1.5, z is 0.15-0.45, and the Fe... x In 2-x S3 is obtained by doping In2S3 with Fe, where x represents the amount of Fe doping, i.e., the molar percentage, and y represents the doping content of BiVO4 and Fe. x In 2-x The molar ratio of S3, where z represents Ag and (BiVO4). y / Fe x In 2-x The mass ratio of S3.

[0006] The preparation method of the modified memory photoresponse material of the present invention includes the following steps:

[0007] (1) BiVO4 was synthesized by solid-liquid reaction method: surfactant, bismuth oxide and vanadium pentoxide were dissolved in dilute nitric acid solution, mixed and stirred, centrifuged, washed and dried to obtain yellow product BiVO4;

[0008] (2) Synthesis of (BiVO4) using a hydrothermal method y / Fe x In 2-x S3: Dissolve the surfactant, ferric chloride hexahydrate, and indium trichloride tetrahydrate in ethanol, add thioacetamide and BiVO4, stir vigorously at room temperature, perform hydrothermal reaction, wash, and dry to obtain (BiVO4). y / Fe x In 2-x S3;

[0009] (3) Catalyst (BiVO4) prepared by photoreduction deposition. y / Ag z / Fe x In 2-x S3: (BiVO4) y / Fe x In 2-x S3 powder and surfactant were dispersed in a methanol solution, and silver nitrate solution was added dropwise. The mixture was stirred thoroughly to obtain a mixed solution. The mixture was then irradiated under a xenon lamp while being stirred, filtered, washed, and dried to obtain (BiVO4). y / Ag z / Fe x In 2-x S3 ternary composite material;

[0010] (4) Preparation of porous spherical catalysts by extrusion molding: (BiVO4) y / Ag z / Fe x In 2-x S3 ternary composite material, reinforcing material, molding agent, and pore-forming agent are placed in a hydraulic extruder and extruded to form porous spherical catalysts. The extruded catalysts are then placed in a furnace for sintering to obtain shaped photocatalysts (BiVO4). y / Ag z / Fe x In 2-x S3.

[0011] In step (1), the surfactant is one or more of sodium linear alkylbenzene sulfonate, sodium α-olefin sulfonate, and sodium dodecyl sulfate.

[0012] In step (1), the molar ratio of bismuth oxide to vanadium pentoxide is 0.66-1:1.

[0013] In step (1), the concentration of the dilute nitric acid solution is 0.3-0.8 mol / L.

[0014] In step (1), the solid-liquid ratio of the surfactant, bismuth oxide and dilute nitric acid solution is 0.1-0.9:1.5-2.5:50-150g / g / mL.

[0015] In step (1), the mixing temperature is 20-60℃ and the mixing time is 80-100h.

[0016] In step (1), the drying temperature is 60-100℃.

[0017] In step (2), the surfactant is one or more of sodium alkylbenzene sulfonate, polyethylene glycol sulfate, polyethylene glycol ether, acrylic acid / acrylamide methyl propane sulfonic acid copolymer, and sodium dodecyl sulfonate.

[0018] In step (2), the molar ratio of the surfactant, ferric chloride hexahydrate, indium trichloride tetrahydrate, thioacetamide and BiVO4 is 0.05-0.25:1:1-10.1:0.66-1.5.

[0019] In step (2), the time for vigorous stirring is 20-60 minutes.

[0020] In step (2), the temperature of the hydrothermal reaction is 160℃-200℃, and the time of the hydrothermal reaction is 12-19h.

[0021] In step (3), the surfactant is one or more of sodium octanoate and dodecyl octanoate.

[0022] In step (3), the molar mass ratio of the methanol solution is 10-30%.

[0023] In step (3), the concentration of the silver nitrate solution is 200-600 mg / L.

[0024] In step (3), the (BiVO4) y / Fe x In 2-x The solid-liquid ratio of S3 powder, surfactant, methanol solution, and silver nitrate solution is 1-3:0.1-0.5:200-300:375-3375 g / g / mL / mL.

[0025] In step (3), the power of the xenon lamp is 200-500w.

[0026] In step (3), the illumination time is 30-90 minutes.

[0027] In step (4), the reinforcing material is one or more of silicate reinforcing agents and cobalt reinforcing agents.

[0028] In step (4), the molding agent is one or more of ethylene-acrylic acid copolymer, phenol, and aluminum phosphate sol.

[0029] In step (4), the pore-forming agent is one or more of the following: three-dimensional ordered mesoporous carbon material, silicon dioxide, tetrapropylammonium hydroxide, and hydrogen phosphate.

[0030] In step (4), the extrusion pressure of the extruder is 5-8 MPa, the extrusion speed is 15-25 r / min, the die plate of the extruder is spherical, and the diameter of the die plate is 2 mm.

[0031] In step (4), the sintering temperature is 450-860℃ and the sintering time is 1-2h.

[0032] The (BiVO4) prepared in this invention y / Ag z / Fe x In 2-x S3 memory-type photocatalysts exhibit high light utilization and photocatalytic activity. Fe-modified In2S3 by doping with Fe yields Fe... x In 2-x S3, Fe 3+ Ion doping substitution for In 3+Ions increase the carrier concentration in the system, causing charge exchange interactions that produce many-body effects or overlap between impurity and defect bands, resulting in a redshift of the light absorption edge, narrowing of the band gap, and enhanced redox capability. Simultaneously, Fe doping... 3+ It can improve the thermal stability of materials, broaden the light absorption range, and extend the lifetime of photogenerated carriers.

[0033] In the synthesis of (BiVO4) y / Fe x In 2-x Adding surfactants at step S3 alters the shape and size of the photocatalyst nanoparticles, exposing their highly active lattice surfaces and exhibiting the largest specific surface area. This results in a more ordered photocatalyst structure, thus affecting its photocatalytic efficiency. Simultaneously, surfactant modification of some defect vacancies improves the separation and migration efficiency of photogenerated carriers, accelerating the generation of active free radicals.

[0034] Add Ag to (BiVO4) y / Fe x In 2-x The S3 catalyst forms a photocatalyst with a memory effect, using readily available raw materials, with mild reaction conditions and simple operation. Ag plays three main roles: 1) Due to its excellent conductivity, noble metal nanoparticles can act as electron bridges in the composite photocatalyst, retaining the redox capabilities of the semiconductor while reducing electron-hole recombination efficiency. 2) Surface plasmon resonance enhances the catalyst's absorption of visible light. 3) Under light irradiation, the material forms intermediate compounds to store electrons during the catalytic reaction; under no light irradiation, these intermediate compounds release electrons. Specifically, under light irradiation, electrons are excited from the valence band (VB) to the conduction band (CB) and participate in the photocatalytic reaction, while excess electrons are stored in the photocatalytic memory material and released in darkness to continue the catalytic reaction. This allows for continuous, round-the-clock treatment of pollutants in the environment, significantly enhancing the treatment effect of photocatalysis on antibiotic wastewater and reducing treatment costs and energy consumption. Simultaneously, the resulting spherical photocatalyst exhibits high mechanical strength, long lifespan, and can be recycled multiple times. In the synthesis of spherical photocatalysts, porous or non-porous hard solid materials are added as pore-forming agents. The hard template is removed by high-temperature calcination, and the pore structure of the spherical catalytic structure is modified. The resulting shaped catalyst with a porous structure can effectively improve the diffusion and mass transfer efficiency in the reaction process while maintaining the original advantages of the spherical shape, such as high stability and strong flowability. It also expands the contact area, ensures sufficient contact between wastewater and catalyst, and improves catalytic performance.

[0035] The application of the modified memory photoresponsive material described in this invention in the treatment of naphthalene-containing industrial wastewater.

[0036] The COD value of the naphthalene-containing industrial wastewater is 10,000-30,000 mg / L.

[0037] A modular dual-reaction integrated treatment system for treating naphthalene-containing industrial wastewater using the modified memory photoresponsive material described in this invention is disclosed. The system comprises a filtration module, a pH adjustment module, a heat exchange module, a photocatalytic reaction module, and a storage module connected in sequence. A gas absorption module is connected to the top of the photocatalytic reaction module, and the storage module is connected to the pH adjustment module. The pH adjustment module includes a pH adjustment tank connected to an acid storage tank and an alkali storage tank. The reaction module includes a main reaction tank, which is divided into a first-stage reaction tank and a second-stage reaction tank connected from top to bottom. A hydrogen peroxide tank is connected to the outside of the first-stage reaction tank, and a catalyst stainless steel partition is located in the middle of the first-stage reaction tank. The modified memory photoresponsive material described in this invention is placed in the middle of the stainless steel partition. Multiple light sources extend from top to bottom inside the first-stage reaction tank. A catalyst outlet box is located at the bottom of the second-stage reaction tank, which is connected to the storage module via a pipeline equipped with an online COD detection system. The first-stage reaction tank is connected to the gas absorption module.

[0038] The present invention also includes a method for treating naphthalene-containing industrial wastewater using the modular dual-reaction integrated treatment system, comprising the following steps:

[0039] (1) Naphthalene-containing industrial wastewater enters the filtration module. After filtration, the wastewater enters the pH adjustment tank. The pH of the wastewater is adjusted by adding chemicals through the acid storage tank and / or alkali storage tank. Then the wastewater is sent to the heat exchange module for heat exchange.

[0040] (2) The wastewater after heat exchange enters the first-stage reaction tank, and undergoes photocatalytic reaction under the irradiation of a light source through the modified memory light-response material described in this invention in the stainless steel partition of the first-stage catalyst and the hydrogen peroxide input in the hydrogen peroxide tank. Then it enters the second-stage reaction tank for dark reaction.

[0041] (3) After the dark reaction is completed, the COD in the wastewater is tested by the COD online detection system to see if it is qualified. When the COD is qualified, the waste liquid is transported to the storage module. When the COD is unqualified, the waste liquid is transported back to the pH adjustment tank after passing through the storage module and recirculated. The gas is transported to the gas absorption module for absorption and the modified memory light response material described in this invention is recovered through the catalyst outlet box.

[0042] The acid storage tank stores 10-30% hydrochloric acid solution, preferably 10%, and the alkali storage tank stores 20-50% sodium hydroxide solution, preferably 20%.

[0043] The pH value is 5-8.

[0044] The solid-liquid ratio of the modified memory photoresponse material to the naphthalene-containing industrial wastewater is 35-50:1 g / L, preferably 35%.

[0045] The temperature of the wastewater after heat exchange is 45-65℃.

[0046] The concentration of hydrogen peroxide is 10-30%, and the volume ratio of hydrogen peroxide to wastewater is 0.01-0.06:1.

[0047] The light source is a xenon lamp with a power of 200-500W.

[0048] The photocatalytic reaction takes 1-3 hours, preferably 1.5 hours.

[0049] The dark reaction takes 1-3 hours, preferably 2 hours.

[0050] The gas absorption module is equipped with a spray device at its upper part, and the absorption liquid sprayed by the spray device is a mixed solution of sodium bicarbonate and sodium carbonate.

[0051] The concentrations of sodium bicarbonate and sodium carbonate in the mixed solution are 5-20 g / mL and 2-15 g / mL, respectively.

[0052] The COD test qualification means that the COD value is less than 4000 mg / L.

[0053] The modular dual-reaction integrated treatment system of this invention incorporates a filtration module before the catalytic reaction tank to remove particulate matter from naphthalene-containing industrial wastewater, preventing equipment clogging and damage, and improving photocatalytic efficiency. Simultaneously, a pH adjustment device is used for efficient pH regulation. Addressing the challenges of continuous photocatalytic degradation of naphthalene-containing industrial wastewater due to its complex composition, high cost, high energy consumption, and strong light pollution, making continuous and uninterrupted water treatment difficult, this invention employs a dual-stage reaction zone (a first-stage reaction tank and a second-stage reaction tank). The photocatalytic reaction occurs first, followed by a dark reaction, and new photocatalytic reactions can occur simultaneously during the dark reaction, improving efficiency. Furthermore, the dual-stage reaction tank includes a catalyst recovery tank, solving the problem of difficult catalyst recovery in traditional devices, achieving efficient catalyst recycling and reducing costs. This supporting system also includes a gas absorption module to effectively prevent secondary pollution and promote sustainable development.

[0054] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages:

[0055] (1) Through Fe 3+Ion doping of In2S3 introduces additional electron and hole carriers. By controlling the trap depth, doping concentration, and trapping cross section, the optical performance of the material is improved. Furthermore, it is effectively combined with BiVO4 to extend the lifetime of photogenerated carriers, thus initially improving the photocatalytic performance.

[0056] (2) By introducing Ag, (BiVO4) y / Ag z / Fe x In 2-x S3 exhibits a surface plasmon resonance effect, enhancing the catalyst's absorption under visible light. Under photoexcitation, BiVO4 and Fe... x In 2-x S3 generates electrons, which Ag can store as acceptors. Ag changes from a high-valence state to a low-valence state, accelerating the separation of photogenerated carriers. Furthermore, it can release photogenerated electrons in the dark, thus giving the sample "catalytic memory" activity and reducing the cost of photocatalytic wastewater degradation. Extrusion molding is used to process the catalyst into spherical products, solving the problem of easy agglomeration of powdered catalysts in aqueous solutions. This improves the catalyst's mechanical strength, extends its service life, and enables highly efficient removal of naphthalene-containing industrial wastewater, achieving a primary COD removal rate of over 65%.

[0057] (3) The modular dual-reaction integrated treatment system for naphthalene-containing industrial wastewater, which is equipped with the composite photocatalyst of this invention, adopts a partitioned bipolar reaction tank for first performing the light reaction and then the dark reaction. A new batch of light reactions can be carried out simultaneously with the dark reaction, significantly improving time and cost. The short lamp-on time effectively reduces light pollution, and the exhaust gas absorption device eliminates secondary pollution from gas emissions, making it more environmentally friendly. The water pressure sensor and pressure gauge can detect leaks and water pressure online, ensuring safety. The online detection system can efficiently and promptly monitor the wastewater treatment status, and its efficient cooperation with the recycling system ensures that recalcitrant pollutants are treated to meet standards. Attached Figure Description

[0058] Figure 1 A process flow diagram for treating naphthalene-containing industrial wastewater using the modular dual-reaction integrated treatment system described in this invention;

[0059] Figure 2 This is a schematic diagram of the cross-section of a porous spherical catalyst. Detailed Implementation

[0060] The technical solution of the present invention will be further described below with reference to the accompanying drawings.

[0061] Example 1

[0062] like Figure 1As shown, the modular dual-reaction integrated treatment system for treating naphthalene-containing industrial wastewater using a memory-type photocatalyst according to the present invention includes a filtration module, a pH adjustment module, a heat exchange module, a photocatalytic reaction module, a gas absorption module, and a storage module connected in sequence. The filtration module, pH adjustment module, heat exchange module, photocatalytic reaction module, and gas absorption module are connected in sequence, and the storage module is also connected to the pH adjustment module.

[0063] The filter module includes a filter cylinder 1, a stainless steel filter grid 2, and a stainless steel filter woven mesh 3. The stainless steel filter grid 2 is fixed at an angle of 120° above the water inlet of the filter cylinder 1, and the stainless steel filter woven mesh 3 is fixed at an angle of 120° below the water outlet of the filter cylinder 1.

[0064] The pH adjustment module includes a pH adjustment tank 7, which is connected to a filtration module. The pH adjustment tank 7 is connected to an acid storage tank 5 and an alkali storage tank 6. The pH adjustment tank 7 contains an ultrasonic stirrer and a pH electrode 9, which is externally connected to a central pH control box 10. The pH adjustment tank 7 is connected to a heat exchange module via an angle shut-off valve 11 and a second wastewater treatment pump 12. The acid storage tank 5 stores a 10% hydrochloric acid solution, and the alkali storage tank 6 stores a 20% sodium hydroxide solution.

[0065] The heat exchange module includes a spiral plate heat exchanger 13, which is connected to the second sewage pump 12. The heat exchanger 13 is connected to the photocatalytic reaction module through the third sewage treatment pump 14.

[0066] The reaction module includes a main reaction tank 15, which is divided into a first-stage reaction tank 16 and a second-stage reaction tank 17 from top to bottom. The first-stage reaction tank 16 and the second-stage reaction tank 17 are connected by a distributed cage-type shut-off valve 24. A hydrogen peroxide tank 19 is connected to the outside of the first-stage reaction tank 16 via a hydrogen peroxide flow pump 18. The hydrogen peroxide tank 19 contains hydrogen peroxide with a concentration of 30%. A catalyst stainless steel partition 20 is located in the middle of the first-stage reaction tank 16, and the modified memory photoresponse material described in this invention is placed in the middle of the stainless steel partition 20. Two xenon lamp light sources 21 extend from top to bottom inside the first-stage reaction tank 16, and the power of the xenon lamp light sources 21 is 300W. The xenon lamp light sources 21 are protected by quartz lamp covers to prevent damage. Two ultrasonic stirring rods 22 and a water level sensor 23 are located at the bottom of the first-stage reaction tank 16. The second-stage reaction vessel 17 is equipped with a stirring paddle 25. At the bottom of the second-stage reaction vessel 17 are a catalyst buffer screen 26 and a catalyst outlet box 27. An outlet box switch 28 is located outside the catalyst outlet box 27. The second-stage reaction vessel 17 is connected to the storage module via a pipeline, on which an online COD monitoring system 29 is installed. The first-stage reaction vessel 16 is connected to the gas absorption module via an exhaust valve 33. A pressure gauge 37 is located on the upper part of the first-stage reaction vessel 16.

[0067] The storage module includes a waste liquid storage tank 32, which is connected to a metering pump 30 and a pH adjustment tank 7 via a pneumatic three-way valve 31. The second-stage reaction tank 17 is connected to the metering pump 30 via a pipeline, and the COD online detection system 29 is connected to this pipeline.

[0068] The gas absorption module includes an absorption tower 34, with a spray device 35 at the bottom and a multi-layer packing module 36 in the middle. The absorption liquid sprayed by the spray device 35 is a mixed solution of sodium bicarbonate and sodium carbonate, with concentrations of 18 g / mL and 12 g / mL for sodium bicarbonate and sodium carbonate, respectively.

[0069] The method for treating naphthalene-containing industrial wastewater using the above-mentioned modular dual-reaction integrated treatment system includes the following steps:

[0070] (1) Naphthalene-containing industrial wastewater enters the filter tank 1 with stainless steel filter grid 2. The stainless steel filter grid 2 filters and removes the suspended particles in the wastewater. The stainless steel filter mesh 3 further treats the small suspended particles. The filtered wastewater is then transported to the pH adjustment tank 7 by the first sewage treatment pump 4. The pH control box 10 can automatically add chemicals through the acid storage tank 5 and / or the alkali storage tank 6 until the pH electrode 9 measures a value of 5-8. During this process, the ultrasonic stirrer 8 is used to accelerate pH adjustment and reduce time costs. After the pH adjustment is successful, the angle shut-off valve 11 is opened, and the wastewater is sent to the spiral plate heat exchanger 13 for heat exchange through the second sewage treatment pump 12.

[0071] (2) The wastewater after heat exchange is pumped to the first-stage reaction tank 16 by the third sewage treatment pump 14. The first-stage reaction tank 16 contains the modified memory photoresponse material of the present invention, separated by a catalyst stainless steel partition 20. 30% of the hydrogen peroxide in the hydrogen peroxide tank 19 is pumped to the first-stage reaction tank 16 by the metering pump 18. The xenon lamp light source 21 and the ultrasonic stirrer 22 are turned on to ensure sufficient contact between the wastewater, catalyst and hydrogen peroxide for photocatalytic reaction. The water level sensor 23 ensures safety during the photocatalytic reaction. After reacting in the first-stage reaction tank 16 for 1.5 hours, the distributed cage shut-off valve 24 is opened to transport the wastewater and the photostimulated catalyst to the second-stage reaction tank 17 for dark reaction for 1-3 hours. The distributed cage shut-off valve 24 separates the water and catalyst for transport. The catalyst buffer net 26 helps to avoid mechanical damage to the catalyst during transport. Turning on the stirrer 25 can accelerate the reaction speed. While the dark reaction is in progress, a new batch of photocatalytic reaction can be carried out in the first-stage reaction tank 16, saving time and costs.

[0072] (3) After the dark reaction is completed, the COD in the wastewater is detected by the COD online detection system 29 to determine whether it is up to standard, and the destination of the treated wastewater is controlled. When the COD is less than 4000 mg / L, it is considered up to standard, and the pneumatic three-way ball valve 31 is opened to transport the waste liquid to the waste liquid storage tank 32. When the COD is greater than or equal to 4000 mg / L, it is considered down to standard, and the pneumatic three-way ball valve 31 is opened to transport the waste liquid back to the pH adjustment tank 7 for recirculation. The opening of the shut-off valve 33 transports the gas to the bottom of the absorption tower 34 for absorption from bottom to top. The mixed solution sprayed by the spray device 35 at the top of the absorption tower 34 absorbs the waste liquid generated during the reaction. After the total reaction is completed, the catalyst outlet box 27 is opened by the catalyst outlet box switch 28 to take out the catalyst for recycling.

[0073] Example 2

[0074] (1) Preparation of BiVO4

[0075] Vanadium pentoxide 4.659 g, bismuth oxide 1.810 g, and sodium linear alkylbenzene sulfonate 0.56 g were dissolved in 100 mL of 0.5 mol / L dilute nitric acid solution at a molar ratio of 1:1. The solution was stirred at 25 °C for 96 h, and the yellow product BiVO4 was obtained by centrifugation, washing, and drying.

[0076] (2)(BiVO4) 1.2 / Fe 0.5 In 1.5 Preparation of S3

[0077] 0.95 g of ferric chloride hexahydrate, 2.19 g of indium chloride tetrahydrate, and 0.54 g of polyethylene glycol sulfate were dissolved in 80 mL of ethanol. Then, 1.125 g of thioacetamide and 1.81 g of BiVO4 were added, and the mixture was vigorously stirred at room temperature for 30 min to obtain a clear solution. The homogeneous clear solution was then transferred to a Teflon-lined steel autoclave. The autoclave was sealed and maintained at 180 °C for 16 hours, followed by cooling to room temperature. Subsequently, all samples were washed with deionized water, and finally dried in air to obtain (BiVO4). 1.2 / Fe 0.5 In 1.5 S3 powder;

[0078] (3) Memory-type photocatalyst (BiVO4) 1.2 / Ag 0.25 / Fe 0.5 In 1.5 Preparation of S3

[0079] (BiVO4) was prepared using photoreduction deposition. 1.2 / Ag 0.25 / Fe0.5 In 1.5 S3 ternary composite material, 1.6g (BiVO4) 1.2 / Fe 0.5 In 1.5 S3 powder and 0.35 g of sodium octanoate were dispersed in 300 mL of 20% (v / v) methanol solution. 1000 mL of silver nitrate solution (400 mg / L) was added dropwise to the mixture, and the mixture was stirred thoroughly. The mixture was then irradiated under a 300 W deuterium lamp for 1 hour while stirring. After filtration, washing, and drying, the precipitate was obtained as (BiVO4). 1.2 / Ag 0.25 / Fe 0.5 In 1.5 S3 ternary composite material;

[0080] (4) Using extrusion molding to turn powdered catalyst into spherical catalyst: 0.26g silicate and 1.5g (BiVO4) 1.2 / Ag 0.25 / Fe 0.5 In 1.5 S3 catalyst, 0.12g ethylene-acrylic acid copolymer, and 0.2g silica were placed in a hydraulic extruder to transform the powdered catalyst into porous spherical catalysts. The extruded catalysts were then sintered in a furnace at 460℃ for 1.2h to obtain porous spherical (BiVO4) catalysts. 1.2 / Ag 0.25 / Fe 0.5 In 1.5 S3 catalyst.

[0081] The porous spherical (BiVO4) prepared in this embodiment 1.2 / Ag 0.25 / Fe 0.5 In 1.5 A schematic diagram of the cross-section of the S3 catalyst is shown below. Figure 2 As shown.

[0082] (5) Utilizing the above (BiVO4) 1.2 / Ag 0.25 / Fe 0.5 In 1.5 The S3 catalyst and the modular dual-reaction integrated treatment system and method shown in Example 1 degrade naphthalene-containing industrial wastewater with complex components and high water quality fluctuations.

[0083] The wastewater, consisting of 30L of complex-composition industrial wastewater containing naphthalene, had a COD of 12940mg / L. A stainless steel partition 20 contained (BiVO4) prepared in this embodiment. 1.2 / Ag 0.25 / Fe 0.5 In 1.51050g of S3 catalyst, the solid-liquid ratio of modified memory photoresponse material to naphthalene-containing industrial wastewater is 35:1g / L, the pH value is adjusted to 6, the temperature of the wastewater after heat exchange is 45-65℃, 0.6L of 30% hydrogen peroxide is added, the power of the xenon lamp is 300W, the first-stage photocatalytic reaction time is 1.5h, and the second-stage dark reaction time is 2h.

[0084] (BiVO4) prepared in this embodiment 1.2 / Ag 0.25 / Fe 0.5 In 1.5 After treatment with S3 catalyst, the COD level was measured at 1941 mg / L by the COD online monitoring system, which is qualified and the COD removal rate is 85.3%.

[0085] Comparative Example 1

[0086] (1) Preparation of BiVO4

[0087] The experimental procedure is the same as step (1) in Example 2;

[0088] (2)(BiVO4) 1.2 / Fe 0.5 In 1.5 Preparation of S3

[0089] The experimental procedure is the same as step (2) in Example 2;

[0090] (3) Using extrusion molding to turn powdered catalysts into spherical catalysts

[0091] The experimental procedure was the same as step (4) in Example 2, and the spherical catalyst (BiVO4) was obtained. 1.2 / Fe 0.5 In 1.5 S3.

[0092] (4) The spherical catalyst (BiVO4) prepared using this comparative example 1.2 / Fe 0.5 In 1.5 S3 and Example 1 Modular dual-reaction integrated treatment system and method for degrading complex naphthalene-containing industrial wastewater. Other settings are the same as step (5) in Example 2. Among them, 30L of naphthalene-containing industrial wastewater (COD is 12940mg / L) has a COD of 8926mg / L after treatment, which is unqualified. The COD removal rate is 31%, and it needs to be returned to pH adjustment tank 7 for retreatment.

[0093] Example 3

[0094] (1) Preparation of BiVO4

[0095] The experimental procedure is the same as step (1) in Example 2;

[0096] (2)(BiVO4) 1.2 / Fe 0.5 In 1.5 Preparation of S3

[0097] The experimental procedure is the same as step (2) in Example 2;

[0098] (3) Memory-type photocatalyst (BiVO4) 1.2 / Ag 0.15 / Fe 0.5 In 1.5 Preparation of S3

[0099] The experimental procedure is the same as step (3) in Example 2, except for the amount of silver nitrate solution used, i.e., (BiVO4) is prepared by photoreduction deposition. 1.2 / Ag 0.15 / Fe 0.5 In 1.5 S3 ternary composite material, 1.6g (BiVO4) 1.2 / Fe 0.5 In 1.5 S3 powder was dispersed in 300 mL of a 20% (v / v) methanol solution. 600 mL of silver nitrate solution (400 mg / L) was added dropwise to the mixture, and the mixture was stirred thoroughly. The mixture was then irradiated under a 300 W lamp for 1 hour while stirring. After filtration, washing, and drying of the precipitate, (BiVO4) was obtained. 1.2 / Ag 0.15 / Fe 0.5 In 1.5 S3 ternary composite material;

[0100] (4) Using extrusion molding to transform powdered catalyst into porous spherical catalyst (BiVO4). 1.2 / Ag 0.15 / Fe 0.5 In 1.5 S3

[0101] The experimental procedure is the same as step (4) in Example 2.

[0102] (5) The porous spherical catalyst (BiVO4) prepared using this embodiment 1.2 / Ag 0.15 / Fe 0.5 In 1.5S3 and Example 1 Modular dual-reaction integrated treatment system and method for degrading complex naphthalene-containing industrial wastewater. Other settings are the same as step (5) in Example 2. Among them, 30L of naphthalene-containing industrial wastewater (COD is 12940mg / L) was treated and the COD was 6211mg / L, which was unqualified. The COD removal rate was 52%, and it needed to be returned to pH adjustment tank 7 for retreatment.

[0103] Example 4

[0104] (1) Preparation of BiVO4

[0105] The experimental procedure is the same as step (1) in Example 2;

[0106] (2)(BiVO4) 1.2 / Fe 0.5 In 1.5 Preparation of S3

[0107] The experimental procedure is the same as step (2) in Example 2;

[0108] (3) Memory-type photocatalyst (BiVO4) 1.2 / Ag 0.45 / Fe 0.5 In 1.5 Preparation of S3

[0109] The experimental procedure is the same as step (3) in Example 2, except for the amount of silver nitrate solution used, i.e., (BiVO4) is prepared by photoreduction deposition. 1.2 / Ag 0.15 / Fe 0.5 In 1.5 S3 ternary composite material, 1.6g (BiVO4) 1.2 / Fe 0.5 In 1.5 S3 powder was dispersed in 300 mL of a 20% (v / v) methanol solution. 600 mL of silver nitrate solution (400 mg / L) was added dropwise to the mixture, and the mixture was stirred thoroughly. The mixture was then irradiated under a 300 W lamp for 1 hour while stirring. After filtration, washing, and drying of the precipitate, (BiVO4) was obtained. 1.2 / Ag 0.45 / Fe 0.5 In 1.5 S3 ternary composite material;

[0110] (4) Using extrusion molding to transform powdered catalyst into porous spherical catalyst (BiVO4). 1.2 / Ag 0.45 / Fe 0.5 In 1.5 S3

[0111] The experimental procedure is the same as step (4) in Example 2.

[0112] (5) The porous spherical catalyst (BiVO4) prepared using this embodiment 1.2 / Ag 0.45 / Fe 0.5 In 1.5 The modular dual-reaction integrated treatment system and method described in S3 and Example 1 degrades complex naphthalene-containing industrial wastewater. Other settings are the same as in step (5) of Example 2. Among them, 30L of naphthalene-containing industrial wastewater (COD of 12940mg / L) has a COD of 4658.4mg / L after treatment, which is unqualified. The COD removal rate is 64%, and it needs to be returned to pH adjustment tank 7 for retreatment.

[0113] Comparative Example 2

[0114] (1) Preparation of BiVO4

[0115] The experimental procedure is the same as step (1) in Example 2;

[0116] (2)(BiVO4) 1.2 Preparation of / In2S3

[0117] The experimental procedure was the same as step (2) in Example 2, except that ferric chloride hexahydrate was not used. Instead, 2.19 g of indium chloride tetrahydrate and 0.54 g of polyethylene glycol sulfate were added to 80 ml of ethanol, followed by the addition of 1.125 g of thioacetamide and 1.81 g of BiVO4. The mixture was stirred vigorously at room temperature for 30 min to obtain a clear solution. The homogeneous clear solution was then transferred to a Teflon-lined steel autoclave. The autoclave was sealed and kept at 180°C for 16 hours, then cooled to room temperature. Subsequently, all samples were washed with deionized water, and finally dried in air to obtain (BiVO4). 1.2 / In2S3 powder;

[0118] (3) Memory-type photocatalyst (BiVO4) 1.2 / Ag 0.25 Preparation of / In2S3

[0119] The experimental procedure is the same as step (3) in Example 2;

[0120] (4) Using extrusion molding to turn powdered catalyst into spherical catalyst (BiVO4). 1.2 / Ag 0.25 / In2S3

[0121] The experimental procedure is the same as step (4) in Example 2.

[0122] (5) The spherical catalyst (BiVO4) prepared using this comparative example1.2 / Ag 0.25 The modular dual-reaction integrated treatment system and method described in / In2S3 and Example 1 degrade complex naphthalene-containing industrial wastewater. Other settings are the same as step (5) in Example 2. Among them, 30L of naphthalene-containing industrial wastewater (COD of 12940mg / L) has a COD of 11387mg / L after treatment, which is unqualified. The COD removal rate is 12%, and it needs to be returned to pH adjustment tank 7 for retreatment.

[0123] Example 5

[0124] (1) Preparation of BiVO4

[0125] The experimental procedure is the same as step (1) in Example 2;

[0126] (2)(BiVO4) 0.66 / Fe 0.5 In 1.5 Preparation of S3

[0127] The experimental procedure was the same as step (1) in Example 2, except that the amount of BiVO4 used was different. Specifically, 0.95 g of ferric chloride hexahydrate, 2.19 g of indium chloride tetrahydrate, and 0.54 g of polyethylene glycol sulfate were added to 80 ml of ethanol, followed by the addition of 1.125 g of thioacetamide and 1.45 g of BiVO4. The mixture was stirred vigorously at room temperature for 30 min to obtain a transparent solution. The homogeneous transparent solution was then transferred to a Teflon-lined steel autoclave. The autoclave was sealed and maintained at 180°C for 16 hours, then cooled to room temperature. Subsequently, all samples were washed with deionized water, and finally dried in air to obtain (BiVO4). 0.66 / Fe 0.5 In 1.5 S3 powder;

[0128] (3) Memory-type photocatalyst (BiVO4) 0.66 / Ag 0.25 / Fe 0.5 In 1.5 Preparation of S3

[0129] The experimental procedure is the same as step (3) in Example 2;

[0130] (4) Using extrusion molding to transform powdered catalyst into porous spherical catalyst (BiVO4). 0.66 / Ag 0.25 / Fe 0.5 In 1.5 S3

[0131] The experimental procedure is the same as step (4) in Example 2.

[0132] (5) The porous spherical catalyst (BiVO4) prepared using this embodiment 0.66 / Ag 0.25 / Fe 0.5 In 1.5 The modular dual-reaction integrated treatment system and method described in S3 and Example 1 degrades complex naphthalene-containing industrial wastewater. Other settings are the same as in step (5) of Example 2. Among them, 30L of naphthalene-containing industrial wastewater (COD of 12940mg / L) is treated to a COD of 3105mg / L, which is qualified and the COD removal rate is 76%.

[0133] Example 6

[0134] (1) Preparation of BiVO4

[0135] The experimental procedure is the same as step (1) in Example 2;

[0136] (2)(BiVO4) 1.5 / Fe 0.5 In 1.5 Preparation of S3

[0137] The experimental procedure was the same as step (2) in Example 2, except that the amount of BiVO4 used was different. Specifically, 0.95 g of ferric chloride hexahydrate, 2.19 g of indium chloride tetrahydrate, and 0.54 g of polyethylene glycol sulfate were added to 80 ml of ethanol, followed by the addition of 1.125 g of thioacetamide and 2.26 g of BiVO4. The mixture was stirred vigorously at room temperature for 30 min to obtain a transparent solution. The homogeneous solution was then transferred to a Teflon-lined steel autoclave. The prepared sample was sealed and kept at 180°C for 16 hours, then cooled to room temperature. Subsequently, all samples were washed with deionized water, and finally dried in air to obtain (BiVO4). 1.5 / Fe 0.5 In 1.5 S3 powder;

[0138] (3) Memory-type photocatalyst (BiVO4) 1.5 / Ag 0.25 / Fe 0.5 In 1.5 Preparation of S3

[0139] The experimental procedure is the same as step (3) in Example 2;

[0140] (4) Using extrusion molding to transform powdered catalyst into porous spherical catalyst (BiVO4). 1.5 / Ag 0.25 / Fe 0.5 In 1.5 S3

[0141] The experimental procedure is the same as step (4) in Example 2.

[0142] (5) The porous spherical catalyst (BiVO4) prepared using this embodiment 1.5 / Ag 0.25 / Fe 0.5 In 1.5 The S3 and modular dual-reaction integrated treatment system and method degrade complex naphthalene-containing industrial wastewater. Other settings are the same as step (5) in Example 2. Among them, 30L of naphthalene-containing industrial wastewater (COD is 12940mg / L) is treated to COD of 4140mg / L, which is unqualified. The COD removal rate is 68%, and it needs to be returned to pH adjustment tank 7 for retreatment.

[0143] Comparative Example 3

[0144] The porous spherical catalyst (BiVO4) prepared in Example 2 1.2 / Ag 0.25 / Fe 0.5 In 1.5 The modular dual-reaction integrated treatment system and method described in S3 and Example 1 degrades complex naphthalene-containing industrial wastewater. The difference lies in the setup conditions: all wastewater is reacted in the first-stage reaction tank 16 for 3.5 hours and then directly flows through the second reaction tank 17. The results show that the COD after treatment is 1384 mg / L, which meets the test requirements, and the COD removal rate is 89.3%.

[0145] Comparative Example 4

[0146] (BiVO4) obtained using step (3) in Example 2 1.2 / Ag 0.25 / Fe 0.5 In 1.5 The S3 powder and the modular dual-reaction integrated treatment system and method described in Example 1 degrade complex naphthalene-containing industrial wastewater. Other settings are the same as step (5) in Example 2. Among them, 30L of naphthalene-containing industrial wastewater (COD of 12940mg / L) is treated to a COD of 3364mg / L, which is qualified and the COD removal rate is 80%. However, the powder catalyst is easy to accumulate and agglomerate, which is not easy to recover and is easy to clog the instrument.

[0147] Example 7

[0148] The porous spherical catalyst (BiVO4) prepared in Example 2 1.2 / Ag 0.25 / Fe 0.5 In 1.5The modular dual-reaction integrated treatment system and method described in S3 and Example 1 degrades complex naphthalene-containing industrial wastewater. The experimental process is the same as step (5) in Example 2. In the first-stage reaction tank 16, the photocatalytic reaction is carried out for 1 hour, and the dark reaction is carried out in the second-stage reaction tank 17 for 2.2 hours. After treatment, the water is tested for COD. The results show that the COD after treatment is 2826 mg / L, which is qualified and the COD removal rate is 78%.

[0149] Example 8

[0150] The porous spherical catalyst (BiVO4) prepared in Example 2 1.2 / Ag 0.25 / Fe 0.5 In 1.5 The modular dual-reaction integrated treatment system and method described in S3 and Example 1 degraded complex naphthalene-containing industrial wastewater. The experimental process was the same as step (5) in Example 2. After 10 cycles, the COD value of the wastewater was measured. The specific treatment results are shown in Table 1:

[0151]

[0152] Based on Examples 2-8 and Comparative Examples 1-4, it can be seen that neither too much nor too little Ag increases COD degradation efficiency compared to an appropriate amount. Without Ag, electron-hole recombination efficiency is high, and BiVO4 and Fe... x In 2-x The redox ability of S3 monomer is lost, and the amount of active free radicals generated decreases. Too little Ag addition is detrimental to the absorption and utilization of visible light, while too much Ag addition reduces the number of active sites. Comparative Example 2 illustrates the effect of Fe... 3+The degradation effect of ionic catalysts is significantly reduced because the band structure of undoped In2S3 and bismuth vanadate is mismatched, leading to increased electron-hole recombination efficiency. Examples 5 and 6 show that both excessive and insufficient BiVO4 significantly reduce the degradation effect, as the content affects the lattice matching of the heterojunction. If the lattice constants of the two are similar, there will be better lattice matching at the interface, which is beneficial for reducing the interface energy. Comparative Example 3 demonstrates the effectiveness and feasibility of combining photo-reaction and dark-reaction processes. Using all the time for the dark-reaction process for the photo-reaction and combining the photo-reaction and dark-reaction processes yields comparable COD degradation rates, but the combined photo-reaction and dark-reaction process has lower reaction costs, higher sustainability, and allows for uninterrupted reaction, resulting in higher overall time efficiency. Comparative Example 4 shows that there is a difference in COD degradation efficiency between powdered catalysts and molded catalysts for the same antibiotic wastewater, mainly because powdered catalysts are prone to agglomeration and are difficult to recover, easily clogging instruments. Example 7, combined with Comparative Example 3, shows that a photo-reaction time of 1.5 hours is most suitable; too short a time results in low COD degradation efficiency. Example 8 demonstrates that the catalyst does not lose activity after multiple catalytic reactions, exhibiting excellent recyclability.

Claims

1. A modified memory photoresponse material, characterized in that, The modified memory photoresponsive material is (BiVO4) y / Ag z / Fe x In 2-x S3, wherein x is 0.18-1, y is 0.66-1.5, and z is 0.15-0.45, and the Fe x In 2-x S3 is modified by doping Fe.

2. The method for preparing the modified memory photoresponse material according to claim 1, characterized in that, Includes the following steps: (1) BiVO4 was synthesized by solid-liquid reaction method: surfactant, bismuth oxide and vanadium pentoxide were dissolved in dilute nitric acid solution, mixed and stirred, centrifuged, washed and dried to obtain yellow product BiVO4; (2) Synthesis of (BiVO4) by hydrothermal method y / Fe x In 2-x S3: Dissolve the surfactant, ferric chloride hexahydrate and indium trichloride tetrahydrate in ethanol, add thioacetamide and BiVO4, stir vigorously at room temperature, hydrothermal reaction, wash, dry, and obtain (BiVO4) y / Fe x In 2-x S3; (3) Catalyst (BiVO4) prepared by photoreduction deposition method y / Ag z / Fe x In 2-x S3: (BiVO4) y / Fe x In 2-x S3 powder and surfactant were dispersed in a methanol solution, and silver nitrate solution was added dropwise. The mixture was stirred thoroughly to obtain a mixed solution. The mixture was then irradiated under a xenon lamp while being stirred, filtered, washed, and dried to obtain (BiVO4). y / Ag z / Fe x In 2-x S3 ternary composite material; (4) Preparation of porous sphere-forming catalysts by extrusion molding: (BiVO4) y / Ag z / Fe x In 2-x S3 ternary composite material, reinforcing material, molding agent, and pore-forming agent are placed in a hydraulic extruder and extruded to form porous spherical catalysts. The extruded catalysts are then placed in a furnace for sintering to obtain shaped photocatalysts (BiVO4). y / Ag z / Fe x In 2-x S3.

3. The method for preparing the modified memory photoresponse material according to claim 2, characterized in that, In step (1), the surfactant is one or more of sodium linear alkylbenzene sulfonate, sodium α-alkenyl sulfonate, and sodium dodecyl sulfate; the molar ratio of bismuth oxide to vanadium pentoxide is 0.66-1:1; the concentration of the dilute nitric acid solution is 0.3-0.8 mol / L; the solid-liquid ratio of the surfactant, bismuth oxide, and dilute nitric acid solution is 0.1-0.9:1.5-2.5:50-150 g / g / mL; the mixing temperature is 20-60℃; the mixing time is 80-100 h; and the drying temperature is 60-100℃.

4. The method for preparing the modified memory photoresponse material according to claim 2, characterized in that, In step (2), the surfactant is one or more of sodium alkylbenzene sulfonate, polyethylene glycol sulfate, polyethylene glycol ether, acrylic acid / acrylamide methyl propane sulfonic acid copolymer, and sodium dodecyl sulfonate. The time for vigorous stirring is 20-60 min, the temperature of the hydrothermal reaction is 160℃-200℃, and the time of the hydrothermal reaction is 12-19 h.

5. The method for preparing the modified memory photoresponse material according to claim 2, characterized in that, In step (3), the surfactant is one or more of sodium octanoate and dodecyl octanoate, the volume fraction of the methanol solution is 10-30%, the concentration of the silver nitrate solution is 200-600 mg / L, and the (BiVO4) y / Fe x In 2-x The solid-liquid ratio of S3 powder, surfactant, methanol solution, and silver nitrate solution is 1-3:0.1-0.5:200-300:375-3375 g / g / mL / mL, the power of the xenon lamp is 200-500 W, and the illumination time is 30-90 min.

6. The method for preparing the modified memory photoresponse material according to claim 2, characterized in that, In step (4), the reinforcing material is one or more of silicate reinforcing agents and cobalt reinforcing agents; the molding agent is one or more of ethylene-acrylic acid copolymer, phenol, and aluminum phosphate sol; the pore-forming agent is one or more of three-dimensional ordered mesoporous carbon material, silica, tetrapropylammonium hydroxide, and hydrogen ammonium phosphate; the extruder has an extrusion pressure of 5-8 MPa and an extrusion speed of 15-25 r / min; the extruder has a spherical die plate with a diameter of 2 mm; the sintering temperature is 450-860℃; and the sintering time is 1-2 h.

7. The application of the modified memory photoresponsive material according to claim 1 in the treatment of naphthalene-containing industrial wastewater.

8. A modular dual-reaction integrated treatment system for treating naphthalene-containing industrial wastewater using the modified memory photoresponsive material as described in claim 1, characterized in that, The modular dual-reaction integrated processing system includes a filtration module, a pH adjustment module, a heat exchange module, a photocatalytic reaction module, and a storage module connected in sequence. The top of the photocatalytic reaction module is connected to a gas absorption module, and the storage module is connected to the pH adjustment module. The pH adjustment module includes a pH adjustment tank (7), which is connected to an acid storage tank (5) and an alkali storage tank (6). The reaction module includes a main reaction tank (15), which is divided from top to bottom into a first-stage reaction tank (16) and a second-stage reaction tank (17). The tank (16) is connected to a hydrogen peroxide tank (19) on the outside. The first-stage reaction tank (16) is provided with a catalyst stainless steel partition (20) in the middle. The modified memory light response material as described in claim 1 is installed in the middle of the stainless steel partition (20). Multiple light sources (21) extend from top to bottom inside the first-stage reaction tank (16). The catalyst outlet box (27) is provided at the bottom of the second-stage reaction tank (17). The second-stage reaction tank (17) is connected to the storage module through a pipe. A COD online detection system (29) is provided on the pipe. The first-stage reaction tank (16) is connected to the gas absorption module.

9. A method for treating naphthalene-containing industrial wastewater using the modular dual-reaction integrated treatment system of claim 8, characterized in that, Includes the following steps: (1) Naphthalene-containing industrial wastewater enters the filtration module. After filtration, the wastewater enters the pH adjustment tank (7). The pH of the wastewater is adjusted by adding chemicals through the acid storage tank (5) and the alkali storage tank (6). Then the wastewater is sent to the heat exchange module for heat exchange. (2) The wastewater after heat exchange enters the first-stage reaction tank (16), and undergoes photocatalytic reaction under the irradiation of the light source (21) through the modified memory photoresponse material described in claim 1 and the hydrogen peroxide tank (19) in the catalyst stainless steel partition (20), and then enters the second-stage reaction tank (17) for dark reaction. (3) After the dark reaction is completed, the COD in the wastewater is tested by the COD online detection system (29) to see if it is qualified. When the COD is qualified, the waste liquid is transported to the storage module. When the COD is unqualified, the waste liquid is transported back to the pH adjustment tank (7) after passing through the storage module and is recycled again. The gas is transported to the gas absorption module for absorption and the modified memory light response material described in claim 1 is recovered through the catalyst outlet box (27).

10. The method according to claim 9, characterized in that, The acid storage tank (5) stores 10-30% hydrochloric acid solution, and the alkali storage tank (6) stores 20-50% sodium hydroxide solution. The pH value is 5-8. The solid-liquid ratio of the modified memory photoresponse material to the naphthalene-containing industrial wastewater is 35-50:1 g / L. The temperature of the wastewater after heat exchange is 45-65℃. The concentration of hydrogen peroxide is 10-30%. The volume ratio of hydrogen peroxide to wastewater is 0.01-0.06:

1. The light source is a xenon lamp. The photocatalytic reaction time is 1-3 h. The dark reaction time is 1-3 h. The COD test qualification means that the COD value is less than 4000 mg / L.

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