MOFs-loaded polymer material, preparation method, equipment and application

Abstract

The invention provides a polymer material loaded with MOFs, a preparation method, equipment and application, and relates to the technical field of chemical production, surface and interface engineering and environmental engineering. Commercial low-cost thermoplastic polymer particles are used as a substrate, the interface microenvironment of the MOFs and the thermoplastic polymer particles is regulated and controlled through a unique surface hot melting-cooling forming method, the MOFs powder is uniformly loaded on the surfaces of the polymer particles subjected to surface modification, and in combination with self-developed automatic equipment, the MOFs / thermoplastic polymer composite material is obtained. And batch preparation of the granular immobilized water environment functional catalyst material is realized. The preparation method of the catalytic material provides a sustainable technology and strategy for the field of sustainable water environment restoration of MOFs.

Description

Technical Field

[0001] The present invention relates to the technical fields of chemical production, interfacial engineering and environmental engineering, and particularly relates to a polymer material loaded with MOFs, a preparation method, equipment and an application thereof. Background Art

[0002] Due to the unique structure and catalytic performance of metal-organic framework (MOFs) materials, they have become a "star material" in the 21st century. In the field of water purification, MOFs can be used as an effective pretreatment or advanced treatment functional material. It can not only be used as an adsorbent to adsorb and remove various pollutants, but also degrade various new pollutants with strong stability and toxicity in water through different advanced oxidation technologies to improve the biodegradability or safety of wastewater.

[0003] However, since most of the prepared MOFs materials are powders, they are unstable when dispersed in water, prone to agglomeration problems, and are easily lost, making it difficult to recycle them from water for reuse. In addition, powdered MOFs will also cause a huge pressure drop in the fixed-bed reactor in the actual water treatment facility, thus affecting the normal operation of the reactor. To enhance the application potential of MOFs powder materials in the actual water treatment field, it is necessary to fix the MOFs powder on a macroscopic substrate material to prepare granular or membrane-like catalytic reaction devices. However, the current methods for fixing MOFs on various substrates generally require expensive reagent assistance and complex surface modification engineering, and the high cost makes it difficult to be widely applied in actual water treatment projects. Therefore, it is necessary to select an ideal loading substrate and develop a method for preparing MOFs powder into a macroscopic material, ultimately promoting the sustainable application of MOFs-based materials in the actual water treatment field.

[0004] In recent years, thermoplastic polymers have received extensive attention due to their relatively low price, strong flexibility, processability, and solvent stability. They are considered an ideal loading substrate. If MOFs can be effectively combined with thermoplastic polymers to form a new type of catalyst, it may become an ideal strategy to improve the recyclability and durability of MOFs in the field of water treatment. However, the current method of integrating MOFs into thermoplastic polymers still remains at the hot melt-extrusion method, that is, mixing MOFs and thermoplastic polymer powders in an extruder, heating to the polymer melting temperature and then extruding again to form a mixed material with a certain particle size. Due to the closed and non-porous nature of most polymer particles, it is difficult to expose the MOFs incorporated inside the polymer particles to the external environment in this preparation method, resulting in only a small amount of MOFs exposed on the surface of the polymer particles being able to contact the target pollutants. On the one hand, it wastes the MOFs materials doped inside the polymer, and on the other hand, it also leads to poor treatment effects of the target pollutants. At the same time, this method of integrating MOFs into thermoplastic polymers has relatively complex technological processes and requires the purchase of large-scale equipment such as blending equipment, with a high input cost. Therefore, it is necessary to develop a new and low-cost preparation method and strategy for MOFs / polymer particle catalysts. Summary of the Invention

[0005] The technical problems solved by the present invention are: the problems of instability, difficult recovery, easy loss, and easy blockage of reactors of MOFs powder in the actual field of water treatment, as well as the problems of high cost, complex processes, high labor costs, poor environmental friendliness, and poor material availability in the preparation process of MOFs macro materials.

[0006] To solve the above technical problems, the present invention provides a polymer material loaded with MOFs, a preparation method, equipment, and applications. The technical solutions adopted are as follows:

[0007] In the first aspect, the present invention provides a polymer catalyst loaded with MOFs, which is obtained by loading MOFs powder on the surface of polymer particles.

[0008] Preferably, the MOFs in the polymer catalyst loaded with MOFs are selected from MOFs powder materials with a thermal decomposition temperature higher than 120 °C, preferably at least one of ZIF-8, ZIF-67, ZIF-L, ZIF-9, ZIF-90, PCN-222, PCN-224, IRMOF-3, IRMOF-8, IRMOF-9, HKUST-1 / MOF-199 / CuBTC, Cu-TCPP, MOF-5 / IRMOF-1, MOF-74, MOF-808, MOF-525, MIL-53(Cr / Al / Fe), MIL-100(Fe / Cr), MIL-101(Fe / Cr), MIL-125(Ti), MIL-88A(Fe), MIL-88B(Fe), MIL-68(Al / Fe), NH2-MIL-125(Ti), NH2-MIL-88B(Fe), NH2-MIL-53(Fe), UiO-66(Zr), NH2-UiO-66(Zr), UiO-66(Zr)-(OH)2, UiO-66-COOH, UiO-66-SO3H, UiO-67(Zr), and UiO-68, and more preferably at least one of ZIF-8, ZIF-67, ZIF-L, ZIF-9, ZIF-90, MIL-53(Cr / Al / Fe), MIL-100(Fe / Cr), MIL-101(Fe / Cr), MIL-125(Ti), MIL-88A(Fe), MIL-88B(Fe), MIL-68(Al / Fe), NH2-MIL-125(Ti), NH2-MIL-88B(Fe), NH2-MIL-53(Al).

[0009] Preferably, the polymer particles in the polymer catalyst loaded with MOFs are selected from polymer resin materials with a particle size of 1 mm to 5 mm and thermoplastic granular shapes, preferably at least one of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer hot melt adhesive, ethylene-vinyl alcohol copolymer, acrylonitrile-butadiene-styrene terpolymer, polyvinyl chloride, polystyrene, and polyethylene terephthalate, and more preferably at least one of high-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer hot melt adhesive, and acrylonitrile-butadiene-styrene terpolymer.

[0010] In a second aspect, the present invention provides a method for preparing the polymer catalyst loaded with MOFs, including: mixing MOFs powder and polymer particles, performing surface thermal melting treatment, and then using a cooling molding agent to perform a cooling molding treatment on the mixture, so as to load the MOFs powder on the surface of the polymer particles to form the polymer catalyst.

[0011] Preferably, the mixing of the MOFs powder and the polymer particles is carried out by stirring. More preferably, the stirring speed is 20-100 rpm, and further preferably, the stirring speed is 30-50 rpm.

[0012] Preferably, in the surface heat fusion treatment, the heating temperature is 5-20 °C higher than the surface melting temperature of the polymer particles; preferably, the surface heat fusion treatment time is 5-20 min, and more preferably, it is 7 min.

[0013] Preferably, the mass ratio of the MOFs powder to the polymer particles is 1:5-1:20, and preferably, it is 1:5-1:10.

[0014] Preferably, the cooling molding agent is selected from at least one of water, ethanol, and N,N-dimethylformamide, and further preferably, it is water; the mass ratio of the cooling molding agent to the polymer particles is 10:1-100:1, and preferably, it is 50:1; the cooling molding treatment time is 5-10 min, and preferably, it is 5 min.

[0015] In a third aspect, the present invention provides a device for preparing the polymer catalyst loaded with MOFs. The device includes: a device body (4'), a heating plate (1') is provided inside the device body (4'), and a stirrer (2') is provided above the heating plate (1'); a temperature control panel (5') and a time control panel (8') are also installed on the device body.

[0016] Preferably, the heating plate (1') is a circular magnetic conductor, which is arranged 10-15 mm below the upper edge of the device body (4'), and the heating method is electromagnetic heating; the circuit of the heating plate (1') is connected to the temperature control panel (5') and the time control panel (8'), and is controlled by the temperature control panel (5') and the time control panel (8'); preferably, the temperature control range of the heating plate (1') is 50 °C-500 °C, and the time control range is 1 min-30 min.

[0017] Preferably, the stirrer (2') includes 4 stainless steel stirring rods and a driving motor (3'). One end of each of the 4 stainless steel stirring rods is connected to the driving motor (3'), and the included angle between adjacent stirring rods is a right angle; the driving motor (3') is an AC motor and is provided with a pressure sensor; the driving motor (3') is located at the upper center position of the heating plate (1'), and the circuit of the driving motor (3') is connected to the time control panel (8'), and is controlled by the time control panel (8').

[0018] Preferably, the temperature control panel (5') and the time control panel (8') are both located on the outer wall of the body (4'); preferably, the digital display mode is liquid crystal display, and preferably, the touch control mode is capacitive touch control.

[0019] Preferably, a power button (6') is further provided on the device body (4'), the power button (6') is located on the outer wall of the device body (4'), and the power button (6') is connected to the time control panel (8') to control the on and off of the entire circuit; preferably, the touch control mode of the power button (6') is capacitive touch control.

[0020] Preferably, buffer supports (7') are further provided at the bottom of the device body (1'), the buffer supports (7') are made of rubber, and the number is 2, symmetrically distributed on both sides of the bottom of the device body (4') to relieve the vibration caused by stirring.

[0021] Fourthly, the present invention provides a system for preparing the polymer catalyst loaded with MOFs, the system includes the device according to any one of claims 9 to 14, and further includes a cooling and forming device, a washing device and a drying device connected to the device in sequence.

[0022] Fifthly, the present invention provides an application of the polymer catalyst loaded with MOFs, and the application at least includes one of the following: adsorption and removal of pollutants in water, catalytic removal of pollutants in water, improvement of the flame retardant performance of hot melt adhesives in building materials, gas adsorption and storage.

[0023] Preferably, the catalytic removal of pollutants in water includes: degradation of organic pollutants in water and reduction of high-valent metal ions based on photocatalysis, degradation of organic pollutants in water based on activated hydrogen peroxide, degradation of organic pollutants in water based on activated persulfate, degradation of organic pollutants in water based on activated ozone, or coupling of two or more of the foregoing technologies.

[0024] Sixthly, the present invention provides a continuous operation device for realizing the catalytic removal of pollutants in water, the device includes: a liquid inlet system, a reaction system and a liquid discharge system; the liquid inlet system is used to introduce the wastewater to be treated into the reaction system; the reaction system is loaded with the polymer catalyst loaded with MOFs according to any one of claims 1 to 3, and the reaction system is used to remove pollutants from the wastewater to be treated; the liquid discharge system is used to receive the water treated in the reaction system;

[0025] The catalytic removal of water pollutants includes: the degradation of organic pollutants in water and the reduction of high-valent metal ions based on photocatalysis, the degradation of organic pollutants in water based on activated hydrogen peroxide, the degradation of organic pollutants in water based on activated persulfate, the degradation of organic pollutants in water based on activated ozone, or the coupling of two or more of the aforementioned technologies.

[0026] Preferably, the liquid inlet system includes a liquid inlet bucket (1) for placing the wastewater to be treated, and the liquid inlet bucket (1) is connected to the reaction system through a first pipeline (2); a peristaltic pump (3) is provided on the first pipeline (2).

[0027] Preferably, the liquid inlet system further includes a micro automatic continuous syringe for introducing an oxidant into the reaction system. The micro automatic continuous syringe includes a syringe (5), the piston end of the syringe (5) is connected to a syringe piston automatic pusher (4), the needle end of the syringe (5) is connected to a rubber tube (6) with a needle at the end, and the rubber tube (6) is connected to the reaction system.

[0028] Preferably, the reaction system includes a reaction vessel (7), the reaction vessel (7) is loaded with the polymer catalyst (8) loaded with MOFs, and the reaction vessel (7) is connected to the liquid discharge system through a second pipeline (12).

[0029] Preferably, an ultraviolet disinfection lamp tube (9) and an air pump (10) are further provided in the reaction vessel (7).

[0030] Preferably, a barrier net (11) is provided at the connection between the second pipeline (12) and the reaction vessel (7).

[0031] Preferably, the liquid discharge system includes an effluent collection bucket (13), and the effluent collection bucket (13) is connected to the reaction vessel (7).

[0032] In a seventh aspect, the present invention provides a method for continuously catalytically removing water pollutants, which uses the continuous operation device; the method includes: loading the polymer catalyst in the reaction system, and then continuously introducing the wastewater to be treated into the reaction system through the liquid inlet system for catalytic reaction, and discharging the treated water into the liquid discharge system after the reaction ends.

[0033] Preferably, the method is to remove pollutants in water by means of oxidation catalysis. The continuous operation device further includes a micro automatic continuous syringe for introducing an oxidant into the reaction system. The micro automatic continuous syringe includes a syringe (5), the piston end of the syringe (5) is connected to a syringe piston automatic propeller (4), the needle end of the syringe (5) is connected to a rubber tube (6) with a needle at the end, and the rubber tube (6) is connected to the reaction system; the method further includes: while introducing the wastewater to be treated into the reaction system, introducing the oxidant into the reaction system through the micro automatic continuous syringe.

[0034] Preferably, the oxidant is: an aqueous solution of potassium monopersulfate, an aqueous solution of potassium persulfate, or an aqueous solution of hydrogen peroxide with a mass concentration of 30%.

[0035] In an eighth aspect, the present invention provides the use of the MOFs-loaded polymer material in the preparation of flame retardant products.

[0036] The beneficial effects of the present invention are as follows:

[0037] The present invention cleverly utilizes the rigidity of MOFs and the flexibility of polymers, combines the principles of interfacial engineering, and uses self-developed equipment to process MOFs and thermoplastic polymer particles, designing a MOFs-loaded polymer material. This catalyst is expected to achieve stable and continuous degradation and removal of various pollutants in wastewater and is expected to be used as an effective catalyst in small and medium-sized wastewater pretreatment or advanced treatment equipment. The preparation method of this catalyst is simple. Through a unique surface heat fusion-cooling molding method, the efficient automatic preparation of a granular supported catalyst with porous surfaces can be achieved without complex processes, chemicals, and specific temperatures. This method can significantly reduce the labor cost, chemical input cost, and time cost required for per unit mass of MOFs-based granular supported catalysts, while expanding the production scale of MOFs-based granular supported catalysts, improving the environmental friendliness of MOFs-based catalysts during the preparation process, improving the compatibility of MOFs-based catalysts with actual fixed-bed and fluidized-bed reactors, and expanding the application scale of MOFs-based environmental functional materials in the actual water treatment field. Description of the Drawings

[0038] Figure 1 It is a schematic structural diagram of the system for preparing the MOFs-based granular supported catalyst in the present invention, where I is an automatic loading device, II is a screening device, III is a washing device, and IV is a drying device;

[0039] Figure 2 It is a diagram of the thermoplastic polymer particles used in the embodiments of the present invention. Among them, Figure (a) shows a photo of HDPE particles, and Figure (b) shows a photo of EVA particles;

[0040] Figure 3 This is the macroscopic morphology diagram of the successfully prepared granular supported catalysts in the embodiments of the present invention. Among them, Figure (a) shows the photo of the HDPE granular supported catalyst loaded with MIL-88A(Fe), Figure (b) shows the photo of the EVA granular supported catalyst loaded with MIL-88A(Fe), Figure (c) shows the photo of the HDPE granular supported catalyst loaded with ZIF-8, and Figure (d) shows the photo of the EVA granular supported catalyst loaded with ZIF-8;

[0041] Figure 4 This is the scanning electron microscope image of the surface of the MIL-88A(Fe)-based granular supported catalysts successfully prepared in Examples 1 and 2 of the present invention. Among them, Figure (a) shows the energy dispersive spectroscopy element distribution on the surface of the HDPE particles, Figure (b) shows the energy dispersive spectroscopy element distribution on the surface of the HDPE granular supported catalyst loaded with MIL-88A(Fe), Figure (c) shows the energy dispersive spectroscopy element distribution on the surface of the EVA particles, and Figure (d) shows the energy dispersive spectroscopy element distribution on the surface of the EVA granular supported catalyst loaded with MIL-88A(Fe);

[0042] Figure 5 This is the scanning electron microscope image of the surface of the ZIF-8-based granular supported catalysts successfully prepared in Examples 3 and 4 of the present invention. Among them, Figure (a) shows the energy dispersive spectroscopy element distribution on the surface of the HDPE particles, Figure (b) shows the energy dispersive spectroscopy element distribution on the surface of the HDPE granular supported catalyst loaded with ZIF-8, Figure (c) shows the energy dispersive spectroscopy element distribution on the surface of the EVA particles, and Figure (d) shows the energy dispersive spectroscopy element distribution on the surface of the EVA granular supported catalyst loaded with ZIF-8;

[0043] Figure 6 This is the X-ray diffraction pattern of the MOFs powder scraped from the surface of the successfully prepared MOFs-based granular supported catalysts (MHDPE, ZHDPE) in the embodiments of the present invention; among them, Figure (a) shows the X-ray diffraction pattern of MIL-88A(Fe) prepared in Example 1, and Figure (b) shows the X-ray diffraction pattern of ZIF-8 prepared in Example 3;

[0044] Figure 7 This is the X-ray diffraction pattern of the MOFs powder scraped from the surface of the successfully prepared MOFs-based granular supported catalysts (MEVA, ZEVA) in the embodiments of the present invention; among them, Figure (a) shows the X-ray diffraction pattern of MIL-88A(Fe) prepared in Example 2, and Figure (b) shows the X-ray diffraction pattern of ZIF-8 prepared in Example 4;

[0045] Figure 8SEM images of the MOF powders scraped from the surfaces of the MOF-based granular supported catalysts (MHDPE, ZHDPE) successfully prepared in Example 1 of the present invention. Among them, Figure (a) shows the SEM image of MIL-88A(Fe) prepared in Example 1, and Figure (b) shows the SEM image of ZIF-8 prepared in Example 3;

[0046] Figure 9 SEM images of the MOF powders scraped from the surfaces of the MOF-based granular supported catalysts (MEVA, ZEVA) successfully prepared in Example 2 of the present invention. Among them, Figure (a) shows the SEM image of MIL-88A(Fe) prepared in Example 2, and Figure (b) shows the SEM image of ZIF-8 prepared in Example 4;

[0047] Figure 10 Schematic diagram of the preparation principle of the polymer material loaded with MOFs in the present invention;

[0048] Figure 11 Schematic diagram of the equipment for the polymer material loaded with MOFs in the present invention, where 1' is a heating plate, 2' is a stirrer, 3' is a driving motor, 4' is the equipment body, 5' is a temperature control panel, 6' is a power button, 7' is a buffer support, and 8' is a time control panel;

[0049] Figure 12 Schematic diagram of the internal circuit of the equipment for the polymer material loaded with MOFs in the present invention;

[0050] Figure 13 Schematic diagram of the continuous operation device in the present invention;

[0051] Among them, (1) is a liquid inlet bucket, (2) is a rubber tube, (3) is a peristaltic pump, (4) is a syringe piston automatic pusher, (5) is a 50 mL syringe, (6) is a thin rubber tube with a needle at the end, (7) is a transparent cylindrical reaction container made of acrylic material, (8) is the polymer material loaded with MOFs, (9) is an ultraviolet disinfection lamp for aquariums, (10) is an air pump for aquariums, (11) is a barrier net, (12) is a rubber tube, and (13) is an effluent collection bucket.

[0052] Figure 14 For the degradation performance of the organic dye methylene blue and the dissolution of zinc ions in the catalyst by the continuous treatment device in Examples 5-6 of the present invention. Among them, Figure (a) shows the degradation performance of ZHDPE on MB and the dissolution of zinc ions in Example 5, and Figure (b) shows the degradation performance of ZEVA on MB and the dissolution of zinc ions in Example 6;

[0053] Figure 15For the degradation performance of the continuous treatment device for organic dyes rhodamine B and ofloxacin and the dissolution of iron ions in the catalyst in Examples 7-8 of the present invention. Among them, Figure (a) shows the degradation performance of MHDPE for OFL and RB and the dissolution of iron ions in Example 7, and Figure (b) shows the degradation performance of MEVA for OFL and RB and the dissolution of iron ions in Example 8;

[0054] Figure 16 For the degradation performance of the continuous treatment device for organic dyes rhodamine B, ofloxacin, tetracycline hydrochloride, oxytetracycline and chlortetracycline and the dissolution of iron ions in the catalyst in Examples 9-10 of the present invention. Among them, Figure (a) shows the degradation efficiency of MHDPE for RB, OFL, TC, OTC and CTC and the dissolution of iron ions in Example 9, and Figure (b) shows the degradation efficiency of MEVA for RB, OFL, TC, OTC and CTC and the dissolution of iron ions in Example 10;

[0055] Figure 17 For the degradation efficiency of the polymer material loaded with MOFs in multiple rounds of use for ofloxacin in Example 11 of the present invention. Among them, Figure (a) shows the cyclic degradation performance of MHDPE for OFL in Example 11, and Figure (b) shows the cyclic degradation performance of MEVA for OFL in Example 11.

[0056] Figure 18 For the appearance and state of the polymer material loaded with MOFs during heat treatment in Example 12 of the present invention. Among them, Figure (a) shows the state diagram of MHDPE particles during heat treatment; Figure (b) shows the state diagram of ZHDPE particles during heat treatment; Figure (c) shows the state diagram of HDPE particles during heat treatment; Figure (d) shows the state diagram of MEVA particles during heat treatment; Figure (e) shows the state diagram of ZEVA particles during heat treatment; Figure (f) shows the state diagram of EVA particles during heat treatment. Detailed implementation manners

[0057] One of the objectives of the present invention is to provide a method for loading MOFs on the surface of thermoplastic polymer particles to prepare a granular supported catalyst for water treatment. This method does not require the addition of extra chemical reagents and complex surface modification engineering, saving costs. Figure 10 A schematic diagram of the preparation principle of the polymer material loaded with MOFs described in the present invention is provided.

[0058] The preparation method is a unique surface hot-melting and cooling forming method. This method utilizes the characteristic that the melting points of most MOFs are higher than those of common thermoplastic polymer particles, and reasonably regulates the system temperature to make the polymer particles reach the molten state first and just maintain at the boundary between the high-elastic state and the viscous flow state of the polymer. In this state, the molecular chains of the polymer move more intensively, the hydrogen bond and van der Waals force interactions with MOFs are strengthened, and the improvement of the polymer fluidity is also conducive to increasing the permeability of polymer molecules between MOFs particles, thereby further enhancing the meshing between the polymer and MOFs particles. And the cooling forming agent can rapidly reduce the interface temperature, make the polymer molecules stop rotating and undergo a certain degree of shrinkage, so as to rapidly anchor the MOFs particles on the polymer surface.

[0059] The present invention expands the functions of MOFs in the loading process by combining appropriate stirring methods, stirring rates and the mass ratio of MOFs to polymer particles. The MOFs used are not only a raw material, but also act as an anti-sticking agent for the polymer in the system. Utilizing the characteristic of poor interfacial compatibility between MOFs and polymers under low-temperature conditions, micron or nano particles of MOFs will form tiny gaps and protrusions on the surface of the polymer, so as to form an ultra-thin gas film layer between the interfaces of polymer particles, blocking the close contact between polymer particles. At the same time, the MOFs powder greatly reduces the friction coefficient between polymer interfaces, thus effectively preventing the polymer particles from sticking to each other when heated. At the same time, during the stirring process, the rigidity of MOFs particles will form tiny pits and pore structures on the molten surface of the flexible polymer through physical etching, which helps to increase the specific surface area and porosity of the original polymer particles, thereby strengthening the contact and mass transfer of pollutants.

[0060] In addition, the present invention improves the flame retardancy of polymer materials during the loading process by introducing MOFs. When heated, MOFs will not only adhere to the surface of the polymer material, but also form carbonaceous microdomains with higher thermal stability on the surface of the polymer material due to partial pyrolysis. The metal elements in MOFs also have a certain catalytic effect on the formation of carbonaceous microdomains. These carbon layers help to reduce the oxygen concentration in the bulk phase under the surface of the polymer material through the shielding effect, so as to ensure that the polymer material surface will not burn even when heated to the ignition point. The above-mentioned flame retardant effect of MOFs can make the working temperature range of the loading process wider, and the temperature can be increased within 20°C higher than the pyrolysis temperature of the polymer material.

[0061] Specifically, first, MOFs powder and thermoplastic polymer particles in appropriate proportions are directly added to a self-developed loading device. By adjusting the loading temperature, stirring rate, and stirring time, the properties of the surface and interface of the polymer particles are optimized to promote the loading of MOFs powder. Subsequently, a cooling molding agent is used to cool and wash the particle surface, and finally, a polymer material loaded with MOFs is prepared.

[0062] The MOFs powder is selected from MOFs materials with a thermal decomposition temperature higher than 120 °C, preferably at least one of ZIF-8, ZIF-67, ZIF-L, ZIF-9, ZIF-90, PCN-222, PCN-224, IRMOF-3, IRMOF-8, IRMOF-9, HKUST-1 / MOF-199 / CuBTC, Cu-TCPP, MOF-5 / IRMOF-1, MOF-74, MOF-808, MOF-525, MIL-53(Cr / Al / Fe), MIL-100(Fe / Cr), MIL-101(Fe / Cr), MIL-125(Ti), MIL-88A(Fe), MIL-88B(Fe), MIL-68(Al / Fe), NH2-MIL-125(Ti), NH2-MIL-88B(Fe), NH2-MIL-53(Al), UiO-66(Zr), NH2-UiO-66(Zr), UiO-66(Zr)-(OH)2, UiO-66-COOH, UiO-66-SO3H, UiO-67(Zr), and UiO-68. More preferably, it is at least one of ZIF-8, ZIF-67, ZIF-L, ZIF-9, ZIF-90, MIL-53(Cr / Al / Fe), MIL-100(Fe / Cr), MIL-101(Fe / Cr), MIL-125(Ti), MIL-88A(Fe), MIL-88B(Fe), MIL-68(Al / Fe), NH2-MIL-125(Ti), NH2-MIL-88B(Fe), and NH2-MIL-53(Al). All of the above-mentioned MOFs can be prepared by conventional methods or commercially available to those skilled in the art. The preparation methods disclosed in the prior art documents of some MoFs materials used in the present invention are listed below. Specifically, the corresponding references for these preparation methods are shown in Table 1.

[0063] Table 1 Preparation methods of preferred MOFs

[0064]

[0065] The polymer particles are selected from polymer resin materials in the form of thermoplastic granules with a particle size of 1 mm to 5 mm, preferably at least one of high-density polyethylene (HDPE, Shandong Yousuo Chemical Technology Co., Ltd.), low-density polyethylene (LDPE, Shandong Yousuo Chemical Technology Co., Ltd.), linear low-density polyethylene (LLDPE, Shandong Yousuo Chemical Technology Co., Ltd.), polypropylene (PP, Shandong Yousuo Chemical Technology Co., Ltd.), ethylene-vinyl acetate copolymer hot melt adhesive (EVA, Lesu Co.), ethylene-vinyl alcohol copolymer (EVOH, Kuraray Co., Ltd. of Japan), acrylonitrile-butadiene-styrene terpolymer (ABS, Shandong Yousuo Chemical Technology Co., Ltd.), polyvinyl chloride (PVC, Shandong Yousuo Chemical Technology Co., Ltd.), polystyrene (PS, Shandong Yousuo Chemical Technology Co., Ltd.) and polyethylene terephthalate (PET, Shandong Yousuo Chemical Technology Co., Ltd.), and more preferably at least one of high-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer hot melt adhesive, and acrylonitrile-butadiene-styrene terpolymer. The above-mentioned polymers are all commercially available products.

[0066] There are several reasons for selecting HDPE particles (average particle size of 4 mm and melting point of 180 °C) and EVA particles (average particle size of 6 mm and melting point of 80 °C) as the substrates for loading MOFs in the typical embodiments of the present invention: First, HDPE particles and EVA particles are widely used polymer substrates and are very easy to obtain; Second, the prices of HDPE particles and EVA particles are very low, 24 yuan / kg and 16 yuan / kg respectively, which can greatly reduce the preparation cost of the catalytic material; Third, both HDPE particles and EVA particles are thermoplastic materials and have relatively low melting points, 180 °C and 80 °C respectively. Therefore, there is no need for ultra-high temperature treatment during the process of loading MOFs, reducing the energy consumption during the preparation process. Therefore, the selection of HDPE particles and EVA particles in the embodiments has strong representativeness.

[0067] The main reasons for selecting MIL-88A(Fe) and ZIF-8 as the catalysts loaded on the particulate polymer substrate in the typical embodiments of the present invention are as follows: First, MIL-88A(Fe) and ZIF-8 are heat-resistant and can be prepared in large quantities, which meets the requirement for the dosage of a large amount of catalysts in actual water treatment; Second, the precursors used for MIL-88A(Fe) and ZIF-8 are inexpensive. Among them, the selling prices of industrial-grade fumaric acid and industrial-grade ferric chloride used for MIL-88A(Fe) are only 14.8 yuan / kg and 5.8 yuan / kg respectively; the selling price of industrial-grade 2-methylimidazole used for ZIF-8 is only 50 yuan / kg, which can reduce the cost per unit mass of the catalyst; Third, MIL-88A(Fe) and ZIF-8 can degrade various pollutants through advanced oxidation and are relatively ideal catalyst materials; Fourth, MIL-88A(Fe) and ZIF-8 are relatively stable under high-temperature conditions, and their decomposition temperatures are 250°C and 400°C respectively, and they are relatively less likely to undergo physicochemical property changes during the loading process to cause catalyst failure. Therefore, the selection of MIL-88A(Fe) and ZIF-8 in the embodiments has strong representativeness.

[0068] In the typical embodiments of the present invention, 190±10°C and 90±10°C are respectively selected as the preferred temperatures for loading MOFs on the surfaces of HDPE and EVA. When and only when within this temperature range, the surfaces of HDPE and EVA can just be in the viscous flow state and form a molten layer, and thermal decomposition or combustion will not occur. In addition, at this temperature, MIL-88A(Fe) and ZIF-8 will not affect the hydrophilicity of the catalyst due to excessive carbonization. The present invention selects 30 - 50 rpm as the stirring rate of the loading device. Under this stirring condition, the surface friction etching effect of rigid MOFs particles on flexible HDPE and EVA particles is the best, which can promote the roughening of the polymer particle surface and even generate a pore structure, while not damaging the morphology of the polymer particles themselves. The present invention selects the mass ratio of MOFs to polymer as 1:5 - 1:10 as the optimal loading ratio. At this time, the dosage of MOFs is just the minimum dosage to prevent the polymer particles in the surface molten state from sticking to each other.

[0069] The embodiments of the present invention use deionized water as the cooling and shaping agent. Compared with other organic solvents, water has the lowest usage cost, a relatively large specific heat capacity, and has a good absorption effect on heat, which can quickly reduce the temperature of the material surface. At the same time, water is a green and environmentally friendly solvent and will not cause adverse effects on the environment.

[0070] The polymer material of the supported MOFs can be applied to: adsorption and removal of water pollutants, catalytic removal of water pollutants, improvement of the flame retardancy of hot melt adhesives in building materials, gas adsorption and storage. The catalytic removal of water pollutants includes: degradation of organic pollutants in water and reduction of high-valent metal ions based on photocatalysis, degradation of organic pollutants in water based on activated hydrogen peroxide, degradation of organic pollutants in water based on activated persulfate, degradation of organic pollutants in water based on activated ozone, or coupling of two or more of the foregoing technologies. It can also be used to prepare flame retardant products, such as hot melt adhesives with flame retardant properties in building materials.

[0071] Based on the above, the present invention also provides a self-developed automated loading device, which is provided with a heating plate that can control the heating temperature and heating time and a stirrer that can control the stirring time. The stirrer divides the materials of MOFs powder and thermoplastic polymer particles into four partitions, and the materials form an internal circulation between the upper layer and the lower layer and an external circulation of material exchange between partitions in each partition. This design can ensure sufficient contact and uniform heating between the materials. At the same time, the blades in the device can reverse automatically when stuck by the materials, so as to shake off the thermoplastic polymer particles stuck in the impeller and prevent the device from pausing operation. The device can prepare no less than 200 g of particulate catalyst in a single batch.

[0072] As Figure 11 shown, the device includes: a device body 4', and a heating plate 1' and a stirrer 2' are arranged inside the device body 4'; the stirrer 2' is connected to a driving motor 3'; a temperature control panel 5' and a time control panel 8' are also installed on the device body.

[0073] Specifically, the heating plate 1' is a circular magnetic conductor, which is arranged inside the device body 4' 10-15 mm below the edge of the device body 4'. The heating method is electromagnetic heating. The circuit of the heating plate 1' is connected to the temperature control panel 5' and the time control panel 8', and is controlled by the temperature control panel 5' and the time control panel 8'. The temperature control range is 50°C to 500°C, and the time control range is 1 min to 30 min.

[0074] The agitator 2' includes four stirring rods, all made of stainless steel. The ends of the stirring rods are all welded to the drive motor 3'. The included angle between adjacent stirring rods is a right angle. The drive motor 3' is an AC motor and is equipped with a pressure sensor. When the stirring pressure reaches a certain threshold, the AC motor automatically drives the agitator 2' to rotate in the reverse direction. The drive motor 3' is arranged at the upper central position of the heating plate 1'. The drive motor 3' is a commercially available product, with the model 80BL100S40-430TK9 (Super Group Electrical Technology Co., Ltd.). Its circuit is connected to the time control panel 8' and is controlled by the time control panel 8'. The time control range is 1 min to 30 min.

[0075] Further, both the temperature control panel 5' and the time control panel 8' are located on the outer wall of the body 4'. The digital display mode is LCD display, and the touch control mode is capacitive touch control.

[0076] The device is also provided with a power button 6'. The power button 6' is located on the outer wall of the device body 4'. The touch control mode is capacitive touch control. It is connected to the time control panel 8' to control the on and off of the entire circuit.

[0077] The bottom of the device body 4' is also provided with buffer supports 7'. The buffer supports 7' are made of rubber and are welded to the device body 4'. The number is 2, and they are respectively arranged on both sides of the bottom of the device body 4' in a symmetric distribution to relieve the vibration caused by stirring.

[0078] Figure 12 A circuit control schematic diagram of the above device is also provided.

[0079] The present invention also provides a system for preparing the polymer material loaded with MOFs as described above, as Figure 1 shown. The system includes the above device, and also includes a screening device, a washing device, and a drying device for cooling and forming, which are connected to the device in sequence. Among them, I is an automatic loading device, II is a screening device (specifically a sieve in the embodiment part), III is a washing device, and IV is a drying device (specifically an oven in the embodiment part).

[0080] The present invention also provides a continuous operation device for realizing the catalytic removal of water pollutants, as Figure 13 shown. The device includes: a liquid inlet system, a reaction system, and a liquid discharge system. The liquid inlet system is used to introduce the wastewater to be treated into the reaction system. The reaction system is loaded with the polymer material loaded with MOFs. The liquid discharge system is used to receive the water treated in the reaction system.

[0081] Specifically, the liquid inlet system includes a liquid inlet bucket 1 for placing the wastewater to be treated, and the liquid inlet bucket 1 is connected to the reaction system through a first pipeline 2; a peristaltic pump 3 is provided on the first pipeline 2.

[0082] The liquid inlet system further includes a micro automatic continuous syringe for introducing an oxidant into the reaction system. The micro automatic continuous syringe includes a syringe 5, the piston end of the syringe 5 is connected to a syringe piston automatic propeller 4, the needle end of the syringe 5 is connected to a rubber tube 6 with a needle at the end, and the rubber tube 6 is connected to the reaction system.

[0083] The reaction system includes a reaction vessel 7 which is a transparent cylinder made of acrylic. The reaction vessel 7 is loaded with the polymer material 8 loaded with MOFs, and the reaction vessel 7 is connected to the liquid discharge system through a second pipeline 12.

[0084] An ultraviolet disinfection lamp tube 9 and an air pump 10 are further provided in the reaction vessel 7. The optical power of the ultraviolet disinfection lamp tube 9 is 5W, and the ultraviolet disinfection lamp tube 9 and the air pump 10 are perpendicularly inserted into the exact middle of the interior of the reaction vessel 7. The polymer material 8 loaded with MOFs is dispersed inside the reaction vessel 7. When the interior of the reaction vessel 7 is filled with water, the air flow rate of the air pump 10 is 1.5 L / min -1 , and the generated air flow will cause the polymer material 8 to move irregularly around the ultraviolet disinfection lamp tube 9 inside the reaction vessel 7.

[0085] Furthermore, a barrier net 11 is provided at the connection between the second pipeline 12 and the reaction vessel 7 to prevent the polymer material 8 from flowing out of the reaction vessel 7 and causing its loss.

[0086] The liquid discharge system includes an effluent collection bucket 13, and the effluent collection bucket 13 is connected to the reaction vessel 7 through the second pipeline 12.

[0087] The present invention also provides a method for continuously catalytically removing pollutants in water, which uses the continuous operation device and the polymer material described above; the method includes: loading the polymer material in the reaction system, and then continuously introducing the wastewater to be treated into the reaction system through the liquid inlet system for catalytic reaction, and discharging the treated water into the liquid discharge system after the reaction ends.

[0088] If the oxidation catalysis method is adopted to remove pollutants in water, the continuous operation device further includes a micro automatic continuous syringe for introducing an oxidant into the reaction system. The micro automatic continuous syringe includes a syringe 5, the piston end of the syringe 5 is connected with a syringe piston automatic pusher 4, the needle end of the syringe 5 is connected with a rubber tube 6 with a needle at the end, and the rubber tube 6 is connected with the reaction system; The method further includes: while introducing the wastewater to be treated into the reaction system, introducing the oxidant into the reaction system through the micro automatic continuous syringe.

[0089] Further, the oxidant is: an aqueous solution of potassium monopersulfate, an aqueous solution of potassium persulfate or an aqueous solution of hydrogen peroxide with a mass concentration of 30%.

[0090] The sources of raw materials and equipment used in the embodiments of the present invention are shown in Table 2:

[0091] Table 2 Sources of raw materials and equipment used

[0092]

[0093]

[0094] The following examples detail the method for preparing the polymer material loaded with MOFs and the application process of the polymer material. The reagents in the preparation method include MIL-88A(Fe) powder, ZIF-8 powder, HDPE particles and EVA particles. Figure 2 The physical pictures of HDPE particles and EVA particles are given.

[0095] Among them, as Figure 11 shown, the maximum heating temperature of the equipment is not lower than 300 °C, the stirring speed is 30 rpm, the aperture of the sieve should not be greater than 20 mesh, the MIL-88A(Fe) powder is prepared by the method used in the research (DOI: 10.1016 / j.materresbull.2020.110806), 95% ethanol is used as the solvent, ferric chloride and fumaric acid are used as precursors, and then separated by a centrifuge and dried. The ZIF-8 powder is prepared by the method used in the patent "Batch Electrochemical Synthesis Device for Metal-Organic Framework Materials" (Patent Application No.: ZL 2016 2 1258739.3), 95% ethanol is used as the solvent, 2-methylimidazole is used as the precursor, and then separated by a centrifuge and dried.

[0096] Example 1: Preparation of HDPE granular supported catalyst loaded with MIL-88A(Fe)

[0097] Pour 30 g of MIL-88A(Fe) powder and 150 g of HDPE particles into asFigure 11 In the device shown, the heating temperature was set at 200 °C. After stirring for 5 min, the internal mixture was poured into a sieve and shaken. The unloaded MIL-88A(Fe) powder was filtered off, and then the particles on the sieve were repeatedly rinsed with deionized water. Finally, the moisture on the surface of the particles was dried using an oven. The particles are the HDPE granular supported catalyst loaded with MIL-88A(Fe). This catalyst was named MHDPE, and the physical picture is as Figure 3 (a) shown.

[0098] X-ray diffraction analysis and scanning electron microscopy were used to characterize the MIL-88A(Fe) powder scraped from the surface of the prepared catalyst. The test results are as follows:

[0099] The X-ray diffraction analysis results are as Figure 6 (a) shown. The diffraction peak pattern of MIL-88A(Fe) is the same as the simulated pattern in its CIF file and related references (DOI: 10.1016 / j.materresbull.2020.110806), indicating that the recycled MIL-88A(Fe) by this method has good crystallinity and purity.

[0100] The scanning electron microscopy analysis is as Figure 8 (a) shown. It can be observed that the prepared MIL-88A(Fe) particles exhibit a spindle-like morphology with uniform size, and the size is in the range of 0.5 μm to 1.0 μm, which is consistent with the morphology of MIL-88A(Fe) particles in related references (DOI: 10.1016 / j.materresbull.2020.110806), indicating that the morphology of MIL-88A(Fe) on the surface of the granular catalyst prepared by this method is well retained.

[0101] Scanning electron microscopy was used to characterize the surface of the prepared granular catalyst. The test results are as follows:

[0102] The scanning electron microscopy analysis is as Figure 4 (a-b) shown. It can be observed that the surface of the HDPE particles after being treated by this method changes from smooth to rough, the pore structure increases, and a layer of spindle-like MIL-88A(Fe) particles with a size in the range of 0.5 μm to 1.0 μm is uniformly attached. Elemental analysis of the surface of the HDPE particles after being treated by this method using scanning electron microscopy coupled with energy dispersive spectroscopy found that the density of Fe elements on the surface of the treated HDPE particles increases significantly, indicating that MIL-88A(Fe) is successfully loaded on the surface of the HDPE particles.

[0103] Example 2: Preparation of EVA granular supported catalyst loaded with MIL-88A(Fe)

[0104] Pour 30 g of MIL-88A(Fe) powder and 150 g of EVA particles into the device as shown in Figure 11 below. Set the heating temperature to 100 °C. After stirring for 5 min, pour the internal mixture into a sieve and shake it to filter out the unloaded MIL-88A(Fe) powder. Then, repeatedly rinse the particles on the sieve with deionized water. Finally, dry the moisture on the surface of the particles using an oven. The resulting particles are the EVA particle-supported catalyst loaded with MIL-88A(Fe). Name this catalyst MEVA, and the physical picture is as shown in Figure 3 (b).

[0105] Characterize the MIL-88A(Fe) powder scraped from the surface of the prepared catalyst using X-ray diffraction analysis and scanning electron microscopy. The test results are as follows:

[0106] The results of X-ray diffraction analysis are as shown in Figure 7 (a). The diffraction peak pattern of MIL-88A(Fe) is the same as the simulated pattern in its CIF file and relevant references (DOI: 10.1016 / j.materresbull.2020.110806), indicating that the recovered MIL-88A(Fe) using this method has good crystallinity and purity.

[0107] The analysis of the scanning electron microscopy images is as shown in Figure 9 (a). It can be observed that the prepared MIL-88A(Fe) particles exhibit a spindle-like morphology with uniform size, ranging from 0.5 μm to 1.0 μm, which is consistent with the morphology of MIL-88A(Fe) particles in relevant references (DOI: 10.1016 / j.materresbull.2020.110806), indicating that the morphology of MIL-88A(Fe) on the surface of the prepared particulate catalyst is well retained.

[0108] Characterize the surface of the prepared particulate catalyst using scanning electron microscopy. The test results are as follows:

[0109] The analysis of the scanning electron microscopy images is as shown in Figure 4 (c-d). It can be observed that the pore structure on the surface of the EVA particles after being treated by this method is more abundant, and a layer of spindle-like MIL-88A(Fe) particles is evenly attached, with a size ranging from 0.5 μm to 1.0 μm. The elemental analysis of the surface of the EVA particles treated by this method using scanning electron microscopy coupled with energy dispersive spectroscopy shows that the density of Fe elements on the surface of the treated EVA particles increases significantly, indicating that MIL-88A(Fe) is successfully loaded on the surface of the EVA particles.

[0110] Example 3: Preparation of HDPE granular supported catalyst loaded with ZIF-8

[0111] Pour 30 g of ZIF-8 powder and 150 g of HDPE granules into the equipment as shown in Figure 11 . Set the heating temperature to 200 °C. After stirring for 5 min, pour the internal mixture into a sieve and shake it. Filter out the unloaded ZIF-8 powder. Then rinse the granules on the sieve repeatedly with deionized water. Finally, dry the moisture on the surface of the granules using an oven. The granules are the HDPE granular supported catalyst loaded with ZIF-8. Name this catalyst ZHDPE. The physical picture is as shown in Figure 3 (c).

[0112] Use X-ray diffraction analysis and scanning electron microscopy to characterize the ZIF-8 powder scraped from the surface of the prepared catalyst. The test results are as follows:

[0113] The X-ray diffraction analysis results are as shown in Figure 6 (b). The diffraction peak pattern of ZIF-8 is the same as the simulated pattern in its CIF file and relevant references (DOI: 10.1039 / C4RA08820D), indicating that the recycled ZIF-8 by this method has good crystallinity and purity.

[0114] The scanning electron microscopy analysis is as shown in Figure 8 (b). It can be observed that the prepared ZIF-8 particles show a uniform dodecahedral morphology with sizes in the range of 0.5 μm to 3.0 μm, which is similar to the morphology of ZIF-8 particles in relevant references (patent application number: ZL 201621258739.3), indicating that the morphology of ZIF-8 on the surface of the granular catalyst prepared by this method is well retained.

[0115] Use scanning electron microscopy to characterize the surface of the prepared granular catalyst. The test results are as follows:

[0116] The scanning electron microscopy analysis is as shown in Figure 5 (a-b). It can be observed that the surface roughness of the HDPE granules after being treated by this method increases, and pores are generated. A layer of dodecahedral ZIF-8 particles with sizes in the range of 0.5 μm to 3.0 μm is uniformly attached to it. Elemental analysis of the surface of the HDPE granules after being treated by this method using scanning electron microscopy coupled with energy dispersive spectroscopy finds that the density of Zn element on the surface of the treated HDPE granules increases significantly, indicating that ZIF-8 is successfully loaded on the surface of the HDPE granules.

[0117] Example 4: Preparation of EVA granular supported catalyst loaded with ZIF-8

[0118] Pour 30 g of ZIF-8 powder and 150 g of EVA particles into the device as shown in Figure 11 . Set the heating temperature to 100 °C. After stirring for 5 min, pour the internal mixture into a sieve and shake it to filter out the unloaded ZIF-8 powder. Then, repeatedly rinse the particles on the sieve with deionized water. Finally, dry the moisture on the surface of the particles using an oven. The resulting particles are the EVA particle-supported catalyst loaded with ZIF-8. Name this catalyst ZEVA. The physical picture is as shown in Figure 3 Figure d.

[0119] Use X-ray diffraction analysis and scanning electron microscopy to characterize the ZIF-8 powder scraped from the surface of the prepared catalyst. The test results are as follows:

[0120] The X-ray diffraction analysis results are as shown in Figure 7 (b). The diffraction peak pattern of ZIF-8 is the same as the simulated pattern in its CIF file and related references (DOI: 10.1039 / C4RA08820D), indicating that the recovered ZIF-8 by this method has good crystallinity and purity.

[0121] The scanning electron microscopy image analysis is as shown in Figure 9 (b). It can be observed that the prepared ZIF-8 particles exhibit a uniform dodecahedral morphology with sizes in the range of 0.5 μm to 3.0 μm, which is similar to the morphology of ZIF-8 particles in related references (patent application number: ZL 201621258739.3), indicating that the morphology of ZIF-8 on the surface of the prepared particulate catalyst is well retained.

[0122] Use scanning electron microscopy to characterize the surface of the prepared particulate catalyst. The test results are as follows:

[0123] The scanning electron microscopy image analysis is as shown in Figure 5 (c - d). It can be observed that the pore structure on the surface of the EVA particles after being treated by this method is more abundant, and a layer of dodecahedral ZIF-8 particles with sizes in the range of 0.5 μm to 3.0 μm is uniformly attached thereto. Elemental analysis of the surface of the EVA particles treated by this method using scanning electron microscopy coupled with energy dispersive spectroscopy reveals that the density of Zn elements on the surface of the treated EVA particles increases significantly, indicating that ZIF-8 is successfully loaded on the surface of the EVA particles.

[0124] Figure 3(a-d) are the macroscopic morphology diagrams of polymer particles and the successfully prepared MIL-88A(Fe)-based granular supported catalysts. It can be observed that the surfaces of HDPE and EVA treated by Examples 1-4 changed from transparent to reddish-brown and white respectively, indicating that MIL-88A(Fe) and ZIF-8 were successfully loaded onto the surfaces of HDPE and EVA respectively.

[0125] The following examples provide a continuous treatment method capable of continuously degrading organic pollutants in wastewater through photocatalytic reactions. The device used is as Figure 13 shown. The reagents in the continuous treatment device include methylene blue (MB). The polymer materials loaded with MOFs added in the continuous device are ZHDPE and ZEVA prepared in Examples 3 and 4.

[0126] Example 5: Photocatalytic degradation of MB by loading ZHDPE in the continuous treatment device

[0127] Prepare an MB solution with a concentration of 10 mg L -1 using deionized water. Take a small amount of the sample, filter it using a 0.22 μm polyethersulfone microporous filter membrane, and then measure the initial absorbance C of the solution at a wavelength of 664 nm using a UV-visible spectrophotometer 0,MB . Subsequently, add the MB solution to the feed bucket (1), add 100 g of ZHDPE catalyst to the reaction vessel (7), disconnect the connection between the thin rubber tube (6) and the rubber tube (2), turn on the peristaltic pump (3), adjust the pump speed of the peristaltic pump to 3 rpm, turn on the UV disinfection lamp tube (9) and the air pump (10). When liquid starts to flow out of the rubber tube (12), start timing. At the same time, take a sample from the outlet of the rubber tube (12) (the sampling volume is not less than 5 mL), filter it using a 0.22 μm polyethersulfone microporous filter membrane, measure the absorbance of the sample at a wavelength of 664 nm using a UV-visible spectrophotometer, and measure the Zn ion concentration in the remaining sample using an inductively coupled plasma optical emission spectrometer (ICP-OES). Then take a sample from the outlet of the rubber tube (12) every 4 h, process the sample using the same method and measure its absorbance and Zn ion concentration, which are denoted as C t,MB and C t,Zn , where t is the operating time of the device corresponding to the sample taken since the start of timing. Plot the curve of C t / C0 varying with time within 72 h. Evaluate the long-term degradation performance of the continuous treatment device for MB and the durability of the catalyst according to the curve of C t,MB / C 0,MB varying with time; evaluate the ion dissolution of the catalyst in the continuous treatment device at different times according to the curve of C t,Zn varying with time, and then analyze the stability of the catalyst.

[0128] To exclude the contributions of the substrate and pure light irradiation conditions to the degradation of pollutants, ZHDPE was replaced with HDPE particles of the same mass and added to the reaction vessel (7). With other conditions unchanged, Example 5 was repeated, and the curve of C t,MB / C 0,MB changing with time was plotted.

[0129] As shown in Figure 14 (a), within the 72-hour continuous operation time of the device, the catalyst can achieve a degradation efficiency of more than 80% for MB. This device can cumulatively treat 70.2 L of wastewater containing 10 mg L -1 of the organic dye MB. Among them, the contributions of pure HDPE and ultraviolet light to the degradation of MB are not significant. During the treatment process, the concentration of zinc ions (Zn ion leaching) dissolved by the catalyst is relatively low, less than 1 mg L after 12 h -1 , only slightly higher than 2 mg L at the initial stage -1 , indicating the good stability and durability of ZHDPE.

[0130] Example 6: Continuous treatment device loaded with ZEVA for photocatalytic degradation of MB

[0131] A MB solution with a concentration of 10 mg L was prepared using deionized water. A small amount of sample was taken from it, filtered using a 0.22 μm polyethersulfone microporous membrane, and then the initial absorbance C of this solution was measured using a UV-visible spectrophotometer at a wavelength of 664 nm -1 . Subsequently, the MB solution was added to the inlet bucket (1), 100 g of ZEVA catalyst was added to the reaction vessel (7), the connection between the thin rubber tube (6) and the rubber tube (2) was disconnected, the peristaltic pump (3) was turned on, the pump speed of the peristaltic pump was adjusted to 3 rpm, the UV disinfection lamp tube (9) and the air pump (10) were turned on. When liquid began to flow out of the rubber tube (12), timing started. At the same time, a sample was taken from the outlet of the rubber tube (12) (the sampling volume was not less than 5 mL), filtered using a 0.22 μm polyethersulfone microporous membrane, the absorbance of the sample was measured using a UV-visible spectrophotometer at a wavelength of 664 nm, and the Zn ion concentration in the remaining sample was measured using an inductively coupled plasma optical emission spectrometer (ICP-OES). After that, a sample was taken from the outlet of the rubber tube (12) every 4 h, and the sample was processed and its absorbance and Zn ion concentration were measured using the same method, denoted as C 0,MB and C t,MB and C t,Zn , where t is the operation time of the device corresponding to the sample taken since the start of timing. The curve of C t / C0 changing with time was plotted. According to C t,MB / C 0,MBThe curve varying with time evaluates the degradation performance of the continuous treatment device for MB over a long time and the durability of the catalyst; according to C t,Zn The curve varying with time evaluates the ion leaching of the catalyst in the continuous treatment device at different times, and then analyzes the stability of the catalyst.

[0132] To exclude the contribution of the substrate and pure light irradiation conditions to the degradation of pollutants, ZEVA was replaced with EVA particles of the same mass and added to the reaction vessel (7). Other conditions remained unchanged, and Example 6 was repeated to plot C within 72 h t,MB / C 0,MB The curve varying with time.

[0133] From Figure 14 (b) As shown, within the 72-hour continuous operation time of the device, the catalyst can achieve a degradation efficiency of more than 70% for MB. The device can cumulatively treat 70.2 L of wastewater containing 10 mg L -1 of the organic dye MB. Among them, the contributions of pure EVA and ultraviolet light to the degradation of MB are not significant. During the treatment process, the concentration of zinc ions leached from the catalyst is relatively low, less than 1 mg L after 8 h -1 , only slightly higher than 2 mg L at the initial stage -1 , indicating the good stability and durability of ZEVA.

[0134] The following examples provide a continuous operation method capable of continuously degrading organic pollutants in wastewater through photocatalytic coupling with the Fenton-like reaction. The device used is as Figure 13 shown. The reagents in the continuous treatment device include rhodamine B (RB), ofloxacin (OFL), and 30% hydrogen peroxide aqueous solution (30% H2O2). The polymer materials loaded with MOFs added in the continuous device are MHDPE and MEVA prepared in Examples 1 and 2.

[0135] Example 7: The continuous treatment device loaded with MHDPE photocatalytically couples with the Fenton-like reaction to degrade RB and OFL

[0136] Use deionized water to prepare a mixed solution of RB and OFL with a concentration of 10 mg L -1 . Take a small amount of sample from it, filter it with a 0.22 μm polyethersulfone microporous membrane, and then use a UV-visible spectrophotometer to measure the initial absorbance C of this solution at a wavelength of 554 nm 0,RB , and use a high-performance liquid chromatograph to measure the initial concentration C of OFL in this solution 0,OFLThen, the solution was added to the liquid inlet barrel (1), 100 g of MHDPE catalyst was added to the reaction vessel (7), 30% H2O2 solution was added to the syringe (5), the thin rubber tube (6) was connected to the rubber tube (2), the peristaltic pump (3) was turned on, and the pump speed of the peristaltic pump was adjusted to 3 rpm; the piston automatic propeller (4) was turned on, and the flow rate was adjusted to 0.5 mL h -1 , turn on the ultraviolet disinfection lamp (9) and the air pump (10), when liquid begins to flow out of the rubber tube (12), start timing, and simultaneously take a sample from the water outlet of the rubber tube (12) (the sampling volume is not less than 5 mL), filter using a 0.22 μm polyethersulfone microporous filter membrane, use a UV-visible spectrophotometer to measure the absorbance of the sample at a wavelength of 554 nm, and use a high performance liquid chromatograph to measure the residual concentration of OFL in the sample, and use an inductively coupled plasma emission spectrometer (ICP-OES) to measure the Fe ion concentration in the remaining sample. After that, take a sample from the water outlet of the rubber tube (12) every 4 hours, use the same method to treat the sample and measure its absorbance, OFL residual concentration and Fe ion concentration, which are recorded as C respectively. t,RB , C t,OFL and C t,Fe . Where t is the device operation time corresponding to the sample taken from the start of timing. Plot C within 72h t The curve of / C0 changing with time. t,RB / C 0,RB and C t,OFL / C 0,OFL The time-varying curves evaluate the long-term degradation performance of RB and OFL in the continuous treatment unit and the durability of the catalyst; according to C t,Fe The time-varying curves evaluate the ion dissolution of the catalyst at different times in the continuous processing unit and thus analyze the stability of the catalyst.

[0137] In order to exclude the contribution of substrate and pure light conditions to the degradation of pollutants, MHDPE was replaced with HDPE particles of the same mass and added to the reaction vessel (7). Other conditions remained unchanged and Example 7 was repeated to plot the C t,RB / C 0,RB and C t,OFL / C 0,OFL A curve that changes over time.

[0138] Depend on Figure 15 As shown in (a), during the continuous operation time of the device for 72 hours, the catalyst can achieve a degradation efficiency of more than 90% for RB and OFL. The device can cumulatively process 70.2L of 10mg L -1Wastewater of organic dyes RB and OFL. Among them, the contributions of pure HDPE and ultraviolet light to the degradation of RB and OFL are not significant. During the treatment process, the concentration of iron ions leached from the catalyst (Fe ion leaching) is low, less than 1 mg / L after 16 h, and only slightly higher than 4 mg / L at the beginning, indicating the good stability and durability of MHDPE. -1 and only slightly higher than 4 mg / L at the beginning -1 , indicating the good stability and durability of MHDPE.

[0139] Example 8: A continuous treatment device is loaded with MEVA photocatalytic coupled Fenton-like to degrade RB and OFL

[0140] Prepare a mixed solution of RB and OFL with a concentration of 10 mg / L using deionized water. Take a small amount of the sample, filter it with a 0.22 μm polyethersulfone microporous membrane, and then measure the initial absorbance C of the solution at a wavelength of 554 nm using a UV-visible spectrophotometer -1 , and measure the initial concentration C of OFL in the solution using a high-performance liquid chromatograph 0,RB . Subsequently, add the solution to the feed bucket (1), add 100 g of MEVA catalyst to the reaction vessel (7), add 30% H2O2 solution to the syringe (5), connect the thin rubber tube (6) to the rubber tube (2), turn on the peristaltic pump (3), and adjust the pump speed of the peristaltic pump to 3 rpm; turn on the piston automatic propeller (4) and adjust the flow rate to 0.5 mL / h 0,OFL , turn on the UV disinfection lamp tube (9) and the air pump (10). When liquid starts to flow out of the rubber tube (12), start timing. At the same time, take samples from the outlet of the rubber tube (12) (the sampling volume is not less than 5 mL), filter them with a 0.22 μm polyethersulfone microporous membrane, measure the absorbance of the samples at a wavelength of 554 nm using a UV-visible spectrophotometer, and measure the remaining concentration of OFL in the samples using a high-performance liquid chromatograph. At the same time, measure the Fe ion concentration in the remaining samples using an inductively coupled plasma optical emission spectrometer (ICP-OES). Then take samples from the outlet of the rubber tube (12) every 4 h, process the samples using the same method and measure their absorbance, remaining concentration of OFL, and Fe ion concentration, which are denoted as C -1 , C t,RB , C t,OFL , and C t,Fe . Among them, t is the operation time of the device corresponding to the samples taken since the start of timing. Plot the curve of C t / C0 changing with time within 72 h. According to C t,RB / C 0,RB and C t,OFL / C 0,OFL changing with time, evaluate the long-term degradation performance of the continuous treatment device for RB and OFL and the durability of the catalyst; according to Ct,Fe The curve changing with time evaluates the ion dissolution of the catalyst in the continuous treatment device at different times, and then analyzes the stability of the catalyst.

[0141] To exclude the contributions of the substrate and pure light illumination conditions to the degradation of pollutants, MEVA was replaced with EVA particles of the same mass and added to the reaction vessel (7). Other conditions remained unchanged, and Example 8 was repeated to plot C t,RB / C 0,RB and C t,OFL / C 0,OFL curves changing with time.

[0142] As shown by Figure 15 (b), within the 72-hour continuous operation time of the device, the catalyst can achieve a degradation efficiency of more than 80% for RB and OFL. This device can cumulatively treat 70.2 L of wastewater containing 10 mg L -1 organic dyes RB and OFL. Among them, the contributions of pure EVA and ultraviolet light to the degradation of RB and OFL are not significant. During the treatment process, the concentration of iron ions dissolved by the catalyst is relatively low, less than 1 mg L -1 after 16 h, only slightly higher than 4 mg L -1 at the initial stage, indicating the good stability and durability of MEVA.

[0143] The following examples provide a continuous treatment method capable of continuously degrading organic pollutants in wastewater through a photocatalytic coupled activation of persulfate reaction, and the device used is as Figure 13 shown. The reagents in the continuous treatment device include rhodamine B (RB), ofloxacin (OFL), tetracycline hydrochloride (TC), oxytetracycline (OTC), chlortetracycline (CTC), and potassium peroxymonosulfate (KHSO5). The granular supported catalyst added in the continuous device is MHDPE and MEVA.

[0144] Example 9: The continuous treatment device is loaded with MHDPE for photocatalytic activation of persulfate to degrade RB, OFL, TC, OTC, and CTC

[0145] A 0.5 M aqueous solution of potassium peroxymonosulfate (0.5 M PMS solution) was prepared using deionized water and potassium peroxymonosulfate, and a mixed solution of RB, OFL, TC, OTC, and CTC with a concentration of 10 mg L -1 was prepared using deionized water. A small amount of sample was taken from it, filtered using a 0.22 μm polyethersulfone microporous membrane filter, and then the initial absorbance C 0,RB of this solution was measured using a UV-visible spectrophotometer at a wavelength of 554 nm, and the initial concentrations C 0,OFL, C 0,TC , C 0,OTC and C 0,CTC . Subsequently, the solution was added to the feed bucket (1), 100 g of MHDPE catalyst was added to the reaction vessel (7), 0.5 M PMS solution was added to the syringe (5), the thin rubber tube (6) was connected to the rubber tube (2), the peristaltic pump (3) was turned on, and the pump speed of the peristaltic pump was adjusted to 3 rpm; the piston auto - injector (4) was turned on and the flow rate was adjusted to 0.6 mL h -1 , the ultraviolet disinfection lamp (9) and the air pump (10) were turned on. When liquid began to flow out of the rubber tube (12), timing started. At the same time, samples were taken from the outlet of the rubber tube (12) (the sampling volume was not less than 5 mL), filtered using a 0.22 - μm polyethersulfone microporous membrane, the absorbance of the sample was measured at a wavelength of 554 nm using a UV - Vis spectrophotometer, and the remaining concentrations of OFL, TC, OTC, and CTC in the sample were measured using a high - performance liquid chromatograph. At the same time, the Fe ion concentration in the remaining sample was measured using an inductively coupled plasma optical emission spectrometer (ICP - OES). After that, samples were taken from the outlet of the rubber tube (12) every 4 h, and the samples were processed and their absorbance, remaining concentration of OFL, remaining concentration of TC, remaining concentration of OTC, remaining concentration of CTC, and Fe ion concentration were measured using the same method, and were denoted as C t,RB , C t,OFL , C t,TC , C t,OTC , C t,CTC and C t,Fe . Among them, t is the operation time of the device corresponding to the sample taken since the start of timing. Draw the curve of C t / C0 varying with time within 72 h. According to C t,RB / C 0,RB , C t,OFL / C 0,OFL , C t,TC / C 0,TC , C t,OTC / C 0,OTC and C t,CTC / C 0,CTC varying with time, evaluate the long - term degradation performance of the continuous treatment device for RB, OFL, TC, OTC, and CTC and the durability of the catalyst; according to the curve of C t,Fe varying with time, evaluate the ion dissolution of the catalyst in the continuous treatment device at different times, and then analyze the stability of the catalyst.

[0146] To exclude the contribution of the substrate and pure light conditions to the degradation of pollutants, MHDPE was replaced with HDPE particles of the same mass and added to the reaction vessel (7), and other conditions remained unchanged. Example 9 was repeated, and the curve of C t,RB / C 0,RB and C t,OFL / C 0,OFL and C t,TC / C 0,TC and C t,OTC / C 0,OTC and C t,CTC / C 0,CTC curves varying with time.

[0147] As shown in Figure 16 (a), within the continuous operation time of 72 h of the device, the catalyst can achieve a degradation efficiency of more than 90% for RB, OFL, TC, OTC, and CTC. The device can cumulatively treat 70.2 L of wastewater containing 10 mg L -1 of organic dyes RB, OFL, TC, OTC, and CTC. Among them, the contributions of pure HDPE and ultraviolet light to the degradation of RB, OFL, TC, OTC, and CTC are not significant. During the treatment process, the concentration of iron ions dissolved by the catalyst is relatively low, lower than 1 mg L -1 after 12 h, only slightly higher than 4 mg L -1 at the initial stage, indicating the good stability and durability of MHDPE.

[0148] Example 10: Continuous treatment device loaded with MEVA for photocatalytic activation of persulfate to degrade RB, OFL, TC, OTC, and CTC

[0149] Prepare an aqueous solution of potassium persulfate with a concentration of 0.5 M (0.5 M PMS solution) using deionized water and potassium hydrogen persulfate, and prepare a mixed solution of RB, OFL, TC, OTC, and CTC with a concentration of 10 mg L -1 using deionized water. Take a small amount of the sample from it, filter it using a 0.22 μm polyethersulfone microporous membrane filter, and then measure the initial absorbance C 0,RB of the solution at a wavelength of 554 nm using a UV-visible spectrophotometer, and use a high-performance liquid chromatograph to measure the initial concentrations C 0,OFL 、C 0,TC 、C 0,OTC and C 0,CTC of OFL, TC, OTC, and CTC in the solution respectively. Subsequently, add the solution to the feed bucket (1), add 100 g of MEVA catalyst to the reaction vessel (7), add the 0.5 M PMS solution to the syringe (5), connect the thin rubber tube (6) to the rubber tube (2), turn on the peristaltic pump (3), and adjust the pump speed of the peristaltic pump to 3 rpm; turn on the piston automatic pusher (4) and adjust the flow rate to 0.6 mL h -1, turn on the ultraviolet disinfection lamp (9) and the air pump (10), when liquid begins to flow out of the rubber tube (12), start timing, and at the same time take a sample from the water outlet of the rubber tube (12) (the sampling volume is not less than 5mL), filter using a 0.22μm polyethersulfone microporous filter membrane, use a UV-visible spectrophotometer to measure the absorbance of the sample at a wavelength of 554nm, and use a high performance liquid chromatograph to measure the residual concentrations of OFL, TC, OTC and CTC in the sample, and use an inductively coupled plasma emission spectrometer (ICP-OES) to measure the Fe ion concentration in the remaining sample. After that, take a sample from the water outlet of the rubber tube (12) every 4 hours, use the same method to treat the sample and measure its absorbance, OFL residual concentration, TC residual concentration, OTC residual concentration, CTC residual concentration and Fe ion concentration, respectively recorded as C t,RB , C t,OFL , C t,TC , C t,OTC , C t,CTC and C t,Fe . Where t is the device operation time corresponding to the sample taken from the start of timing. Plot C within 72h t The curve of / C0 changing with time. t,RB / C 0,RB , C t,OFL / C 0,OFL , C t,TC / C 0,TC , C t,OTC / C 0,OTC and C t,CTC / C 0,CTC The time-varying curves evaluate the long-term degradation performance of the continuous treatment unit for RB, OFL, TC, OTC and CTC and the durability of the catalyst; according to C t,Fe The time-varying curves evaluate the ion dissolution of the catalyst at different times in the continuous processing unit and thus analyze the stability of the catalyst.

[0150] In order to exclude the contribution of the substrate and pure light conditions to the degradation of pollutants, MEVA was replaced with EVA particles of the same mass and added to the reaction vessel (7). Other conditions remained unchanged and Example 10 was repeated to plot the C t,RB / C 0,RB , C t,OFL / C 0,OFL , C t,TC / C 0,TC , C t,OTC / C 0,OTC and C t,CTC / C 0,CTC A curve that changes over time.

[0151] Depend on Figure 16(b) As shown, within the continuous operation time of the device for 72 h, the catalyst can achieve a degradation efficiency of over 80% for RB, OFL, TC, OTC, and CTC. This device can cumulatively treat 70.2 L of wastewater containing 10 mg L -1 of organic dyes RB, OFL, TC, OTC, and CTC. Among them, the contributions of pure EVA and ultraviolet light to the degradation of RB, OFL, TC, OTC, and CTC are not significant. During the treatment process, the concentration of iron ions dissolved by the catalyst is relatively low, below 1 mg L after 16 h -1 , only slightly higher than 4 mg L at the initial stage -1 , indicating the good stability and durability of MEVA.

[0152] Example 11

[0153] To further confirm the durability and recyclability of the catalyst loaded with MOFs, a mixed solution of OFL with a concentration of 10 mg L was prepared using deionized water -1 . A small amount of sample was taken from it, filtered using a 0.22 μm polyethersulfone microporous membrane filter, and then the initial concentration C of OFL in this solution was measured using a high-performance liquid chromatograph 0,OFL . Then the prepared solution was poured into two 50 mL beakers, 20 μL of 30% H2O2 solution and 1 g of MHDPE / MEVA were added respectively. The two beakers were placed in sunlight and stirred using a magnetic stirrer. At regular intervals, 2.5 mL of the solution in the two beakers was sampled, filtered using a 0.22 μm polyethersulfone microporous membrane filter, and then the initial concentration C of OFL in this solution was measured using a high-performance liquid chromatograph t,OFL . A curve of C t,OFL / C 0,OFL changing with time within 100 min was plotted. Then MHDPE and MEVA were taken out from the two beakers respectively, rinsed with deionized water and dried. The above operations were repeated, and the recycled degradation experiment of OFL was carried out again using the dried MHDPE and MEVA, and multiple curves of C t,OFL / C 0,OFL changing with time within 100 min were plotted.

[0154] Recycled degradation experiment results of MHDPE for OFL Figure 17 (a) As shown, within 5 cycles, the degradation efficiency of MHDPE for OFL within the same time almost remains unchanged, always higher than 90%, and the mass loss of MHDPE after the 5th cycle is less than 1%, indicating the high stability, recyclability, and reusability of the MHDPE catalyst; Recycled degradation experiment results of MEVA for OFL Figure 17As shown in (b), within 5 cycles, the degradation efficiency of MHDPE for OFL remains almost unchanged over the same time, always higher than 95%, and the mass loss of MHDPE after the 5th cycle is less than 0.5%, indicating that the MEVA catalyst has high stability, recyclability and reusability.

[0155] Example 12

[0156] To further confirm the flame retardancy of the polymer materials loaded with MOFs, 10 g of the MHDPE, MEVA, ZHDPE and ZEVA particles prepared in Examples 1-4 were weighed and added to a 500 mL glass beaker, and continuously heated on an electric furnace at a heating temperature of 400 °C, which is higher than the pyrolysis temperature of HDPE and EVA particles, for 30 min. At the same time, as a control, 10 g of HDPE and EVA particles without loaded MOFs were treated in the same way. The carbonization degree of the particles was judged by observing the final appearance of different particles to evaluate the combustion intensity of the materials.

[0157] From Figure 18 it can be seen that after heating for 30 min, HDPE and EVA were all melted and carbon black was formed on the surface, indicating that the materials had undergone pyrolysis reaction and smoldering process; in contrast, the MHDPE, MEVA, ZHDPE and ZEVA particles showed no obvious change, indicating the excellent thermal stability of the polymer materials loaded with MOFs.

[0158] The above embodiments only represent several implementation manners of the present invention, and their descriptions are relatively specific and detailed, but should not be construed as limiting the scope of the present invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several deformations and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. A polymer material loaded with MOFs is obtained by loading MOFs powder on the surface of polymer particles.

2. The polymer material loaded with MOFs according to claim 1, characterized in that, The MOFs in the polymer material loaded with MOFs are selected from MOFs powder materials with a thermal decomposition temperature higher than 120 °C, preferably at least one of ZIF-8, ZIF-67, ZIF-L, ZIF-9, ZIF-90, PCN-222, PCN-224, IRMOF-3, IRMOF-8, IRMOF-9, HKUST-1 / MOF-199 / CuBTC, Cu-TCPP, MOF-5 / IRMOF-1, MOF-74, MOF-808, MOF-525, MIL-53(Cr / Al / Fe), MIL-100(Fe / Cr), MIL-101(Fe / Cr), MIL-125(Ti), MIL-88A(Fe), MIL-88B(Fe), MIL-68(Al / Fe), NH2-MIL-125(Ti), NH2-MIL-88B(Fe), NH2-MIL-53(Al), UiO-66(Zr), NH2-UiO-66(Zr), UiO-66(Zr)-(OH)2, UiO-66-COOH, UiO-66-SO3H, UiO-67(Zr), and UiO-68; more preferably at least one of ZIF-8, ZIF-67, ZIF-L, ZIF-9, ZIF-90, MIL-53(Cr / Al / Fe), MIL-100(Fe / Cr), MIL-101(Fe / Cr), MIL-125(Ti), MIL-88A(Fe), MIL-88B(Fe), MIL-68(Al / Fe), NH2-MIL-125(Ti), NH2-MIL-88B(Fe), NH2-MIL-53(Al).

3. The polymer material loaded with MOFs according to claim 1, wherein The polymer particles in the polymer material loaded with MOFs are selected from polymer resin materials with a particle size of 1 mm to 5 mm and thermoplastic granular form, preferably at least one of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer hot melt adhesive, ethylene-vinyl alcohol copolymer, acrylonitrile-butadiene-styrene terpolymer, polyvinyl chloride, polystyrene, and polyethylene terephthalate; more preferably at least one of high-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer hot melt adhesive, and acrylonitrile-butadiene-styrene terpolymer.

4. The preparation method of the polymer material loaded with MOFs according to any one of claims 1 to 3, comprising: Mix the MOFs powder and the polymer particles, and perform surface heat melting treatment, and then use a cooling molding agent to perform cooling molding treatment on the mixture, so as to load the MOFs powder on the surface of the polymer particles to form the polymer material.

5. The preparation method of the polymer material loaded with MOFs according to claim 4, wherein the mixing of the MOFs powder and the polymer particles is preferably carried out by stirring, more preferably at a stirring speed of 20-100 rpm, and still more preferably at a stirring speed of 30-50 rpm.

6. The preparation method of the polymer material loaded with MOFs according to claim 4, characterized in that in the surface heat fusion treatment, the heating temperature is 5-20 °C higher than the surface melting temperature of the polymer particles; preferably, the surface heat fusion treatment time is 5-20 min, and more preferably 7 min.

7. The preparation method of the polymer material loaded with MOFs according to claim 4, characterized in that, The mass ratio of the MOFs powder to the polymer particles is 1:5-1:20, preferably 1:5-1:

10.

8. The preparation method of the supported MOFs polymer material according to claim 4, wherein, The cooling molding agent is selected from at least one of water, ethanol, and N,N-dimethylformamide, preferably water; the mass ratio of the cooling molding agent to the polymer particles is 10:1-100:1, preferably 50:1; the cooling molding treatment time is 5-10 min, preferably 5 min.

9. An apparatus for preparing a polymer material loaded with MOFs according to any one of claims 1-3, characterized in that, The device includes: a device body (4'), a heating plate (1') is provided in the device body (4'), and a stirrer (2') is provided above the heating plate (1'); a temperature control panel (5') and a time control panel (8') are also installed on the device body.

10. The device of the polymer material loaded with MOFs according to claim 9, characterized in that, The heating plate (1') is a circular magnetic conductor and is provided in the device body (4'); preferably, the heating plate (1') is provided 10-15 mm below the upper edge of the device body (4'), and the heating method is electromagnetic heating; the circuit of the heating plate (1') is connected to the temperature control panel (5') and the time control panel (8'), and is controlled by the temperature control panel (5') and the time control panel (8'); preferably, the temperature control range of the heating plate (1') is 50 °C to 500 °C, and the time control range is 1 min to 30 min.

11. The device of the polymer material loaded with MOFs according to claim 9, characterized in that, The stirrer (2') includes 4 stainless steel stirring rods and a driving motor (3'), one end of each of the 4 stainless steel stirring rods is connected to the driving motor (3'), and the included angle between adjacent stirring rods is a right angle; the driving motor (3') is an AC motor and is provided with a pressure sensor; preferably, the driving motor (3') is located at the upper center position of the heating plate (1'), and the circuit of the driving motor (3') is connected to the time control panel (8'), and is controlled by the time control panel (8').

12. The device of the polymer material loaded with MOFs according to claim 9, characterized in that, The temperature control panel (5') and the time control panel (8') are both located on the outer wall of the body (4'); preferably, the digital display mode is liquid crystal display, and the touch control mode is preferably capacitive touch control.

13. The device of the polymer material loaded with MOFs according to any one of claims 9 to 12, characterized in that, A power button (6') is also provided on the device body (4'), the power button (6') is located on the outer wall of the device body (4'), the power button (6') is connected to the time control panel (8'), and controls the on and off of the entire circuit; the power button (6') preferably has a capacitive touch control mode.

14. The device of the polymer material loaded with MOFs according to any one of claims 9 to 13, characterized in that, A buffer support (7') is also provided at the bottom of the device body (1'), the material of the buffer support (7') is rubber, and the number is 2, symmetrically distributed on both sides of the bottom of the device body (4'), for relieving the vibration caused by stirring.

15. A system for preparing the polymer material loaded with MOFs as claimed in claim 1, characterized in that: The system includes the device according to any one of claims 9 to 14, and further includes a cooling and forming device, a washing device, and a drying device sequentially connected to the device.

16. Use of the polymer material loaded with MOFs according to any one of claims 1 to 3, characterized in that, The application at least includes one of the following: adsorption and removal of water pollutants, catalytic removal of water pollutants, improvement of the flame retardant performance of hot melt adhesives in building materials, gas adsorption and storage.

17. Use of the polymer material loaded with MOFs according to claim 16, characterized in that, The catalytic removal of water pollutants includes: degradation of organic pollutants in water and reduction of high-valent metal ions based on photocatalysis, degradation of organic pollutants in water based on activated hydrogen peroxide, degradation of organic pollutants in water based on activated persulfate, degradation of organic pollutants in water based on activated ozone, or coupling of two or more of the foregoing technologies.

18. A continuous operation device for catalytic removal of pollutants in water, characterized in that, The device includes: a liquid inlet system, a reaction system, and a liquid discharge system; the liquid inlet system is used to introduce the wastewater to be treated into the reaction system; the reaction system is loaded with the polymer material loaded with MOFs according to any one of claims 1 to 3, and the reaction system is used to remove pollutants from the wastewater to be treated; the liquid discharge system is used to receive the water treated in the reaction system; The catalytic removal of water pollutants includes: degradation of organic pollutants in water and reduction of high-valent metal ions based on photocatalysis, degradation of organic pollutants in water based on activated hydrogen peroxide, degradation of organic pollutants in water based on activated persulfate, degradation of organic pollutants in water based on activated ozone, or coupling of two or more of the foregoing technologies.

19. The continuous operating device according to claim 18, characterized in that, The liquid inlet system includes a liquid inlet barrel (1) for placing the wastewater to be treated, and the liquid inlet barrel (1) is connected to the reaction system through a pipeline one (2); preferably, a peristaltic pump (3) is provided on the pipeline one (2).

20. The continuous running device according to claim 18 or 19, characterized in that, The liquid inlet system further includes a micro automatic continuous syringe for introducing an oxidant into the reaction system. The micro automatic continuous syringe includes a syringe (5), the piston end of the syringe (5) is connected with a syringe piston automatic pusher (4), the needle end of the syringe (5) is connected with a rubber tube (6), and the rubber tube (6) is connected to the reaction system; preferably, one end of the rubber tube (6) connected to the reaction system is provided with a needle.

21. The continuous operating device according to any one of claims 18 - 20, characterized in that, The reaction system includes a reaction vessel (7), the reaction vessel (7) is loaded with the polymer material loaded with MOFs (8), and the reaction vessel (7) is connected to the liquid discharge system through a pipeline two (12).

22. The continuous operating device according to any one of claims 18-21, characterized in that, An ultraviolet disinfection lamp tube (9) and an air pump (10) are further provided in the reaction vessel (7).

23. The continuous running device according to claim 21 or 22, characterized in that, A barrier net (11) is provided at the connection of the pipeline two (12) and the reaction vessel (7).

24. The continuous operating device according to any one of claims 18 - 23, characterized in that, The liquid discharge system includes an effluent collection barrel (13), and the effluent collection barrel (13) is connected to the reaction vessel (7).

25. A continuous catalytic removal method for water pollutants, characterized in that, It is a continuous operation device described in any one of claims 18 to 24; the method includes: loading the polymer material in the reaction system, and then continuously introducing the wastewater to be treated into the reaction system through the liquid inlet system for catalytic reaction, and discharging the treated water into the liquid discharge system after the reaction ends.

26. The method according to claim 25, wherein The method uses an oxidation catalysis method to remove pollutants in water. The continuous operation device further includes a micro automatic continuous syringe for introducing an oxidant into the reaction system. The micro automatic continuous syringe includes a syringe (5), the piston end of the syringe (5) is connected to a syringe piston automatic pusher (4), the needle end of the syringe (5) is connected to a rubber tube (6), and the rubber tube (6) is connected to the reaction system; preferably, one end of the rubber tube (6) connected to the reaction system is provided with a needle; the method further includes: while introducing the wastewater to be treated into the reaction system, introducing the oxidant into the reaction system through the micro automatic continuous syringe.

27. The method according to claim 26, wherein The oxidant is: an aqueous solution of potassium monopersulfate, an aqueous solution of potassium persulfate or an aqueous solution of hydrogen peroxide with a mass concentration of 30%.

28. Use of the polymer material loaded with MOFs described in any one of claims 1 to 3 in the preparation of flame retardant products.

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