An apparatus, method for removing organic contaminants from industrial water

Abstract

The application provides a device and method for removing organic pollutants in industrial water, which comprises a shell, the side wall of the shell is sequentially provided with a water inlet, at least two oxidant adding ports and a water outlet along the height direction of the shell, and the inside of the shell is provided with a selective adsorption catalytic unit, which is located between the two oxidant adding ports along the height direction of the shell; the selective adsorption catalytic unit is provided with a selective adsorption catalytic material, the selective adsorption catalytic material comprises a porous matrix and a catalytically active component, the porous matrix comprises a novel supramolecular polymer, and the catalytically active component comprises a transition metal oxide. The device provided by the application can not only selectively adsorb organic pollutants in wastewater by using the selective adsorption catalytic unit, but also has the effect of enriching oxidants, so that the oxidants can quickly and accurately react with the adsorbed organic pollutants, and the oxidation and decomposition efficiency of the organic pollutants is improved.

Description

Technical Field

[0001] This invention relates to the field of water treatment, and more particularly to an apparatus and method for removing organic pollutants from industrial water. Background Technology

[0002] Currently, advanced treatment technologies for organic pollutants in industrial wastewater include adsorption, advanced oxidation, and membrane separation. Adsorption transfers target pollutants from water to adsorbent materials, but the high cost and low regeneration efficiency of these materials limit its application in industrial wastewater treatment. Traditional advanced oxidation technologies decompose organic pollutants in water by generating highly oxidizing active substances such as hydroxyl radicals and superoxide radicals. However, actual water bodies, especially industrial wastewater, contain large amounts of inorganic anions and natural organic matter. Since highly oxidizing active substances lack selectivity, they can react with these background substances, reducing the removal efficiency of organic pollutants and potentially leading to the generation of byproducts. Therefore, treating organic pollutants in actual industrial wastewater usually requires increased input of oxidants or energy. This high-energy- and high-material-consumption approach to ensuring effluent quality is no longer sufficient to meet the development needs of low-carbon, high-efficiency water treatment technologies in the new era. While membrane separation technology can achieve efficient separation of pollutants from water, it faces challenges such as membrane fouling and lifespan issues, and the resulting concentrate still requires further treatment. Summary of the Invention

[0003] The present invention provides an apparatus for removing organic pollutants from industrial water, which can be used to remove organic pollutants from industrial water.

[0004] The present invention also provides a method for removing organic pollutants from water. This method utilizes the above-mentioned device to improve the efficiency of oxidative decomposition of organic pollutants, which helps to reduce the amount of oxidant added and energy consumption, thereby further reducing operating costs.

[0005] On one hand, the present invention provides an apparatus for removing organic pollutants from industrial water, comprising a shell, wherein an inlet, at least two oxidant dosing ports and an outlet are sequentially provided on the side wall of the shell along the height direction of the shell, and a selective adsorption catalytic unit is provided inside the shell, wherein the selective adsorption catalytic unit is located between the two oxidant dosing ports along the height direction of the shell.

[0006] The selective adsorption catalytic unit is provided with a selective adsorption catalytic material, which includes a porous matrix and catalytically active components doped or supported on at least a portion of the surface of the porous matrix. The porous matrix includes a novel supramolecular polymer, and the catalytically active components include transition metal oxides.

[0007] Furthermore, the specific surface area of ​​the novel supramolecular polymer is 100–2000 m². 2 / g;

[0008] And / or, the average pore size of the novel supramolecular polymer is no greater than 2 nm.

[0009] Furthermore, the surface properties of the selective adsorption catalytic material are one or more of the following: hydrophilic, hydrophobic, negatively charged, and positively charged.

[0010] Furthermore, the catalytically active component also includes the complex formed by the transition metal oxide and oxalic acid.

[0011] Furthermore, the catalytically active component also includes at least one heteroatom selected from N, P, B, and S.

[0012] Furthermore, an oxidant dosing port is provided near the water outlet.

[0013] Furthermore, the top of the housing includes an exhaust port, at which an ozone decomposition and destruction system is provided.

[0014] Furthermore, the selective adsorption catalytic material is prepared by a method comprising the following steps:

[0015] The supramolecular polymer monomer, crosslinking agent, transition metal oxide and potassium carbonate are dispersed in a solvent. The resulting mixture is placed in a high-pressure reactor and stirred at 85-90°C for 48-96 hours under a protective atmosphere. After washing, separation and freeze-drying, the selective adsorption catalytic material is obtained.

[0016] Furthermore, after freeze-drying, the following processes are also included:

[0017] The product obtained by freeze-drying was placed in an oxalic acid solution for adsorption.

[0018] On the other hand, the present invention provides a method for removing organic pollutants from industrial wastewater using the above-mentioned apparatus, comprising the following steps:

[0019] Industrial wastewater enters the device through the inlet, while an oxidant containing ozone enters the device through the oxidant dosing port. The industrial wastewater and oxidant pass through a selective adsorption catalytic unit to purify organic pollutants.

[0020] The device provided by this invention utilizes a selective adsorption catalytic unit that not only selectively adsorbs organic pollutants in wastewater but also enriches oxidants, enabling the oxidants to react quickly and precisely with the adsorbed organic pollutants. This achieves efficient and selective removal of the pollutants, reduces competitive reactions with background substances and ineffective decomposition of oxidizing active substances, and improves the oxidative decomposition efficiency of organic pollutants. It also reduces the amount of oxidant added, energy consumption, and operating costs while minimizing the generation of toxic and harmful byproducts.

[0021] Compared to traditional adsorption methods, the selective adsorption catalytic unit used in this invention is specifically selected based on the properties of the pollutants to selectively adsorb such organic pollutants, thereby reducing the amount of adsorption material used and the investment cost. For organic pollutants adsorbed on the selective adsorption catalytic unit, the oxidant and the active substances produced by its decomposition can achieve efficient and selective removal, and restore the adsorption capacity of the adsorption material in situ, reducing the regeneration cost of the adsorption material and saving regeneration time. Compared with traditional advanced oxidation processes, the selective adsorption catalytic unit of this invention selectively enriches organic pollutants in water, and the strong oxidizing active substances produced by the oxidant during the oxidation process can react quickly and accurately with the enriched organic pollutants, reducing the competitive reaction of background substances and the ineffective decomposition of active substances, thereby improving the oxidation and decomposition efficiency of organic pollutants. Attached Figure Description

[0022] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0023] Figure 1 This invention provides a specific embodiment of an apparatus for removing organic pollutants from industrial water.

[0024] In the diagram, 001 is the inlet, 002 is the oxidant dosing port, 003 is the selective adsorption catalytic unit, 004 is the outlet, 005 is the sludge discharge port, and 006 is the exhaust port.

[0025] The accompanying drawings have illustrated specific embodiments of the invention, which will be described in more detail below. These drawings and descriptions are not intended to limit the scope of the invention in any way, but rather to illustrate the concept of the invention to those skilled in the art through reference to particular embodiments. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of the application will be clearly and completely described below in conjunction with the embodiments of the invention. Obviously, the described embodiments are only some embodiments of the invention, not all embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0027] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components, unless otherwise explicitly limited. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0028] In the accompanying drawings of the embodiments of the present invention, the same or similar reference numerals correspond to the same or similar components. In the description of the present invention, it should be understood that if terms such as "upper," "lower," "left," and "right" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, they are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or component referred to must have a specific orientation or be constructed and operated in a specific orientation. Therefore, the terms describing positional relationships in the drawings are only for illustrative purposes and should not be construed as limiting the present invention. Those skilled in the art can understand the specific meaning of the above terms according to the specific circumstances.

[0029] In a first aspect, the present invention provides an apparatus for removing organic pollutants from industrial water, comprising a shell, wherein an inlet 001, at least two oxidant dosing ports 002 and an outlet 004 are sequentially provided on the side wall of the shell along the height direction of the shell, and a selective adsorption catalytic unit 003 is provided inside the shell, wherein the selective adsorption catalytic unit is located between the two oxidant dosing ports along the height direction of the shell.

[0030] The selective adsorption catalytic unit is provided with a selective adsorption catalytic material, which includes a porous matrix and catalytically active components doped or supported on at least a portion of the surface of the porous matrix. The porous matrix includes a novel supramolecular polymer, and the catalytically active components include transition metal oxides.

[0031] It should be noted that the pore structure of the aforementioned porous matrix mainly originates from the molecular cavity of the novel supramolecular polymer. Therefore, if the catalytically active component is supported, it is mainly supported in the molecular cavity of the novel supramolecular polymer.

[0032] For example, the above-mentioned novel supramolecular polymer is a supramolecular polymer with a molecular cavity obtained by polymerizing cyclodextrin, columnar[5]arene, calix[4]pyrrole, etc.

[0033] The aforementioned selective adsorption catalytic material can simultaneously adsorb oxidants and organic pollutants, and promote the reaction between the two within the molecular cavity of the novel supramolecular polymer. The highly oxidizing active substances generated by the oxidant oxidize and decompose the organic pollutants while also restoring the adsorption capacity of the selective adsorption catalytic material. As for the oxidant dosing port and the number of selective adsorption catalytic units, technicians can set up multiple sets of oxidant + selective adsorption catalytic units according to the concentration of organic pollutants in the wastewater, and can flexibly adjust the types of oxidants and selective adsorption catalytic materials for pollutants of different properties.

[0034] The doping or loading of the catalytic active component can be adjusted according to the concentration of organic pollutants in the wastewater. However, in order to ensure that the adsorption of the porous matrix is ​​kept within a high range, the doping or loading of the catalytic active component is preferably 0.1 to 10 mg / g.

[0035] In one specific embodiment, the specific surface area of ​​the novel supramolecular polymer is 100–2000 m². 2 / g;

[0036] And / or, the average pore size of the novel supramolecular polymer is no greater than 2 nm.

[0037] In one specific embodiment, the surface properties of the selective adsorption catalytic material are one or more of the following: hydrophilic, hydrophobic, negatively charged, and positively charged.

[0038] Among them, the surface properties of selective adsorption catalytic materials are mainly determined by the surface properties of novel supramolecular polymers. The hydrophilicity, hydrophobicity and charge of the surface of selective adsorption catalytic materials can promote the adsorption of hydrophilic or charged pollutants. For example, hydrophobic surfaces can enhance the adsorption of pollutants by interacting with their hydrophobic groups under hydrophobic forces; negatively charged surfaces can form electrostatic attraction with positively charged pollutants, promoting the transfer and adsorption of pollutants to the material surface.

[0039] In one specific embodiment, the catalytically active component further includes at least one heteroatom selected from N, P, B, and S.

[0040] Among them, heteroatoms can regulate the distribution of electron clouds on the surface of selective adsorption catalytic materials, promote electron transfer between oxidants, selective adsorption catalytic materials and pollutants, and enhance the oxidative removal of pollutants.

[0041] In one specific embodiment, the catalytically active component includes a complex formed by the transition metal oxide and oxalic acid.

[0042] It is understood that the process of forming a complex between the aforementioned transition metal oxide and oxalic acid includes at least one chemical reaction, which includes the following process: the transition metal oxide is reduced by oxalic acid to the ionic form of the transition metal, and the transition metal ion and oxalic acid complex together to form a complex.

[0043] In the above embodiments, if ozone is used as an oxidant, on the one hand, the novel supramolecular polymer can promote ozone molecules to enter the molecular cavity, prolong the residence time of ozone, and improve the removal efficiency of organic pollutants. On the other hand, the transition metal-oxalic acid complex in the molecular cavity can promote the oxidation of organic pollutants by ozone to generate carbon free radicals, and can also further reduce metal ions to achieve recycling.

[0044] In one specific embodiment, the transition metal includes one or more of Fe, Co, Ce, Mn, Cu, Al, and La.

[0045] In one specific embodiment, an oxidant dosing port is provided near the water outlet.

[0046] In one specific embodiment, the bottom of the shell includes a mud discharge port 005.

[0047] In one specific embodiment, the top of the housing includes an exhaust port 006, and an ozone decomposition and destruction system is provided at the exhaust port.

[0048] In one specific embodiment, the method for preparing a selective adsorption catalytic material includes the following steps:

[0049] The selective adsorption catalytic material is prepared by a method comprising the following process:

[0050] The supramolecular polymer monomer, crosslinking agent, transition metal oxide and potassium carbonate are dispersed in a solvent. The resulting mixture is placed in a high-pressure reactor and stirred at 85-90°C for 48-96 hours under a protective atmosphere. After washing, separation and freeze-drying, the selective adsorption catalytic material is obtained.

[0051] By combining various conditions, the above preparation method can produce pores with an average pore size of no more than 2 nm and a specific surface area of ​​100–2000 m². 2 A novel supramolecular polymer with a transition metal loaded in its inner cavity per g, namely the selective adsorption catalytic material mentioned above.

[0052] Furthermore, after freeze-drying, the following processes are also included:

[0053] The product obtained by freeze-drying was placed in an oxalic acid solution for adsorption.

[0054] For example, the crosslinking agents mentioned above include, but are not limited to, tetrafluoroterephthalonitrile, decafluorobiphenyl or phenylenediamine, etc.; the supramolecular polymer monomers mentioned above include, but are not limited to, cyclodextrin, columnar[5]arene, calix[4]pyrrole, etc.

[0055] Regarding the above-mentioned cleaning and separation steps, the present invention will not provide any special explanation. Technicians may select appropriate conventional methods according to the different properties of the products. For example, the above-mentioned cleaning and separation includes the following steps: after the reaction vessel is cooled to room temperature, the orange suspension is transferred to a 1 mol / L hydrochloric acid solution to remove excess potassium carbonate; finally, the product is separated by a 0.45 μm filter membrane and washed several times with ethanol and deionized water in sequence.

[0056] For example, the above freeze drying specifically refers to vacuum freeze drying at -40°C for 48 hours.

[0057] Secondly, the present invention provides a method for removing organic pollutants from industrial wastewater using the above-mentioned apparatus, comprising the following steps:

[0058] Industrial wastewater enters the device through inlet 001, and ozone-containing oxidant enters the device through oxidant dosing port 002. The industrial wastewater and oxidant pass through selective adsorption catalysis unit 003 to purify organic pollutants.

[0059] It is understood that the above method may also include: periodically discharging sludge generated during the operation or cleaning of the device from the sludge discharge port 005, and discharging gas generated during the operation or cleaning of the device from the exhaust port 006, while an ozone decomposition and destruction system is installed at the exhaust port.

[0060] In one specific embodiment, the oxidant addition point can also serve as a gas-liquid backwashing device for the apparatus to remove particulate matter clogging the apparatus.

[0061] In one specific embodiment, the oxidant type includes gaseous ozone and one or more of the following oxidants: ozone solution, hydrogen peroxide, persulfate, sodium hypochlorite, peracetic acid, potassium permanganate, percarbonate, ferrate, etc.

[0062] The present invention will be described in detail below with reference to specific embodiments:

[0063] Example 1

[0064] This example provides a device for removing organic pollutants from industrial water, combined with... Figure 1The device includes: a housing, wherein the sidewall of the housing is provided with an inlet 001, at least three oxidant dosing ports 002 and an outlet 004 in sequence along the height direction of the housing; the interior of the housing is provided with two selective adsorption catalytic units 003, which are located between the two oxidant dosing ports along the height direction of the housing; the bottom of the housing also includes a sludge discharge port 005, and the top of the housing also includes an exhaust port 006.

[0065] The selective adsorption catalytic unit is provided with a selective adsorption catalytic material, which includes a porous matrix and catalytically active components doped or supported on at least a portion of the surface of the porous matrix. The porous matrix includes novel supramolecular polymers, and the catalytically active components include oxides of transition metals.

[0066] Among them, the specific surface area of ​​the novel supramolecular polymer is 850 m². 2 / g, average pore size 1.21nm; surface properties hydrophobic, contact angle 108°, transition metal Fe, a selective adsorption catalytic material preparation method including the following steps:

[0067] ① Add appropriate amounts of supramolecular polymer monomer β-cyclodextrin (3.0 g, 2.65 mmol), tetrafluoroterephthalonitrile (1.5 g, 7.5 mmol), Fe2O3 nanoparticles (20 nm, 40 mg), and potassium carbonate (4.5 g, 32.5 mmol) to anhydrous tetrahydrofuran (60 mL), and then degas it with nitrogen for 5 minutes; ② Transfer the degassed mixture to a 120 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner, and stir at 85 °C for 48 hours; ③ After the reactor cools to room temperature, transfer the orange suspension to a 1 mol / L hydrochloric acid solution to remove excess potassium carbonate; ④ Finally, separate the pale yellow product using a 0.45 μm filter membrane, wash it several times with ethanol and deionized water, and freeze-dry the obtained sample under vacuum at -40 °C for 48 hours.

[0068] Example 2

[0069] This is essentially the same as Example 1, except that the specific surface area of ​​the novel supramolecular polymer is 1300 m². 2 / g, average pore size 0.98nm; surface properties are hydrophilic, contact angle 38°, transition metal is Co; preparation method of selective adsorption catalytic material includes the following steps:

[0070] ① Add appropriate amounts of supramolecular polymer monomer column[5] aromatics (1.13g, 1mmol), phenylenediamine (0.32g, 3mmol), Co3O4 nanoparticles (10nm, 10mg) and potassium carbonate (4.5g, 32.5mmol) to dimethylamide (60mL), and then degas it with nitrogen for 5 minutes; ② Transfer the degassed mixture to a stainless steel high-pressure reactor with a volume of 120mL and a polytetrafluoroethylene liner, and stir at 90℃ for 96 hours; ③ After the reactor cools to room temperature, transfer the orange suspension to a 1mol / L hydrochloric acid solution to remove excess potassium carbonate; ④ Finally, separate the pale yellow product with a 0.45μm filter membrane, wash it several times with ethanol and deionized water, and freeze-dry the obtained sample under vacuum at -40℃ for 48 hours.

[0071] Example 3

[0072] This is essentially the same as Example 1, except that the specific surface area of ​​the novel supramolecular polymer is 1000 m². 2 / g, average pore size 1.13nm; surface properties hydrophobic, contact angle 128°, transition metal Mn, selective adsorption catalytic material preparation method includes the following steps: ① Add appropriate amounts of supramolecular polymer monomer β-cyclodextrin (3.0g, 2.65mmol), decafluorobiphenyl (1.5g, 7.5mmol), MnO2 nanoparticles (30nm, 30mg) and potassium carbonate (4.5g, 32.5mmol) to anhydrous tetrahydrofuran (60mL), then use nitrogen gas to... ① The mixture was degassed for 5 minutes; ② The degassed mixture was transferred to a 120 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner and stirred at 85 °C for 48 hours; ③ After the reactor cooled to room temperature, the orange suspension was transferred to a 1 mol / L hydrochloric acid solution to remove excess potassium carbonate; ④ Finally, the pale yellow product was separated using a 0.45 μm filter membrane, washed several times with ethanol and deionized water, and the resulting sample was freeze-dried under vacuum at -40 °C for 48 hours.

[0073] Example 4

[0074] This is essentially the same as Example 1, except that the specific surface area of ​​the novel supramolecular polymer is 1100 m². 2 / g, average pore size 1.3nm; surface property is positively charged, transition metal is Mn, selective adsorption catalytic material preparation method includes the following steps: ① Add appropriate amounts of carboxyl-modified supramolecular polymer monomer β-cyclodextrin (3.0g, 2.65mmol), tetrafluoroterephthalonitrile (1.5g, 7.5mmol), MnO2 nanoparticles (30nm, 30mg) and potassium carbonate (4.5g, 32.5mmol) to anhydrous tetrahydrofuran (60mL), and then use nitrogen gas to... ① The mixture was degassed for 5 minutes; ② The degassed mixture was transferred to a 120 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner and stirred at 85 °C for 48 hours; ③ After the reactor cooled to room temperature, the orange suspension was transferred to a 1 mol / L hydrochloric acid solution to remove excess potassium carbonate; ④ Finally, the pale yellow product was separated using a 0.45 μm filter membrane, washed several times with ethanol and deionized water, and the resulting sample was freeze-dried under vacuum at -40 °C for 48 hours.

[0075] Example 5

[0076] This is essentially the same as Example 1, except that the specific surface area of ​​the novel supramolecular polymer is 1100 m². 2 / g, average pore size 1.3nm, catalytically active components include a complex formed by transition metal oxides and oxalic acid, with Ce as the transition metal, and a method for preparing selective adsorption catalytic material, including the following steps: ① Add appropriate amounts of quaternary amino-modified supramolecular polymer monomer β-cyclodextrin (3.0g, 2.65mmol), tetrafluoroterephthalonitrile (1.5g, 7.5mmol), Ce2O3 nanoparticles (20nm, 30mg), and potassium carbonate (4.5g, 32.5mmol) to anhydrous tetrahydrofuran (60mL), and then degas it with nitrogen for 5 minutes. 1. Transfer the degassed mixture to a 120 mL stainless steel high-pressure reactor lined with polytetrafluoroethylene and stir at 85 °C for 48 hours. 2. After the reactor cools to room temperature, transfer the orange suspension to a 1 mol / L hydrochloric acid solution to remove excess potassium carbonate. 3. Finally, separate the pale yellow product with a 0.45 μm filter membrane, wash it several times with ethanol and deionized water, and freeze-dry the obtained sample under vacuum at -40 °C for 48 hours. 4. Place the obtained polymer in a 300 mL, 10 mg / L oxalic acid solution for pre-adsorption for 1 h.

[0077] Comparative Example 1

[0078] It is basically the same as Example 1, except that the device does not have a selective adsorption catalytic unit.

[0079] Comparative Example 2

[0080] It is basically the same as Example 1, except that the selective adsorption catalytic material of this device is only a porous matrix.

[0081] Comparative Example 3

[0082] This is essentially the same as Example 1, except that the novel supramolecular polymer is replaced with activated carbon or other adsorbent materials, and the specific surface area of ​​the activated carbon is 1200 m². 2 / g, average pore size 1.5nm; hydrophobic surface properties, contact angle 105°; preparation method of selective adsorption catalytic material, including the following steps:

[0083] The powdered activated carbon was first ultrasonically cleaned for 1 hour; 1.5g of FeCl3 was dissolved in 50ml of water, and 3g of the cleaned activated carbon was added; after stirring evenly, it was pyrolyzed at 110℃ for 24 hours; the solid was washed with water 5 times and then dried at 45℃.

[0084] Experimental Example 1

[0085] This example utilizes the apparatus provided in the embodiments and comparative examples to remove organic pollutants from industrial water. In this example, the concentration of ciprofloxacin in the industrial wastewater to be treated is 5 mg / L. The method includes the following steps:

[0086] Industrial wastewater continuously enters the device through inlet 001 at a flow rate of 0.5 L / min and a residence time of 2 hours. Gaseous ozone enters the device through oxidant inlet 002 at a flow rate of 0.2 L / min and an ozone concentration of 20 mg / L. The industrial wastewater and oxidant pass through selective adsorption catalytic unit 003, with a selective adsorption catalytic material dosage of 1 g / L.

[0087] The method for calculating ozone utilization efficiency in this experimental example is as follows:

[0088] Simultaneously measure the gas flow rate and ozone concentration at exhaust port 006, and simultaneously determine the ozone concentration in the water. Calculate the ozone dosage (m³) per unit volume of oxidant added at oxidant dosing port 002. 总 Subtracting the residual ozone in the water (m0) and the unused ozone emitted from vent 006 (m1) yields the actual amount used (m2). Ozone utilization efficiency = m 2 / m 总 ×100%.

[0089] Experimental results:

[0090] The device in Example 1 achieved a ciprofloxacin removal efficiency of 70% after 1 hour of treatment and 97.5% after 2 hours.

[0091] The device in Example 2 achieved a ciprofloxacin removal efficiency of 80% after 1 hour of treatment and 98% after 2 hours.

[0092] The device in Example 3 achieved a ciprofloxacin removal efficiency of 75% after 1 hour of treatment and 98% after 2 hours.

[0093] The device in Example 5 achieved a ciprofloxacin removal efficiency of 95% after 1 hour of treatment, and maintained a removal efficiency of over 90% after 8 hours of continuous use. Compared with other examples, this example demonstrates that the formation of a complex between pre-adsorbed oxalic acid and transition metals in the selective adsorption material promotes the conversion between metal valence states, further improving catalytic efficiency and pollutant removal effect.

[0094] The device in Comparative Example 1 achieved a ciprofloxacin removal efficiency of 23% after 1 hour of treatment and 37% after 2 hours, with an ozone utilization efficiency of approximately one-third that of Example 1.

[0095] The device in Comparative Example 2 achieved a ciprofloxacin removal efficiency of 57% after 1 hour of treatment and 72% after 2 hours, with an ozone utilization efficiency approximately half that of Example 1.

[0096] The device in Comparative Example 4 achieved a ciprofloxacin removal efficiency of 50% after 1 hour of treatment and 70% after 2 hours, with an ozone utilization efficiency of approximately 53% of that in Example 1.

[0097] Experimental Example 2

[0098] This example utilizes the apparatuses provided in Examples 2 and 4 to remove organic pollutants from industrial water. The industrial wastewater to be treated in this example contains phenol, diclofenac, tetracycline, ciprofloxacin, diclofenac, and sulfamethoxazole at a concentration of 1 mg / L. The method includes the following steps:

[0099] Industrial wastewater enters the device through inlet 001 at a flow rate of 0.5 L / min. Gaseous ozone enters the device through oxidant inlet 002 at a flow rate of 0.2 L / min and an ozone concentration of 20 mg / L. The industrial wastewater and oxidant pass through selective adsorption catalytic unit 003, with a selective adsorption catalytic material dosage of 1 g / L.

[0100] Experimental results:

[0101] After one hour of treatment, the device in Example 2 showed a removal efficiency of 50% to 100% for different pollutants, and the removal efficiency showed a good linear relationship with the adsorption performance of the material for the pollutants. Therefore, the method described in this invention can optimize the adsorption catalytic material according to the properties of organic pollutants in actual wastewater, and successfully achieve selective removal of specific organic pollutants.

[0102] After 1 hour of treatment, the device in Example 4 achieved a removal efficiency of over 90% for positively charged tetracycline and ciprofloxacin, while the removal rate for negatively charged sulfamethoxazole was only 50%. The prepared negatively charged selective adsorption catalytic material preferentially removes positively charged pollutants through electrostatic adsorption, thus enhancing their removal.

[0103] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application.

Claims

1. An apparatus for removing organic pollutants from industrial water, characterized in that, The device includes a shell, and the sidewall of the shell is provided with an inlet, at least two oxidant dosing ports and an outlet in sequence along the height direction of the shell. The shell is provided with a selective adsorption catalytic unit, which is located between the two oxidant dosing ports along the height direction of the shell. The selective adsorption catalytic unit is provided with a selective adsorption catalytic material, which includes a porous matrix and catalytically active components doped or loaded on at least a portion of the surface of the porous matrix. The porous matrix includes a novel supramolecular polymer, and the catalytically active components include transition metal oxides. The novel supramolecular polymer is a supramolecular polymer with a molecular cavity obtained by polymerizing cyclodextrin, columnar[5]arene, or calix[4]pyrrole. The pore structure of the porous matrix originates from the molecular cavity of the novel supramolecular polymer. The selective adsorption catalytic material is used to simultaneously adsorb oxidants and organic pollutants, and to promote the reaction between the two within the molecular cavity of the novel supramolecular polymer. The average pore size of the novel supramolecular polymer is no greater than 2 nm.

2. The apparatus according to claim 1, characterized in that, The specific surface area of ​​the novel supramolecular polymer is 100~2000 m². 2 / g.

3. The apparatus according to any one of claims 1-2, characterized in that, The surface properties of the selective adsorption catalytic material are one or more of the following: hydrophilic, hydrophobic, negatively charged, and positively charged.

4. The apparatus according to any one of claims 1-2, characterized in that, The catalytically active component also includes the complex formed by the transition metal oxide and oxalic acid.

5. The apparatus according to any one of claims 1-2, characterized in that, The catalytically active component also includes at least one heteroatom selected from N, P, B, and S.

6. The apparatus according to claim 1, characterized in that, The top of the housing includes an exhaust port, at which an ozone decomposition and destruction system is provided.

7. The apparatus according to claim 1, characterized in that, The selective adsorption catalytic material is prepared by a method comprising the following process: The supramolecular polymer monomer, crosslinking agent, transition metal oxide and potassium carbonate are dispersed in a solvent. The resulting mixture is placed in a high-pressure reactor and stirred at 85-90°C for 48-96 hours under a protective atmosphere. After washing, separation and freeze-drying, the selective adsorption catalytic material is obtained.

8. The apparatus according to claim 7, characterized in that, After freeze-drying, the following processes are also included: The product obtained by freeze-drying was placed in an oxalic acid solution for adsorption.

9. A method for removing organic pollutants from industrial wastewater using the apparatus according to any one of claims 1-8, characterized in that, Includes the following steps: Industrial wastewater enters the device through the inlet, while an oxidant containing ozone enters the device through the oxidant dosing port. The industrial wastewater and oxidant pass through a selective adsorption catalytic unit to purify organic pollutants.

Images