A composite catalytic fiber of polymer metal phthalocyanine supported on activated carbon fiber, its preparation method and application

Abstract

The present invention provides a composite catalytic fiber of polymerized metal phthalocyanine supported on activated carbon fiber, its preparation method and application, which relates to the technical field of catalysts. In the present invention, metal phthalocyanine polymer (MPPc) is used as the active component, and MPPc is loaded on the activated carbon fiber carrier, which not only expands the conjugated system of the π electrons of MPc and increases the active centers; at the same time, it avoids the aggregation of MPPc molecules due to strong π-π interactions, making the central metal of the active component fully exposed, thus significantly improving the catalytic activity and stability of the catalyst; moreover, the activated carbon fiber can effectively adsorb organic pollutants to promote their catalytic degradation, and can also provide electrons for MPPc to improve the catalytic activity of MPPc, so as to efficiently degrade organic pollutants such as antibiotics in high-salt wastewater and reduce their biological toxicity, providing a new method for the pollution control of antibiotics.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and specifically relates to an activated carbon fiber supported polymeric metal phthalocyanine composite catalytic fiber, its preparation method and application. Background Art

[0002] Phthalocyanine (Pc) is a highly coplanar 18-electron large π-conjugated system composed of four isoindole units. A hole with a diameter of 2.7 nm is formed at the center of the phthalocyanine molecule. Fe 2+ 、Co 2+ 、Cu 2+ 、Zn 2+ More than 70 metal elements such as etc. can replace two hydrogen atoms at the center of the phthalocyanine molecule to obtain metal phthalocyanine (MPc). Its aromatic ring is both an electron donor and an electron acceptor, and the catalytic reaction can occur at the axial position of the plane. Due to its special structure, MPc has a high carrier mobility, excellent electrical conductivity and nonlinear optical activity, and plays an important role in fields such as catalytic degradation, optical devices, and energy conversion.

[0003] There are many types of antibiotics, such as tetracyclines, sulfonamides, quinolones, etc. Most of them have broad-spectrum antibacterial effects and are widely used in the fields of human medicine, animal husbandry and aquaculture. The wastewater generated in the production of antibiotics usually has a high salt concentration (>1%). The high osmotic pressure caused by the high salt concentration and the residual antibiotics in the wastewater will inhibit the growth of microorganisms and is not conducive to biodegradation. When using MPc as a catalyst to degrade antibiotics in high-salt wastewater, due to the strong π-π interaction between the metal molecules of MPc, aggregation is likely to occur, which is not conducive to the exposure of the catalytic center, resulting in the limitation of its catalytic activity. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide an activated carbon fiber supported polymeric metal phthalocyanine composite catalytic fiber, its preparation method and application. The activated carbon fiber supported polymeric metal phthalocyanine composite catalytic fiber provided by the present invention has high catalytic activity, and solves the problem that when metal phthalocyanine or metal phthalocyanine polymer is directly used as a catalyst in the prior art, aggregation is likely to occur, which is not conducive to the exposure of the catalytic center, thereby inhibiting its catalytic performance.

[0005] In order to achieve the above invention purpose, the present invention provides the following technical solutions:

[0006] The present invention provides an activated carbon fiber supported polymeric metal phthalocyanine composite catalytic fiber, the chemical composition of which includes activated carbon fiber and a metal phthalocyanine polymer supported on the activated carbon fiber.

[0007] Preferably, the content of the metal phthalocyanine polymer in the activated carbon fiber supported polymeric metal phthalocyanine composite catalytic fiber is 1-10 wt%.

[0008] The metal in the metal phthalocyanine polymer includes one or more of Fe, Co, Cu, Zn, Mn, and Ni.

[0009] Preferably, the length of the activated carbon fiber is 0.5 - 500 mm, and the diameter is 0.01 - 0.1 mm.

[0010] The present invention provides a method for preparing the activated carbon fiber supported polymerized metal phthalocyanine composite catalytic fiber described in the above technical solution, comprising the following steps:

[0011] Mix the activated carbon fiber, metal source, ammonium halide, nitrogen source, ammonium molybdate, and pyromellitic dianhydride, and perform calcination to obtain the activated carbon fiber supported polymerized metal phthalocyanine composite catalytic fiber; the metal species in the metal source is the same as the metal species in the metal phthalocyanine polymer.

[0012] Preferably, the mass ratio of the activated carbon fiber to the metal source is 1:1 - 4;

[0013] The mass ratio of the activated carbon fiber to the ammonium halide is 1:0.5 - 10;

[0014] The mass ratio of the activated carbon fiber to the nitrogen source is 1:5 - 100;

[0015] The mass ratio of the activated carbon fiber to the ammonium molybdate is 1:0.01 - 0.08;

[0016] The mass ratio of the activated carbon fiber to the pyromellitic dianhydride is 1:1 - 10.

[0017] Preferably, the calcination is programmed calcination, and the programmed calcination includes successively performing a first heating stage, a first heat preservation stage, a second heating stage, and a second heat preservation stage. The heating rates of the first heating stage and the second heating stage are independently 1 - 5 °C / min; the temperature of the first heat preservation stage is 100 - 140 °C, and the heat preservation time is 30 - 60 min; the temperature of the second heat preservation stage is 200 - 280 °C, and the heat preservation time is 0.5 - 5 h.

[0018] Preferably, the activated carbon fiber is pretreated before use, and the pretreatment includes: boiling the activated carbon fiber in water and then drying.

[0019] The present invention provides the use of the activated carbon fiber supported polymerized metal phthalocyanine composite catalytic fiber described in the above technical solution or the activated carbon fiber supported polymerized metal phthalocyanine composite catalytic fiber prepared by the preparation method described in the above technical solution in the degradation of organic pollutants.

[0020] Preferably, the organic pollutants include antibiotics.

[0021] The present invention also provides a method for degrading antibiotics in high-salt wastewater, which includes the following steps: mixing a catalyst, high-salt wastewater containing antibiotics, and hydrogen peroxide to catalytically degrade the antibiotics; the catalyst is the activated carbon fiber-supported polymeric metal phthalocyanine composite catalytic fiber described in the above technical solution or the activated carbon fiber-supported polymeric metal phthalocyanine composite catalytic fiber prepared by the preparation method described in the above technical solution.

[0022] The present invention provides an activated carbon fiber-supported polymeric metal phthalocyanine composite catalytic fiber, the chemical composition of which includes activated carbon fiber and a metal phthalocyanine polymer supported on the activated carbon fiber; the metal phthalocyanine polymer has one or more of the structures shown in formulas (a), (b), and (c). Compared with metal phthalocyanine, the present invention uses a metal phthalocyanine polymer (MPPc) as the active component and loads MPPc on the activated carbon fiber carrier, which not only expands the π-electron conjugate system of MPc and increases the active centers; at the same time, it avoids the aggregation of MPPc molecules due to strong π-π interactions, making the central metal of the active component fully exposed, thereby significantly improving the catalytic activity and stability of the catalyst; moreover, the activated carbon fiber can effectively adsorb organic pollutants to promote their catalytic degradation, and can also provide electrons for MPPc to improve the catalytic activity of MPPc, so that the activated carbon fiber-supported polymeric metal phthalocyanine composite catalytic fiber provided by the present invention can efficiently degrade organic pollutants such as antibiotics in high-salt wastewater, reduce their biological toxicity, and provide a new method for the pollution control of antibiotics. Moreover, the activated carbon fiber-supported polymeric metal phthalocyanine composite catalytic fiber provided by the present invention is easy to separate from the reaction solution, can be reused without secondary pollution. As shown by the test results of the examples, the degradation rate of SCP by the activated carbon fiber-supported polymeric metal phthalocyanine composite catalytic fiber provided by the present invention can reach more than 98% within 120-180 minutes, indicating that the activated carbon fiber-supported polymeric metal phthalocyanine composite catalytic fiber provided by the present invention has high catalytic activity. By adsorbing organic pollutants with activated carbon fiber, the contact probability between the oxidation active species and the organic pollutants is increased, and the influence of high salt in the organic pollutant solution is reduced.

[0023] The present invention provides a preparation method for the activated carbon fiber-supported polymeric metal phthalocyanine composite catalytic fiber described in the above technical solution. The preparation method provided by the present invention in-situ thermosynthesizes the metal phthalocyanine polymer onto the activated carbon fiber without adding organic solvents, with simple process, simple operation, low energy consumption, low production cost, environmental friendliness, and suitability for industrial production. Detailed implementation mode

[0024] The present invention provides an activated carbon fiber-supported polymeric metal phthalocyanine composite catalytic fiber, the chemical composition of which includes activated carbon fiber and a metal phthalocyanine polymer supported on the activated carbon fiber.

[0025] In the present invention, the content of the metal phthalocyanine polymer in the activated carbon fiber-supported polymerized metal phthalocyanine composite catalytic fiber is preferably 1 to 0 wt%, more preferably 2 to 8 wt%, and further preferably 2 to 5 wt%. In the present invention, the metal in the metal phthalocyanine polymer preferably includes one or more of Fe, Co, Cu, Zn, Mn, and Ni.

[0026] In the present invention, the length of the activated carbon fiber is preferably 0.5 to 500 mm, more preferably 50 to 400 mm, and further preferably 100 to 300 mm; the diameter of the activated carbon fiber is preferably 0.01 to 0.1 mm, more preferably 0.02 to 0.08 mm, and further preferably 0.04 to 0.06 mm. In the present invention, the activated carbon fiber preferably includes one or more of activated carbon fiber cloth, activated carbon fiber felt, and activated carbon fiber cotton.

[0027] The present invention provides a method for preparing the activated carbon fiber-supported polymerized metal phthalocyanine composite catalytic fiber described in the above technical solution, which includes the following steps: mixing activated carbon fiber, metal source, ammonium halide, nitrogen source, ammonium molybdate, and pyromellitic dianhydride, and performing calcination to obtain the activated carbon fiber-supported polymerized metal phthalocyanine composite catalytic fiber; the type of metal in the metal source is the same as the type of metal in the metal phthalocyanine polymer.

[0028] Unless otherwise specified, the raw materials used in the present invention are all commercially available products.

[0029] In the present invention, the activated carbon fiber is preferably pretreated before use, and the pretreatment preferably includes: boiling the activated carbon fiber in water and then drying. In the present invention, the mass ratio of the activated carbon to water is preferably 1:100 to 500, more preferably 1:200 to 500, and further preferably 1:300 to 500; the water preferably includes deionized water. In the present invention, the boiling time is preferably 1 to 3 h, more preferably 1 to 2 h; the purpose of boiling is to remove impurities such as inorganic salts and dust on the surface of the activated carbon fiber. In the present invention, the drying temperature is preferably 150 to 250 °C, more preferably 150 to 200 °C. There is no special limitation on the drying time in the present invention, and it can be dried to constant weight.

[0030] In the present invention, the metal source is preferably a metal salt, more preferably one or more of nitrate, hydrochloride, sulfate, and citrate. In the present invention, the mass ratio of the activated carbon fiber to the metal source is preferably 1:1 to 4, more preferably 1:1 to 3.5, and further preferably 1:1 to 3. In the present invention, the ammonium halide preferably includes ammonium chloride and / or ammonium bromide. In the present invention, the mass ratio of the activated carbon fiber to the ammonium halide is preferably 1:0.5 to 10, more preferably 1:0.5 to 5, and further preferably 1:0.5 to 2.5. In the present invention, the nitrogen source preferably includes urea and / or melamine. In the present invention, the mass ratio of the activated carbon fiber to the nitrogen source is preferably 1:5 to 100, more preferably 1:5 to 30, and further preferably 1:5 to 15. In the present invention, the mass ratio of the activated carbon fiber to ammonium molybdate is preferably 1:0.01 to 0.08, more preferably 1:0.01 to 0.05, and further preferably 1:0.01 to 0.04. In the present invention, the mass ratio of the activated carbon fiber to pyromellitic dianhydride is preferably 1:1 to 10, more preferably 1:1.5 to 5, and further preferably 1:1.5 to 3.

[0031] In the present invention, the mixing is preferably grinding mixing, and there is no special limitation on the grinding mixing in the present invention, as long as the raw materials can be mixed evenly.

[0032] In the present invention, the calcination is preferably programmed calcination. The programmed calcination preferably includes a first heating stage, a first heat preservation stage, a second heating stage, and a second heat preservation stage in sequence. The heating rate of the first heating stage and the second heating stage is independently preferably 1 to 5 °C / min, more preferably 1 to 4 °C / min, and further preferably 2 to 3 °C / min. The starting temperature of the first heating stage is preferably room temperature; the temperature of the first heat preservation stage is preferably 100 to 140 °C, more preferably 110 to 140 °C, and further preferably 130 to 140 °C. The heat preservation time of the first heat preservation stage is preferably 30 to 60 min, more preferably 40 to 60 min, and further preferably 50 to 60 min; the temperature of the second heat preservation stage is preferably 200 to 280 °C, more preferably 210 to 280 °C, and further preferably 220 to 280 °C. The heat preservation time of the second heat preservation stage is preferably 0.5 to 5 h, more preferably 1 to 3 h, and further preferably 1 to 2 h; the atmosphere of the calcination is preferably air. In the present invention, during the calcination process, the nitrogen source, the metal source, pyromellitic dianhydride, and ammonium halide generate a metal phthalocyanine polymer, and the generated metal phthalocyanine polymer is thermally synthesized in-situ onto the activated carbon fiber.

[0033] After the calcination, the present invention preferably further includes cooling the obtained calcined product to room temperature, then dispersing it in a detergent for mixed washing and then performing solid-liquid separation, and drying the obtained solid product to obtain an active carbon fiber-supported polymeric metal phthalocyanine composite catalytic fiber. The present invention has no special limitation on the cooling, and any cooling method well-known to those skilled in the art can be used, such as natural cooling. In the present invention, the detergent preferably includes one or more of water, ethanol, tetrahydrofuran, and N,N-dimethylformamide; the water preferably includes deionized water; the number of times of mixed washing is preferably 2 to 5 times, more preferably 3 to 4 times. In the present invention, the solid-liquid separation is preferably centrifugal separation, the rotation speed of the centrifugal separation is preferably 5000 to 8000 r / min, more preferably 7000 to 8000 r / min; the time of the centrifugal separation is preferably 5 to 15 min, more preferably 5 to 10 min. In the present invention, the drying temperature is preferably 100 to 250 °C, more preferably 100 to 120 °C. The present invention has no special limitation on the drying time, and it can be dried to constant weight.

[0034] Loading polymeric metal phthalocyanine on an inorganic material is usually obtained by an impregnation method or a vapor deposition method. The impregnation method is to impregnate the carrier in a polymeric metal phthalocyanine dispersion solution and make it loaded on the carrier through physical adsorption. The preparation process of this method is simple, but due to the poor water solubility of the metal phthalocyanine polymer, a large amount of organic solvents need to be consumed. The vapor deposition method is to vaporize the metal phthalocyanine polymer by means of evaporation, sputtering, etc., and then deposit it on the surface of the carrier. This method has high energy consumption and low efficiency, and is not conducive to the batch preparation of catalytic materials. The preparation method provided by the present invention in-situ thermosynthesizes the metal phthalocyanine polymer onto the active carbon fiber without adding organic solvents, greatly reducing the production cost, and having a simple process, simple operation, low energy consumption, environmental friendliness, and being suitable for industrial production.

[0035] The present invention provides the use of the activated carbon fiber supported polymeric metal phthalocyanine composite catalytic fiber as described in the above technical solution or the activated carbon fiber supported polymeric metal phthalocyanine composite catalytic fiber prepared by the preparation method as described in the above technical solution in the degradation of organic pollutants. In the present invention, the use is preferably the use in the degradation of high-salt wastewater containing organic pollutants. The inorganic salts in the high-salt wastewater preferably include one or more of sodium chloride, sodium sulfate, sodium carbonate, sodium nitrate and sodium bicarbonate. The concentration of the inorganic salts in the high-salt wastewater is preferably ≥ 1 g / L, more preferably ≥ 5 g / L. In a specific embodiment of the present invention, the concentration of the inorganic salts is preferably 10 g / L. The organic pollutants preferably include antibiotics, and the antibiotics preferably include one or more of sulfonamide antibiotics, tetracycline antibiotics and quinolone antibiotics. The sulfonamide antibiotics preferably include one or more of sulfachloropyridazine (SCP), sulfachinoxaline and sulfamethoxazole. The tetracycline antibiotics preferably include tetracycline hydrochloride. In the present invention, when the organic pollutant is an antibiotic, the degradation of the antibiotic is preferably carried out under the condition of the presence of persulfate. The persulfate preferably includes monopersulfate or dipersulfate. The monopersulfate preferably includes one or both of potassium monopersulfate and sodium monopersulfate. The dipersulfate preferably includes one or both of potassium dithionate and sodium dithionate. On the one hand, the polymeric metal phthalocyanine is supported on the activated carbon fiber to avoid aggregation, and the activated carbon fiber can effectively adsorb organic pollutants to promote catalytic degradation. On the other hand, the activated carbon fiber provides electrons for the polymeric metal phthalocyanine to improve the efficiency of activating hydrogen peroxide. Therefore, it can efficiently activate hydrogen peroxide to degrade organic pollutants such as antibiotics in high-salt wastewater and reduce their biological toxicity, providing a new method for the pollution control of organic pollutants.

[0036] The present invention provides a method for degrading antibiotics in high-salt wastewater, comprising the following steps: mixing a catalyst, high-salt wastewater containing antibiotics, and hydrogen peroxide to catalytically degrade the antibiotics; the catalyst is the activated carbon fiber supported polymeric metal phthalocyanine composite catalytic fiber as described in the above technical solution or the activated carbon fiber supported polymeric metal phthalocyanine composite catalytic fiber prepared by the preparation method described in the above technical solution. In the present invention, the antibiotics, high-salt wastewater, and hydrogen peroxide are preferably the same as the aforementioned antibiotics, high-salt wastewater, and hydrogen peroxide, and will not be elaborated herein one by one. In the present invention, the mixing is preferably: adding the catalyst to the high-salt wastewater containing antibiotics for adsorption, and then adding hydrogen peroxide for mixing; the present invention has no special limitation on the adsorption time, and the adsorption equilibrium of the catalyst to the antibiotics can be achieved (when the concentration of organic pollutants no longer decreases under the condition of no hydrogen peroxide, the adsorption equilibrium is reached). In the present invention, the molar ratio of the antibiotics to hydrogen peroxide is preferably 1:1 to 10, more preferably 1:2.4. In the present invention, the mass ratio of the catalyst to the amount of substance of the antibiotics is preferably 1 g:1 to 10 mol, more preferably 1 g:2.5 mol.

[0037] In the present invention, the temperature of the degradation is preferably room temperature, and the degradation is preferably carried out under dark conditions. In the present invention, during the degradation process, the activated carbon fiber supported polymeric metal phthalocyanine composite fiber activates persulfate to generate active free radicals to oxidize and degrade antibiotics.

[0038] Next, the technical solutions in the present invention will be clearly and completely described in conjunction with the embodiments in the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0039] In the following embodiments, the length of the activated carbon fiber used is 0.5 to 50 mm, and the diameter is 0.01 to 0.1 mm.

[0040] Example 1

[0041] a. Place the activated carbon fiber in deionized water and boil for 1 h, and then dry to constant weight at 150 °C to obtain pretreated activated carbon fiber, wherein the mass ratio of the activated carbon fiber to deionized water is 1:200.

[0042] b. Grind and mix 1.675 g of the pretreated activated carbon fiber, 1.675 g of ferric citrate, 1 g of ammonium chloride, 10 g of urea, 25 mg of ammonium molybdate, and 1.74 g of pyromellitic dianhydride in a mortar to obtain a solid-phase mixture.

[0043] c. Heat the solid-phase mixture from 25°C to 140°C at a heating rate of 2.5°C / min, keep it calcined in an air atmosphere for 1 h, then heat it to 280°C at a heating rate of 2.5°C / min, and keep it calcined in an air atmosphere for 1 h to obtain a calcined product.

[0044] d. Cool the calcined product to room temperature, then disperse it in ethanol and wash it three times, and centrifuge it at 8000 r / min for 8 min. Dry the obtained solid product at 100°C to constant weight to obtain a composite fiber of activated carbon fiber supported with polymeric metal phthalocyanine.

[0045] Example 2

[0046] a. Boil the activated carbon fiber in deionized water for 1 h, then dry it to constant weight at 150°C to obtain a pretreated activated carbon fiber, where the mass ratio of the activated carbon fiber to deionized water is 1:500.

[0047] b. Grind and mix 1.675 g of the pretreated activated carbon fiber, 3.59 g of ferric nitrate, 4 g of ammonium chloride, 20 g of urea, 40 mg of ammonium molybdate, and 3.25 g of pyromellitic dianhydride evenly in a mortar to obtain a solid-phase mixture.

[0048] c. Heat the solid-phase mixture from 25°C to 140°C at a heating rate of 2.5°C / min, keep it calcined in an air atmosphere for 1 h, then heat it to 220°C at a heating rate of 2.5°C / min, and keep it calcined in an air atmosphere for 2 h to obtain a calcined product.

[0049] d. Cool the calcined product to room temperature, then disperse it in deionized water and wash it three times, and centrifuge it at 8000 r / min for 8 min. Dry the obtained solid product at 100°C to constant weight to obtain a composite fiber of activated carbon fiber supported with polymeric metal phthalocyanine.

[0050] Example 3

[0051] a. Boil the activated carbon fiber in deionized water for 1 h, then dry it to constant weight at 130°C to obtain a pretreated activated carbon fiber, where the mass ratio of the activated carbon fiber to deionized water is 1:300.

[0052] b. Grind and mix 1.675 g of the pretreated activated carbon fiber, 4.875 g of ferric chloride, 3.05 g of ammonium chloride, 20 g of urea, 40 mg of ammonium molybdate, and 5.025 g of pyromellitic dianhydride evenly in a mortar to obtain a solid-phase mixture.

[0053] c. Heat the solid-phase mixture from 25 °C to 140 °C at a heating rate of 2.5 °C / min, keep it calcined for 3 h in an air atmosphere, then heat it to 280 °C at a heating rate of 2.5 °C / min, and keep it calcined for 1 h in an air atmosphere to obtain a calcined product.

[0054] d. Cool the calcined product to room temperature, then disperse it in tetrahydrofuran and wash it 3 times, and centrifuge it at 8000 r / min for 8 min. Dry the obtained solid product at 120 °C until constant weight to obtain the activated carbon fiber supported polymeric metal phthalocyanine composite fiber.

[0055] Test Example 1

[0056] Evaluate the performance of the activated carbon fiber supported polymeric metal phthalocyanine composite catalytic fiber (denoted as ACF-FePPc) prepared in Examples 1 to 3 for the degradation of sulfachloropyridazine (SCP).

[0057] Use a 20 mL mixed aqueous solution of sodium chloride - sulfachloropyridazine - hydrogen peroxide (sulfachloropyridazine concentration is 0.025 mol / L, sodium chloride concentration is 10 g / L, hydrogen peroxide concentration is 60 mmol / L) as the target pollutant, and add 10 mg of ACF-FePPc prepared in Examples 1 to 3 respectively, and carry out the degradation reaction under dark reaction conditions.

[0058] For the activated carbon fiber supported polymeric metal phthalocyanine composite catalytic fiber prepared in Example 1, the degradation rate of SCP is above 98% at 180 min of the reaction. For the activated carbon fiber supported polymeric metal phthalocyanine composite catalytic fiber prepared in Example 2, the degradation rate of SCP is above 98% at 140 min of the reaction. For the activated carbon fiber supported polymeric metal phthalocyanine composite catalytic fiber prepared in Example 3, the degradation rate of SCP is above 98% at 120 min of the reaction. It shows that the catalytic activity of the activated carbon fiber supported polymeric metal phthalocyanine composite catalytic fiber prepared by the present invention is high.

[0059] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. Application of an activated carbon fiber-supported polymeric metal phthalocyanine composite catalytic fiber in catalytic degradation of antibiotics, characterized in that: The chemical composition of the activated carbon fiber supported polymerized metal phthalocyanine composite catalytic fiber includes activated carbon fiber and metal phthalocyanine polymer supported on the activated carbon fiber; The content of the metal phthalocyanine polymer in the activated carbon fiber-supported polymerized metal phthalocyanine composite catalytic fiber is 1 to 10 wt %; The metal in the metal phthalocyanine polymer includes one or more of Fe, Co, Cu, Zn, Mn and Ni; The preparation method of the activated carbon fiber-supported polymerized metal phthalocyanine composite catalytic fiber comprises the following steps: mixing activated carbon fiber, a metal source, ammonium halide, a nitrogen source, ammonium molybdate and pyromellitic anhydride, and calcining to obtain the activated carbon fiber-supported polymerized metal phthalocyanine composite catalytic fiber; the metal type in the metal source is the same as the metal type in the metal phthalocyanine polymer; The mass ratio of the activated carbon fiber to the metal source is 1:1-4; The mass ratio of the activated carbon fiber to the ammonium halide is 1:0.5-10; The mass ratio of the activated carbon fiber to the nitrogen source is 1:5-100; The mass ratio of the activated carbon fiber to ammonium molybdate is 1:0.01-0.08; The mass ratio of the activated carbon fiber to pyromellitic anhydride is 1:1-10.

2. The use according to claim 1, characterized in that The activated carbon fiber has a length of 0.5-500 mm and a diameter of 0.01-0.1 mm.

3. The use according to claim 1, characterized in that The calcination is programmed calcination, which includes a first heating stage, a first insulation stage, a second heating stage and a second insulation stage in sequence, wherein the heating rates of the first heating stage and the second heating stage are independently 1-5°C / min; the temperature of the first insulation stage is 100-140°C, and the insulation time is 30-60min; the temperature of the second insulation stage is 200-280°C, and the insulation time is 0.5-5h.

4. The use according to claim 1, characterized in that The activated carbon fibers are pretreated before use, and the pretreatment comprises: boiling the activated carbon fibers in water and then drying them.

5. The use according to any one of claims 1 to 4, characterized in that The application comprises the following steps: Activated carbon fiber loaded polymerized metal phthalocyanine composite catalytic fiber, high-salt wastewater containing antibiotics and hydrogen peroxide are mixed to catalytically degrade the antibiotics.