A copper-manganese-based fiber catalytic material, a preparation method and application thereof

Abstract

The application belongs to the technical field of new materials, and discloses a copper-manganese-based fiber catalytic material and a preparation method and application thereof, and the preparation method is as follows: copper ions are loaded on a polymer fiber to obtain a copper-loaded polymer fiber; the copper-loaded polymer fiber is subjected to pre-oxidation treatment to obtain a pre-oxidized copper-loaded polymer fiber; the pre-oxidized copper-loaded polymer fiber is subjected to in-situ oxidation by using a potassium permanganate in-situ oxidation method to obtain a copper-manganese-based polymer fiber catalytic material precursor; the copper-manganese-based polymer fiber catalytic material precursor is subjected to ozone in-situ activation treatment by using an ozone gas flow, and the copper-manganese-based fiber catalytic material is obtained. The copper-manganese-based fiber catalytic material prepared by the application has the advantages of simple preparation process, no need for high-temperature calcination, stable oxidation resistance, high thermal oxidation stability, good water vapor resistance, excellent catalytic performance, and no limitation on the form, which can be applied to any form such as random fibers, wool yarns, needle punched fabrics, knitted fabrics and the like, and not only is the filling convenient, but also greatly widens the use depth and breadth of the catalytic material.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of new materials, and particularly relates to a copper-manganese-based fiber catalytic material and a preparation method and application thereof. BACKGROUND

[0002] Functionalization of common textile fibers (synthetic fibers and natural fibers) to maintain the original characteristics and advantages of the fibers and have various special properties and uses has attracted increasing attention in recent years. Textile fibers are abundant in supply, diverse in variety and suitable in price, and are a good source of raw materials for obtaining new materials. Chemical modification is an important means of functionalization of fibers. Through chemical reaction of active chemical groups on the fibers with certain molecules or ions, or through ultrasonic, microwave or heat-assisted chemical reaction, the fibers have new surface chemical properties, thereby having new functions such as antistatic, water absorption and moisture retention, adsorption and separation, antibacterial and deodorization, catalysis and the like. Chemical modification can use different fibers as raw materials and be realized through different treatment methods and processes. At present, most of the supported metal oxide catalysts use metal oxides or molecular sieves and the like as substrates. Although the catalysts prepared by using these substrate materials have excellent stability and dispersibility, their form is not easy to change, and they are difficult to fill in industrial applications. Moreover, most of the active sites of the molecular sieve or metal oxide-based catalysts are located inside the particles, and the internal diffusion process has a great influence on the catalytic performance in the actual reaction process. At the same time, the intermediate product particles generated in the reaction are easy to deposit in the pores of the catalyst, thereby causing plugging and reducing the activity of the catalyst. Research shows that the rich acid-base microenvironment on the surface of the catalyst is of great significance to improving the catalytic performance of the catalyst. However, due to the involvement of organic polymer fibers, the active sites of the prepared catalyst are more or less covered by organic fragments or inactive components, but the inorganic carriers cannot be oxidized and activated at high temperature, so that the surface active sites of the prepared fibers are less and are seriously covered by organic fragments, resulting in a significant reduction in the catalytic performance of the fibers compared with the catalytic performance of the inorganic carrier catalysts. In addition, the literature“Duan W, Tang K, Zhao L, et al. MnO xNanoparticle-loaded polyacrylonitrile fibers for efficient catalytic ozonation of toluene[J]. Atmospheric Pollution Research, 2024, 15 (5): 102079” research shows that during the process of catalytic ozonation degradation of toluene by using manganese oxide loaded polymer fiber, the polymer fiber carrier is degraded, and water vapor has an inhibitory effect on the catalytic activity of the fiber catalyst, although the inhibitory effect is reversible, but water vapor is one of the influencing factors widely existing in actual waste gas. Therefore, for organic fiber catalysts, when they are used for catalytic ozonation reaction, their heat oxidation resistance, water vapor resistance and catalytic activity need to be further improved. SUMMARY

[0003] In view of the problems and deficiencies in the prior art, the purpose of the present application is to provide a copper-manganese-based fiber catalyst material and a preparation method and application thereof.

[0004] To achieve the purpose of the application, the technical scheme adopted by the present application is as follows:

[0005] The present application provides a preparation method of a copper-manganese-based fiber catalyst material, comprising the following steps:

[0006] (1) loading copper ions on a polymer fiber to obtain a copper-loaded polymer fiber;

[0007] (2) pre-oxidizing the copper-loaded polymer fiber to obtain a pre-oxidized copper-loaded polymer fiber; in-situ oxidizing the pre-oxidized copper-loaded polymer fiber by using a potassium permanganate in-situ oxidation method to obtain a copper-manganese-based polymer fiber catalyst material precursor;

[0008] (3) in-situ activating the copper-manganese-based polymer fiber catalyst material precursor by using an ozone gas flow to obtain a copper-manganese-based fiber catalyst material.

[0009] According to the above preparation method, preferably, in step (3), the temperature of the in-situ activation treatment by ozone is 110-130℃, and the time is 6-14h. More preferably, the temperature of the in-situ activation treatment by ozone is 110-120℃, and the time is 8-12h.

[0010] According to the above preparation method, preferably, in step (3), the concentration of ozone in the ozone gas flow is 10-40mg / L, and more preferably, the concentration of ozone in the ozone gas flow is 10-30mg / L.

[0011] According to the preparation method, preferably, in step (3), the mass space velocity of the ozone gas flow during the in-situ activation treatment of ozone is 240000-1200000 mL / (g·h). More preferably, the mass space velocity of the ozone gas flow during the in-situ activation treatment of ozone is 480000-1200000 mL / (g·h).

[0012] According to the preparation method, preferably, in step (1), the operation of loading copper ions on the polymer fiber is as follows: the polymer fiber is immersed in a copper ion solution, and after the immersion is completed, the copper-loaded polymer fiber is obtained by washing and drying.

[0013] According to the preparation method, preferably, the concentration of copper ions in the copper ion solution is 20-1000 mg / L; and the copper ion solution is a copper sulfate solution or a copper nitrate solution. More preferably, the copper ion solution is a copper nitrate solution.

[0014] According to the preparation method, preferably, the operation of in-situ oxidation of the pre-oxidized polymer fiber by using the in-situ oxidation method of potassium permanganate is as follows: the pre-oxidized copper-loaded polymer fiber is added into a potassium permanganate solution for oxidation reaction, and after the reaction is completed, the pre-oxidized copper-loaded polymer fiber is collected, and the pre-oxidized copper-loaded polymer fiber is washed and dried to obtain a copper-manganese-based polymer fiber catalytic material precursor.

[0015] According to the preparation method, preferably, the concentration of the potassium permanganate solution is 20-100 mmol / L, the liquid-solid ratio of the potassium permanganate solution to the pre-oxidized polymer fiber is (20-200) mL:1 g, the temperature of the oxidation reaction is 10-40 ℃, and the time of the oxidation reaction is 0.5-12 h.

[0016] According to the preparation method, preferably, the pre-oxidation treatment is that the copper-loaded polymer fiber is heat-treated in an oxygen-containing gas. More preferably, the temperature of the heat treatment is 200-250 ℃, and the time of the heat treatment is 0.5-4 h; and the flow rate of the oxygen-containing gas is 100-500 mL / min.

[0017] According to the preparation method, preferably, the pre-oxidation treatment is that the copper-loaded polymer fiber is placed in an oxygen-containing gas, heated to 200-250 ℃, and heat-treated for 0.5-4 h. More preferably, the heating rate of the heating is 2-20 ℃ / min.

[0018] According to the preparation method, preferably, in step (1), the polymer fiber is acrylic fiber or modified acrylic fiber.

[0019] According to the preparation method, preferably, the modified acrylic fiber is an acrylic fiber grafted with amine groups, the amine groups are grafted on the acrylic fiber by reacting a polyamine compound with -CN groups in the acrylic fiber.

[0020] According to the preparation method, preferably, the preparation method of the acrylic fiber grafted with amine groups is: swelling treatment of the acrylic fiber in a polyamine compound solution, reaction at 100-150℃ for 1-12h after swelling, cooling, washing and drying after reaction, to obtain the acrylic fiber grafted with amine groups. More preferably, the swelling treatment temperature is 60-80℃, and the swelling treatment time is 4-12h.

[0021] According to the preparation method, preferably, the polyamine compound is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine and polyethylene polyamine.

[0022] According to the preparation method, preferably, the amount of the polyamine compound solution used is: 20ml-200ml of the polyamine compound solution is added to 1g of the acrylic fiber for swelling treatment, and the mass fraction of the polyamine compound in the polyamine compound solution is 5-100%.

[0023] According to the preparation method, preferably, the solvent of the polyamine compound solution is water, ethylene glycol, propylene glycol or glycerol.

[0024] According to the preparation method, preferably, the amine groups include primary amine groups or / and secondary amine groups. More preferably, the nitrogen heterocycle is generated by cyclization of one or more of cyano groups, amide groups and amine groups.

[0025] The second aspect of the present application provides a copper-manganese-based fiber catalytic material prepared by the preparation method of the first aspect.

[0026] According to the copper-manganese-based fiber catalytic material, preferably, the form of the copper-manganese-based fiber catalytic material is one or more of fiber, wool, needle-punched cloth and knitted cloth.

[0027] The third aspect of the present application provides an application of the copper-manganese-based fiber catalytic material of the second aspect in a catalyst.

[0028] According to the application, preferably, the catalyst includes a catalyst in an ozone oxidation process; more preferably, the ozone oxidation includes ozone oxidation degradation of benzene series in gas phase; the benzene series includes toluene and / or benzene; the degradation temperature is 70-110℃.

[0029] Compared with the prior art, the present application has the following positive and beneficial effects:

[0030] (1) Due to the participation of the organic polymer fiber, the prepared catalyst active sites are more or less covered by organic fragments or inactive components, but cannot be oxidized and activated at high temperature like inorganic carriers, so that the prepared fiber surface active sites are less and are seriously covered by organic fragments, resulting in that the catalytic activity is significantly reduced compared with the catalytic performance of the same inorganic carrier catalyst; in the application, acrylic fiber is used as the base material, a large number of amine group functional groups are grafted on the surface of the acrylic fiber by the chemical grafting method to prepare amine group fiber (i.e. acrylic fiber grafted with amine group), then the amine group fiber is immersed in a copper ion solution to obtain copper-loaded amine group fiber, and the copper-loaded amine group fiber is placed in an air atmosphere for temperature pre-oxidation to obtain pre-oxidized copper-loaded amine group fiber, and then the pre-oxidized copper-loaded amine group fiber is prepared into a copper-manganese-based polymer fiber catalytic material precursor by using a potassium permanganate in-situ oxidation method, and then the manganese-based polymer fiber catalytic material precursor is treated by ozone in-situ activation, and in the ozone in-situ activation process, based on the catalytic activity of part of the manganese oxides on the surface of the polymer fiber, the organic fragments covering the surface of the catalytically active sites are stripped and degraded by self-catalytic ozone oxidation, so that the number of exposed manganese oxide catalytically active sites on the surface of the polymer fiber catalytic material is increased, thereby improving the catalytic performance of the polymer fiber catalytic material, and effectively solving the problem of low activity or inactivation of the catalytic material caused by the coverage of the catalytically active sites on the surface of the manganese-based polymer fiber catalytic material.

[0031] (2) The copper-manganese-based fiber catalytic material prepared in the application can be used for catalytic ozone oxidation degradation of pollutants such as volatile organic compounds and malodorous pollutants, and when the pollution gas with a concentration of 100 ppm of toluene or benzene is treated by the copper-manganese-based fiber catalytic material prepared in the application under the conditions of an air speed of 120000 mL / (g·h), a reaction temperature of 100℃ and an ozone concentration of 4.0-4.5 mg / L, the removal rate of toluene or benzene reaches 96.4%-100%; under the same degradation conditions, the removal rate of toluene is only 51%-78% when the copper-manganese-based polymer fiber material precursor without ozone activation is used as the catalyst; therefore, compared with the process without ozone in-situ activation treatment, the catalytic activity of the copper-manganese-based fiber catalytic material prepared by the ozone in-situ activation treatment in the application is significantly improved.

[0032] (3) The copper-manganese-based fiber catalytic material of the present application is doped with copper and manganese at the same time, on the one hand, copper can produce strong chelation with functional groups (-NH2, -NH-, etc.) in the polymer fiber, and then crosslink the polymer fiber, and participate in the crosslinking cyclization of nitrogen-containing groups in the thermal oxidation process, thereby improving the thermal oxidation stability of the prepared fiber catalytic material; the technical problem of poor thermal oxidation stability of the existing manganese oxide fiber catalytic material and easy degradation of the polymer fiber carrier in the process of catalyzing ozone oxidation degradation of benzene series is solved. On the other hand, when the existing manganese-based fiber catalytic material is used to catalyze ozone oxidation degradation of benzene series-containing gas, the removal rate of benzene series is low when the relative humidity of the benzene series-containing gas increases to 20%, because the competitive adsorption of water vapor, benzene series and ozone on the active sites of the catalyst dominates, which leads to a significant decrease in the removal rate of benzene series; however, when the copper-manganese-based fiber catalytic material of the present application is used to catalyze ozone oxidation degradation of benzene series-containing gas with high humidity, in the presence of water vapor, the copper species in the copper-manganese-based fiber catalytic material can provide adsorption sites for benzene series, and the presence of copper is more conducive to catalyzing the decomposition of ozone to generate strong oxidizing hydroxyl radicals, thereby improving the performance of the polymer fiber catalytic material in catalyzing the degradation of benzene series, so the introduction of copper significantly improves the water vapor stability of the existing manganese-based fiber catalytic material, and solves the technical problem that the water vapor inhibits the catalytic activity of the polymer catalytic material when the existing polymer fiber catalytic material is used to catalyze the degradation of benzene series-containing gas with high humidity, resulting in a low removal rate of benzene series. Therefore, the copper-manganese-based fiber catalytic material prepared by the present application not only has good catalytic degradation performance for pollutants (benzene series), but also has good thermal oxidation stability and water vapor resistance, and is more suitable for treating benzene series-containing gas with high humidity.

[0033] (4) The present application performs thermal oxidation treatment on the polymer fiber in an oxygen-containing gas, which can crosslink and cyclize part of the functional groups on the surface of the fiber, thereby improving the thermal oxidation stability and oxidation resistance of the polymer fiber catalytic material, and solving the technical problems of poor thermal oxidation stability and poor oxidation resistance of the existing manganese-based polymer fiber catalytic material.

[0034] (5) The copper-manganese-based fiber catalytic material prepared by the present application has stable oxidation resistance, high thermal oxidation stability, good water vapor resistance and excellent catalytic performance, and can be applied in any form such as random fiber, wool, needle punched fabric, knitted fabric, etc., which is not only convenient to fill, but also greatly widens the depth and breadth of the use of the catalytic material.

[0035] (6) The preparation method of the copper-manganese-based fiber catalytic material of the present application is simple in operation, mild in conditions and easy to be industrialized and applied. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1SEM characterization diagram of copper-manganese-based fiber catalytic material precursor, copper-manganese-based fiber catalytic material prepared in embodiment 1 of the present application; wherein a1-a3 are different microscale morphology diagrams of the copper-manganese-based fiber catalytic material precursor, b1-b3 are different microscale morphology diagrams of the copper-manganese-based fiber catalytic material;

[0037] Figure 2 EDS surface scanning diagram of copper-manganese-based fiber catalytic material prepared in embodiment 1 of the present application, wherein A is the micro-morphology of the EDS surface scanning area, B is the Mn element distribution diagram in the scanning area, and C is the Cu element distribution diagram in the scanning area;

[0038] Figure 3 Degradation effect detection result diagram of copper-manganese-based fiber catalytic material, manganese-based fiber catalytic material catalytic ozone oxidation degradation of toluene in different humidity gases; wherein a is the detection result of the copper-manganese-based fiber catalytic material prepared in embodiment 1, b is the detection result of the pure manganese fiber catalytic material prepared according to the method recorded in the literature, X tol. represents the removal rate of toluene, X ozo. represents the ozone decomposition rate, and Relative humidity represents the relative humidity of the gas. DETAILED DESCRIPTION

[0039] In order for those skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present application will be described in detail below in combination with specific embodiments.

[0040] The following detailed description is exemplary and is intended to provide further explanation of the present application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs.

[0041] It should be noted that the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. In addition, it should be understood that when the terms "comprise" and / or "include" are used in the present specification, they indicate the presence of a feature, step, operation, component and / or their combination.

[0042] The experimental methods in the following examples, which are not specified with specific conditions, all use conventional techniques in the art, or follow the conditions recommended by the manufacturer; the reagents or instruments used, which are not specified by the manufacturer, are all conventional products that can be obtained by purchase.

[0043] Example 1:

[0044] A preparation method of a copper-manganese-based fiber catalytic material, specifically:

[0045] The commercial acrylic fibers were washed with deionized water for three times and dried at 60℃ until constant weight. A three-neck flask was charged with 200 mL of triethylenetetramine, and then 2 g of the pretreated acrylic fibers were weighed and immersed in the triethylenetetramine for swelling at 60℃ for 12 h, and then the temperature was raised to 150℃ for reaction for 3 h, and then cooled, washed, and dried at 60℃ until constant weight to obtain amine group fibers, and the exchange capacity of which was measured to be 5.93 mmol / g; 1 g of the obtained amine group fibers were immersed in 0.2 L of a copper nitrate solution with a copper ion concentration of 400 mg / L, and oscillated at 25℃ for 12 h, and then washed and dried at 60℃ until constant weight to obtain copper-loaded amine group fibers. 1 g of the copper-loaded amine group fibers were placed in a tube furnace, air was passed into the tube furnace at a flow rate of 200 mL / min for 30 min, and then the temperature was raised to 200℃ at a rate of 10℃ / min and kept constant for 4 h, and then cooled and sealed for storage to obtain pre-oxidized copper-loaded amine group fibers; 0.5 g of the pre-oxidized copper-loaded amine group fibers were placed in a triangular flask containing 100 mL of a potassium permanganate solution with a concentration of 25 mmol / L, and oscillated at 15℃ for reaction for 2 h, and then taken out, washed with water until the washing liquid was colorless, and dried at 60℃ until constant weight to obtain a copper-manganese group fiber catalytic material precursor. The copper-manganese group fiber catalytic material precursor was activated in situ in an ozone gas stream with an ozone concentration of 20 mg / L, a mass space velocity of 1,200,000 mL / (g·h), and a temperature of 110℃ for 10 h to obtain a copper-manganese group fiber catalytic material. It was detected that the copper content in the copper-manganese group fiber catalytic material was 20 mg / g, and the manganese content was 204 mg / g.

[0046] The copper-manganese group fiber catalytic material and the copper-manganese group fiber catalytic material precursor prepared in this example were respectively used to catalyze the ozone oxidation degradation of toluene in a gas; the degradation experiment conditions were as follows: a space velocity of 1,200,000 mL / (g·h), a reaction temperature of 100℃, a toluene concentration in the gas of 100 ppm, an ozone concentration of 4.0-4.5 mg / L, and a humidity of the gas of 0-10%. After the degradation reaction was completed, the content of toluene in the gas was detected and the removal rate of toluene was calculated.

[0047] It was detected that the removal rate of toluene in the gas by the copper-manganese group fiber catalytic material prepared in this example was 100%, and the removal rate of toluene in the gas by the copper-manganese group fiber catalytic material precursor was 78%. It was thus illustrated that the catalytic performance of the copper-manganese group fiber catalytic material prepared in this example was significantly higher than that of the copper-manganese group fiber catalytic material precursor which was not subjected to ozone in-situ activation treatment, and the copper-manganese group fiber catalytic material could be used to catalyze the ozone oxidation degradation of toluene pollutants in a gas.

[0048] Example 2:

[0049] A preparation method of a copper-manganese group fiber catalytic material, specifically comprising:

[0050] The commercial acrylic fiber is washed with deionized water for three times and dried at 60℃ until constant weight. A three-necked flask is added with 200 mL of diethylene triamine solution (the mass fraction of diethylene triamine in the diethylene triamine solution is 20%, and the solvent of the diethylene triamine solution is ethylene glycol), and then 2 g of the pretreated acrylic fiber is weighed and immersed in the diethylene triamine solution for swelling at 80℃ for 4 h, and then the temperature is increased to 130℃ for reaction for 5 h, and then the fiber is cooled, washed, and dried at 60℃ until constant weight to obtain an amine group fiber, and the exchange capacity of which is measured to be 4.05 mmol / g; 2 g of the obtained amine group fiber is immersed in 1 L of a copper sulfate solution with a copper ion concentration of 20 mg / L, and oscillated at 25℃ for 6 h, and then washed and dried at 60℃ until constant weight to obtain a copper-loaded amine group fiber. 2 g of the copper-loaded amine group fiber is placed in a tube furnace, air is introduced into the tube furnace at a flow rate of 100 mL / min for 30 min, and then the temperature is increased to 250℃ at a rate of 20℃ / min and kept constant for 0.5 h, and then the fiber is cooled and sealed for storage to obtain a pre-oxidized copper-loaded amine group fiber; 1 g of the pre-oxidized copper-loaded amine group fiber is placed in a triangular flask containing 200 mL of a potassium permanganate solution with a concentration of 100 mmol / L, and oscillated at 10℃ for 12 h, and then taken out, washed with water until the washing liquid is colorless, and dried at 60℃ until constant weight to obtain a copper-manganese group fiber catalytic material precursor. The copper-manganese group fiber catalytic material precursor is activated in situ in an ozone gas stream with an ozone concentration of 30 mg / L, a mass space velocity of 960000 mL / (g·h), and a temperature of 120℃ for 6 h to obtain a copper-manganese group fiber catalytic material. It is detected that the copper content in the copper-manganese group fiber catalytic material is 5 mg / g, and the manganese content is 120 mg / g.

[0051] The copper-manganese group fiber catalytic material and the copper-manganese group fiber catalytic material precursor prepared in this example are respectively used to catalyze the ozone oxidation degradation of benzene in a gas; the degradation experiment conditions are as follows: the space velocity is 120000 mL / (g·h), the reaction temperature is 100℃, the concentration of benzene in the gas is 100 ppm, the ozone concentration is 4.0-4.5 mg / L, and the humidity of the gas is 0-10%. After the degradation reaction is completed, the content of benzene in the gas is detected and the removal rate of benzene is calculated.

[0052] It is detected that the removal rate of benzene in the gas by the copper-manganese group fiber catalytic material prepared in this example is 96.4%, and the removal rate of benzene in the gas by the copper-manganese group fiber catalytic material precursor is 51%. It is thus illustrated that the catalytic performance of the copper-manganese group fiber catalytic material prepared in this example is significantly higher than that of the copper-manganese group fiber catalytic material precursor which is not subjected to ozone in-situ activation treatment, and the copper-manganese group fiber catalytic material can be used to catalyze the ozone oxidation degradation of benzene pollutants in a gas.

[0053] Example 3:

[0054] A preparation method of a copper-manganese group fiber catalytic material, specifically comprising:

[0055] The commercial acrylic fibers are washed with deionized water for three times and dried at 60℃ until constant weight. A three-necked flask is added with 40 mL of ethylenediamine solution (the mass fraction of ethylenediamine in the ethylenediamine solution is 40%, and the solvent of the ethylenediamine solution is glycerol), and then 2 g of the pretreated acrylic fibers are weighed and immersed in the ethylenediamine solution for swelling at 60℃ for 12 h, and then the temperature is increased to 100℃ for reaction for 12 h, and then the fibers are cooled, washed, and dried at 60℃ until constant weight to obtain amine group fibers, and the exchange capacity of which is measured to be 3.06 mmol / g; 2 g of the obtained amine group fibers are immersed in 0.2 L of a copper nitrate solution with a copper ion concentration of 1000 mg / L, oscillated at 25℃ for 2 h, washed, and dried at 60℃ until constant weight to obtain copper-loaded amine group fibers. 2 g of the copper-loaded amine group fibers are placed in a tube furnace, air is introduced into the tube furnace at a flow rate of 500 mL / min for 30 min, and then the temperature is increased to 220℃ at a rate of 2℃ / min and kept constant for 2 h, and then the fibers are cooled and sealed for storage to obtain pre-oxidized copper-loaded amine group fibers; 1 g of the pre-oxidized copper-loaded amine group fibers are placed in a triangular flask containing 100 mL of a potassium permanganate solution with a concentration of 50 mmol / L, and oscillated at 25℃ for 6 h, taken out, washed with water until the washing liquid is colorless, and dried at 60℃ until constant weight to obtain a copper-manganese-based fiber catalytic material precursor. The copper-manganese-based fiber catalytic material precursor is activated in situ in an ozone gas stream with an ozone concentration of 10 mg / L, a mass space velocity of 480000 mL / (g·h), and a temperature of 115℃ for 14 h to obtain a copper-manganese-based fiber catalytic material. It is detected that the copper content in the copper-manganese-based fiber catalytic material is 50 mg / g, and the manganese content is 89 mg / g.

[0056] The copper-manganese-based fiber catalytic material and the copper-manganese-based fiber catalytic material precursor prepared in this example are respectively used to catalyze the ozone oxidation degradation of toluene in a gas; the degradation experiment conditions are as follows: the space velocity is 120000 mL / (g·h), the reaction temperature is 100℃, the toluene concentration in the gas is 100 ppm, the ozone concentration is 4.0-4.5 mg / L, and the humidity of the gas is 0-10%. After the degradation reaction is completed, the content of toluene in the gas is detected and the removal rate of toluene is calculated.

[0057] It is detected that the removal rate of toluene in the gas by the copper-manganese-based fiber catalytic material prepared in this example is 100%, and the removal rate of toluene in the gas by the copper-manganese-based fiber catalytic material precursor is 62%. It is thus illustrated that the catalytic performance of the copper-manganese-based fiber catalytic material prepared in this example is significantly higher than that of the copper-manganese-based fiber catalytic material precursor without ozone in-situ activation treatment, and the copper-manganese-based fiber catalytic material can be used to catalyze the ozone oxidation degradation of toluene pollutants in a gas.

[0058] Comparative Example 1

[0059] A preparation method of a manganese-based fiber catalytic material, specifically comprising:

[0060] The commercial acrylic fibers were washed with deionized water for three times, and dried at 60℃ until constant weight. A three-neck flask was charged with 200 mL of triethylenetetramine, and then 2 g of the pretreated acrylic fibers were weighed and immersed in the triethylenetetramine for swelling at 60℃ for 12 h, and then the temperature was raised to 150℃ for reaction for 3 h, and then cooled, washed, and dried at 60℃ until constant weight to obtain the amine group fiber, and the exchange capacity of which was measured to be 5.93 mmol / g; 1 g of the obtained amine group fiber was placed in a tube furnace, and air was passed into the tube furnace at a flow rate of 200 mL / min for 30 min, and then the temperature was raised to 200℃ at a rate of 10℃ / min and kept at 200℃ for 4 h, and then cooled and sealed to obtain the pre-oxidized amine group fiber; 0.5 g of the pre-oxidized amine group fiber was placed in a triangular flask containing 100 mL of a potassium permanganate solution with a concentration of 25 mmol / L, and oscillated at 15℃ for 2 h, and then taken out, washed with water until the washing liquid was colorless, and dried at 60℃ until constant weight to obtain the manganese group fiber catalytic material precursor. The manganese group fiber catalytic material precursor was activated in situ in an ozone gas stream with an ozone concentration of 20 mg / L, a mass space velocity of 1,200,000 mL / (g·h), and a temperature of 110℃ for 4 h to obtain the manganese group fiber catalytic material. It was detected that the manganese content in the manganese group fiber catalytic material was 219 mg / g.

[0061] The manganese group fiber catalytic material prepared in the present comparative example was used to catalyze the ozone oxidation degradation of toluene in a gas; the degradation experiment conditions were as follows: the space velocity was 1,200,000 mL / (g·h), the reaction temperature was 100℃, the toluene concentration in the gas was 100 ppm, the ozone concentration was 4.0-4.5 mg / L, and the humidity of the gas was 0-10%. After the degradation reaction was completed, the content of toluene in the gas was detected and the removal rate of toluene was calculated. It was detected that the removal rate of toluene in the gas by the manganese group fiber catalytic material prepared in the present example was 100%.

[0062] (I) SEM characterization of the copper manganese group fiber catalytic material prepared in the present application

[0063] The SEM characterization of the copper manganese group fiber catalytic material precursor and the copper manganese group fiber catalytic material prepared in Example 1 of the present application was performed, and the SEM characterization graph is shown in Figure 1

[0064] As can be seen from Figure 1 , the surface of the copper manganese group fiber material precursor contains many particles smaller than 100 nm, and after in-situ activation by ozone, the small particles on the surface of the fiber are aggregated into large particles, which is mainly due to the fact that the organic fragments covering the active sites are stripped and degraded under the self-catalytic ozone oxidation, and the exposed active species are aggregated to form larger particles of active species. Although the active species particles become larger, the actual effective site area exposed increases due to the oxidation and stripping of the surface covering organic fragments, so that the catalytic performance of the fiber is greatly improved. ​

[0065] (II) EDS surface scanning characterization of the copper-manganese-based fiber catalytic material prepared in this invention

[0066] EDS surface scanning was performed on the copper-manganese-based fiber catalytic material prepared in Example 1 of this invention. The EDS surface scanning results are as follows: Figure 2 As shown.

[0067] Depend on Figure 2 It can be seen that the copper-manganese-based fiber catalytic material prepared by this invention contains more manganese and less copper on its surface, and the distribution is uniform. This confirms that the active species of copper and manganese are uniformly loaded onto the fiber surface, and the prepared fiber catalyst is a copper-manganese-based fiber catalytic material.

[0068] (III) Test of the water vapor resistance stability of the copper-manganese-based fiber catalytic material prepared in this invention

[0069] To investigate the water vapor resistance of the copper-manganese-based fiber catalytic material prepared in this application, the copper-manganese-based fiber catalytic material prepared in Example 1 of this invention and the manganese-based fiber catalytic material prepared in Comparative Example 1 were used to catalyze the ozone oxidation degradation of toluene in the gas. The degradation experimental conditions were: space velocity 120000 mL / (g·h), reaction temperature 100℃, toluene concentration in the gas 100 ppm, ozone concentration 4.0-4.5 mg / L, and relative humidity of the gas 65%. After the degradation reaction was completed, the toluene content in the gas was detected and the toluene removal rate was calculated.

[0070] Testing revealed that the copper-manganese-based fiber catalytic material prepared in Example 1 of this invention achieved a 100% removal rate of toluene from the gas, while the manganese-based fiber catalytic material prepared in Comparative Example 1 achieved a 91% removal rate of toluene from the gas. This indicates that, compared with the manganese-based fiber catalytic material, the introduction of copper gives the copper-manganese-based fiber catalytic material prepared in this invention excellent water vapor resistance and makes it more suitable for treating gases containing pollutants (benzene series compounds) with high humidity.

[0071] In addition, to further investigate the effect of different gas humidity on the performance of the copper-manganese-based fiber catalytic material of this invention in catalyzing the ozone oxidation degradation of toluene in the gas, the copper-manganese-based fiber catalytic material prepared in Example 1 of this invention was used to catalyze the ozone oxidation degradation of toluene in gases with different humidity levels. The degradation experimental conditions were: mass hourly space velocity 240,000 mL / (g·h), reaction temperature 100℃, toluene concentration in the gas 100 ppm, and ozone concentration 4.0-4.5 mg / L. After the degradation reaction was completed, the toluene content in the gas was detected and the toluene removal rate was calculated. The experimental results are as follows: Figure 3 As shown in Figure a.

[0072] According to the literature "Duan W, Tang K, Zhao L, et al. MnO xThe catalyst for the preparation of pure manganese fiber supported by potassium permanganate direct oxidation method described in "Nanoparticle-loaded polyacrylonitrile fibers for efficient catalytic ozonation of toluene[J]. Atmospheric Pollution Research, 2024, 15 (5): 102079" was determined to have a manganese content of 215.3 mg / g. This pure manganese fiber catalyst was then used to catalyze the ozone oxidation degradation of toluene in gases with different humidity levels. The degradation experimental conditions were: mass hourly space velocity 80000 mL / (g·h), reaction temperature 100℃, toluene concentration in the gas 120 ppm, and ozone concentration 7.6-7.8 mg / L. After the degradation reaction, the toluene content in the gas was detected and the toluene removal rate was calculated. The experimental results are as follows: Figure 3 As shown in b.

[0073] Depend on Figure 3 As shown in section a, for copper-manganese-based fiber catalysts, when the relative humidity of the gas increases to 56%-69% (70-160 min), the toluene removal rate increases from 0.58 to 0.71, indicating that the introduction of water vapor helps to remove toluene. This is mainly because, in the presence of water vapor, copper-manganese-based fiber catalysts more readily catalyze the decomposition of ozone to generate highly oxidizing hydroxyl radicals. Furthermore, manganese species primarily provide active sites for ozone decomposition, while copper species primarily provide active sites for toluene adsorption, thus promoting the oxidative degradation of toluene. For pure manganese polymer fiber catalysts, increasing the relative humidity reduces the toluene removal rate, especially when the relative humidity increases to above 20%, where the toluene removal rate decreases significantly. This is mainly because the competitive adsorption of water vapor, toluene, and ozone at the catalyst's active sites becomes dominant. Figure 3 As shown in Figure b, maintaining a constant relative humidity during the first 120 minutes of the reaction, the toluene removal rate decreased from 77.2% to 71.6%, mainly due to the adsorption of toluene by the fiber catalyst. When the relative humidity increased from 9.7% to 33.3%, the toluene removal rate remained essentially unchanged; after humidification was stopped, the toluene removal rate increased from 72.9% to 77.8%, mainly due to the upward fluctuation of ozone concentration. At 250 minutes, increasing the relative humidity again to 20-21% caused the toluene removal rate to drop to 64.5%, indicating that water vapor inhibited the catalytic reaction. Therefore, the introduction of copper significantly improved the water vapor resistance stability of the pure manganese polymer fiber catalyst.

[0074] The experimental results prove again that the introduction of copper significantly improves the water vapor stability of the existing manganese-based fiber catalytic material, and solves the technical problem that the existing polymer fiber catalytic material has low removal rate of benzene series when catalyzing the degradation of the gas containing benzene series with high humidity, and the water vapor inhibits the catalytic activity of the polymer catalytic material.

[0075] Finally, it should be noted that the above examples are only preferred embodiments of the present application, and are not intended to limit the present application in other forms. Any person skilled in the art can use the above technical content as inspiration to make changes or modifications. The equivalent embodiments of such equivalent changes. However, any simple modification, equivalent change and modification made according to the technical essence of the present application to the above examples without departing from the technical concept of the present application still falls within the protection scope of the present application.

Claims

1. A method for preparing a copper-manganese-based fibrous catalytic material, characterized in that, The method comprises the following steps: (1) loading copper ions on polymer fibers to obtain copper-loaded polymer fibers; the polymer fibers are acrylic fibers or modified acrylic fibers; the modified acrylic fibers are acrylic fibers grafted with amine groups, and the amine groups are grafted on the acrylic fibers by reacting polyamine compounds with-CN groups in the acrylic fibers; (2) performing pre-oxidation treatment on the copper-loaded polymer fibers to obtain pre-oxidized copper-loaded polymer fibers; performing in-situ oxidation on the pre-oxidized copper-loaded polymer fibers by using a potassium permanganate in-situ oxidation method to obtain a copper-manganese-based polymer fiber catalytic material precursor; (3) performing ozone in-situ activation treatment on the copper-manganese-based polymer fiber catalytic material precursor by using an ozone gas flow to obtain a copper-manganese-based fiber catalytic material; the ozone in-situ activation treatment is performed at a temperature of 110-130 ℃ for 6-14 h; the concentration of ozone in the ozone gas flow is 10-40 mg / L, and the mass space velocity of the ozone gas flow during the ozone in-situ activation treatment is 240000-1200000 mL / (g·h).

2. The production method according to claim 1, characterized by, The operation of loading copper ions on polymer fibers is as follows: the polymer fibers are immersed in a copper ion solution, and then washed and dried after the immersion to obtain copper-loaded polymer fibers.

3. The production method according to claim 2, characterized by, The concentration of copper ions in the copper ion solution is 20-1000 mg / L; the copper ion solution is a copper sulfate solution or a copper nitrate solution; the operation of performing in-situ oxidation on the pre-oxidized copper-loaded polymer fibers by using the potassium permanganate in-situ oxidation method is as follows: the pre-oxidized copper-loaded polymer fibers are added into a potassium permanganate solution for oxidation reaction, and then the pre-oxidized copper-loaded polymer fibers are collected after the reaction, and washed and dried to obtain a copper-manganese-based polymer fiber catalytic material precursor.

4. The production method according to claim 3, characterized by, The concentration of the potassium permanganate solution is 20-100 mmol / L, the liquid-solid ratio of the potassium permanganate solution to the pre-oxidized copper-loaded polymer fibers is (20-200) mL:1 g, the temperature of the oxidation reaction is 10-40 ℃, and the time of the oxidation reaction is 0.5-12 h.

5. The method of any one of claims 1-4, wherein, In step (2), the pre-oxidation treatment is specifically as follows: the copper-loaded polymer fibers are heat-treated in an oxygen-containing gas, the temperature of the heat treatment is 200-250 ℃, the time of the heat treatment is 0.5-4 h, and the flow rate of the oxygen-containing gas is 100-500 mL / min.

6. A copper-manganese-based fiber catalytic material prepared by using the preparation method in any one of claims 1-5.

7. The copper-manganese-based fibrous catalytic material according to claim 6, characterized in that, The morphology of the copper-manganese-based fiber catalytic material is one or more of fiber, wool thread, needle punched cloth, and knitted cloth.

8. Application of the copper-manganese-based fiber catalytic material in claim 6 or 7 in a catalyst.

9. Use according to claim 8, characterized in that, The catalyst is a catalyst used in an ozone oxidation process; the ozone oxidation includes ozone oxidation degradation of benzene series in a gas phase; the benzene series includes toluene and / or benzene; and the degradation temperature is 70-110 ℃.

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