High-humidity-resistant multispectral protective carbon and preparation method thereof

Abstract

The invention relates to the technical field of protective materials, in particular to high-humidity-resistant multispectral protective carbon and a preparation method thereof. The preparation raw materials of the high-humidity-resistant multispectral protective carbon comprise the following components in parts by weight: 30-50 parts of an activated carbon composite carrier, 6-10 parts of basic cupric carbonate, 3-5 parts of basic zinc carbonate, 3-5 parts of ferrous sulfate and 3-5 parts of cobalt nitrate. The high-humidity-resistant multi-spectrum protective carbon is prepared by dipping an activated carbon composite carrier into metal salt, so that various toxic gases such as benzene, ammonia gas, hydrogen sulfide, sulfur dioxide, cyanogen chloride and phosgene are efficiently removed, and excellent protective performance is still kept in a high-humidity environment.

Description

Technical Field

[0001] The present invention relates to the technical field of protective materials, and particularly relates to a high-humidity-resistant multi-spectrum protective carbon and a preparation method thereof. Background Art

[0002] With the development of the chemical industry, the importance of occupational health and safety environment has been gradually increasing. Especially, the purification and protection of toxic and harmful gases under high-humidity conditions have become an urgent technical problem to be solved. In industries such as petrochemical, chemical, pharmaceutical, and semiconductor industries, there are various types of common toxic and harmful gases. Especially typical representatives such as benzene, ammonia, hydrogen sulfide, sulfur dioxide, cyanogen chloride, and phosgene not only have high toxicity, but also once released in a high-humidity environment, they will accelerate the failure of protective equipment and pose a serious threat to human health and environmental safety. Currently, the protective carbon used in the market for purifying and protecting such gases still has the following deficiencies: First, the protection spectrum is relatively single, and it is difficult to simultaneously achieve efficient removal of multiple toxic and harmful substances; Second, it is greatly affected by environmental humidity, and the adsorption performance rapidly decays under high-humidity conditions, resulting in a significant decrease in purification efficiency. In order to achieve multi-spectrum protection against the above-mentioned toxic and harmful gases and at the same time overcome the adverse effects of high-humidity environment on the performance of adsorption materials, it is urgent to develop a new type of protective carbon with excellent moisture resistance and multi-spectrum protection. This type of multi-spectrum protective carbon can be used for personnel safety protection in high-humidity and toxic and harmful environments such as chemical industry, pharmaceutical industry, metallurgy, and semiconductor, and can also be applied to air purification where the above-mentioned toxic and harmful substances exist. Summary of the Invention

[0003] Aiming at the deficiencies of the prior art, the present invention provides a high-humidity-resistant multi-spectrum protective carbon and a preparation method thereof.

[0004] The present invention is realized through the following technical solutions: A high-humidity-resistant multi-spectrum protective carbon, the preparation raw materials of which include the following components in parts by weight: 30-50 parts of activated carbon composite carrier, 6-10 parts of basic copper carbonate, 3-5 parts of basic zinc carbonate, 3-5 parts of ferrous sulfate, and 3-5 parts of cobalt nitrate.

[0005] Furthermore, the preparation method of the activated carbon composite carrier includes the following steps: (1) Wash the coconut shell activated carbon and then vacuum-dry it at 80-90 °C. Mix it evenly with KOH and distilled water in a ratio of 5-6 g:1 g:1 mL, dry it at 80 °C, place it in a tubular furnace, heat it up to 800 °C under a nitrogen atmosphere, keep it warm for 1 h, cool it to room temperature, and then wash it with 1 mol / L HCl and deionized water until neutral. Dry it at 60 °C to constant weight, grind it, and pass it through a 80-100 mesh sieve to obtain activated activated carbon; (2) Dissolve PEI in deionized water to prepare a 40 mg / mL PEI solution. Add the activated carbon obtained in step (1) to 50%wt sodium hydroxide solution and ethanol, stir and react at 70 °C for 30 min, add epichlorohydrin, continue to stir and react at 70 °C for 4 h, cool, filter, wash the filter cake with ethanol and deionized water, dry at 50 °C, mix with the PEI solution and DMF, react at 70 °C for 4 h, filter, wash with ethanol, and dry in vacuum to obtain modified activated carbon; (3) Add cellulose to deionized water and disperse it evenly by ultrasonic wave to obtain a cellulose dispersion. Prepare a 4 mmol / mL NaOH solution, add the cellulose dispersion to the NaOH solution and mix well. Dropwise add a 4 mol / L 2-bromoethylamine hydrobromide (2-BEA) solution under stirring at 800 r / min until the final concentration of 2-bromoethylamine hydrobromide in the reaction system is 0.1 g / mL. After the addition is completed, continue to stir for 20 - 30 min, filter, wash the filter cake with deionized water, and dry in vacuum to obtain modified cellulose; (4) Mix the modified activated carbon, modified cellulose and triethylamine in tetrahydrofuran, dropwise add a tetrahydrofuran solution of hexachlorocyclotriphosphazene, stir and react at 50 °C and 150 - 200 rpm for 5 - 6 h, cool to room temperature, filter, wash the filter cake with acetone and deionized water, and dry in vacuum to obtain an activated carbon composite support.

[0006] Further, in step (2), the dosage ratio of the activated carbon, 50%wt sodium hydroxide solution, ethanol and epichlorohydrin is 1 g:3 mL:20 mL:3 mL.

[0007] Further, in step (2), the dosage ratio of the activated carbon, PEI solution and DMF is 0.1 g:10 mL:25 mL.

[0008] Further, in step (3), the cellulose is preferably corn straw cellulose.

[0009] Further, in step (3), the mass concentration of cellulose in the cellulose dispersion in deionized water is 10 mg / mL.

[0010] Further, in step (3), the mass ratio of cellulose to sodium hydroxide is 1:15.

[0011] Further, in step (4), the dosage ratio of the modified activated carbon, modified cellulose, triethylamine, tetrahydrofuran and hexachlorocyclotriphosphazene is 2 - 3 g:1 g:6 - 9 mL:50 - 70 mL:1 - 2 g.

[0012] Further, in step (4), the mass concentration of hexachlorocyclotriphosphazene in the tetrahydrofuran solution of hexachlorocyclotriphosphazene is 50 mg / mL in tetrahydrofuran.

[0013] Further, the present invention also provides a method for preparing the anti-high humidity multi-spectrum protective carbon, comprising the following steps: S1: Take basic copper carbonate and basic zinc carbonate and put them into 20-25% ammonia water, heat and stir to dissolve at 70 °C to obtain impregnating solution A; take ferrous sulfate and cobalt nitrate and add them into 0.1 mol / L sulfuric acid solution, heat and stir to dissolve at 70 °C to obtain impregnating solution B; S2: Immerse the activated carbon composite support into impregnating solution A for 60 min, after impregnation, spread it out evenly and dry it naturally. Under a nitrogen atmosphere, heat it to 120 °C at a rate of 10 °C / min, keep it warm for 1-1.5 h, then heat it to 180 °C at a rate of 10 °C / min, keep it warm for 0.5-1 h, and then heat it to 280 °C at a rate of 10 °C / min, keep it warm for 0.5 h; S3: Immerse the product obtained in step S2 into impregnating solution B for 40 min, spread it out and dry it naturally, and dry it at 120 °C to obtain the anti-high humidity multi-spectrum protective carbon.

[0014] Further, in step S1, the mass concentration of basic copper carbonate in ammonia water is 0.1 g / mL.

[0015] Further, in step S1, the mass concentration of ferrous sulfate in sulfuric acid solution is 50 mg / mL.

[0016] Compared with the prior art, the present invention has the following beneficial effects: The present invention provides a high-humidity-resistant multi-spectrum protective carbon. Through the synergistic effect of composite carrier design and multiple active components, the problems of single protective spectrum of existing protective carbon and performance attenuation in high-humidity environments are effectively solved. The present invention realizes multi-spectrum protection through the synergistic effect of multiple active components and composite carriers. Coconut shell activated carbon is activated by KOH to form a rich pore structure, and the surface is rich in hydroxyl groups. It is modified with epichlorohydrin to graft epoxy groups on the surface of the activated carbon. Through the ring-opening reaction of the epoxy groups with the amino groups of PEI, the activated carbon and PEI materials are compounded to obtain modified activated carbon rich in amino groups. Cellulose is modified with 2-bromoethylamine to introduce amino groups to obtain modified cellulose. The modified cellulose, modified activated carbon and hexachlorocyclotriphosphazene are crosslinked to enhance the adsorption capacity for polar gases, promote the uniform loading of metal salts, and improve the protective performance. The modified activated carbon and modified cellulose are crosslinked through phosphazene bonds to form a three-dimensional network structure containing nitrogen and phosphorus, enhancing the mechanical strength of the carrier, reducing the capillary condensation of water vapor on the surface of the carrier, and inhibiting the excessive adsorption of water. The present invention uses metal salts such as basic copper carbonate, basic zinc carbonate, ferrous sulfate, and cobalt nitrate to prepare an impregnating solution, which forms metal oxides after high-temperature treatment, has a catalytic oxidation effect on toxic gases, and an electron coordination adsorption effect. The multiple metal components cover the removal requirements of different gases, forming a synergistic mechanism of "physical adsorption-chemical catalysis-functional group reaction", significantly improving the protection time for various gases such as benzene, ammonia, hydrogen sulfide, sulfur dioxide, cyanogen chloride, and phosgene. The step-by-step impregnation process is used to further ensure the uniform distribution of metal components on the surface and in the pores of the carrier, improve the utilization rate of active sites, and avoid performance attenuation caused by local agglomeration. In addition, the metal oxides cover the surface of the carrier, which can form a "hydrophobic barrier" to reduce the direct interaction between water molecules and the activated carbon matrix, ensuring that the adsorption sites of toxic gases are not occupied by water. The present invention effectively reduces the influence of high-humidity environments on adsorption performance through surface modification of the carrier and pore structure regulation. The pore distribution not only ensures the diffusion channels of toxic gases but also partially fills the micropores through metal salt impregnation, reducing the occupation of micropores by water vapor, enabling the carrier to still retain an effective adsorption space in high-humidity environments, and achieving a double improvement in multi-spectrum protection and anti-humidity stability. Description of the Drawings [[ID=,4]]

[0017] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only those of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0018] Figure 1 It is the scanning electron micrograph of the modified activated carbon described in Example 1 of the present invention; Figure 2For the anti-moisture effect of the protective carbon described in Embodiments 1-3 and Comparative Examples 1-3 of the present invention. Detailed implementation manners

[0019] To make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with specific embodiments. However, the present invention is not limited to the following embodiments. It should be noted that unless otherwise specified, the chemical reagents involved in the present invention are purchased through commercial channels.

[0020] Embodiment 1: A high-moisture-resistant multi-spectrum protective carbon, the preparation raw materials of which include the following components in parts by weight: 50 parts of activated carbon composite carrier, 10 parts of basic copper carbonate, 5 parts of basic zinc carbonate, 5 parts of ferrous sulfate, and 5 parts of cobalt nitrate.

[0021] The preparation method of the activated carbon composite carrier includes the following steps: (1) Wash the coconut shell activated carbon and dry it in vacuum at 90 °C, mix it evenly with KOH and distilled water in a ratio of 6 g:1 g:1 mL, dry it at 80 °C, place it in a tubular furnace, heat it up to 800 °C under a nitrogen atmosphere, keep it warm for 1 h, cool it to room temperature, wash it with 1 mol / L HCl and deionized water until neutral, dry it at 60 °C to constant weight, grind it through a 100-mesh sieve to obtain activated activated carbon; (2) Dissolve PEI in deionized water to prepare a 40 mg / mL PEI solution. Add 1 g of the activated activated carbon obtained in step (1) to 3 mL of 50%wt sodium hydroxide solution and 20 mL of ethanol, stir and react at 70 °C for 30 min, add 3 mL of epichlorohydrin, continue to stir and react at 70 °C for 4 h, cool, filter, wash the filter cake with ethanol and deionized water, dry it at 50 °C, mix it with 100 mL of PEI solution and 250 mL of DMF, react at 70 °C for 4 h, filter, wash with ethanol, and dry in vacuum to obtain modified activated carbon; (3) Add 1 g of cellulose to 100 mL of deionized water and disperse it evenly by ultrasonic wave to obtain a cellulose dispersion. Prepare a 4 mmol / mL NaOH solution with 15 g of NaOH, add the cellulose dispersion to the NaOH solution and mix well. Dropwise add a 4 mol / L 2-bromoethylamine hydrobromide solution dropwise under stirring at 800 r / min until the final concentration of 2-bromoethylamine hydrobromide in the reaction system is 0.1 g / mL. After the addition is completed, continue to stir for 30 min, filter, wash the filter cake with deionized water, and dry in vacuum to obtain modified cellulose; (4) Add 2 g of hexachlorocyclotriphosphazene to 40 mL of tetrahydrofuran and mix well to prepare a tetrahydrofuran solution of hexachlorocyclotriphosphazene. Add 3 g of modified activated carbon, 1 g of modified cellulose, and 9 mL of triethylamine to 70 mL of tetrahydrofuran and mix well. Slowly dropwise add the tetrahydrofuran solution of hexachlorocyclotriphosphazene, and stir and react at 50 °C and 200 rpm for 6 h. Cool to room temperature, filter by suction, wash the filter cake with acetone and deionized water, and dry under vacuum to obtain an activated carbon composite support.

[0022] This example also provides a method for preparing the anti-high humidity multi-spectrum protective carbon, including the following steps: S1: Take 10 g of basic copper carbonate and 5 g of basic zinc carbonate and put them into 100 mL of 25% ammonia water, heat and stir to dissolve at 70 °C to obtain impregnating solution A; take 5 g of ferrous sulfate and 5 g of cobalt nitrate and add them to 100 mL of 0.1 mol / L sulfuric acid solution, heat and stir to dissolve at 70 °C to obtain impregnating solution B; S2: Immerse 50 g of the activated carbon composite support in impregnating solution A for 60 min, spread it evenly after impregnation and dry it naturally in air. Under a nitrogen atmosphere, heat it to 120 °C at a rate of 10 °C / min, keep it warm for 1.5 h, then heat it to 180 °C at a rate of 10 °C / min, keep it warm for 1 h, and then heat it to 280 °C at a rate of 10 °C / min, keep it warm for 0.5 h; S3: Immerse the product obtained in step S2 in impregnating solution B for 40 min, spread it out and dry it naturally, and dry it at 120 °C to obtain the anti-high humidity multi-spectrum protective carbon.

[0023] Example 2: An anti-high humidity multi-spectrum protective carbon, the preparation raw materials include the following components in parts by weight: 30 parts of activated carbon composite support, 6 parts of basic copper carbonate, 3 parts of basic zinc carbonate, 3 parts of ferrous sulfate, and 3 parts of cobalt nitrate.

[0024] The preparation method of the activated carbon composite support includes the following steps: (1) Wash the coconut shell activated carbon and dry it under vacuum at 80 °C, mix it evenly with KOH and distilled water in a ratio of 5 g:1 g:1 mL, dry it at 80 °C, place it in a tubular furnace, heat it to 800 °C under a nitrogen atmosphere, keep it warm for 1 h, cool to room temperature, wash it with 1 mol / L HCl and deionized water until neutral, dry it at 60 °C to constant weight, grind it and pass through an 80-mesh sieve to obtain activated carbon; (2) Dissolve PEI in deionized water to prepare a 40 mg / mL PEI solution. Add 1 g of the activated carbon obtained in step (1) to 3 mL of 50%wt sodium hydroxide solution and 20 mL of ethanol, stir and react at 70 °C for 30 min, add 3 mL of epichlorohydrin, continue to stir and react at 70 °C for 4 h, cool, filter by suction, wash the filter cake with ethanol and deionized water, dry at 50 °C, mix with 100 mL of PEI solution and 250 mL of DMF, react at 70 °C for 4 h, filter, wash with ethanol, and dry under vacuum to obtain modified activated carbon; (3) Add 1 g of cellulose to 100 mL of deionized water and disperse it evenly by ultrasonic treatment to obtain a cellulose dispersion. Prepare a 4 mmol / mL NaOH solution with 15 g of NaOH, add the cellulose dispersion to the NaOH solution and mix well. Dropwise add a 4 mol / L 2-bromoethylamine hydrobromide solution under stirring at 800 r / min until the final concentration of 2-bromoethylamine hydrobromide in the reaction system is 0.1 g / mL. After the addition is complete, continue to stir for 20 min, filter by suction, wash the filter cake with deionized water, and dry under vacuum to obtain modified cellulose; (4) Add 1 g of hexachlorocyclotriphosphazene to 20 mL of tetrahydrofuran and mix well to prepare a tetrahydrofuran solution of hexachlorocyclotriphosphazene. Add 2 g of modified activated carbon, 1 g of modified cellulose, and 6 mL of triethylamine to 50 mL of tetrahydrofuran and mix well. Dropwise add the tetrahydrofuran solution of hexachlorocyclotriphosphazene, stir and react at 50 °C and 150 rpm for 5 h, cool to room temperature, filter by suction, wash the filter cake with acetone and deionized water, and dry under vacuum to obtain an activated carbon composite support.

[0025] This example also provides a method for preparing the anti-high-humidity multi-spectrum protective carbon, including the following steps: S1: Take 6 g of basic copper carbonate and 3 g of basic zinc carbonate and place them in 60 mL of 20% ammonia water, heat and stir to dissolve at 70 °C to obtain impregnation solution A; take 3 g of ferrous sulfate and 3 g of cobalt nitrate and add them to 60 mL of 0.1 mol / L sulfuric acid solution, heat and stir to dissolve at 70 °C to obtain impregnation solution B; S2: Immerse 30 g of the activated carbon composite support in impregnation solution A for 60 min, after impregnation, spread it out evenly and dry it naturally. Under a nitrogen atmosphere, heat it to 120 °C at a rate of 10 °C / min, keep it warm for 1 h, then heat it to 180 °C at a rate of 10 °C / min, keep it warm for 0.5 h, and then heat it to 280 °C at a rate of 10 °C / min, keep it warm for 0.5 h; S3: Immerse the product obtained in step S2 in impregnation solution B for 40 min, spread it out and dry it naturally, and dry it at 120 °C to obtain the anti-high-humidity multi-spectrum protective carbon.

[0026] Example 3: A multi-spectrum protective carbon resistant to high humidity, the preparation raw materials include the following components in parts by weight: 40 parts of activated carbon composite carrier, 8 parts of basic copper carbonate, 4 parts of basic zinc carbonate, 4 parts of ferrous sulfate, and 4 parts of cobalt nitrate.

[0027] The preparation method of the activated carbon composite carrier includes the following steps: (1) Wash the coconut shell activated carbon and dry it in vacuum at 85 °C. Mix it evenly with KOH and distilled water in a ratio of 5.5 g:1 g:1 mL, dry it at 80 °C, place it in a tubular furnace, heat it to 800 °C under a nitrogen atmosphere, keep it warm for 1 h, cool it to room temperature, wash it with 1mol / L HCl and deionized water until neutral, dry it at 60 °C to constant weight, grind it and pass through an 80-100 mesh sieve to obtain activated activated carbon; (2) Dissolve PEI in deionized water to prepare a 40 mg / mL PEI solution. Add 1 g of the activated activated carbon obtained in step (1) to 3 mL of 50%wt sodium hydroxide solution and 20 mL of ethanol, stir and react at 70 °C for 30 min, add 3 mL of epichlorohydrin, continue to stir and react at 70 °C for 4 h, cool, filter, wash the filter cake with ethanol and deionized water, dry it at 50 °C, mix it with 100 mL of PEI solution and 250 mL of DMF, react at 70 °C for 4 h, filter, wash with ethanol, and dry in vacuum to obtain modified activated carbon; (3) Add 1 g of cellulose to 100 mL of deionized water and disperse it evenly by ultrasonic to obtain a cellulose dispersion. Prepare a 4 mmol / mL NaOH solution with 15 g of NaOH, add the cellulose dispersion to the NaOH solution and mix well. Dropwise add a 4 mol / L 2-bromoethylamine hydrobromide solution under stirring at 800 r / min until the final concentration of 2-bromoethylamine hydrobromide in the reaction system is 0.1 g / mL. After dropping, continue to stir for 25 min, filter, wash the filter cake with deionized water, and dry in vacuum to obtain modified cellulose; (4) Add 1.5 g of hexachlorocyclotriphosphazene to 30 mL of tetrahydrofuran and mix well to prepare a tetrahydrofuran solution of hexachlorocyclotriphosphazene. Add 2.5 g of modified activated carbon, 1 g of modified cellulose and 8 mL of triethylamine to 60 mL of tetrahydrofuran and mix well. Dropwise add the tetrahydrofuran solution of hexachlorocyclotriphosphazene, stir and react at 50 °C and 180 rpm for 5.5 h, cool to room temperature, filter, wash the filter cake with acetone and deionized water, and dry in vacuum to obtain the activated carbon composite carrier.

[0028] This example also provides a preparation method of the multi-spectrum protective carbon resistant to high humidity, including the following steps: S1: Take 8 g of basic copper carbonate and 4 g of basic zinc carbonate, put them into 80 mL of 20 - 25% ammonia water, heat and stir to dissolve at 70 °C to obtain impregnating solution A; take 4 g of ferrous sulfate and 4 g of cobalt nitrate, add them into 80 mL of 0.1 mol / L sulfuric acid solution, heat and stir to dissolve at 70 °C to obtain impregnating solution B. S2: Immerse 40 g of the activated carbon composite support into impregnating solution A for 60 min. After impregnation, spread it out evenly and dry it naturally. Under a nitrogen atmosphere, heat it to 120 °C at a rate of 10 °C / min, keep it warm for 1.2 h, then heat it to 180 °C at a rate of 10 °C / min, keep it warm for 0.8 h, and then heat it to 280 °C at a rate of 10 °C / min, keep it warm for 0.5 h. S3: Immerse the product obtained in step S2 into impregnating solution B for 40 min, spread it out and dry it naturally, and dry it at 120 °C to obtain the high - humidity - resistant multi - spectrum protective carbon.

[0029] The difference between Comparative Example 1 and Example 1 is only that the activated carbon composite support is used instead of the high - humidity - resistant multi - spectrum protective carbon.

[0030] The difference between Comparative Example 2 and Example 1 is only that the modified activated carbon is used instead of the high - humidity - resistant multi - spectrum protective carbon.

[0031] The difference between Comparative Example 3 and Example 1 is only that the activated activated carbon is used instead of the high - humidity - resistant multi - spectrum protective carbon.

[0032] Experimental Example 1: Evaluate the various protective performances and air flow resistances of the samples prepared in Examples 1 - 3 and Comparative Examples 1 - 3. The evaluation conditions are: test temperature 25 °C, relative humidity 50%RH, 95%RH, air flow specific velocity 0.25 L / min×cm 2 , bed height 2 cm, and the concentrations of the test gases in the raw material gas are as follows: benzene 1000 ppm; sulfur dioxide 1000 ppm; hydrogen sulfide 1000 ppm; cyanogen chloride 1600 ppm; ammonia 1000 ppm; phosgene 5000 ppm. The test method for phosgene adopts GJB 3662 - 1999 "Test Methods for Military Filtering Gas Masks", and the evaluation methods for the other gases are based on GB 2890 - 2009, "Respiratory Protection - Self - Priming Filtering Gas Masks". The test results of the protective time for each gas are shown in Table 1.

[0033] Table 1:

[0034] Table 1 results show that the multi-spectrum protective carbon of the present invention all has certain high-humidity resistance protective performance. Among them, the comprehensive protective performance of Examples 1-3 is better than that of Comparative Examples 1-3. In Comparative Example 1, an activated carbon composite support was used to replace the high-humidity resistant multi-spectrum protective carbon without metal impregnation, and the protective performance decreased; in Comparative Example 2, modified activated carbon was used to replace the high-humidity resistant multi-spectrum protective carbon, and the protective ability decreased; in Comparative Example 3, activated activated carbon was used to replace the high-humidity resistant multi-spectrum protective carbon, and the protection against toxic gases decreased. Each multi-spectrum protective carbon still maintains good adsorption ability in a high-humidity environment, indicating that its material design has good performance in anti-humidity stability.

[0035] Experimental Example 2: The modified activated carbon prepared in Example 1 was observed and photographed with a scanning electron microscope, and the scanning electron micrograph is as Figure 1 shown.

[0036] Figure 1 The results show that the modified activated carbon prepared in Example 1 contains a large number of pore structures, which is beneficial to subsequent treatment and the loading of active components, is beneficial to the adsorption of toxic gases, and can effectively carry out gas protection through the synergistic action of metal catalysis and physical adsorption.

[0037] Experimental Example 3: The samples prepared in Examples 1-3 and Comparative Examples 1-3 were tested. Groups of materials with the same volume were respectively placed in a closed container with a relative humidity of RH100% and adsorbed for 24 h. By weighing the weight gain of the samples, the saturated water vapor adsorption amount of each group of materials was obtained, and the results are as Figure 2 shown.

[0038] Figure 2 The results show that the saturated water vapor adsorption amounts of the groups of Examples 1-3 are significantly lower than those of Comparative Examples 1-3. The composite supports of Examples 1-3 were impregnated with metal salts, which can efficiently load active components. The pores may be partially blocked, and the metal compounds cover the surface, which can inhibit the competitive adsorption of water on the pores in a high-humidity environment, and the water absorption rate is the lowest; in Comparative Example 1, an activated carbon composite support was used to replace the high-humidity resistant multi-spectrum protective carbon without metal impregnation, and the water absorption is higher; in Comparative Example 2, modified activated carbon was used to replace the high-humidity resistant multi-spectrum protective carbon, and modified activated carbon was not cross-linked with modified cellulose, and the moisture resistance decreased; in Comparative Example 3, it was only activated by KOH, with a high porosity but fewer surface functional groups and lower hydrophilicity. The above results show that the multi-spectrum protective carbon of the present invention has good anti-humidity effect.

[0039] Those of ordinary skill in the art should understand that: the discussion of any above embodiment is only exemplary, and is not intended to imply that the scope of the present invention is limited to these examples; under the idea of the present invention, the technical features between the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations in different aspects of the present invention as described above, and they are not provided in detail for the sake of brevity.

Claims

1. A high-humidity-resistant multi-spectrum protective carbon, characterized in that, The preparation raw materials include the following components in parts by weight: 30-50 parts of activated carbon composite carrier, 6-10 parts of basic copper carbonate, 3-5 parts of basic zinc carbonate, 3-5 parts of ferrous sulfate, and 3-5 parts of cobalt nitrate; The preparation method of the activated carbon composite carrier includes the following steps: (1) Wash and dry the coconut shell activated carbon, mix it with KOH and distilled water, dry it by baking, heat it up to 800 °C, keep it warm, wash it after cooling, dry it, and grind it to obtain activated carbon; (2) Prepare a 40 mg / mL PEI solution. Add the activated carbon obtained in step (1) to 50%wt sodium hydroxide solution and ethanol, stir, add epichlorohydrin, stir, filter by suction, wash, dry, mix and react with the PEI solution and DMF, filter, wash, and dry to obtain modified activated carbon; (3) Disperse cellulose in deionized water to obtain a cellulose dispersion. Prepare a 4 mmol / mL NaOH solution, mix the cellulose dispersion and the NaOH solution, dropwise add 2-BEA solution under stirring, stir, filter by suction, wash, and dry to obtain modified cellulose; (4) Mix the modified activated carbon, modified cellulose, and triethylamine in tetrahydrofuran, dropwise add a tetrahydrofuran solution of hexachlorocyclotriphosphazene, stir and react, cool, filter by suction, wash, and dry to obtain an activated carbon composite carrier.

2. The anti-high-humidity multi-spectrum protective carbon according to claim 1, characterized in that, In step (2), the dosage ratio of the activated carbon, 50%wt sodium hydroxide solution, ethanol, and epichlorohydrin is 1 g:3 mL:20 mL:3 mL; the dosage ratio of the activated carbon, PEI solution, and DMF is 0.1 g:10 mL:25 mL.

3. The anti-high humidity multi-spectrum protective carbon according to claim 2, characterized in that In step (3), the mass concentration of cellulose in the cellulose dispersion in deionized water is 10 mg / mL; the mass ratio of cellulose to sodium hydroxide is 1:

15.

4. The anti-high-humidity multi-spectrum protective carbon according to claim 3, wherein In step (4), the dosage ratio of the modified activated carbon, modified cellulose, triethylamine, tetrahydrofuran, and hexachlorocyclotriphosphazene is 2-3 g:1 g:6-9 mL:50-70 mL:1-2 g; the mass concentration of hexachlorocyclotriphosphazene in the tetrahydrofuran solution of hexachlorocyclotriphosphazene in tetrahydrofuran is 50 mg / mL.

5. A method for preparing the high-humidity-resistant multi-spectrum protective carbon according to any one of claims 1-4, characterized in that, It includes the following steps: S1: Take basic copper carbonate and basic zinc carbonate, put them into ammonia water and heat to dissolve to obtain impregnation solution A; take ferrous sulfate and cobalt nitrate, add them to sulfuric acid solution, and heat to dissolve to obtain impregnation solution B; S2: Immerse the activated carbon composite carrier in impregnation solution A, air-dry it, and keep it warm at 120 °C, 180 °C, and 280 °C under a nitrogen atmosphere; S3: Immerse the product obtained in step S2 in impregnation solution B, air-dry it, and dry it by baking to obtain a high-humidity-resistant multi-spectrum protective carbon.

Images