Long-acting filter material for gas mask filter cartridge and preparation method of long-acting filter material

Abstract

The invention discloses a long-acting filter material used in a gas mask filter cartridge and a preparation method of the long-acting filter material, and belongs to the technical field of gas mask adsorption materials, the key point of the technical scheme is that the preparation method of the long-acting filter material used in the gas mask filter cartridge comprises the following preparation steps: S1, preparing a long-acting filter material at room temperature; the preparation method comprises the following steps: putting copper nitrate trihydrate powder and a nano additive into deionized water, and performing ultrasonic dispersion to dissolve the copper nitrate trihydrate powder and the nano additive; s2, metal organic framework powder is added into the solution obtained in the step S1, stirring and centrifugal drying are carried out, a modified metal organic framework material is obtained, copper nitrate trihydrate accounts for 10-15% of the weight of the metal organic framework powder, and a nano additive accounts for 2-6% of the weight of the metal organic framework powder; and S3, grinding the modified metal organic framework material obtained in the step S2, and calcining to obtain the filter material. The effects of improving the adsorption capacity of the gas mask on toxic gas and reducing the inspiration resistance of the gas mask are achieved.

Description

Technical Field

[0001] The invention relates to the technical field of gas mask adsorption materials, in particular to a long-acting filter material used in a gas mask filter box and a preparation method thereof. Background Art

[0002] A gas mask is a protective device used to protect the respiratory organs, eyes and face from direct damage by toxic agents, radioactive particles and aerosols, among which filter-type gas masks are widely used.

[0003] A gas mask is generally composed of a mask and a canister. Its protective effect is mainly achieved by filtering toxic and harmful substances through a filter box or canister. The canister contains two layers: a filling layer and a filter layer. The filling layer is filled with adsorbent materials for adsorbing harmful gases, and the filter layer is filled with fiber materials such as asbestos, cellulose, cotton fiber, and glass fiber for filtering harmful aerosols. The anti-toxic ability of the canister in a gas mask mainly depends on the adsorption protective materials in the filling layer. These protective materials can effectively block toxic substances such as poison agents, radioactive dust, and smoke by physical and chemical adsorption.

[0004] The commonly used adsorption material for gas masks is activated carbon. In order to make activated carbon able to adsorb more types of toxic gases, the activated carbon needs to be modified with acid, alkali, and metal salts respectively to adsorb toxic gases of different properties in the environment. However, after the activated carbon is modified with acid and alkali respectively, the acid and base functional groups on the activated carbon will react with each other, thereby reducing the reactivity with toxic gases and not increasing the adsorption width of the activated carbon. In order to increase the adsorption amount, more activated carbon needs to be added to the mask, which makes the gas mask bulky. The addition of too much activated carbon makes the inhalation resistance of the gas mask too large. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a long-lasting filter material for use in a gas mask filter box and a preparation method thereof, which can improve the gas mask's adsorption capacity for toxic gases while reducing the gas mask's inhalation resistance.

[0006] The first aspect of the present invention is to provide a method for preparing a long-lasting filter material for a gas mask filter box, using the following technical scheme: A method for preparing a long-lasting filter material for a gas mask filter box comprises the following preparation steps: S1. Place copper nitrate trihydrate powder and nano additives in deionized water at room temperature, and dissolve them by ultrasonic dispersion. Then; S2. Add metal organic framework powder to the solution obtained in step S1, stir, and centrifuge to obtain a modified metal organic framework material, wherein the copper nitrate trihydrate accounts for 10-15% of the weight of the metal organic framework powder, and the nano additive accounts for 2-6% of the weight of the metal organic framework powder; S3, grinding the modified metal organic framework material obtained in step S2 and then calcining it to obtain a filter material.

[0007] Preferably, the step S1 further comprises manganese dioxide, and the weight ratio of the manganese dioxide to copper nitrate trihydrate is (0.6-0.9):1.

[0008] Preferably, the metal organic framework powder is obtained by the following preparation method: L-aspartic acid is dissolved in a sodium hydroxide solution, and then a copper nitrate solution is added and stirred to react for 2.5-3.5 hours. After the reaction is completed, the solid product is centrifuged to obtain a solid product, and then the solid product is washed, dried at 100°C for 24 hours, and then crushed to obtain the metal organic framework powder.

[0009] Preferably, the weight ratio of L-aspartic acid to copper nitrate is 1:(1.8-2.2).

[0010] Preferably, the metal organic framework powder further comprises an adsorbent, and the amount of the adsorbent added is 3-7% of the weight of the L-aspartic acid.

[0011] Preferably, the adsorbent is obtained by the following preparation method: sodium alginate and chitosan are mixed in a weight ratio of 3:2 to prepare a 3% aqueous solution, ethanol is added, and a gel is precipitated by wet spinning. The precipitated gel is further solidified in a 5% copper nitrate aqueous solution, dried, and then placed in a furnace for carbonization at 800°C for 2 hours to obtain the adsorbent after crushing.

[0012] Preferably, the drying temperature is 60±5°C.

[0013] Preferably, the nano additive is nano titanium dioxide.

[0014] The second aspect of the present invention is to provide a long-lasting filter material in a gas mask filter box obtained by the above-mentioned method for preparing the long-lasting filter material in a gas mask filter box.

[0015] In summary, the present invention has the following beneficial effects: 1. In the present application, after the metal organic framework material is mixed with copper nitrate and nano additives and calcined, the adsorption capacity of the metal organic framework material to toxic gases is effectively increased, thereby reducing the amount of long-term filter material added to the filter box. The reduction in the amount of filter material added can reduce the inhalation resistance of the gas mask and provide better protection for the user. In addition, due to the reduction in the amount of long-term filter material added, the weight of the filter box can reach a range of 240±10g, so that the weight of the gas mask can be further reduced.

[0016] 2. The addition of adsorbents in the preparation of metal-organic framework materials can increase the active adsorption sites of the metal-organic framework materials, and at the same time, it can also make the final long-lasting filter material have water vapor resistance and stability, thereby increasing the service life of the long-lasting filter material. DETAILED DESCRIPTION

[0017] The present invention is further described in detail below with reference to the embodiments.

[0018] The raw materials used in this application are all commercially available.

[0019] Preparation Example 1 A preparation method of a metal organic framework material comprises the following preparation steps: dissolving 10g of L-aspartic acid in 20mL of sodium hydroxide solution, then adding 200mL of copper nitrate solution (adding 18g of copper nitrate to 182mL of water), magnetically stirring and reacting for 2.5h, centrifuging after the reaction to obtain a solid product, then washing the solid product multiple times with deionized water and ethanol water (the volume ratio of ethanol to water is 1:1), drying at 100°C for 24h after washing, and then crushing to obtain a metal organic framework powder.

[0020] Preparation Example 2 A preparation method of a metal organic framework material comprises the following preparation steps: dissolving 10g of L-aspartic acid in 20mL of sodium hydroxide solution, then adding 200mL of copper nitrate solution (adding 20g of copper nitrate to 180mL of water) and magnetically stirring to react for 3h, centrifuging to obtain a solid product after the reaction is completed, then washing the solid product multiple times with deionized water and ethanol water (the volume ratio of ethanol to water is 1:1), drying at 100°C for 24h after washing, and then crushing to obtain a metal organic framework powder.

[0021] Preparation Example 3 A preparation method of a metal organic framework material comprises the following preparation steps: dissolving 10 g of L-aspartic acid in 20 mL of sodium hydroxide solution, then adding 200 mL of copper nitrate solution (adding 22 g of copper nitrate to 178 mL of water), magnetically stirring and reacting for 3.5 hours, centrifuging after the reaction to obtain a solid product, then washing the solid product multiple times with deionized water and ethanol water (the volume ratio of ethanol to water is 1:1), drying at 100°C for 24 hours after washing, and then crushing to obtain a metal organic framework powder.

[0022] Preparation Example 4 A preparation method of a metal organic framework material comprises the following preparation steps: dissolving 10g of L-aspartic acid in 20mL of sodium hydroxide solution, adding 0.3g of an adsorbent at the same time, ultrasonically shaking for 30min, then adding 200mL of copper nitrate solution (adding 20g of copper nitrate to 180mL of water), magnetically stirring and reacting for 3h, centrifuging after the reaction to obtain a solid product, then washing the solid product with deionized water and ethanol water (the volume ratio of ethanol to water is 1:1) for multiple times, drying at 100°C for 24h after washing, and then crushing to obtain a metal organic framework powder; The adsorbent is prepared by the following method: sodium alginate and chitosan are mixed in a weight ratio of 3:2 to prepare a 3% aqueous solution, ethanol is added, and a gel is precipitated by wet spinning. The precipitated gel is further solidified in a 5% copper nitrate aqueous solution, dried at 60±5°C, and then placed in a Maboise furnace for carbonization at 800°C for 2 hours to obtain the adsorbent after being crushed.

[0023] Preparation Example 5 A preparation method of a metal organic framework material comprises the following preparation steps: dissolving 10g of L-aspartic acid in 20mL of sodium hydroxide solution, adding 0.5g of an adsorbent, and then ultrasonically shaking for 30min, then adding 200mL of copper nitrate solution (adding 20g of copper nitrate to 180mL of water), and magnetically stirring to react for 3h, and after the reaction is completed, centrifuging to obtain a solid product, and then washing the solid product with deionized water and ethanol water (the volume ratio of ethanol to water is 1:1) for multiple times, and drying at 100°C for 24h after washing, and then crushing to obtain a metal organic framework powder; The adsorbent is prepared by the following method: sodium alginate and chitosan are mixed in a weight ratio of 3:2 to prepare a 3% aqueous solution, ethanol is added, and a gel is precipitated by wet spinning. The precipitated gel is further solidified in a 5% copper nitrate aqueous solution, dried at 60±5°C, and then placed in a Maboise furnace for carbonization at 800°C for 2 hours to obtain the adsorbent after being crushed.

[0024] Preparation Example 6 A preparation method of a metal organic framework material comprises the following preparation steps: dissolving 10g of L-aspartic acid in 20mL of sodium hydroxide solution, adding 0.7g of an adsorbent at the same time, ultrasonically shaking for 30min, then adding 200mL of copper nitrate solution (adding 20g of copper nitrate to 180mL of water), magnetically stirring and reacting for 3h, centrifuging after the reaction to obtain a solid product, then washing the solid product with deionized water and ethanol water (the volume ratio of ethanol to water is 1:1) for multiple times, drying at 100°C for 24h after washing, and then crushing to obtain a metal organic framework powder; The adsorbent is prepared by the following method: sodium alginate and chitosan are mixed in a weight ratio of 3:2 to prepare a 3% aqueous solution, ethanol is added, and a gel is precipitated by wet spinning. The precipitated gel is further solidified in a 5% copper nitrate aqueous solution, dried at 60±5°C, and then placed in a Maboise furnace for carbonization at 800°C for 2 hours to obtain the adsorbent after being crushed.

[0025] Example 1 A method for preparing a long-lasting filter material for a gas mask filter box comprises the following preparation steps: S1. At room temperature, 0.1 kg of copper nitrate trihydrate powder and 0.02 kg of nano titanium dioxide were placed in deionized water and ultrasonically dispersed to dissolve them. Then; S2, adding 1 kg of the metal organic framework powder obtained in Preparation Example 1 to the solution obtained in step S1, stirring, and centrifugally drying to obtain a modified metal organic framework material, wherein copper nitrate trihydrate accounts for 10% of the weight of the metal organic framework powder, and the nano additive accounts for 2% of the weight of the metal organic framework powder; S3, grinding the modified metal organic framework material obtained in step S2, and calcining it at a temperature of 500° C. for 2 h to obtain a filter material.

[0026] Example 2 A method for preparing a long-lasting filter material for a gas mask filter box comprises the following preparation steps: S1. At room temperature, 0.12 kg of copper nitrate trihydrate powder and 0.04 kg of nano titanium dioxide were placed in deionized water and ultrasonically dispersed to dissolve them. Then; S2, adding 1 kg of the metal organic framework powder obtained in Preparation Example 1 to the solution obtained in step S1, stirring, and centrifugally drying to obtain a modified metal organic framework material, wherein copper nitrate trihydrate accounts for 12% of the weight of the metal organic framework powder, and the nano additive accounts for 4% of the weight of the metal organic framework powder; S3, grinding the modified metal organic framework material obtained in step S2, and calcining it at a temperature of 500° C. for 2 h to obtain a filter material.

[0027] Example 3 A method for preparing a long-lasting filter material for a gas mask filter box comprises the following preparation steps: S1. At room temperature, 0.15 kg of copper nitrate trihydrate powder and 0.06 kg of nano-titanium dioxide were placed in deionized water and ultrasonically dispersed to dissolve them. Then; S2, adding 1 kg of the metal organic framework powder obtained in Preparation Example 1 to the solution obtained in step S1, stirring, and centrifugally drying to obtain a modified metal organic framework material, wherein copper nitrate trihydrate accounts for 15% of the weight of the metal organic framework powder, and the nano additive accounts for 6% of the weight of the metal organic framework powder; S3, grinding the modified metal organic framework material obtained in step S2, and calcining it at a temperature of 500° C. for 2 h to obtain a filter material.

[0028] Example 4 A method for preparing a long-lasting filter material for a gas mask filter box comprises the following preparation steps: S1. At room temperature, 0.12 kg of copper nitrate trihydrate powder, 0.04 kg of nano titanium dioxide, and 0.072 kg of manganese dioxide were placed in deionized water and ultrasonically dispersed to dissolve them, and then; S2, adding 1 kg of the metal organic framework powder obtained in Preparation Example 1 to the solution obtained in step S1, stirring, and centrifugally drying to obtain a modified metal organic framework material, wherein copper nitrate trihydrate accounts for 12% of the weight of the metal organic framework powder, and the nano additive accounts for 4% of the weight of the metal organic framework powder; S3, grinding the modified metal organic framework material obtained in step S2, and calcining it at a temperature of 500° C. for 2 h to obtain a filter material.

[0029] Example 5 A method for preparing a long-lasting filter material for a gas mask filter box comprises the following preparation steps: S1. At room temperature, 0.12 kg of copper nitrate trihydrate powder, 0.04 kg of nano titanium dioxide, and 0.108 kg of manganese dioxide were placed in deionized water and ultrasonically dispersed to dissolve them, and then; S2, adding 1 kg of the metal organic framework powder obtained in Preparation Example 1 to the solution obtained in step S1, stirring, and centrifugally drying to obtain a modified metal organic framework material, wherein copper nitrate trihydrate accounts for 12% of the weight of the metal organic framework powder, and the nano additive accounts for 4% of the weight of the metal organic framework powder; S3, grinding the modified metal organic framework material obtained in step S2, and calcining it at a temperature of 500° C. for 2 h to obtain a filter material.

[0030] Example 6 A method for preparing a long-lasting filter material for a gas mask filter box, which is different from Example 4 in that the metal organic framework powder adopts the metal organic framework powder obtained in Preparation Example 2.

[0031] Example 7 A method for preparing a long-lasting filter material for a gas mask filter box, which is different from Example 4 in that the metal organic framework powder adopts the metal organic framework powder obtained in Preparation Example 3.

[0032] Example 8 A method for preparing a long-lasting filter material for a gas mask filter box, which is different from Example 4 in that the metal organic framework powder adopts the metal organic framework powder obtained in Preparation Example 4.

[0033] Example 9 A method for preparing a long-lasting filter material for a gas mask filter box, which is different from Example 4 in that the metal organic framework powder adopts the metal organic framework powder obtained in Preparation Example 5.

[0034] Example 10 A method for preparing a long-lasting filter material for a gas mask filter box, which is different from Example 4 in that the metal organic framework powder adopts the metal organic framework powder obtained in Preparation Example 6.

[0035] Comparative Example 1 A method for preparing a long-lasting filter material for a gas mask filter box, which is different from Example 2 in that the long-lasting filter material only uses the metal organic framework powder obtained in Preparation Example 1.

[0036] Comparative Example 2 A method for preparing a long-lasting filter material for a gas mask filter box, which is different from Example 2 in that nano titanium dioxide is missing in step S1, and the rest is the same as Example 2.

[0037] Comparative Example 3 A method for preparing a long-lasting filter material for a gas mask filter box, which is different from Example 2 in that the added amount of nano titanium dioxide is 10% of the weight of the metal organic framework powder, that is, the added amount of nano titanium dioxide is 0.1 kg, and the rest is the same as Example 2.

[0038] Performance Testing The long-lasting filter materials obtained in the above embodiments and comparative examples were applied to the filter box of the gas mask to test the inhalation resistance, filtration efficiency and filtration time in accordance with the relevant provisions of GB2890-2022 "Respiratory Protection Self-priming Filtering Gas Mask". The test results are shown in Table 1.

[0039] The medium concentration of cyclohexane is 3.5 mg / L, and the protection time specified in GB2890-2022 is ≥60 min; The medium concentration of sulfur dioxide is 2.7 mg / L, and the protection time specified in GB2890-2022 is ≥25 minutes; The medium concentration of carbon monoxide is 5.8mg / L, and the protection time specified in GB2890-2022 is ≥20min Table 1 Performance test results of various long-term filter materials From the table above we can see that: After the long-lasting filter material obtained in Examples 1-3 of the present application is applied to the filter box of the gas mask, the suction pressure is less than 100Pa, the filtration efficiency for sulfur dioxide, carbon monoxide and cyclohexane is more than 99.5%, and the protection time is greater than the minimum standard specified in the GB2890-2022 standard. It can be seen that the long-lasting filter material obtained in the present application has a good adsorption effect on toxic gases.

[0040] Compared with Example 2, after manganese dioxide is added in step S1, under the condition of the same loading amount, the inhalation pressure of the gas mask is further reduced, and the protection time against sulfur dioxide, carbon monoxide and cyclohexane is further improved. It can be seen that the addition of manganese dioxide can further improve the adsorption capacity of the filter material for toxic gases.

[0041] When the adsorbent is added to the metal organic framework material, the long-acting filter material obtained by using Examples 8-10 is compared with the long-acting filter material obtained by Example 4. Under the condition of the same loading amount, the suction pressure is further reduced, and the protection time for sulfur dioxide, carbon monoxide and cyclohexane is further improved. It can be seen that the addition of the adsorbent to the metal organic framework material can effectively improve the adsorption capacity of the gas mask for toxic gases.

[0042] Compared with Example 2, when the long-acting filter material only uses the metal organic framework material obtained in Preparation Example 1, under the same load, the inhalation pressure of the gas mask of Example 1 is significantly increased compared with that of Example 2, and the protection time for sulfur dioxide, carbon monoxide and cyclohexane is reduced; in Comparative Example 2, when the raw materials lack nano titanium dioxide, the inhalation pressure of the gas mask of Comparative Example 2 is significantly increased compared with that of Example 2, and the protection time for sulfur dioxide, carbon monoxide and cyclohexane is reduced; in Comparative Example 3, when the addition amount of nano titanium dioxide exceeds the maximum amount specified in this application, the inhalation pressure of the gas mask of Comparative Example 3 is increased and the protection time is reduced. It can be seen that the combined use of the raw materials in this application can effectively improve the adsorption capacity of the long-acting filter material for toxic gases, and at the same time can also reduce the inhalation pressure of the gas mask.

[0043] The embodiments of this specific implementation method are all preferred embodiments of the present invention, and are not intended to limit the protection scope of the present invention. Therefore, any equivalent changes made based on the structure, shape, and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a long-lasting filter material for a gas mask filter box, characterized in that: The method comprises the following preparation steps: S1. Place copper nitrate trihydrate powder and nano additives in deionized water at room temperature, and dissolve them by ultrasonic dispersion. Then; S2, adding metal organic framework powder to the solution obtained in step S1, stirring, and centrifugally drying to obtain a modified metal organic framework material, wherein the copper nitrate trihydrate accounts for 10-15% of the weight of the metal organic framework powder, and the nano additive accounts for 2-6% of the weight of the metal organic framework powder; S3, grinding the modified metal organic framework material obtained in step S2 and then calcining it to obtain a filter material.

2. The method for preparing a long-lasting filter material for a gas mask filter box according to claim 1, characterized in that: The step S1 also includes manganese dioxide, and the weight ratio of manganese dioxide to copper nitrate trihydrate is (0.6-0.9):

1.

3. The method for preparing a long-lasting filter material for a gas mask filter box according to claim 1, characterized in that: The metal organic framework powder is obtained by the following preparation method: L-aspartic acid is dissolved in a sodium hydroxide solution, and then a copper nitrate solution is added and stirred to react for 2.5-3.5 hours. After the reaction is completed, the solid product is obtained by centrifugation, and then the solid product is washed, dried at 100° C. for 24 hours, and then crushed to obtain the metal organic framework powder.

4. The method for preparing a long-lasting filter material for a gas mask filter box according to claim 3, characterized in that: The weight ratio of the L-aspartic acid to copper nitrate is 1:(1.8-2.2).

5. The method for preparing a long-lasting filter material for a gas mask filter box according to claim 3, characterized in that: The metal organic framework powder also includes an adsorbent, and the added amount of the adsorbent is 3-7% of the weight of the L-aspartic acid.

6. The method for preparing a long-lasting filter material for a gas mask filter box according to claim 5, characterized in that: The adsorbent is prepared by the following method: sodium alginate and chitosan are mixed in a weight ratio of 3:2 to prepare a 3% aqueous solution, ethanol is added, and a gel is precipitated by wet spinning. The precipitated gel is further solidified in a 5% copper nitrate aqueous solution, dried, and then placed in a furnace for carbonization at 800°C for 2 hours to obtain the adsorbent after being crushed.

7. The method for preparing a long-lasting filter material for a gas mask filter box according to claim 6, characterized in that: The drying temperature is 60±5°C.

8. The method for preparing a long-lasting filter material for a gas mask filter box according to claim 1, characterized in that: The nano additive is nano titanium dioxide.

9. A long-lasting filter material in a gas mask filter box obtained according to the method for preparing a long-lasting filter material in a gas mask filter box according to any one of claims 1 to 8.

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