Quaternary ammonium salt grafted porous unfired ceramsite as well as preparation method and application thereof

Abstract

The invention relates to quaternary ammonium salt grafted porous unfired ceramsite as well as a preparation method and application thereof. The method comprises the following steps: mixing bentonite, natural zeolite powder, fly ash and biomass ash which are weighed in percentage by mass; transferring part of the porous unfired ceramsite raw material mixed powder into a granulator, and stirring to obtain spherical particles; mixing water and a curing agent, spraying the mixture into the pelletizer at a constant speed through a high-pressure spraying can, continuously adding the residual porous unfired ceramsite raw material mixed powder into the pelletizer during the period, and taking out the mixture until the diameter of spherical particles in the pelletizer is 8-12mm; transferring the spherical particles into a standard curing box for curing; carrying out amination treatment on the porous unfired ceramsite matrix; and by taking the aminated porous unfired ceramsite matrix as a carrier, grafting a quaternary ammonium salt bactericide on the surface of an inner pore to obtain the quaternary ammonium salt grafted porous unfired ceramsite. According to the present invention, the quaternary ammonium salt sterilization group is introduced into the activated porous non-sintered ceramsite, such that the residual toxicity problem of the conventional sterilization carrier is solved;

Description

Technical Field

[0001] The present disclosure relates to the technical field of lightweight building materials, and more specifically to a quaternary ammonium salt grafted porous non-fired ceramsite and its preparation method and application. Background Art

[0002] Non-fired ceramsite has the following advantages compared with traditional ceramsite: First, the production process does not require high-temperature sintering, and the energy consumption is reduced by 30%-50%, which is more energy-saving and environmentally friendly; second, industrial waste residues (such as fly ash and slag) are used as the main raw materials, and the solid waste utilization rate can reach more than 80%, meeting the requirements of circular economy; third, the physical properties are excellent, and the adjustable range of bulk density (300-900 kg / m³) and cylinder compressive strength (1.5-6.5 MPa) is wider, and the water absorption rate (5%-15%) is lower than that of traditional ceramsite; fourth, there is no emission of waste gases such as sulfur dioxide and nitrogen oxides during the production process, and the carbon emission is reduced by more than 60%. These characteristics make non-fired ceramsite more sustainable in the applications such as lightweight concrete and sewage treatment.

[0003] Harmful substances such as pathogens and ammonia nitrogen inorganic salts in sewage will cause great harm to the human body and the environment. At present, there have been studies on using ceramsite in the field of sewage treatment. First, using the porous characteristics of ceramsite, it can be used as a water treatment filter material to adsorb and remove particulate matter and pathogens in sewage through physical filtration. This can only achieve preliminary filtration. It can also use the method of loading bactericides on ceramsite, including loading chlorine, chlorine dioxide, silver, and copper ions, etc. By slowly releasing bactericides in sewage, the microbial biofilm is destroyed to achieve the antibacterial function. However, releasing these bactericides into the environment will cause environmental pollution problems, and it has disadvantages such as poor repeatability, poor stability and persistence, and easy separation from the carrier. Summary of the Invention

[0004] In view of this, the present disclosure provides a quaternary ammonium salt grafted porous non-fired ceramsite and its preparation method and application to solve the problems of residual toxicity of conventional antibacterial carriers and non-reusability of antibacterial ceramsite.

[0005] According to one aspect of the present disclosure, a preparation method of a quaternary ammonium salt grafted porous non-fired ceramsite is provided, including:

[0006] S1: Weigh raw materials according to the following mass percentages: bentonite 15% - 32%, natural zeolite powder 10% - 15%, fly ash 15% - 19%, biomass ash 10% - 12%, curing agent 8% - 10%, and the balance is water;

[0007] S2: Mix bentonite, natural zeolite powder, fly ash, and biomass ash to obtain a mixed powder of raw materials for porous non-fired ceramsite;

[0008] S3: Transfer the mixed powder of partial raw materials of porous non-fired ceramsite to a granulator for stirring to obtain spherical particles;

[0009] S4: Mix water and a curing agent and spray them evenly into the granulator through a high-pressure sprayer. During this period, continuously add the remaining mixed powder of raw materials of porous non-fired ceramsite into the granulator until the spherical particles in the granulator have a diameter of 8 mm to 12 mm and then take them out;

[0010] S5: Transfer the taken-out spherical particles to a standard curing box for curing to obtain a porous non-fired ceramsite matrix;

[0011] S6: Perform amination treatment on the porous non-fired ceramsite matrix to increase the binding sites for bactericides;

[0012] S7: Use the aminated porous non-fired ceramsite matrix as a carrier and graft a quaternary ammonium salt bactericide on the inner pore surface to obtain a quaternary ammonium salt-grafted porous non-fired ceramsite.

[0013] In the above solution, the particle sizes of the bentonite, natural zeolite powder, fly ash, and biomass ash described in step S1 are not less than 200 mesh; the mass percentage content of montmorillonite in the bentonite described in step S1 is 85% - 90%; the mass percentage content of natural zeolite in the natural zeolite powder described in step S1 is more than 50%, and the ammonia absorption value is greater than 100 mmol / 100 g; the fly ash described in step S1 is grade II ash; the biomass ash described in step S1 is one of rice husk ash, bagasse ash, and corn cob ash, and the silicon content is not less than 75%; the curing agent described in step S1 is solid sodium metaaluminate and solid sodium silicate, and the mass ratio is 3:1 to 1:2.

[0014] In the above solution, for the stirring described in step S3, stirring is carried out at a rotation speed of 45 - 65 r / min for 5 - 10 min.

[0015] In the above solution, for the curing described in step S5, the spherical particles are transferred to a standard curing box for curing for 28 days.

[0016] In the above solution, the amination treatment of the porous non-fired ceramsite matrix described in step S6 includes: mixing and cleaning the porous non-fired ceramsite matrix with an organic solvent and deionized water to remove impurities on the surface of the ceramsite; soaking the cleaned porous non-fired ceramsite matrix in a toluene solution of aminosilane for a water bath reaction; washing away the unreacted aminosilane on the surface and in the pores of the porous non-fired ceramsite matrix with an ethanol solution, and drying for later use.

[0017] In the above solution, the organic solvent is one of ethanol or acetone; the amino silane is one of 3-aminopropyltriethoxysilane (APTES) or 3-aminopropyltrimethoxysilane (APTMS), and the mass percentage concentration is 1% - 5%; for the water bath reaction, it is reacted in a water bath at 40 °C for 8 to 12 hours.

[0018] In the above solution, in step S7, using the aminated porous fired-free ceramsite matrix as a carrier, grafting a quaternary ammonium salt bactericide on the inner pore surface includes: dissolving the quaternary ammonium salt in an ethanol solution to obtain a quaternary ammonium salt reaction solution; mixing the aminated porous fired-free ceramsite matrix and the quaternary ammonium salt reaction solution according to a weight ratio of 1:0.6 - 1.5, and performing a water bath reaction; cleaning with an absolute ethanol solution to remove unreacted quaternary ammonium salt and by-products, and drying to obtain the quaternary ammonium salt-grafted porous fired-free ceramsite.

[0019] In the above solution, the quaternary ammonium salt is one of epoxy quaternary ammonium salt and haloalkyl quaternary ammonium salt, and the mass percentage concentration of the quaternary ammonium salt in the quaternary ammonium salt reaction solution is 1% to 10%; for the water bath reaction, it is reacted in a water bath at 40 °C for 12 to 24 hours, and the pH value of the reaction environment is controlled to be 7 to 10; the drying is carried out at 55 °C for 0.5 to 1 hour.

[0020] According to another aspect of the present disclosure, there is provided a quaternary ammonium salt-grafted porous fired-free ceramsite prepared by the above method.

[0021] According to still another aspect of the present disclosure, there is provided an application of the quaternary ammonium salt-grafted porous fired-free ceramsite prepared by the above method in the fields of environmental protection filter materials, sewage treatment or transportation.

[0022] The quaternary ammonium salt-grafted porous fired-free ceramsite provided by the present disclosure, its preparation method and application have the following beneficial effects compared with the prior art:

[0023] (1) The quaternary ammonium salt-grafted porous fired-free ceramsite provided by the present disclosure and its preparation method introduce a quaternary ammonium salt bactericidal group into the activated porous fired-free ceramsite. The antibacterial mode is contact sterilization rather than slow-release sterilization, which solves the problem of residual toxicity of conventional sterilization carriers and at the same time endows the sterilized ceramsite with reusability.

[0024] (2) The quaternary ammonium salt-grafted porous fired-free ceramsite provided by the present disclosure and its preparation method use the porous fired-free ceramsite matrix as a carrier and graft a quaternary ammonium salt bactericide on the inner pore surface. Since the bactericidal groups are concentrated on the inner pore surface of the ceramsite, a high-concentration sterilization and disinfection area is formed, with high sterilization efficiency, avoiding secondary pollution of water bodies, strong safety, and reusability (instead of releasing bactericidal groups, but making full use of the bactericidal groups concentrated in the pores of the ceramsite to contact bacteria).

[0025] (3) The quaternary ammonium salt grafted porous non - fired ceramsite and its preparation method provided by the present disclosure. Bentonite, natural zeolite powder, and biomass ash are all natural lightweight porous materials, which play a role in adsorbing organic matter, ammonia nitrogen inorganic salts, etc. in sewage treatment. Under the action of a curing agent, a hydration reaction occurs to form porous ceramsite with a certain strength. Under high porosity and high specific surface area, the bactericide can be enriched in the internal pores and on the surface of the ceramsite. By changing the surface morphology of the carrier, the bactericidal efficiency is enhanced, and the bactericidal efficiency against anaerobic bacteria is above 90%.

[0026] (4) The quaternary ammonium salt grafted porous non - fired ceramsite and its preparation method provided by the present disclosure. Adding sodium aluminate to the curing agent will make the siliceous precursor in the raw materials have more crystallization order, and at a higher Al / Si ratio, the bridging oxygen sites in Si - O - Al are more active, the interlayer water molecules are more easily dissociated, and more hydroxyl groups are generated in the gel, providing a larger number of amino binding sites for the next step of amination and enhancing the quaternary ammonium salt binding ability.

[0027] (5) The quaternary ammonium salt grafted porous non - fired ceramsite and its preparation method provided by the present disclosure. Before introducing the quaternary ammonium salt bactericidal group into the porous non - fired ceramsite, first soak the non - fired ceramsite in a toluene solution of amino - silane to aminate the internal pores and surface of the porous ceramsite. Select a quaternary ammonium salt bactericide containing reactive groups (such as epoxy groups, haloalkyl groups, etc.) to facilitate reaction with amino groups, covalently bind the quaternary ammonium group in the ceramsite, making the bactericidal group in the ceramsite more stable, insoluble in water and organic solvents, and inhibiting or killing bacteria through direct contact between the bactericidal group and bacteria. It has reusability and good environmental stability. Description of the Drawings

[0028] Through the following description of the embodiments of the present disclosure with reference to the drawings, the above - mentioned content and other objects, features, and advantages of the present disclosure will become clearer. In the drawings:

[0029] Figure 1 A flowchart showing the method for preparing quaternary ammonium salt grafted porous non - fired ceramsite according to an embodiment of the present disclosure is shown. Detailed Embodiments

[0030] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. However, it should be understood that these descriptions are only exemplary and are not intended to limit the scope of the present disclosure. In the following detailed description, for the sake of explanation, many specific details are set forth to provide a comprehensive understanding of the embodiments of the present disclosure. However, obviously, one or more embodiments can also be implemented without these specific details. In addition, in the following description, descriptions of well - known structures and technologies are omitted to avoid unnecessarily confusing the concepts of the present disclosure.

[0031] The terms used herein are merely for describing specific embodiments and are not intended to limit the present disclosure. The terms "including", "comprising" and the like used herein indicate the presence of the described features, steps, operations and / or components, but do not preclude the presence or addition of one or more other features, steps, operations or components.

[0032] All terms used herein (including technical and scientific terms) have the meanings commonly understood by those of ordinary skill in the art, unless otherwise defined. It should be noted that the terms used herein should be interpreted as having a meaning consistent with the context of this specification, and should not be interpreted in an idealized or overly rigid manner.

[0033] To solve the problems of residual toxicity of conventional bactericidal carriers and the non-reusability of bactericidal ceramsite, the present disclosure utilizes the adsorption characteristics of natural porous materials (bentonite, zeolite powder), the active silicon sources in fly ash and biomass ash, and under the action of a curing agent (which generates more hydroxyl groups in the ceramsite) and water, first prepares non-fired ceramsite. The prepared ceramsite is soaked in aminosilane for amination (with hydroxyl groups as the main reaction sites). Next, quaternary ammonium salt groups are grafted onto the non-fired ceramsite (with amino groups as the main reaction sites at this time).

[0034] As Figure 1 shown, Figure 1 The flowchart of the method for preparing quaternary ammonium salt grafted porous non-fired ceramsite according to an embodiment of the present disclosure is shown, and the method includes the following steps:

[0035] S1: Weigh raw materials according to the following mass percentages: 15% - 32% of bentonite, 10% - 15% of natural zeolite powder, 15% - 19% of fly ash, 10% - 12% of biomass ash, 8% - 10% of curing agent, and the balance is water;

[0036] In this step, the particle sizes of the bentonite, natural zeolite powder, fly ash, and biomass ash are all not less than 200 mesh;

[0037] The mass percentage content of montmorillonite in the bentonite is 85% - 90%;

[0038] The mass percentage content of natural zeolite in the natural zeolite powder is more than 50%, and the ammonia absorption value is greater than 100 mmol / 100 g;

[0039] The fly ash is grade II ash;

[0040] The biomass ash is one of rice husk ash, bagasse ash, and corn cob ash, and the silicon content is not less than 75%;

[0041] The curing agent is solid sodium metaaluminate and solid sodium silicate, and the mass ratio is 3:1 - 1:2.

[0042] S2: Mix bentonite, natural zeolite powder, fly ash, and biomass ash to obtain a mixed powder of raw materials for porous non-fired ceramsite.

[0043] S3: Transfer part of the mixed powder of raw materials for porous non-fired ceramsite to a granulator and stir to obtain spherical particles;

[0044] In this step, the stirring is carried out at a rotational speed of 45 - 65 r / min for 5 - 10 min.

[0045] S4: Mix water and a curing agent and evenly spray them into the granulator through a high-pressure sprayer. During this period, continuously add the remaining mixed powder of raw materials for porous non-fired ceramsite to the granulator until the spherical particles in the granulator reach a diameter of 8 mm - 12 mm and then take them out.

[0046] S5: Transfer the taken-out spherical particles to a standard curing box for curing to obtain a porous non-fired ceramsite matrix;

[0047] In this step, the curing is to transfer the spherical particles to a standard curing box for 28 days of curing.

[0048] S6: Perform amination treatment on the porous non-fired ceramsite matrix to increase the binding sites for fungicides;

[0049] In this step, the amination treatment of the porous non-fired ceramsite matrix includes:

[0050] S61: Mix the porous non-fired ceramsite matrix with an organic solvent and deionized water for cleaning to remove impurities on the surface of the ceramsite; Optionally, the organic solvent is one of ethanol or acetone;

[0051] S62: Immerse the cleaned porous non-fired ceramsite matrix in a toluene solution of aminosilane for a water bath reaction; Optionally, the aminosilane is one of 3-aminopropyltriethoxysilane (APTES) or 3-aminopropyltrimethoxysilane (APTMS), with a mass percentage concentration of 1% - 5%; The water bath reaction is carried out in a 40 °C water bath for 8 to 12 hours;

[0052] S63: Wash away the unreacted aminosilane on the surface and in the pores of the porous non-fired ceramsite matrix with an ethanol solution, and dry it for later use.

[0053] S7: Using the aminated porous non-fired ceramsite matrix as a carrier, graft a quaternary ammonium salt fungicide on the inner pore surface to obtain a quaternary ammonium salt-grafted porous non-fired ceramsite, including:

[0054] S71: Dissolve the quaternary ammonium salt in an ethanol solution to obtain a quaternary ammonium salt reaction solution; optionally, the quaternary ammonium salt is one of an epoxy quaternary ammonium salt and a haloalkyl quaternary ammonium salt, and the mass percentage concentration of the quaternary ammonium salt in the quaternary ammonium salt reaction solution is 1% to 10%;

[0055] S72: Mix the aminated porous non-fired ceramsite matrix and the quaternary ammonium salt reaction solution according to a weight ratio of 1:0.6 - 1.5, and carry out a water bath reaction; optionally, the water bath reaction is carried out in a 40°C water bath for 12 to 24 hours, and the pH value of the reaction environment is controlled to be 7 to 10;

[0056] S73: Wash with an anhydrous ethanol solution to remove unreacted quaternary ammonium salt and by-products, and obtain quaternary ammonium salt grafted porous non-fired ceramsite after drying; optionally, the drying is carried out at 55°C for 0.5 to 1 hour.

[0057] Based on the above Figure 1 The method for preparing quaternary ammonium salt grafted porous non-fired ceramsite shown, the following combines Examples 1 - 2 and Comparative Example 1 to detail the method for preparing quaternary ammonium salt grafted porous non-fired ceramsite provided by the present disclosure.

[0058] Example 1:

[0059] In this example, the sterilizing group uses an epoxy quaternary ammonium salt, and the ceramsite raw materials include the following components: 18% bentonite, 12 parts of natural zeolite powder, 17% fly ash, 10 parts of biomass ash, 10 parts of curing agent, and 33 parts of water. First, mix bentonite, natural zeolite powder, fly ash, rice husk ash, and curing agent to obtain a mixed powder of non-fired ceramsite raw materials;

[0060] Prepare lightweight porous non-fired ceramsite according to the preparation method in the previous text, and characterize its antibacterial performance by testing its minimum inhibitory concentration in an Escherichia coli solution. Immerse the non-fired ceramsite in deionized water, and characterize its stability by testing the dissolution amount of quaternary ammonium groups in the deionized water solution of the non-fired ceramsite. The test results are shown in Table 1.

[0061] Example 2:

[0062] In this example, the sterilizing group uses a chloroalkyl quaternary ammonium salt, and the ceramsite raw materials include the following components: 18% bentonite, 12 parts of natural zeolite powder, 17% fly ash, 10 parts of biomass ash, 10 parts of curing agent, and 33 parts of water. First, mix bentonite, natural zeolite powder, fly ash, rice husk ash, and curing agent to obtain a mixed powder of non-fired ceramsite raw materials;

[0063] Lightweight porous non - fired ceramsite was prepared according to the preparation method in the previous text. Its antibacterial performance was characterized by testing its minimum inhibitory concentration in Escherichia coli solution. The non - fired ceramsite was soaked in deionized water, and its stability was characterized by testing the dissolution amount of quaternary ammonium groups in the deionized aqueous solution of the non - fired ceramsite. The test results are shown in Table 1 in detail.

[0064] Comparative Example 1:

[0065] In this comparative example, the sterilizing group was epoxy - based quaternary ammonium salt. The raw materials of the ceramsite included the following components: 18% bentonite, 12 parts of natural zeolite powder, 17% fly ash, 10 parts of biomass ash, 10 parts of curing agent, and 33 parts of water. First, bentonite, natural zeolite powder, fly ash, rice husk ash, and curing agent were mixed to obtain a mixed powder of raw materials for non - fired ceramsite;

[0066] Lightweight porous non - fired ceramsite was prepared according to the preparation method in the previous text, but it was not aminated, and the remaining steps were the same. Its antibacterial performance was characterized by testing its minimum inhibitory concentration in Escherichia coli solution. The non - fired ceramsite was soaked in deionized water, and its stability was characterized by testing the dissolution amount of quaternary ammonium groups in the deionized aqueous solution of the non - fired ceramsite. The test results are shown in Table 1 in detail.

[0067]

[0068] Table 1

[0069] It can be seen from the data in Table 1 that both Example 1 and Example 2 have a relatively low minimum inhibitory concentration, indicating strong antibacterial performance, and Example 1 shows the best antibacterial activity, indicating that the epoxy - based quaternary ammonium salt has strong bactericidal ability. The antibacterial property and stability of Comparative Example 1 are relatively poor, indicating that for non - fired ceramsite without amination, the combination of quaternary ammonium salt is mainly physical adsorption, and the chemical bonding is unstable.

[0070] Thus, it can be seen that the preparation method of the quaternary ammonium salt - grafted porous non - fired ceramsite provided by the present disclosure, by introducing a quaternary ammonium salt sterilizing group into the activated porous non - fired ceramsite, the antibacterial mode is contact sterilization rather than slow - release sterilization, solving the problem of residual toxicity of conventional sterilization carriers, and at the same time endowing the sterilizing ceramsite with reusability. The preparation method of the quaternary ammonium salt - grafted porous non - fired ceramsite provided by the present disclosure uses the porous non - fired ceramsite matrix as a carrier, and grafts quaternary ammonium salt bactericides on the inner pore surface. Since the sterilizing groups are concentrated on the inner pore surface of the ceramsite, a high - concentration sterilization and disinfection area is formed, with high sterilization efficiency, avoiding secondary pollution of water bodies, strong safety, and reusability (instead of releasing sterilizing groups, but making full use of the sterilizing groups concentrated in the pores of the ceramsite to contact bacteria).

[0071] Furthermore, based on the above preparation method of quaternary ammonium salt grafted porous non-fired ceramsite, the present disclosure also provides a quaternary ammonium salt grafted porous non-fired ceramsite prepared by the described method. This quaternary ammonium salt grafted porous non-fired ceramsite does not require sintering, is energy-saving and environmentally friendly, has the characteristics of light weight and high strength, and heat insulation, and can be widely applied in industries such as lightweight concrete and thermal insulation blocks.

[0072] Furthermore, based on the above quaternary ammonium salt grafted porous non-fired ceramsite and its preparation method, the present disclosure also provides an application of the quaternary ammonium salt grafted porous non-fired ceramsite prepared by the described method in the fields of environmental protection filter materials, sewage treatment or transportation, and it can be widely applied in fields such as lightweight concrete and thermal insulation blocks.

[0073] Those skilled in the art can understand that the features described in the various embodiments of the present disclosure can be combined and / or combined in various ways, even if such combinations or combinations are not explicitly described in the present disclosure. In particular, without departing from the spirit and teachings of the present disclosure, the features described in the various embodiments of the present disclosure can be combined and / or combined in various ways. All such combinations and / or combinations fall within the scope of the present disclosure.

[0074] The above describes the embodiments of the present disclosure. However, these embodiments are only for illustrative purposes and not for limiting the scope of the present disclosure. Although the embodiments are described separately above, this does not mean that the measures in each embodiment cannot be used advantageously in combination. Without departing from the scope of the present disclosure, those skilled in the art can make various substitutions and modifications, and all such substitutions and modifications should fall within the scope of the present disclosure.

Claims

1. A preparation method of quaternary ammonium salt grafted porous non-fired ceramsite, characterized in that, Including: S1: Weigh raw materials according to the following mass percentages: bentonite 15% - 32%, natural zeolite powder 10% - 15%, fly ash 15% - 19%, biomass ash 10% - 12%, curing agent 8% - 10%, and the balance is water; S2: Mix bentonite, natural zeolite powder, fly ash and biomass ash to obtain a mixed powder of raw materials for porous non - fired ceramsite; S3: Transfer part of the mixed powder of raw materials for porous non - fired ceramsite to a granulator and stir to obtain spherical particles; S4: Mix water and curing agent and spray them into the granulator evenly through a high - pressure sprayer. During this period, continuously add the remaining mixed powder of raw materials for porous non - fired ceramsite to the granulator until the spherical particles in the granulator have a diameter of 8 mm - 12 mm and then take them out; S5: Transfer the taken - out spherical particles to a standard curing box for curing to obtain a porous non - fired ceramsite matrix; S6: Perform amination treatment on the porous non - fired ceramsite matrix to increase the binding sites for fungicides; S7: Use the aminated porous non - fired ceramsite matrix as a carrier and graft quaternary ammonium salt fungicides on the inner pore surface to obtain quaternary ammonium salt - grafted porous non - fired ceramsite.

2. The preparation method of the quaternary ammonium salt - grafted porous non - fired ceramsite according to claim 1, wherein the particle sizes of the bentonite, natural zeolite powder, fly ash and biomass ash described in step S1 are all not less than 200 mesh; the mass percentage content of montmorillonite in the bentonite described in step S1 is 85% - 90%; the mass percentage content of natural zeolite in the natural zeolite powder described in step S1 is more than 50%, and the ammonia absorption value is greater than 100 mmol / 100 g; the fly ash described in step S1 is grade II ash; the biomass ash described in step S1 is one of rice husk ash, sugarcane bagasse ash and corn cob ash, and the silicon content is not less than 75%; the curing agent described in step S1 is solid sodium meta - aluminate and solid sodium silicate, and the mass ratio is 3:1 - 1:

2.

3. The preparation method of the quaternary ammonium salt grafted porous non-fired ceramsite according to claim 1, characterized in that, The stirring described in step S3 is carried out at a rotation speed of 45 - 65 r / min for 5 - 10 min.

4. The preparation method of the quaternary ammonium salt grafted porous non-fired ceramsite according to claim 1, characterized in that, The curing described in step S5 is to transfer the spherical particles to a standard curing box for 28 days of curing.

5. The preparation method of the quaternary ammonium salt grafted porous non-fired ceramsite according to claim 1, characterized in that, The amination treatment of the porous non - fired ceramsite matrix described in step S6 includes: Mix the porous non - fired ceramsite matrix with an organic solvent and deionized water for cleaning to remove impurities on the surface of the ceramsite; Immerse the cleaned porous non - fired ceramsite matrix in a toluene solution of aminosilane for a water - bath reaction; Wash away the unreacted aminosilane on the surface and in the pores of the porous non - fired ceramsite matrix with an ethanol solution, and dry it for later use.

6. The preparation method of the quaternary ammonium salt - grafted porous non - fired ceramsite according to claim 5, wherein the organic solvent is one of ethanol or acetone; the aminosilane is one of 3 - aminopropyltriethoxysilane (APTES) or 3 - aminopropyltrimethoxysilane (APTMS), and the mass percentage concentration is 1% - 5%; the water - bath reaction is carried out in a 40 °C water - bath for 8 to 12 hours.

7. The preparation method of the quaternary ammonium salt grafted porous non-fired ceramsite according to claim 1, characterized in that, Using the aminated porous non - fired ceramsite matrix described in step S7 as a carrier, grafting quaternary ammonium salt bactericides on the inner pore surface, including: Dissolve the quaternary ammonium salt in an ethanol solution to obtain a quaternary ammonium salt reaction solution; Mix the aminated porous non - fired ceramsite matrix with the quaternary ammonium salt reaction solution in a weight ratio of 1:0.6 - 1.5, and carry out a water - bath reaction; Wash with an anhydrous ethanol solution to remove unreacted quaternary ammonium salt and by - products, and obtain quaternary ammonium salt - grafted porous non - fired ceramsite after drying.

8. The preparation method of the quaternary ammonium salt - grafted porous non - fired ceramsite according to claim 7, characterized in that The quaternary ammonium salt is one of epoxy - based quaternary ammonium salt and haloalkyl quaternary ammonium salt, and the mass percentage concentration of the quaternary ammonium salt in the quaternary ammonium salt reaction solution is 1% to 10%; The water - bath reaction is carried out in a water - bath at 40 °C for 12 to 24 hours, and the pH value of the reaction environment is controlled to be 7 to 10; The drying is carried out at 55 °C for 0.5 to 1 hour.

9. A quaternary ammonium salt - grafted porous non - fired ceramsite prepared by the method according to any one of claims 1 to 8.

10. Application of a quaternary ammonium salt - grafted porous non - fired ceramsite prepared by the method according to any one of claims 1 to 8 in the fields of environmental protection filter materials, sewage treatment or transportation.

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