Drinking water antibacterial adsorption purification material and preparation method and application thereof

Abstract

The present invention belongs to the technical field of drinking water purification, and discloses an antibacterial adsorption purification material for drinking water, a preparation method and an application thereof. The preparation method of the antibacterial adsorption purification material for drinking water comprises the following steps: (1) introducing an acidic group on the surface of a carbon material to obtain a first modified material; (2) introducing an amino group on the surface of the first modified material to obtain a second modified material; (3) introducing palladium on the surface of the second modified material to obtain a third modified material; (4) introducing copper on the surface of the third modified material to obtain an antibacterial adsorption purification material for drinking water. The process of the present invention is simple and controllable, and easy to implement. The obtained purification material has triple purification functions of adsorption, catalytic degradation and antibacterial, has good stability, and has no new pollution in the effluent. It is very suitable for drinking water purification applications and has good practicality.

Description

Technical Field

[0001] The present invention relates to the technical field of drinking water purification, and in particular to an antibacterial adsorption purification material for drinking water and a preparation method and application thereof. Background Art

[0002] Water purifiers meet people's needs for clean water sources. In the standard of whether the water from the water purifier is drinkable, the microbial index is the top priority. Whether the microbial content meets the standard determines whether the water from the water purifier can be directly drunk. At present, fiber filter membranes and silver-loaded activated carbon materials are commonly used in water purifiers for antibacterial and sterilization. The above two have certain defects to a certain extent. The former requires a certain pressure and is relatively expensive, and the latter may have metal dissolution in a water-soluble state, resulting in failure to meet the drinking water metal index. Therefore, based on the above problems, it is particularly important to study a filter material that can both resist bacteria and ensure that the effluent water is free of new pollution. Summary of the invention

[0003] The technical problem to be solved by the present invention is to provide an antibacterial adsorption purification material for drinking water with good antibacterial effect and no new pollution in effluent water, as well as a preparation method and application thereof.

[0004] In order to achieve the above object, the present invention first provides a method for preparing an antibacterial adsorption and purification material for drinking water, and the technical scheme is as follows:

[0005] The preparation method of the antibacterial adsorption and purification material for drinking water comprises the following steps:

[0006] (1) introducing acidic groups onto the surface of the carbon material to obtain a first modified material;

[0007] (2) introducing amino groups on the surface of the first modified material to obtain a second modified material;

[0008] (3) introducing palladium onto the surface of the second modified material to obtain a third modified material;

[0009] (4) Copper is introduced onto the surface of the third modified material to obtain an antibacterial adsorption and purification material for drinking water.

[0010] In the above-mentioned preparation method, acidic groups are first introduced on the surface of the carbon material to increase the hydrophilicity and reactivity of the surface of the purification material, provide necessary chemical active sites for the subsequent introduction of amino groups and metal particles, enhance the adhesion of the modified groups, and avoid new pollution; this step also improves the adsorption capacity of the purification material and pollutants in water (especially positively charged microorganisms, metal ions, etc.), thereby providing a good foundation for the purification process. Secondly, the introduction of amino groups on the surface of the first modified material can increase its adsorption capacity for negatively charged pollutants; at the same time, the amino groups provide coordination sites for metal ions and loading anchor points for metal nanoparticles for the subsequent introduction of palladium and copper, so that the subsequent steps can proceed smoothly. Then, the palladium further introduced has excellent catalytic properties and certain antibacterial properties, which can be used to degrade certain organic pollutants and provide catalytic centers for the subsequent deposition of copper. The copper introduced at last has strong antibacterial properties, and copper and palladium form a bimetallic system to produce a synergistic antibacterial effect, and copper is relatively cheap, which can reduce material costs.

[0011] In summary, the present invention introduces acidic groups, amino groups and metal particles on the surface of carbon materials for gradual modification and mutual enhancement, and the resulting purification material has the following effects: (1) Highly efficient antibacterial: The synergistic effect of the palladium-copper bimetallic system gives the material strong antibacterial properties, which can quickly inhibit or kill bacteria in water after contact, reducing water microbial contamination. (2) Excellent adsorption capacity: The introduction of acidic groups and amino groups enables the purification material to have the ability to adsorb charged impurities, and can remove pollutants in water, including metal ions, charged particles, etc., thereby improving the purification effect. (3) Surface stability: The modified carbon material has good stability in different environments, strong durability, suitable for long-term use, and reduces the need for frequent replacement. (4) Triple purification function: The adsorption, catalytic degradation and antibacterial functions are organically combined to form a multifunctional composite material that meets the needs of debacterization and de-impurity in drinking water, providing comprehensive protection for water quality safety.

[0012] As a further improvement of the preparation method of the above-mentioned antibacterial adsorption purification material for drinking water: in step (1), the carbon material is soaked in a weak acid solution with a pH of 5.5 to 6.5, the solid-liquid ratio of the carbon material to the weak acid solution is 1g: (30 to 50) mL, the soaking time is 30 to 60 minutes, and the solid is collected after soaking and washed with pure water until neutral, so as to obtain a first modified material with an acidic group. Thus, by introducing the acidic group by soaking in a weak acidic solution, the acidic group can be slowly introduced on the surface of the purification material at a relatively low concentration, thereby avoiding excessive corrosion or structural damage. In addition, the reaction rate of the weak acid is relatively slow, which makes the process of introducing the acidic group easier to control, and the acid concentration and soaking time can be adjusted according to the experimental requirements to obtain an appropriate surface activation effect.

[0013] As a further improvement of the preparation method of the above-mentioned antibacterial adsorption purification material for drinking water: in step (2), the first modified material is soaked in a first modified solution with a pH of 10.5 to 11.5, a solvent of water and ethanol, and a solute of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and the solid is collected and washed to a pH of 7 to 8, so as to obtain a second modified material with an amino group; wherein the volume ratio of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, water and ethanol in the first modified solution is 1:15:175, and equal volumes are used for soaking, and the soaking time is 60 to 120 minutes. N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane has two amino groups (-NH and -NH2) as active sites, and the surface of the first modified material can be modified under relatively mild conditions without the use of strong alkali or other harsh conditions. It has higher flexibility, versatility and biocompatibility, and can significantly improve the hydrophilicity of the purification material.

[0014] As a further improvement of the preparation method of the above-mentioned antibacterial adsorption purification material for drinking water: in step (3), the second modified material is immersed in a second modified solution containing palladium chloride and hydrochloric acid, and after the immersion is completed, the solid is collected and washed to neutrality, so as to obtain a third modified material with palladium ions; wherein the second modified solution is prepared according to the ratio of adding 0.01-0.04g palladium chloride and 0.8-1.2mL 37% hydrochloric acid to every 100mL pure water, the solid-liquid ratio of the second modified material to the second modified solution is 1g:(6-10)mL, and the immersion time is 20-40min.

[0015] As a further improvement of the preparation method of the above-mentioned antibacterial adsorption and purification material for drinking water: in step (4), the third modified material is placed in a third modified solution containing copper sulfate, potassium sodium tartrate and EDTA, the pH is adjusted to 12.5-13.5, and then methanol is added to reduce the palladium ions and copper ions. After the reaction is completed, the solid is collected and washed to neutrality to obtain the antibacterial adsorption and purification material for drinking water; wherein the concentration of copper sulfate in the third modified solution is 10-20 g / L, the concentration of potassium sodium tartrate is 15-25 g / L, the concentration of EDTA is 20-30 g / L, the solid-liquid ratio of the third modified material to the third modified solution is 1 g: (400-600) mL, the reaction temperature is 50-70°C, and the reaction time is 30-120 min. wherein potassium sodium tartrate and EDTA are complexing agents, which can make copper ions deposited uniformly on the surface of the third modified material with a smaller particle size, and the deposited copper layer is not easy to fall off.

[0016] As a further improvement to the preparation method of the above-mentioned antibacterial adsorption and purification material for drinking water: in step (4), after the copper is introduced, ultraviolet light is used to irradiate the solid to obtain the antibacterial adsorption and purification material for drinking water. Thus, ultraviolet light (especially UV-C light) can destroy the DNA or RNA of microorganisms, achieving a better sterilization effect.

[0017] As a further improvement of the preparation method of the above-mentioned antibacterial adsorption and purification material for drinking water, the method further includes pre-treating the carbon material, including the steps of:

[0018] The carbon material is soaked once with an organic solvent;

[0019] The carbon material is soaked twice with a weak alkaline solution;

[0020] The carbon material was soaked three times in a strong acid solution.

[0021] Preferably, ultrasound is used for auxiliary treatment each time the immersion is performed;

[0022] The solid-liquid ratio for each soaking is 1g:(30-50)mL;

[0023] After each soaking, the solids were collected and washed with pure water until neutral;

[0024] The immersion is performed using at least one of acetone, ethyl acetate and n-hexane for 30 to 150 minutes;

[0025] The second soaking uses a weak alkaline solution with a pH of 8 to 8.5, and the soaking time is 15 to 30 minutes;

[0026] The three soakings use a strong acid solution with a pH of 2 to 2.5, and the soaking time is 3 to 6 minutes.

[0027] First, impurities such as oil, impurities or adsorbed organic matter on the surface of the carbon material that may affect subsequent chemical reactions are removed through a single soaking, which significantly improves the surface physical state of the carbon material and increases the reaction activity. Secondly, some weakly acidic or acidic impurities on the surface of the carbon material and fine impurities that are difficult to remove with organic solvents are removed through a secondary soaking, and a small amount of negative charge is generated on the surface of the carbon material, thereby increasing the affinity of the carbon material surface for the subsequent introduction of acidic groups. Soaking in organic solvents and weak alkaline solutions first can remove impurities without strongly corroding the carbon material, avoid excessive damage caused by strong acid treatment at the beginning, and ensure the mechanical strength and structural integrity of the carbon material. Finally, the surface of the carbon material is etched and activated with a strong acid solution to increase the surface roughness, hydrophilicity and reaction activity. The increase in surface roughness can increase the specific surface area of ​​the purification material, thereby increasing the amount of group introduction, and then improving the antibacterial and adsorption properties.

[0028] In order to achieve the above object, the present invention provides an antibacterial adsorption and purification material for drinking water, and the technical scheme is as follows:

[0029] The antibacterial adsorption and purification material for drinking water is prepared by adopting the above-mentioned preparation method.

[0030] In order to achieve the above object, the present invention further provides a drinking water purification element, and the technical solution is as follows:

[0031] The drinking water purification element comprises the drinking water antibacterial adsorption purification material prepared by the above preparation method.

[0032] In summary, the preparation method of the antibacterial adsorption purification material for drinking water of the present invention is simple and controllable, easy to implement, and the obtained purification material has triple purification functions of adsorption, catalytic degradation and antibacterial, good stability, and no new pollution in the effluent water. It is very suitable for drinking water purification applications and has good practicality.

[0033] The following is a further description of the embodiments of the invention provided in this specification in conjunction with the accompanying drawings and specific implementation methods. Additional aspects and advantages of the embodiments of the invention provided in this specification will be partially given in the following description, and partially will become apparent from the following description, or will be understood through the practice of the embodiments of the invention provided in this specification. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The drawings that constitute part of the embodiments of the inventions provided in this specification are used to assist in understanding the embodiments of the inventions provided in this specification. The contents provided in the drawings and their related descriptions in the embodiments of the inventions provided in this specification can be used to explain the embodiments of the inventions provided in this specification, but do not constitute improper limitations on the embodiments of the inventions provided in this specification.

[0035] Figure 1 This is a low-magnification SEM photograph of the antibacterial adsorption and purification material for drinking water according to Example 6 of the present invention.

[0036] Figure 2 This is a high-magnification SEM photograph of the antibacterial adsorption and purification material for drinking water according to Example 6 of the present invention.

[0037] Figure 3 This is the XPS spectrum of the antibacterial adsorption and purification material for drinking water according to Example 6 of the present invention.

[0038] Figure 4 This is the FITR spectrum of the antibacterial adsorption and purification material for drinking water according to Example 6 of the present invention. DETAILED DESCRIPTION

[0039] The following is a clear and complete description of the embodiments of the inventions provided in this specification in conjunction with the accompanying drawings. A person of ordinary skill in the art will be able to implement the embodiments of the inventions provided in this specification based on these descriptions. Before describing the embodiments of the inventions provided in this specification in conjunction with the accompanying drawings, it should be particularly noted that:

[0040] The technical solutions and technical features provided in each part of the embodiments of the invention provided in this specification, including the following description, may be combined with each other if there is no conflict.

[0041] In addition, the embodiments of the inventions provided in this specification involved in the following descriptions are generally only a partial embodiment of the embodiments of the inventions provided in this specification rather than all the embodiments. Therefore, based on the embodiments of the inventions provided in this specification, all other embodiments obtained by ordinary technicians in this field without making any creative work should fall within the scope of protection of the embodiments of the inventions provided in this specification.

[0042] Regarding the terms and units in the embodiments of the inventions provided in this specification: The terms "including", "comprising", "having" and any variations thereof in the descriptions and claims of the embodiments of the inventions provided in this specification and in the related parts are intended to cover non-exclusive inclusions. In addition, other relevant terms and units in the embodiments of the inventions provided in this specification can be reasonably interpreted based on the relevant contents of the embodiments of the inventions provided in this specification.

[0043] The specific implementation of the drinking water antibacterial adsorption purification material and the preparation method thereof of the present invention comprises the following steps:

[0044] (1) Pre-treating the carbon material, including the steps of:

[0045] The carbon material was soaked once with acetone for 90 min;

[0046] The carbon material is soaked twice in a weak alkaline solution with a pH of 8, wherein the weak alkaline solution is a sodium acetate solution, and the soaking time is 20 minutes;

[0047] The carbon material is soaked three times in a strong acid solution with a pH of 2, wherein the strong acid solution is a mixed acid solution of nitric acid and sulfuric acid, the molar ratio of nitric acid to sulfuric acid is (1-3):(1-3), and the soaking time is 3-6 minutes;

[0048] Ultrasonic treatment was used for auxiliary treatment each time the immersion was performed; the solid-liquid ratio of each immersion was 1 g:40 mL; after each immersion the solid was collected and washed with pure water until it was neutral.

[0049] (2) Introducing acidic groups on the surface of the carbon material to obtain a first modified material, specifically: soaking the carbon material in a weakly acidic solution with a pH of 6, wherein the weakly acidic solution is at least one of oxalic acid solution, acetic acid solution, citric acid solution, and phosphoric acid solution, and the solid-liquid ratio of the carbon material to the weakly acidic solution is 1 g:40 mL. The soaking time is 30 to 60 min. After soaking, the solid is collected and washed with pure water until it is neutral, thereby obtaining a first modified material having an acidic group.

[0050] (3) Introducing amino groups on the surface of the first modified material to obtain a second modified material, specifically: using a modification solution with a pH of 11 (adjusted by sodium hydroxide), a solvent of water and ethanol, and a solute of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane to immerse the first modified material in equal volumes, wherein the volume ratio of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, water and ethanol in the modification solution is 1:15:175, the immersion time is 60 to 120 minutes, and the immersion is accompanied by stirring. After the immersion, the solid is collected and washed to a pH of 7 to 8, thereby obtaining a second modified material having an amino group.

[0051] (4) introducing palladium onto the surface of the second modified material to obtain a third modified material, specifically: immersing the second modified material in a second modified solution containing palladium chloride and hydrochloric acid, collecting the solid after immersion and washing it to neutrality, thereby obtaining a third modified material having palladium ions; wherein the second modified solution is prepared by adding 0.025 g of palladium chloride and 1 mL of 37% hydrochloric acid to every 100 mL of pure water, the solid-liquid ratio of the second modified material to the second modified solution is 1 g:8 mL, and the immersion time is 20 to 40 min.

[0052] (5) Introducing copper onto the surface of the third modified material to obtain an antibacterial adsorption and purification material for drinking water, specifically: placing the third modified material into a third modified solution containing copper sulfate, potassium sodium tartrate and EDTA, adjusting the pH to 13, and then adding 15 mL of methanol to reduce the palladium ions and copper ions. After the reaction is completed, collecting the solid and washing it to neutrality to obtain an antibacterial adsorption and purification material for drinking water; wherein the concentration of copper sulfate in the third modified solution is 15 g / L, the concentration of potassium sodium tartrate is 20 g / L, the concentration of EDTA is 25 g / L, the solid-liquid ratio of the third modified material to the third modified solution is 1 g:500 mL, the reaction temperature is 60°C, and the reaction time is 30 to 120 min.

[0053] The test parameters and antibacterial properties of Examples 1-8 are shown in Table 1.

[0054] Table 1

[0055]

[0056] Example 9: Compared with Example 6, the drinking water antibacterial adsorption purification material and the preparation method thereof of this example are different in that after loading palladium and copper, the solid is collected and washed with pure water until it is neutral. After the solid is dried, it is further irradiated with ultraviolet light using the UVC band, with a distance of 15 cm between the light source and the solid, and irradiated at an intensity of 40 mW / cm² for 30 minutes to obtain the drinking water antibacterial adsorption purification material.

[0057] After testing, the diameter of the antibacterial ring of the purification material of this embodiment is 9.1 mm.

[0058] In the above embodiment, the carbon material is obtained by first subjecting dried fresh bamboo to an oxygen-free heat treatment at 500-700° C. for 1-3 hours and then activating it in a steam atmosphere at 800-1000° C. for 1-3 hours.

[0059] Figure 1 This is a low-magnification SEM photograph of the antibacterial adsorption and purification material for drinking water according to Example 6 of the present invention. Figure 2 This is a high-magnification SEM photo of the antibacterial adsorption and purification material for drinking water according to Example 6 of the present invention. Figure 1-2 It can be seen that the purification material has a transport porous structure.

[0060] Figure 3 This is the XPS spectrum of the antibacterial adsorption and purification material for drinking water according to Example 6 of the present invention. Figure 3 As shown, the purified material has C 1s peak, O 1s peak, Cu 2p peak, Pd 3d peak, and Si 2p peak, indicating that the carbon material has been successfully modified.

[0061] Figure 4 This is the FITR spectrum of the antibacterial adsorption and purification material for drinking water according to Example 6 of the present invention. Figure 4 As shown, the purified material is at 3430 cm -1 The absorption peak at 1500~1650cm belongs to -OH -1 The broad absorption peak at 1108 cm is attributed to NH. -1 The absorption peak at is attributed to Si-O.

[0062] The antibacterial properties of the above purification materials were tested by the Kirby-Bauer disk diffusion method:

[0063] 1) Take a colony of E. coli and place it in 10 mL of LB culture medium and culture it at 36°C for 16 hours;

[0064] 2) Take out the bacterial solution and use a spectrophotometer to adjust the concentration of the bacterial solution to meet the McFarland turbidity value of 0.5;

[0065] 3) Dilute the bacterial solution to a concentration of 10 using 0.9% saline. 6CFU / mL;

[0066] 4) Use a pipette to transfer 0.5 mL of bacterial solution into the MH medium and spread it evenly with a spreading rod.

[0067] 5) Place a certain amount of purification material in MH medium and culture it at 36°C for 16 hours. Finally, measure the diameter of the inhibition zone with a vernier caliper. Perform three parallel tests on each purification material and take the average value of the inhibition zone diameter.

[0068] An embodiment of the drinking water purification element of the present invention is a drinking water antibacterial adsorption purification material prepared by the preparation method of any one of the above embodiments. The water purification element can be but is not limited to any one of a filter membrane structure, a filling column structure, a roll structure, and a pleated structure.

[0069] The above is a description of the relevant contents of the embodiments of the inventions provided in this specification. Based on these descriptions, a person of ordinary skill in the art will be able to implement the embodiments of the inventions provided in this specification. Based on the above contents of the embodiments of the inventions provided in this specification, all other preferred implementations and embodiments obtained by a person of ordinary skill in the art without making any creative work shall fall within the scope of protection of the embodiments of the inventions provided in this specification.

Claims

1. A method for preparing an antibacterial adsorption and purification material for drinking water, characterized in that: The following steps are involved: (1) introducing acidic groups onto the surface of the carbon material to obtain a first modified material; (2) introducing amino groups on the surface of the first modified material to obtain a second modified material; (3) introducing palladium onto the surface of the second modified material to obtain a third modified material; (4) Copper is introduced onto the surface of the third modified material to obtain an antibacterial adsorption and purification material for drinking water.

2. The method for preparing the antibacterial adsorption and purification material for drinking water according to claim 1, characterized in that: In step (1), the carbon material is soaked in a weakly acidic solution with a pH of 5.5 to 6.5, the solid-liquid ratio of the carbon material to the weakly acidic solution is 1 g: (30 to 50) mL, and the soaking time is 30 to 60 min. After soaking, the solid is collected and washed with pure water until it is neutral, thereby obtaining a first modified material having an acidic group.

3. The method for preparing the antibacterial adsorption and purification material for drinking water according to claim 1, characterized in that: In step (2), the first modified material is soaked in a first modified solution having a pH of 10.5 to 11.5, a solvent of water and ethanol, and a solute of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane. After soaking, the solid is collected and washed to a pH of 7 to 8, thereby obtaining a second modified material having an amino group. The volume ratio of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, water and ethanol in the first modified solution is 1:15:175, and equal volume immersion is adopted for 60 to 120 minutes.

4. The method for preparing the antibacterial adsorption and purification material for drinking water according to claim 1, characterized in that: In step (3), the second modified material is immersed in a second modified solution containing palladium chloride and hydrochloric acid, and after the immersion is completed, the solid is collected and washed to neutrality, thereby obtaining a third modified material having palladium ions; The second modified solution is prepared by adding 0.01-0.04 g of palladium chloride and 0.8-1.2 mL of 37% hydrochloric acid to every 100 mL of pure water, the solid-liquid ratio of the second modified material to the second modified solution is 1 g: (6-10) mL, and the immersion time is 20-40 min.

5. The method for preparing the antibacterial adsorption and purification material for drinking water according to claim 1, characterized in that: In step (4), the third modified material is placed in a third modified solution containing copper sulfate, potassium sodium tartrate and EDTA, the pH is adjusted to 12.5-13.5, and then methanol is added to reduce the palladium ions and copper ions. After the reaction is completed, the solid is collected and washed to neutrality to obtain an antibacterial adsorption purification material for drinking water; Among them, the concentration of copper sulfate in the third modified solution is 10-20 g / L, the concentration of potassium sodium tartrate is 15-25 g / L, the concentration of EDTA is 20-30 g / L, the solid-liquid ratio of the third modified material to the third modified solution is 1 g: (400-600) mL, the reaction time is 30-120 min, and the reaction temperature is 50-70°C.

6. The method for preparing the antibacterial adsorption and purification material for drinking water according to claim 1, characterized in that: In step (4), after the copper is introduced, the solid is irradiated with ultraviolet light to obtain an antibacterial adsorption and purification material for drinking water.

7. The method for preparing the antibacterial adsorption and purification material for drinking water according to claim 1, characterized in that: The method also includes pre-treating the carbon material, comprising the steps of: The carbon material is soaked once with an organic solvent; The carbon material is soaked twice with a weak alkaline solution; The carbon material was soaked three times in a strong acid solution.

8. The method for preparing the antibacterial adsorption and purification material for drinking water according to claim 7, characterized in that: Ultrasound is used for auxiliary treatment during each immersion; The solid-liquid ratio for each soaking is 1g:(30-50)mL; After each soaking, the solids were collected and washed with pure water until neutral; The immersion is performed using at least one of acetone, ethyl acetate and n-hexane for 30 to 150 minutes; The second soaking uses a weak alkaline solution with a pH of 8 to 8.5, and the soaking time is 15 to 30 minutes; The three soakings use a strong acid solution with a pH of 2 to 2.5, and the soaking time is 3 to 6 minutes.

9. Antibacterial adsorption and purification material for drinking water, characterized by: The preparation method is described in any one of claims 1 to 8.

10. Drinking water purification element, characterized in that: The antibacterial adsorption and purification material for drinking water is prepared by the preparation method according to any one of claims 1 to 8.

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