A bactericidal nanotube material for wastewater treatment

Abstract

The invention discloses a sterilizing nanotube material for wastewater treatment, comprising the following steps: Step 1: silver acetate and dinitro disulfide with a molar ratio of 1:1 are configured into silver acetate dinitro disulfide solution; Step 2: antimony trichloride and dinitro disulfide with a molar ratio of 1:1 are configured into antimony trichloride dinitro disulfide solution; Step 3: silver acetate dinitro disulfide solution and antimony trichloride dinitro disulfide solution are mixed and polyvinyl pyrrolidone is stirred and mixed; Step 4: warming up to 160 ° C, reacting for 20 to 40 hours, washing with water and washing with alcohol, and obtaining nanotubes after centrifugation. The sterilizing nanotube material for wastewater treatment prepared by the present invention forms a clustered hollow nanotube material, which greatly increases the contact area, improves the ability to treat wastewater, has more powerful bactericidal performance, and can therefore be applied to the treatment of medical wastewater, with broad prospects for use.

Description

Technical Field

[0001] The present invention relates to the field of sewage treatment, and more particularly to a bactericidal nanotube material for wastewater treatment. Background Art

[0002] Medical wastewater has always been the most difficult area to treat in the field of wastewater treatment. In addition to the common COD, some pathogens remain in medical wastewater. Although some disinfection methods are used during the treatment process, the resurrection of pathogens often occurs. The literature "Zhang Yongji, Liu Wenjun. Effect of ultraviolet disinfection on the activity of Escherichia coli during photoreactivation [J]. China Water and Wastewater, 2006, 22(17): 4." reported the problem of Escherichia coli resurrection after disinfection.

[0003] Therefore, how to quickly disinfect medical wastewater has become a major problem. Summary of the invention

[0004] In view of the shortcomings of the prior art, the object of the present invention is to provide a bactericidal nanotube material for wastewater treatment.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] A bactericidal nanotube material for wastewater treatment.

[0007] The reaction comprises the following steps:

[0008] Step 1: dissolving silver acetate and 4,4'-dinitrodiphenyl disulfide in a molar ratio of 1:1 in a solvent to prepare a silver acetate-dinitrodiphenyl disulfide solution;

[0009] Step 2: dissolving antimony trichloride and 4,4'-dinitrodiphenyl disulfide in a molar ratio of 1:1 in a solvent to prepare an antimony trichloride-dinitrodiphenyl disulfide solution;

[0010] Step 3: Mixing the silver acetate-dinitro disulfide solution and the antimony trichloride-dinitro disulfide solution, and stirring the mixture with polyvinyl pyrrolidone;

[0011] Step 4: Raise the temperature to 160°C, react for 20 to 40 hours, wash with water and alcohol, and centrifuge to obtain nanotubes.

[0012] As a further improvement of the present invention,

[0013] The solvent in the silver acetate-dinitrodisulfide solution is ethanol.

[0014] As a further improvement of the present invention,

[0015] The amount of ethanol used in the silver acetate-dinitrodisulfide solution is 20 ml of ethanol per 1 mmol of silver acetate.

[0016] As a further improvement of the present invention,

[0017] The solvent in the antimony trichloride-dinitrodisulfide solution is ethanol.

[0018] As a further improvement of the present invention,

[0019] The amount of ethanol used in the antimony trichloride-dinitrodisulfide solution is 10 ml of ethanol per 1 mmol of antimony trichloride.

[0020] As a further improvement of the present invention,

[0021] In the step three, the molecular weight of polyvinyl pyrrolidone is 1,300,000.

[0022] As a further improvement of the present invention,

[0023] The mixing and stirring time in step 3 is 30 minutes.

[0024] The bactericidal nanotube material for wastewater treatment prepared by the present invention forms a clustered hollow nanotube material, which greatly increases the contact area, can more fully contact the wastewater, improves the ability to treat wastewater, and has a stronger bactericidal performance. Therefore, it can be suitable for the treatment of medical wastewater, thereby reducing the use of antibiotics and other sterilization equipment in medical wastewater and reducing the problem of secondary pollution. It has broad prospects for use.

[0025] In the prior art, a large amount of COD is present at the back end of medical wastewater treatment, and membrane treatment is generally used at the back end. However, due to the large amount of COD, COD itself is an organic matter, and the membrane is generally made of polymer materials. Due to the principle of like dissolves like, the service life of the membrane is greatly reduced. Therefore, a post-treatment membrane that can be suitable for high COD environments and has a sterilization function is needed.

[0026] A post-treatment membrane is prepared by the following steps:

[0027] Step 1: Add N-methylpyrrolidone, polyvinylidene fluoride, polyacrylonitrile, polyethylene glycol (PEG600), polyvinylpyrrolidone (PVP, K30), Tween-80, and bactericidal nanotube material into a reaction kettle, and stir at 70°C to form a mixed solution;

[0028] Step 2: Add the mixed solution into the spinning kettle, stir for 3 hours, let it stand for 3 hours, and vacuum degas;

[0029] Step 3: Open the spinneret installed on the spinning kettle and use 0.2Mpa nitrogen as the pressure source for spinning;

[0030] Step 4: Collect the fiber filaments and place them on a wire arrangement wheel, soak them in deionized water for 24 hours, and then soak them in a 50% glycerol aqueous solution for 24 hours. After drying, a post-processed membrane is obtained.

[0031] The mass ratio of polyvinylidene fluoride, polyacrylonitrile, N-methylpyrrolidone, polyethylene glycol (PEG600), polyvinylpyrrolidone (PVP, K30), Tween-80, and bactericidal nanotube material is 90:10:500:15:30:25:3.

[0032] The post-treatment membrane prepared by the present invention contains the bactericidal nanotube material prepared by the above method, which can greatly improve the service life. During use, the bactericidal nanotube material has a high efficiency bactericidal effect, can remove bacteria in wastewater, etc., and can catalyze the decomposition of COD under light, thereby reducing the COD content in the use environment of the post-treatment membrane and improving its service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The scanning electron microscope of Example 1 Figure 1 ;

[0034] Figure 2 The scanning electron microscope of Example 1 Figure 2 ;

[0035] Figure 3 The scanning electron microscope of Example 1 Figure 3 . DETAILED DESCRIPTION

[0036] The present invention will be further described below in detail with reference to the embodiments shown in the accompanying drawings. Embodiment 1

[0037] A bactericidal nanotube material for wastewater treatment.

[0038] The reaction comprises the following steps:

[0039] Step 1: preparing a silver acetate-dinitrodisulfide solution by mixing silver acetate and dinitrodisulfide in a molar ratio of 1:1;

[0040] Step 2: preparing an antimony trichloride-dinitrodisulfide solution by mixing antimony trichloride and dinitrodisulfide in a molar ratio of 1:1;

[0041] Step 3: Mixing the silver acetate-dinitro disulfide solution and the antimony trichloride-dinitro disulfide solution, and stirring the mixture with polyvinyl pyrrolidone;

[0042] Step 4: Raise the temperature to 160° C., react for 20 hours, wash with water and alcohol, and centrifuge to obtain nanotubes.

[0043] The solvent in the silver acetate-dinitrodisulfide solution is ethanol.

[0044] The amount of ethanol used in the silver acetate-dinitrodisulfide solution is 20 ml of ethanol per 1 mmol of silver acetate.

[0045] The solvent in the antimony trichloride-dinitrodisulfide solution is ethanol.

[0046] The amount of ethanol used in the antimony trichloride-dinitrodisulfide solution is 10 ml of ethanol per 1 mmol of antimony trichloride.

[0047] In the step three, the molecular weight of polyvinyl pyrrolidone is 1,300,000.

[0048] The mixing and stirring time in step 3 is 30 minutes. Embodiment 2

[0049] A post-treatment membrane is prepared by the following steps:

[0050] Step 1: Add N-methylpyrrolidone, polyvinylidene fluoride, polyacrylonitrile, polyethylene glycol (PEG600), polyvinylpyrrolidone (PVP, K30), Tween-80, and bactericidal nanotube material into a reaction kettle, and stir at 70°C to form a mixed solution;

[0051] Step 2: Add the mixed solution into the spinning kettle, stir for 3 hours, let it stand for 3 hours, and vacuum degas;

[0052] Step 3: Open the spinneret installed on the spinning kettle and use 0.2Mpa nitrogen as the pressure source for spinning;

[0053] Step 4: Collect the fiber filaments and place them on a wire arrangement wheel, soak them in deionized water for 24 hours, and then soak them in a 50% glycerol aqueous solution for 24 hours. After drying, a post-processed membrane is obtained.

[0054] The mass ratio of polyvinylidene fluoride, polyacrylonitrile, N-methylpyrrolidone, polyethylene glycol (PEG600), polyvinylpyrrolidone (PVP, K30), Tween-80, and bactericidal nanotube material is 90:10:500:15:30:25:3.

[0055] The post-treatment membrane prepared by the present invention contains the bactericidal nanotube material prepared by the above method, which can greatly improve the service life. During use, the bactericidal nanotube material has a high efficiency bactericidal effect, can remove bacteria in wastewater, etc., and can catalyze the decomposition of COD under light, thereby reducing the COD content in the use environment of the post-treatment membrane and improving its service life.

[0056] Comparative Example 1:

[0057] Nanotube materials,

[0058] The reaction comprises the following steps:

[0059] Step 1: preparing a silver acetate-diphenyl disulfide solution by mixing silver acetate and diphenyl disulfide in a molar ratio of 1:1;

[0060] Step 2: preparing an antimony trichloride-diphenyl disulfide solution by mixing antimony trichloride and diphenyl disulfide in a molar ratio of 1:1;

[0061] Step 3: Mixing the silver acetate-diphenyl disulfide solution and the antimony trichloride-diphenyl disulfide solution, and stirring the mixture with polyvinyl pyrrolidone;

[0062] Step 4: Raise the temperature to 160° C., react for 20 hours, wash with water and alcohol, and centrifuge to obtain nanotubes.

[0063] The solvent in the silver acetate-diphenyl disulfide is ethanol.

[0064] The amount of ethanol used in the silver acetate-diphenyl disulfide solution is 20 ml of ethanol per 1 mmol of silver acetate.

[0065] The solvent in the antimony trichloride-dinitrodisulfide solution is ethanol.

[0066] The amount of ethanol used in the antimony trichloride-diphenyl disulfide solution is 10 ml of ethanol per 1 mmol of antimony trichloride.

[0067] In the step three, the molecular weight of polyvinyl pyrrolidone is 1,300,000.

[0068] The mixing and stirring time in step 3 is 30 minutes.

[0069] Comparative Example 2:

[0070] Step 1: Dissolve 1 mmol of copper acetate and 1 mmol of diphenyl disulfide in 20 ml of ethanol to prepare solution A;

[0071] Step 2: Take 1 mmol of antimony trichloride and 1 mmol of diphenyl disulfide and dissolve them in 10 ml of ethanol to prepare solution B;

[0072] Step 3: Mix solution A and solution B, add polyvinyl pyrrolidone (PVP-1300000), mix and stir;

[0073] Step 4: Raise the temperature to 180° C., react for 36 hours, wash three times with deionized water and ethanol respectively, and obtain nanotube material after centrifugation.

[0074] Ingredients:

[0075]

[0076] test:

[0077] 1. The bactericidal nanotube materials prepared in Example 1 and Comparative Example 1 were observed by scanning electron microscopy.

[0078] Figures 1 to 3 This is an electron microscope photo of Example 1. It can be seen that a cluster of hollow nanotube materials is prepared, which greatly increases the contact area and can more fully contact the wastewater.

[0079] However, no nanotube-like material was found in Comparative Example 1.

[0080] During the research and development process, traditional acetate metal salts all used diphenyl disulfide, but many experiments failed to obtain nanotube materials on silver acetate. This is because silver ions themselves tend to precipitate quickly. After many unsuccessful attempts, dinitro disulfide was used, which enabled the nanomaterials using silver acetate as raw material to form clustered hollow nanotube materials.

[0081] 2. COD test

[0082] The same batch of medical wastewater was taken to measure the initial COD value according to HJ 828-2017, and a photocatalytic degradation experiment was carried out with a 500 W xenon lamp as the visible light source. A filter was placed under the light source to allow only visible light with λ>400 nm to pass through, to ensure that the photocatalytic reaction was carried out under visible light for 24 hours, and the amount of nanomaterials used was 1 g / L.

[0083]

[0084] From the above test, it can be seen that the clustered hollow nanotube material obtained in Example 1 has a better photocatalytic effect of eliminating COD, which is due to the shape of its hollow nanotubes, which has a larger contact area. Since the comparative example 1 cannot form a hollow nanotube material, its catalytic efficiency is relatively low. The nanotube material of comparative example 2 is not very suitable for removing COD in wastewater.

[0085] 3. Sterilization test: refer to GB / T 21510-2008

[0086]

[0087] It can be seen from the above test results that the nanomaterial obtained in Example 1 has a better bactericidal effect, and the comparative example 1 also has a certain bactericidal effect because it is loaded with silver, while the bactericidal effect of the comparative example 2 is greatly reduced.

[0088] In summary, the bactericidal nanotube material for wastewater treatment prepared by the present invention forms a clustered hollow nanotube material, which greatly increases the contact area, can more fully contact the wastewater, improves the ability to treat wastewater, and has a stronger bactericidal performance. Therefore, it can be suitable for the treatment of medical wastewater, thereby reducing the use of antibiotics and other sterilization equipment in medical wastewater and reducing the problem of secondary pollution. It has broad prospects for use.

[0089] The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments. All technical solutions under the concept of the present invention belong to the protection scope of the present invention. It should be pointed out that for ordinary technicians in this technical field, some improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. A bactericidal nanotube material for wastewater treatment, characterized in that: The reaction comprises the following steps: Step 1: dissolving silver acetate and 4,4'-dinitrodiphenyl disulfide in a molar ratio of 1:1 in a solvent to prepare a silver acetate-dinitrodiphenyl disulfide solution; Step 2: dissolving antimony trichloride and 4,4'-dinitrodiphenyl disulfide in a molar ratio of 1:1 in a solvent to prepare an antimony trichloride-dinitrodiphenyl disulfide solution; Step 3: Mixing the silver acetate-dinitro disulfide solution and the antimony trichloride-dinitro disulfide solution, and stirring the mixture with polyvinyl pyrrolidone; Step 4: Raise the temperature to 160°C, react for 20 to 40 hours, wash with water and alcohol, and centrifuge to obtain nanotubes.

2. The bactericidal nanotube material for wastewater treatment according to claim 1, characterized in that: The solvent in the silver acetate-dinitrodisulfide solution is ethanol.

3. The bactericidal nanotube material for wastewater treatment according to claim 2, characterized in that: The amount of ethanol used in the silver acetate-dinitrodisulfide solution is 20 ml of ethanol per 1 mmol of silver acetate.

4. The bactericidal nanotube material for wastewater treatment according to claim 1, characterized in that: The solvent in the antimony trichloride-dinitrodisulfide solution is ethanol.

5. The bactericidal nanotube material for wastewater treatment according to claim 2, characterized in that: The amount of ethanol used in the antimony trichloride-dinitrodisulfide solution is 10 ml of ethanol per 1 mmol of antimony trichloride.

6. The bactericidal nanotube material for wastewater treatment according to claim 1, characterized in that: In the step three, the molecular weight of polyvinyl pyrrolidone is 1,300,000.

7. The bactericidal nanotube material for wastewater treatment according to claim 1, characterized in that: The mixing and stirring time in step 3 is 30 minutes.

8. A post-treatment membrane for wastewater treatment, characterized in that: A post-treatment membrane prepared using the bactericidal nanotube material according to any one of claims 1 to 7.

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