CN211358399U

CN211358399U - Porous titanium dioxide nano antibacterial particle composite polytetrafluoroethylene tubular membrane

Info

Publication number: CN211358399U
Application number: CN201922038442.6U
Authority: CN
Inventors: 段伟; 杨瀚
Original assignee: Shenzhen Reamem Membrane Technology Co ltd
Current assignee: Shenzhen Reamem Membrane Technology Co ltd
Priority date: 2019-11-22
Filing date: 2019-11-22
Publication date: 2020-08-28
Anticipated expiration: 2029-11-22

Abstract

The utility model discloses a compound polytetrafluoroethylene tubular membrane of porous copper clad titanium dioxide nanometer antibacterial particle, including the tubulose wall body, the dispersion embedding has porous copper clad titanium dioxide nanometer antibacterial particle in this tubulose wall body. The density of the porous copper-clad titanium dioxide nano antibacterial particles embedded in the surface layer of the tubular wall body is higher than that of the tubular wall bodyThe density of the porous copper-coated titanium dioxide nano antibacterial particles contained in the inner part. The utility model provides a porous copper-clad TiO₂The nano antibacterial particle composite polytetrafluoroethylene tubular membrane has the advantages of large water flux, bacterial pollution resistance and easy cleaning, and can be widely applied to the application fields of sewage treatment, material concentration, landfill leachate, wastewater with high acidity or alkalinity and the like.

Description

Porous titanium dioxide nano antibacterial particle composite polytetrafluoroethylene tubular membrane

Technical Field

The utility model relates to a membrane separation technical field, concretely relates to compound Polytetrafluoroethylene (PTFE) tubular membrane of porous copper cladding titanium dioxide nanometer antibacterial particle.

Background

With the rapid development of national economy and the continuous improvement of the living standard of people, the requirements on the environment, particularly the water environment safety, are higher and higher. In order to obtain more stable and higher effluent quality, membrane water treatment technology is increasingly adopted in sewage treatment and drinking water treatment processes. The complexity of waste water, especially industrial waste water, is constantly placing increasing demands on membranes, such as the high salinity and strong acidity of landfill leachate, and the membranes are very easily contaminated, which severely limits the service life of the membranes in landfill leachate. Therefore, the tubular membrane is used for treating sewage which is difficult to treat, and the pollution on the surface of the membrane is reduced by utilizing the high-speed flow of fluid in the tube, so that the cleaning frequency of the membrane is reduced, and the service life of the membrane is prolonged. However, in the treatment of some waste liquid with strong acidity or alkalinity, common membrane materials cannot bear, so that the polytetrafluoroethylene membrane is also applied to the sewage treatment with special properties due to the excellent acid and alkali resistance. In conclusion, the polytetrafluoroethylene tubular membrane has a very wide potential application prospect in the aspects of difficult sewage treatment and special sewage treatment, and at present, no polytetrafluoroethylene tubular membrane product exists in the market.

The polytetrafluoroethylene membrane has poor hydrophilicity and also readily adsorbs contaminants by itself. These disadvantages all limit the wide application of polytetrafluoroethylene membranes. Therefore, the anti-pollution performance of the membrane is increased, and the anti-pollution performance of the membrane is of great significance for expanding the application of the membrane.

The hydrophilicity of the membrane surface is increased, so that the pollution resistance of the membrane surface can be reduced, the chemical modification of the membrane surface comprises the steps of radiating and grafting the hydrophilic group, introducing the nano ceramic particles into the membrane material, coating the hydrophilic coating on the membrane surface and the like, so that the hydrophilicity of the membrane surface can be increased.

The tubular membrane is a mode of pressure filtration, pollutants are easy to deposit on the surface of the membrane, and membrane pollution caused by microorganisms such as bacteria becomes an important component of membrane pollution in the water treatment process. Therefore, loading an antibacterial substance on the surface of the membrane, constructing the surface of the membrane with antibacterial performance, and improving the antibacterial performance of the surface of the membrane, so that the effective reduction of biological pollution is also an important means for improving the anti-pollution performance of the membrane.

The antibacterial material mainly comprises inorganic, organic and natural macromolecular antibacterial agents. The research and application of the nano-silver antibacterial agent of the inorganic antibacterial agent are the most extensive, the market share is high, but the countries in Europe and America have found that the nano-silver has safety risks to human health, so that the related application of the nano-silver material is limited. Copper is a trace element needed by human bodies, and in 3 months of 2008, the united states Environmental Protection Agency (EPA) confirms that copper can kill harmful and possibly fatal germs, and copper is the only metal bacteriostatic material which is certified by the united states Environmental Protection Agency (EPA), so that the adoption of nano copper-based antibacterial agents with biological safety becomes a safer choice. This is particularly important for polytetrafluoroethylene tubular membranes used in drinking water treatment. The copper-coated titanium dioxide novel nano antibacterial particle (shown in figures 1 and 3) has a long-acting metal ion release effect, can have a good antibacterial and mildewproof function under a dark condition, and is a novel nano antibacterial particle with biological safety.

Therefore, it is a problem to be solved by the industry to prepare a polytetrafluoroethylene tubular membrane having excellent chemical stability and good hydrophilicity and contamination resistance.

SUMMERY OF THE UTILITY MODEL

The utility model discloses a solve current tubular membrane and can't compromise the technical problem that the membrane surface antibacterial property is good and have membrane flux big again, provide a water flux big, antibacterial pollution, the easy abluent compound polytetrafluoroethylene tubular membrane of porous polytetrafluoroethylene nanometer antibacterial particle.

The utility model provides a compound polytetrafluoroethylene tubular membrane of porous copper clad titanium dioxide nanometer antibacterial particle, it includes that the pore structure is the tubular wall body of polytetrafluoroethylene tubular membrane of symmetric holes, and the dispersion embedding has porous copper clad titanium dioxide nanometer antibacterial particle in this tubular wall body.

Preferably, the density of the porous copper-clad titanium dioxide nano antibacterial particles embedded in the surface layer of the tubular wall body is greater than that of the porous copper-clad titanium dioxide nano antibacterial particles embedded in the tubular film.

Preferably, the porous copper-clad titanium dioxide nano antibacterial particle is provided with a plurality of micro through holes, and the surface of the particle is provided with metal copper particles.

Preferably, the material of the tubular wall body is distributed in the fine through holes in the porous copper-clad titanium dioxide nano antibacterial particles.

The porous copper-clad titanium dioxide nano antibacterial particles used by the utility model have good hydrophilicity, more internal through holes and small aperture (a)<2 nm) and the like, and (1) after the nano antibacterial particles are compounded with the polytetrafluoroethylene tubular membrane, the hydrophilicity of the surface of the membrane can be increased due to the excellent hydrophilicity of the nano antibacterial particles, so that the water flux of the membrane can be improved, and the pollution can be reduced. (2) The nano antibacterial particles are internally provided with a large number of through holes, and the membrane liquid can penetrate into the holes to form wedges to firmly fix the nano antibacterial particles, so that the binding force between the nano antibacterial particles and the membrane material is greatly increased, and the antibacterial effect of the nano antibacterial particles is ensured not to be attenuated along with time (see figure 4). (3) The abundant through holes in the nano antibacterial particles can not block the membrane pores (because water can pass through the pores). Thereby remarkably improving the membrane flux. (4) Copper-coated TiO 2₂The nano particles have excellent antibacterial performance, can be enriched on the surface of the membrane after being compounded into the membrane material, can greatly improve the antibacterial and anti-pollution performance of the surface of the polytetrafluoroethylene tubular membrane, has no biological hazard to human bodies and environment, and has no ecological risk in large-scale use. And the copper compound is cheaper than the silver compound, so that the manufacturing cost of the nano antibacterial particles can be reduced, and the manufacturing cost of the antibacterial film can be reduced. (5) Because the utility model provides a compound polytetrafluoroethylene tubular membrane water flux, antibiotic antipollution can improve, can reduce membrane chemical cleaning frequency by a wide margin, the life of extension membrane to reduce membrane operation and maintenance cost, reduce water treatment engineering operation and maintenance cost.

Drawings

FIG. 1 is a schematic view of a conventional nano-ceramic particle;

figure 2 shows the utility modelPorous copper-coated TiO₂A schematic diagram of nano antibacterial particles;

FIG. 3 is a schematic view of the combination of common nano-ceramic particles and membrane material;

FIG. 4 shows the porous copper-coated TiO film of the present invention₂A schematic diagram of the combination of nano antibacterial particles and a polytetrafluoroethylene tubular membrane;

FIG. 5 shows the porous copper-coated TiO film of the present invention₂The cross section of the nano antibacterial particle composite polytetrafluoroethylene tubular membrane is shown schematically.

Detailed Description

As shown in figure 2, figure 4, figure 5, adopt the utility model provides a porous copper clad titanium dioxide nanometer antibacterial particle composite polytetrafluoroethylene tubular membrane that preparation method prepared, this polytetrafluoroethylene tubular membrane has and is symmetrical structure along the cross section direction, and it includes symmetrical structure's polytetrafluoroethylene tubular membrane tubulose wall body 2, and the porous copper clad titanium dioxide nanometer antibacterial particle 1 of dispersion embedding in this tubulose wall body 2, the outward appearance parcel of this particle has the copper granule, has numerous through-hole 5 wherein, can supply liquid infiltration. The density of the porous copper-clad titanium dioxide nano antibacterial particles 1 embedded in the part close to the surface of the tubular wall body 2 is higher than that of the porous copper-clad titanium dioxide nano antibacterial particles 1 embedded in the tubular wall body 2. The thickness of the film is between 1 and 5 mm. The porous copper-coated titanium dioxide nano antibacterial particles 1 are uniformly dispersed and embedded in a polytetrafluoroethylene tubular membrane 2 and are enriched on the surface of the membrane. The trace components of the polytetrafluoroethylene tubular membrane can also be distributed at the edges of the through holes of the nano antibacterial particles 1 to strengthen the fixation of the nano antibacterial particles.

The porous copper-clad titanium dioxide nano antibacterial particle composite polytetrafluoroethylene tubular film can be obtained by the following steps: the porous copper-clad titanium dioxide nano antibacterial particles 1 are gradually embedded into a tubular wall body 2 of a tetrafluoroethylene tubular membrane, the porous copper-clad titanium dioxide nano antibacterial particles are dispersedly embedded into the tubular wall body 2 and are enriched on the surface of the tetrafluoroethylene tubular membrane, and trace components of the tetrafluoroethylene tubular membrane can be distributed at the edge of a through hole 5 of the nano antibacterial particles 1 or embedded into the through hole 5 so as to strengthen and fix the nano antibacterial particles.

According to the content of the porous copper-clad titanium dioxide nano antibacterial particles added into the composite polytetrafluoroethylene tubular membrane, the following embodiments are provided:

examples 0 to 6:

the basic structures of the composite polytetrafluoroethylene tubular membranes provided by the embodiments 0-6 are the same, except that the contents of the porous copper-clad titanium dioxide nano antibacterial particles compositely embedded in the polytetrafluoroethylene tubular membranes are different, and the ratios of the particles to the polytetrafluoroethylene tubular membranes are respectively as follows: 0% (not added), 3.0%, 4.0%, 5.0%, 6.0%, 7.0%, 8.0%, to obtain seven kinds of composite polytetrafluoroethylene tubular membranes.

Comparative example:

the steps are the same as the above embodiment, except that 8 percent (the ratio of the copper-clad titanium dioxide nano antibacterial particles with no pores to the polytetrafluoroethylene) is embedded into the composite polytetrafluoroethylene tubular membrane.

The pure water flux and the bubble point of the prepared polytetrafluoroethylene tubular membrane are detected by adopting a test method of a separation membrane aperture test method bubble point and average flow method GB/T112 + 2008 and a test method of a hollow fiber membrane microporous filter membrane HY/T051 + 1999. The antibacterial performance of the film is determined by using a standard experimental method for determining the antibacterial activity of the fixed antibacterial agent under the dynamic contact condition in ASTM E2149-2013 a. Table 1 shows the performance parameters of the porous copper-clad titanium dioxide nano antibacterial particle composite polytetrafluoroethylene tubular film prepared in examples 0-6.

TABLE 1

The polytetrafluoroethylene tubular membrane was immersed in tap water, the immersion water was changed every day, and samples were taken every other month to test the antibacterial property of the membrane surface, and the results are shown in table 2. The result shows that the antibacterial effect of the porous antibacterial nanoparticle composite polytetrafluoroethylene tubular membrane is little changed along with time, and the main reason is that the binding force of the porous nanoparticles and the membrane material is high, and the porous antibacterial nanoparticle composite polytetrafluoroethylene tubular membrane cannot fall off and run off, so that the porous antibacterial nanoparticle composite polytetrafluoroethylene tubular membrane can keep good antibacterial performance. Table 2 shows the comparison of the long-term antibacterial properties of example 6 and the comparative examples

TABLE 2

The utility model discloses the porous copper clad titanium dioxide nanometer antibacterial particle of preparation has the metal copper particle at its surface parcel, not only gives the more excellent antibiotic antipollution performance of titanium dioxide nano particle, remains the porous structure of nano particle moreover simultaneously, forms to the pure water passageway. In addition, the copper is adopted to replace silver to wrap the nano particles, so that the cost of the nano antibacterial particles is reduced, and the ecological safety of the nano antibacterial material is improved. Porous copper-clad TiO with long-acting antibacterial effect₂The nano antibacterial particle composite polytetrafluoroethylene tubular membrane is beneficial to embedding a membrane material into pores and enhancing the binding force between the nano particles and the membrane material due to the generation of pores inside the porous nano particles, so that the nano particles cannot fall off and run away in the long-term use process, and the long-acting property of the nano antibacterial effect is ensured; on the other hand, the gaps of the nano particles do not block the water permeation of the pores of the polytetrafluoroethylene tubular membrane, so that the flux of the tubular membrane is not influenced. The utility model discloses a compound polytetrafluoroethylene tubular membrane, flux have the improvement of certain degree, increase substantially membrane surface antibacterial property moreover, can delay the membrane pollution of compound polytetrafluoroethylene tubular membrane, are favorable to reducing compound polytetrafluoroethylene tubular membrane and use and the maintenance cost.

The utility model provides a compound polytetrafluoroethylene tubular membrane of porous copper clad titanium dioxide nanometer antibacterial particle water flux is big, antibacterial pollution, easy washing, can wide application in sewage treatment, application fields such as material concentration, landfill leachate, acid or the high waste water of basicity.

The above description is only for the preferred embodiment of the present invention, and should not be taken as limiting the invention, and any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A porous copper-clad titanium dioxide nano antibacterial particle composite polytetrafluoroethylene tubular film comprises a tubular wall body, and is characterized in that porous copper-clad titanium dioxide nano antibacterial particles are dispersedly embedded in the tubular wall body.

2. The porous copper-clad titanium dioxide nano antibacterial particle composite polytetrafluoroethylene tubular film according to claim 1, wherein the density of the porous copper-clad titanium dioxide nano antibacterial particles embedded in the surface layer of the tubular wall body is greater than that of the porous copper-clad titanium dioxide nano antibacterial particles contained in the tubular wall body.

3. The porous copper-clad titanium dioxide nano antibacterial particle composite polytetrafluoroethylene tubular film according to claim 1, wherein the porous copper-clad titanium dioxide nano antibacterial particles are provided with a plurality of fine through holes, and the surfaces of the particles are provided with metal copper particles.

4. The porous copper-clad titanium dioxide nano antibacterial particle composite polytetrafluoroethylene tubular film according to claim 1, wherein the material of the tubular wall body is distributed in the fine through holes in the porous copper-clad titanium dioxide nano antibacterial particles.