CN110548408B - Blended Cu-Zn inorganic hollow fiber antibacterial film and preparation method and application thereof - Google Patents
Blended Cu-Zn inorganic hollow fiber antibacterial film and preparation method and application thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
Abstract
The invention discloses a blended Cu-Zn inorganic hollow fiber antibacterial film and a preparation method and application thereof. Dissolving polysulfone in an organic solvent, adding Cu-Zn alloy and inorganic powder, stirring and mixing uniformly to obtain a membrane casting solution, carrying out vacuum defoaming on the membrane casting solution, extruding hollow fibers through a spinneret, carrying out phase inversion molding in an internal and external coagulating bath, soaking, naturally air-drying to obtain a hollow fiber membrane precursor, and finally sintering in a mixed atmosphere of nitrogen and hydrogen to obtain the blended Cu-Zn inorganic hollow fiber antibacterial membrane. The preparation method provided by the invention adopts a mode of combining phase inversion sintering, and has the advantages of simple process, lower sintering temperature, low cost, easy realization of industrialization and the like. The blended Cu-Zn inorganic hollow fiber antibacterial membrane provided by the invention has the advantages of large flux, higher mechanical strength, good separation performance, high antibacterial efficiency and the like, and can be applied to the field of water treatment.
Description
Technical Field
The invention belongs to the technical field of inorganic hollow fiber membrane separation, and particularly relates to an inorganic hollow fiber membrane blended with Cu-Zn alloy, and a preparation method and application thereof.
Background
The application of membrane separation technology in water treatment is becoming more and more extensive, wherein the membrane material is a key part, the development of membrane material promotes the improvement and the perfection of membrane separation technology, and the expansion of the application range of membrane separation technology makes the development of new membrane material especially important.
At present, the problem of membrane pollution still remains the main problem of membrane separation technology, most researches are still focused on organic membrane pollution, the researches on ceramic membrane pollution are less, mainly because the ceramic membrane has stable chemical and mechanical properties and can be cleaned and backwashed, but the ceramic membrane has large brittleness and is fragile, particularly the ceramic hollow fiber membrane is easy to break in the process of assembling and cleaning, and in order to solve the problem, the mechanical strength of the hollow fiber membrane is continuously improved, and the membrane material can be improved, so that the pollution resistance of the hollow fiber membrane is improved. The microbial membrane pollution is common pollution in ceramic membrane pollution, and microorganisms are easily bred on the surface during filtration and separation, so that membrane pores are blocked, and the flux is reduced. Therefore, the preparation of the ceramic hollow fiber membrane with the function of resisting the microbial contamination is of great significance.
In recent years, a plurality of patents and documents report that the inorganic antibacterial agent is added into a high molecular polymer to prepare an organic hollow fiber antibacterial membrane, for example, CN108744995A uses silver ions to dope nano zinc oxide or silver ions to dope nano titanium dioxide, polysulfone, a pore-forming agent and polyethylene glycol to blend and modify the hollow fiber membrane, so that the antibacterial rate of the hollow fiber membrane is increased. CN101703892A one or more of nanometer titanium dioxide, nanometer silver, nanometer copper and nanometer zinc are mixed with polysulfone to prepare the antibacterial and bacteriostatic polysulfone hollow fiber ultrafiltration membrane. CN104437139A blending copper nanoparticles and hydrophilic sulfonated polyarylethersulfone into polyethersulfone to prepare the organic-inorganic hybrid antibacterial ultrafiltration membrane. The research on the preparation of inorganic hollow fiber antibacterial films is less, and the antibacterial ceramic films are generally reported in the patent and literature, but the antibacterial ceramic hollow fiber films are not, for example, CN107138049A loads metal copper nanoparticles on titanic acid nanobelts,then adding Cu/TiO2The nano porous ceramic membrane prepared by nano belt tabletting and calcining has the functions of sterilization and separation. CN104128101A mixes silver in the ceramic separation layer, improves the antibacterial property of the ceramic membrane. CN103846019A adds inorganic compounds containing silver ions, copper ions and zinc ions or inorganic antibacterial agents containing nano silver, nano copper and nano gold into diatomite to sinter and prepare the porous ceramic membrane, which has high porosity and durable antibacterial property. In the existing research, silver ions are used for preparing antibacterial films, silver nitrate is mostly used as a metal source for introducing Ag, anions of the Ag are carried in the films and can damage the purified water quality, and the Ag belongs to a noble metal, is expensive and has high cost.
The copper-zinc alloy can remove residual chlorine and harmful heavy metal ions in water, and has the functions of sterilization and antibiosis, and CN102145261A adopts a physical vapor deposition method to deposit the copper-zinc alloy on a substrate to prepare a nanofiltration membrane, wherein the antibacterial rate reaches 99.99 percent, but the preparation process is complex and the requirements on process conditions are high.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a Cu-Zn blended inorganic hollow fiber antibacterial film and a preparation method and application thereof.
According to the preparation method of the blended Cu-Zn inorganic hollow fiber antibacterial membrane, provided by the invention, the phase conversion sintering technology is mainly utilized, the Cu-Zn alloy powder and the inorganic powder are blended to prepare the inorganic hollow fiber antibacterial membrane, the process is simple, no organic additive is required to be added in the preparation process, the preparation process is simple, the cost is low, and the industrialization is easy to realize; the prepared blended Cu-Zn inorganic hollow fiber antibacterial film has high antibacterial rate and can be used for water treatment.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a preparation method of a blended Cu-Zn inorganic hollow fiber antibacterial film, which comprises the following steps:
(1) preparation of organic solutions
Adding anhydrous polysulfone into an organic solvent, and mechanically stirring uniformly in a water bath kettle to obtain a homogeneous organic solution;
(2) preparation of casting solution
Slowly adding anhydrous Cu-Zn alloy powder and inorganic powder into the homogeneous organic solution in the step (1) under a stirring state, uniformly stirring, and defoaming in vacuum to obtain a casting solution;
(3) extrusion molding
Pouring the casting solution obtained in the step (2) into a spinning device, opening an inner coagulation bath valve, simultaneously opening an air pump, extruding the casting solution obtained in the step (2) through a spinning nozzle (extruding at a certain extrusion speed under the pushing of air pressure) to obtain a hollow fiber membrane blank, soaking the hollow fiber membrane blank in an outer coagulation bath, and replacing a solvent with a non-solvent under the action of the inner coagulation bath and the outer coagulation bath; after complete replacement, solidifying and forming, placing the fiber in a dry and ventilated place, taking out the fiber and naturally drying the fiber to obtain a hollow fiber precursor;
(4) sintering
And (3) sintering the hollow fiber membrane precursor obtained in the step (3) in a sintering atmosphere (mixed atmosphere of nitrogen and hydrogen), and removing the organic polymer to obtain the Cu-Zn blended inorganic hollow fiber antibacterial membrane (the hollow fiber membrane only containing Cu-Zn alloy powder and inorganic particles).
Preferably, the stirring in the step (1) is uniform, the polysulfone can be heated and stirred in a water bath kettle, the dissolving rate of the polysulfone in the organic solvent is increased, and the water bath temperature in the water bath kettle can be 65 ℃;
further, the mass of the polysulfone in the step (1) accounts for 4-8% of that of the membrane casting solution in the step (2); the organic solvent in the step (1) comprises N-methyl pyrrolidone; and (3) the mass of the organic solvent in the step (1) accounts for 20-36% of the mass of the casting solution in the step (2).
Further, the stirring speed of the step (2) under the stirring state is 80-120 r/min.
Preferably, the anhydrous Cu-Zn alloy powder and the inorganic powder are added in the step (2), and the two powders can be added at intervals; the stirring speed can be appropriately lowered at the time of addition.
Preferably, the stirring period of the step (2) is 8-12 h.
Preferably, the time for vacuum defoaming in the step (2) is 1 h.
Further, the particle size of the anhydrous Cu-Zn alloy powder in the step (2) is 11-13 μm; the mass ratio of copper to zinc in the Cu-Zn alloy is 60:40-85: 15; and (3) the mass of the Cu-Zn alloy powder accounts for 3-60% of the mass of the casting solution in the step (2).
Further, the inorganic powder of step (2) includes α -Al2O3And diatomaceous earth; the alpha-Al2O3The particle diameter of (A) is 0.5-1 μm; the particle size of the diatomite is 2-6 mu m; and (3) the mass of the inorganic powder accounts for 16-57% of the mass of the casting solution in the step (2).
Further, the polysulfone, the Cu-Zn alloy powder and the inorganic powder are all anhydrous materials.
Further, the outer diameter of the spinneret in the step (3) is 1.5-3.5mm, and the inner diameter is 1-1.1 mm; the extrusion rate of the step (3) is 10-15 mL/min.
Further, the air pressure pushing in the step (3) is air as the driving air pressure.
Further, in the step (3), the inner and outer coagulation baths are both tap water, and the temperature of the bath (including the inner and outer coagulation baths) immersed in the water is both room temperature.
Further, the inner coagulation bath and the outer coagulation bath in the step (3) are both water (tap water); preferably, in the step (3), the soaking time is 24-36 h.
Further, the temperature of the sintering treatment in the step (4) is 1200-1300 ℃, and the sintering time is 1-2 hours.
Further, the sintering atmosphere in the step (4) is a mixed atmosphere of nitrogen and hydrogen.
The invention provides a blended Cu-Zn inorganic hollow fiber antibacterial film prepared by the preparation method.
The Cu-Zn alloy inorganic medium-high fiber membrane prepared by the method has the porosity of 31.79-58.6%, the bending strength of 1.45-8.11MPa, and the tap water flux of 2462.11-26539.28L/(m) under 0.1MPa2H), the filtration sterilization rate is 99.99 percent, and the antibacterial rate is 78.2 to 90.3 percent.
The Cu-Zn blended inorganic hollow fiber antibacterial membrane provided by the invention can be applied to the field of water treatment (filtration and sterilization).
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the blended Cu-Zn inorganic hollow fiber antibacterial membrane provided by the invention has the advantages of high flux, higher mechanical property, good separation performance, good bacteria removal and antibacterial performance and the like.
(2) According to the preparation method provided by the invention, the adopted raw material Cu-Zn alloy has oxidation reduction capability, can remove residual chlorine and also has an antibacterial effect; the method for preparing the hollow fiber membrane by blending the Cu-Zn alloy powder and the inorganic particles overcomes the defects that anions are carried in the membrane, the purified water quality is damaged, the cost of silver is high and the like in the process of preparing the silver-loaded ceramic membrane by taking silver nitrate as a metal source in the prior art, and the Cu-Zn alloy adopted as the raw material contains two metals, has better antibacterial effect compared with a single metal, and can reduce the microbial pollution during the filtration of the ceramic membrane.
(3) The preparation method provided by the invention has simple preparation process; compared with the existing silver-loaded ceramic membrane, the hollow fiber membrane prepared by the method has low cost and is easy to realize industrialization.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the following processes, if not described in particular detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer and are considered to be conventional products available by commercial purchase.
Example 1
The preparation method of the Cu-Zn blended inorganic hollow fiber antibacterial film provided in embodiment 1 includes the following steps:
(1) preparation of organic solutions
Adding 5.16g of anhydrous polysulfone (accounting for 8 percent of the mass of the membrane casting solution) and 20.64g of organic solvent (N-methylpyrrolidone) into a three-fork round-bottom flask, stirring and dissolving, accelerating the dissolving rate under the water bath condition of 65 ℃, and uniformly stirring to obtain a homogeneous organic solution;
(2) preparation of casting solution
35.475g of anhydrous alpha-Al are stirred (stirring rate 90r/min)2O3Powder (anhydrous alpha-Al)2O3The particle size of the powder is 0.5 μm; anhydrous alpha-Al2O3The mass of the powder accounts for 55 percent of the mass of the casting solution) and is added into the homogeneous organic solution in the step (1); 3.225g of anhydrous Cu-Zn alloy powder (the particle size of the anhydrous Cu-Zn alloy powder is 11 mu m, the mass of the anhydrous Cu-Zn alloy powder accounts for 5 percent of the mass of the casting solution, the mass ratio of copper to zinc in the Cu-Zn alloy is 60: 40) is continuously added into the homogeneous organic solution in the step (1) under the stirring state (the stirring speed is 90r/min), and the alpha-Al2O3Adding the powder and Cu-Zn alloy powder at intervals for multiple times, continuously stirring for 8 hours, uniformly stirring, and defoaming in vacuum for 1 hour to obtain a casting solution;
(3) extrusion molding
Pouring the casting solution obtained in the step (2) into a spinning device, opening a water outlet valve of an internal coagulation bath (tap water), simultaneously pushing the casting solution to a spinning nozzle (with the inner diameter of 1mm and the outer diameter of 1.5mm) by air pressure for extrusion molding, wherein the extrusion rate is 14mL/min, and obtaining a hollow fiber membrane blank; soaking in external coagulating bath (tap water) for 24 hr, exchanging solvent and non-solvent under the action of the internal and external coagulating baths, and coagulating to form; taking out and placing in a dry and ventilated place for air drying to obtain the hollow fiber precursor.
(4) Sintering
Sintering the hollow fiber membrane precursor obtained in the step (3) in a sintering atmosphere (mixed atmosphere of nitrogen and hydrogen), wherein the sintering temperature is 1200 ℃, the sintering time is 1h, and removing organic matters to obtain the Cu-Zn blended inorganic hollow fiber antibacterial membrane (alpha-Al blended with Cu-Zn alloy)2O3Hollow fiber antibacterial film).
The porosity is tested by adopting an Archimedes method, and the bending strength and the sterilization rate are tested by adopting a three-point methodA multitube fermentation method specified in the sanitary standard for drinking water GB5749-2006 is adopted in the test, and an oscillation bottle method is adopted in the Escherichia coli antibacterial test. The porosity of the blended Cu-Zn inorganic hollow fiber antibacterial film prepared in example 1 is tested to be 45.33%; the breaking strength is 4.77 MPa; the flux of tap water at 0.1MPa is 4507.94L/(m)2H); the filtration sterilization rate is 99.99 percent; the antibacterial rate of Escherichia coli is 79.1%.
Example 2
The preparation method of the Cu-Zn blended inorganic hollow fiber antibacterial film provided in embodiment 2 includes the following steps:
(1) preparation of organic solutions
Adding 5.16g of anhydrous polysulfone (accounting for 8 percent of the mass of the membrane casting solution) and 20.64g of organic solvent (N-methylpyrrolidone) into a three-fork round-bottom flask, stirring and dissolving, accelerating the dissolving rate under the water bath condition of 65 ℃, and uniformly stirring to obtain a homogeneous organic solution;
(2) preparation of casting solution
35.475g of anhydrous alpha-Al are stirred (stirring rate 80r/min)2O3Powder (anhydrous alpha-Al)2O3The particle size of the powder is 0.7 μm; anhydrous alpha-Al2O3The mass of the powder accounts for 55 percent of the mass of the casting solution) and is added into the homogeneous organic solution in the step (1); 3.225g of anhydrous Cu-Zn alloy powder (the particle size of the anhydrous Cu-Zn alloy powder is 13 mu m, the mass of the anhydrous Cu-Zn alloy powder accounts for 5 percent of the mass of the casting solution, the mass ratio of copper to zinc in the Cu-Zn alloy is 70: 30) is continuously added into the homogeneous organic solution in the step (1) under the stirring state (the stirring speed is 80r/min), and the alpha-Al2O3Adding the powder and Cu-Zn alloy powder at intervals for multiple times, continuously stirring for 8 hours, uniformly stirring, and defoaming in vacuum for 1 hour to obtain a casting solution;
(3) extrusion molding
Pouring the casting solution obtained in the step (2) into a spinning device, opening a water outlet valve of an internal coagulation bath (tap water), and simultaneously pushing the casting solution to a spinning nozzle (with the inner diameter of 1.1mm and the outer diameter of 2.5mm) by air pressure to perform extrusion molding at the extrusion rate of 11mL/min to obtain a hollow fiber membrane blank; soaking in external coagulating bath (tap water) for 36 hr, exchanging solvent and non-solvent under the action of the internal and external coagulating baths, and coagulating to form; taking out and placing in a dry and ventilated place for air drying to obtain the hollow fiber precursor.
(4) Sintering
Sintering the hollow fiber membrane precursor obtained in the step (3) in a sintering atmosphere (mixed atmosphere of nitrogen and hydrogen), wherein the sintering temperature is 1250 ℃, the sintering time is 1.5h, and removing organic matters to obtain the Cu-Zn blended inorganic hollow fiber antibacterial membrane (alpha-Al blended with Cu-Zn alloy)2O3Hollow fiber antibacterial film).
The porosity is tested by adopting an Archimedes method, the bending strength is tested by adopting a three-point method, the bacteria removal rate is tested by adopting a multi-tube fermentation method specified in the sanitary standard GB5749-2006 of the drinking water, and the Escherichia coli antibacterial test adopts an oscillating bottle method. Through testing, the porosity of the blended Cu-Zn inorganic hollow fiber antibacterial film prepared in the testing example 2 is 48.38%; the breaking strength is 3.17 MPa; the flux of tap water at 0.1MPa is 5287.29L/(m)2H); the filtration sterilization rate is 99.99 percent; the antibacterial rate of Escherichia coli is 78.2%.
Example 3
The preparation method of the Cu-Zn blended inorganic hollow fiber antibacterial film provided in embodiment 3 includes the following steps:
(1) preparation of organic solutions
Adding 5.16g of anhydrous polysulfone (accounting for 8 percent of the mass of the membrane casting solution) and 20.64g of organic solvent (N-methylpyrrolidone) into a three-fork round-bottom flask, stirring and dissolving, accelerating the dissolving rate under the water bath condition of 65 ℃, and uniformly stirring to obtain a homogeneous organic solution;
(2) preparation of casting solution
36.765g of anhydrous alpha-Al are stirred (stirring rate 120r/min)2O3Powder (anhydrous alpha-Al)2O3The particle size of the powder is 1 μm; anhydrous alpha-Al2O3The mass of the powder accounts for 57 percent of the mass of the casting solution) and is added into the homogeneous organic solution in the step (1); under stirring conditions (Stirring at a speed of 120r/min) and continuing to prepare 1.935g of anhydrous Cu-Zn alloy powder (the grain diameter of the anhydrous Cu-Zn alloy powder is 12 mu m, and the mass of the anhydrous Cu-Zn alloy powder accounts for 3 percent of that of the casting solution; the mass ratio of copper to zinc in the Cu-Zn alloy is 60: 40) adding the alpha-Al into the homogeneous organic solution in the step (1)2O3Adding the powder and Cu-Zn alloy powder at intervals for multiple times, continuously stirring for 12 hours, uniformly stirring, and defoaming in vacuum for 1 hour to obtain a casting solution;
(3) extrusion molding
Pouring the casting solution obtained in the step (2) into a spinning device, opening a water outlet valve of an internal coagulation bath (tap water), simultaneously pushing the casting solution to a spinning nozzle (with the inner diameter of 1mm and the outer diameter of 1.5mm) by air pressure for extrusion molding, wherein the extrusion rate is 15mL/min, and obtaining a hollow fiber membrane blank; soaking in external coagulating bath (tap water) for 30 hr, exchanging solvent and non-solvent under the action of the internal and external coagulating baths, and coagulating to form; taking out and placing in a dry and ventilated place for air drying to obtain the hollow fiber precursor.
(4) Sintering
Sintering the hollow fiber membrane precursor obtained in the step (3) in a sintering atmosphere (mixed atmosphere of nitrogen and hydrogen), wherein the sintering temperature is 1300 ℃, the sintering time is 2h, and removing organic matters to obtain the Cu-Zn blended inorganic hollow fiber antibacterial membrane (alpha-Al blended with Cu-Zn alloy)2O3Hollow fiber antibacterial film).
The porosity is tested by adopting an Archimedes method, the bending strength is tested by adopting a three-point method, the bacteria removal rate is tested by adopting a multi-tube fermentation method specified in the sanitary standard GB5749-2006 of the drinking water, and the Escherichia coli antibacterial test adopts an oscillating bottle method. The porosity of the blended Cu-Zn inorganic hollow fiber antibacterial film prepared in example 3 is 31.79% through testing; the breaking strength is 8.11 MPa; the flux of tap water at 0.1MPa is 2462.11L/(m)2H); the filtration sterilization rate is 99.99 percent; the antibacterial rate of the escherichia coli is 78.8%.
Example 4
The preparation method of the Cu-Zn blended inorganic hollow fiber antibacterial film provided in embodiment 4 includes the following steps:
(1) preparation of organic solutions
Adding 3.44g of anhydrous polysulfone (accounting for 6 percent of the mass of the membrane casting solution) and 19.49g of organic solvent (N-methylpyrrolidone) into a three-fork round-bottom flask, stirring and dissolving, accelerating the dissolving rate under the water bath condition of 65 ℃, and uniformly stirring to obtain a homogeneous organic solution;
(2) preparation of casting solution
28.667g of anhydrous diatomite (the particle size of the anhydrous diatomite powder is 6 mu m; the mass of the anhydrous diatomite powder accounts for 50 percent of the mass of the casting solution) is added into the homogeneous organic solution in the step (1) under the stirring state (the stirring speed is 100 r/min); continuously adding 5.73g of anhydrous Cu-Zn alloy powder (the particle size of the anhydrous Cu-Zn alloy powder is 13 mu m, the mass of the anhydrous Cu-Zn alloy powder accounts for 10% of the mass of the membrane casting solution, and the mass ratio of copper to zinc in the Cu-Zn alloy is 85:15) into the homogeneous organic solution in the step (1) under the stirring state (the stirring speed is 100r/min), continuously stirring for 8 hours, uniformly stirring, and defoaming in vacuum for 1 hour to obtain the membrane casting solution;
(3) extrusion molding
Pouring the casting solution obtained in the step (2) into a spinning device, opening a water outlet valve of an internal coagulation bath (tap water), simultaneously pushing the casting solution to a spinning nozzle (with the inner diameter of 1mm and the outer diameter of 3.5mm) by air pressure for extrusion molding, wherein the extrusion rate is 12mL/min, and obtaining a hollow fiber membrane blank; soaking in external coagulating bath (tap water) for 36 hr, exchanging solvent and non-solvent under the action of the internal and external coagulating baths, and coagulating to form; taking out and placing in a dry and ventilated place for air drying to obtain the hollow fiber precursor.
(4) Sintering
Sintering the hollow fiber membrane precursor obtained in the step (3) in a sintering atmosphere (mixed atmosphere of nitrogen and hydrogen), wherein the sintering temperature is 1200 ℃, the sintering time is 2 hours, and removing organic matters to obtain the Cu-Zn blended inorganic hollow fiber antibacterial membrane (alpha-Al blended with Cu-Zn alloy)2O3Hollow fiber antibacterial film).
The porosity is tested by adopting an Archimedes method, the bending strength is tested by adopting a three-point method, the bacteria removal rate is tested by adopting a multi-tube fermentation method specified in the sanitary standard GB5749-2006 of the drinking water, and the Escherichia coli antibacterial test adopts an oscillating bottle method. Through testing, the porosity of the blended Cu-Zn inorganic hollow fiber antibacterial film prepared in the example 4 is 56.7%; the breaking strength is 1.45 MPa; the flux of tap water at 0.1MPa is 24840.76L/(m)2H); the filtration sterilization rate is 99.99 percent; the antibacterial rate of the escherichia coli is 80.5%.
Example 5
The preparation method of the Cu-Zn blended inorganic hollow fiber antibacterial film provided in embodiment 5 includes the following steps:
(1) preparation of organic solutions
4.128g of anhydrous polysulfone (accounting for 4 percent of the mass of the membrane casting solution) and 20.64g of organic solvent (N-methyl pyrrolidone, accounting for 20 percent of the mass of the membrane casting solution) are added into a three-fork round-bottom flask to be stirred and dissolved, the dissolution rate is accelerated under the water bath condition with the temperature of 65 ℃, and homogeneous organic solution is obtained after uniform stirring;
(2) preparation of casting solution
16.512g of anhydrous diatomite (the particle size of the anhydrous diatomite powder is 2 mu m; the mass of the anhydrous diatomite powder accounts for 16 percent of the mass of the casting solution) is added into the homogeneous organic solution in the step (1) under the stirring state (the stirring speed is 120 r/min); continuously adding 58.82g of anhydrous Cu-Zn alloy powder (the particle size of the anhydrous Cu-Zn alloy powder is 11 mu m, the mass of the anhydrous Cu-Zn alloy powder accounts for 60% of the mass of the membrane casting solution, and the mass ratio of copper to zinc in the Cu-Zn alloy is 85:15) into the homogeneous organic solution in the step (1) under the stirring state (the stirring speed is 120r/min), wherein the anhydrous diatomite powder and the Cu-Zn alloy powder are added for multiple times at intervals, continuously stirring for 10 hours, uniformly stirring, and defoaming in vacuum for 1 hour to obtain the membrane casting solution;
(3) extrusion molding
Pouring the casting solution obtained in the step (2) into a spinning device, opening a water outlet valve of an internal coagulation bath (tap water), and simultaneously pushing the casting solution to a spinning nozzle (with the inner diameter of 1.1mm and the outer diameter of 3.5mm) by air pressure to extrude and form the hollow fiber membrane blank at the extrusion rate of 10 mL/min; soaking in external coagulating bath (tap water) for 24 hr, exchanging solvent and non-solvent under the action of the internal and external coagulating baths, and coagulating to form; taking out and placing in a dry and ventilated place for air drying to obtain the hollow fiber precursor.
(4) Sintering
Sintering the hollow fiber membrane precursor obtained in the step (3) in a sintering atmosphere (mixed atmosphere of nitrogen and hydrogen), wherein the sintering temperature is 1300 ℃, the sintering time is 1h, and removing organic matters to obtain the Cu-Zn blended inorganic hollow fiber antibacterial membrane (alpha-Al blended with Cu-Zn alloy)2O3Hollow fiber antibacterial film).
The porosity is tested by adopting an Archimedes method, the bending strength is tested by adopting a three-point method, the bacteria removal rate is tested by adopting a multi-tube fermentation method specified in the sanitary standard GB5749-2006 of the drinking water, and the Escherichia coli antibacterial test adopts an oscillating bottle method. Through testing, the porosity of the Cu-Zn blended inorganic hollow fiber antibacterial film prepared in the example 5 is 58.6%; the breaking strength is 1.73 MPa; the flux of tap water at 0.1MPa is 26539.28L/(m)2H); the filtration sterilization rate is 99.99 percent; the antibacterial rate of the escherichia coli is 90.3%.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (7)
1. A preparation method of a Cu-Zn blended inorganic hollow fiber antibacterial film is characterized by comprising the following steps:
(1) preparation of organic solutions
Adding polysulfone into an organic solvent, and uniformly stirring to obtain a homogeneous organic solution;
(2) preparation of casting solution
Adding anhydrous Cu-Zn alloy powder and inorganic powder into the homogeneous organic solution in the step (1) under a stirring state, uniformly stirring, and defoaming in vacuum to obtain a casting solution;
(3) extrusion molding
Pouring the casting solution obtained in the step (2) into a spinning device, opening an inner coagulation bath valve, simultaneously opening an air pump, extruding the casting solution obtained in the step (2) through a spinning nozzle under the pushing of air pressure to obtain a hollow fiber membrane blank, soaking the hollow fiber membrane blank in an outer coagulation bath, performing coagulation forming under the action of the inner coagulation bath and the outer coagulation bath, and naturally air-drying to obtain a hollow fiber precursor;
(4) sintering
Sintering the hollow fiber membrane precursor obtained in the step (3) in a sintering atmosphere to obtain the blended Cu-Zn inorganic hollow fiber antibacterial membrane;
the particle size of the anhydrous Cu-Zn alloy powder in the step (2) is 11-13 mu m; the mass ratio of copper to zinc in the anhydrous Cu-Zn alloy powder is 60:40-85: 15; the mass of the anhydrous Cu-Zn alloy powder accounts for 3-60% of that of the casting solution in the step (2);
the inorganic powder of step (2) comprises alpha-Al2O3Or diatomaceous earth; the alpha-Al2O3The particle diameter of (A) is 0.5-1 μm; the particle size of the diatomite is 2-6 mu m; the mass of the inorganic powder accounts for 16-57% of the mass of the casting solution in the step (2);
the sintering atmosphere in the step (4) is a mixed atmosphere of nitrogen and hydrogen; the sintering treatment temperature in the step (4) is 1200-1300 ℃, and the sintering time is 1-2 hours.
2. The preparation method according to claim 1, wherein the mass of the polysulfone in step (1) is 4-8% of the mass of the membrane casting solution in step (2); the organic solvent in the step (1) comprises N-methyl pyrrolidone; and (3) the mass of the organic solvent in the step (1) accounts for 20-36% of the mass of the casting solution in the step (2).
3. The method according to claim 1, wherein the stirring rate in the stirring state in the step (2) is 80 to 120 r/min.
4. The production method according to claim 1, wherein the spinneret of step (3) has an outer diameter of 1.5 to 3.5mm and an inner diameter of 1 to 1.1 mm; the extrusion rate of the step (3) is 10-15 mL/min.
5. The method according to claim 1, wherein the inner coagulation bath and the outer coagulation bath in step (3) are both water; the soaking time is 24-36 hours.
6. A blended Cu-Zn inorganic hollow fiber antibacterial film produced by the production method described in any one of claims 1 to 5.
7. The use of the Cu-Zn blended inorganic hollow fiber antibacterial film as claimed in claim 6 in the field of water treatment.
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| CN102327745A (en) * | 2010-07-12 | 2012-01-25 | 华东理工大学 | Preparation method of alumina hollow fibre membrane containing inorganic additive |
| CN105854632A (en) * | 2016-05-15 | 2016-08-17 | 东北电力大学 | Method for preparing diatomite hollow fiber ceramic membrane |
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| CN102327745A (en) * | 2010-07-12 | 2012-01-25 | 华东理工大学 | Preparation method of alumina hollow fibre membrane containing inorganic additive |
| CN105854632A (en) * | 2016-05-15 | 2016-08-17 | 东北电力大学 | Method for preparing diatomite hollow fiber ceramic membrane |
| CN108310987A (en) * | 2018-03-01 | 2018-07-24 | 华南理工大学 | A kind of Cu-Zn/ polysulfones inorganic-organic doughnut hybridized film and preparation method thereof |
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