CN115074993A - Bacteriostatic modification method and device of nanofiber membrane - Google Patents
Bacteriostatic modification method and device of nanofiber membrane Download PDFInfo
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- CN115074993A CN115074993A CN202110263535.8A CN202110263535A CN115074993A CN 115074993 A CN115074993 A CN 115074993A CN 202110263535 A CN202110263535 A CN 202110263535A CN 115074993 A CN115074993 A CN 115074993A
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- nanofiber membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 121
- 239000002121 nanofiber Substances 0.000 title claims abstract description 108
- 230000003385 bacteriostatic effect Effects 0.000 title claims abstract description 46
- 238000002715 modification method Methods 0.000 title claims abstract description 27
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 106
- 230000004048 modification Effects 0.000 claims abstract description 86
- 238000012986 modification Methods 0.000 claims abstract description 86
- 239000007788 liquid Substances 0.000 claims abstract description 43
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005751 Copper oxide Substances 0.000 claims abstract description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 15
- 230000003115 biocidal effect Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
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- 125000004122 cyclic group Chemical group 0.000 claims description 5
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- 238000004891 communication Methods 0.000 claims description 3
- 238000010041 electrostatic spinning Methods 0.000 claims description 3
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- 238000001179 sorption measurement Methods 0.000 abstract description 31
- 241000588724 Escherichia coli Species 0.000 abstract description 12
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- 238000002474 experimental method Methods 0.000 abstract description 5
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- 230000005764 inhibitory process Effects 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000010931 gold Substances 0.000 description 10
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- 229920002239 polyacrylonitrile Polymers 0.000 description 7
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- 244000005700 microbiome Species 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
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- 229910052770 Uranium Inorganic materials 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000006146 oximation reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
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- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- 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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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Abstract
The invention provides a bacteriostatic modification method and device for a nanofiber membrane. The bacteriostatic modification method comprises the following steps of S1: mixing an antibacterial agent and the diluent in proportion to prepare an antibacterial solution, wherein the antibacterial agent comprises one or more of silver, silver oxide, titanium oxide, zirconium oxide, aluminum oxide, magnesium oxide and copper oxide nanoparticles; s2: placing the prepared antibacterial liquid into an antibacterial modification tank; s3: placing the nanofiber membrane to be subjected to bacteriostatic modification treatment into a bacteriostatic modification tank for circulating bacteriostatic modification treatment; s4: and drying the nanofiber membrane subjected to the antibacterial modification treatment. The bacteriostatic modification method disclosed by the invention is simple in process, very easy to implement and beneficial to reducing the cost. Experiments prove that the nanofiber membrane prepared by the method has excellent antibacterial performance, for example, the antibacterial rate of gram-negative escherichia coli, gram-positive staphylococcus aureus strains and other bacteria can reach 85-95%, and the nanofiber membrane after antibacterial modification has a more stable structure and higher adsorption capacity.
Description
Technical Field
The invention relates to the field of antibacterial materials, in particular to a method and a device for modifying a nanofiber membrane (comprising a component formed by the nanofiber membrane), and more particularly relates to a method and a device for antibacterial modification of a nanofiber membrane for metal ion adsorption.
Background
The nanofiber material with high-efficiency metal ion adsorption capacity and antibacterial performance is widely applied to the fields of heavy metal adsorption, rare and precious metal recovery, medical treatment, water treatment and the like, and generally comprises polyester, polyacrylonitrile, polyurethane and the like.
Due to the existence of various microorganisms in the use environment, the activity of the adsorption active groups is lost and the strength of the base material is reduced after the nanofiber membrane material is attached by the microorganisms, so that the problems of great reduction of adsorption capacity, low reuse rate and the like easily occur after the nanofiber membrane adsorbs metal ions for a period of time, and the existing antibacterial membrane material has a complex preparation process and leads to the increase of use cost. Therefore, the development of an antibacterial membrane material with simple preparation process, good antibacterial performance and long service life is a key problem to be solved urgently.
Disclosure of Invention
In view of the above disadvantages of the prior art, an object of the present invention is to provide a method for modifying a nanofiber membrane by bacteriostasis and a device for modifying a nanofiber membrane by bacteriostasis, which are used to solve the problems that the nanofiber membrane material in the prior art is attached by microorganisms during use, which results in the loss of the activity of an adsorption active group and the reduction of the strength of a base material, so that after the nanofiber membrane adsorbs metal ions for a period of time, the adsorption capacity is easily reduced greatly, the reuse rate is low, and the preparation process of the existing nanofiber membrane material is complicated.
In order to achieve the above objects and other related objects, the present invention provides a bacteriostatic modifying method for nanofiber membranes, comprising the steps of:
s1: mixing an antibacterial agent and the diluent in proportion to prepare an antibacterial solution, wherein the antibacterial agent comprises one or more of silver, silver oxide, titanium oxide, zirconium oxide, aluminum oxide, magnesium oxide and copper oxide nanoparticles;
s2: placing the prepared antibacterial liquid into an antibacterial modification tank;
s3: placing the nanofiber membrane to be subjected to bacteriostatic modification treatment into a bacteriostatic modification tank for circulating bacteriostatic modification treatment;
s4: and drying the nanofiber membrane subjected to the antibacterial modification treatment.
Optionally, in step S1, the diluent includes one or more of water, methanol, and ethanol; the weight ratio of the antibacterial agent to the diluent is 0.5: 100-5: 100, the mixing time is 0.5-2 hours, and the mixing temperature is 5-80 ℃.
Optionally, the nanofiber membrane comprises any one or two of a membrane sheet and a spiral wound membrane module, and the nanofiber membrane is prepared through an electrostatic spinning process.
Optionally, the time for performing the cyclic antibacterial modification treatment in the step S3 is 0.5 to 600 minutes, the drying temperature in the step S4 is 30 to 90 ℃, and the drying time is 0.1 to 4 hours.
Optionally, the time for performing the cyclic antibacterial modification treatment in the step S3 is 5-60 minutes, the drying temperature in the step S4 is 50-80 ℃, and the drying time is 1-2 hours.
Optionally, before and/or after the nanofiber membrane is subjected to modification treatment, one or more of heat treatment, acid treatment, alkali treatment and functional modification treatment is further performed on the nanofiber membrane.
The invention also provides a nanofiber membrane prepared by the bacteriostatic modification method in any one of the schemes, the nanofiber membrane is used for extracting metal ions, and the metal ions comprise UO 2 (CO 3 ) 3 4- 、Pb 2+ 、Ni 2+ 、Co 2+ 、Ce 3+ 、Cr 6+ 、Au + 、Cu 2+ 、K + 、Ca 2+ 、Mg 2+ 、Na + 、Fe 2+ And Fe 3+ One or more of (a).
The invention also provides a bacteriostatic modification device of the nanofiber membrane, which comprises an antibacterial liquid batching tank, a feeding pump, an antibacterial modification tank, a circulating pump and a distributor, wherein the feeding pump is connected between the antibacterial liquid batching tank and the antibacterial modification tank, the antibacterial modification tank is connected with the circulating pump, and the distributor is positioned in the antibacterial modification tank and communicated with the circulating pump.
Optionally, the distributor is a porous liquid distribution device, and the diameter of the hole is 1-8 mm.
Optionally, a stop valve is arranged on a communication pipeline between the charging pump and the antibacterial modification tank.
As described above, the bacteriostatic modification method and loading of the nanofiber membrane of the invention have the following beneficial effects: the antibacterial modification method of the nanofiber membrane provided by the invention is simple in process and very easy to implement, and the cost of the antibacterial nanofiber membrane material can be greatly reduced. Experiments prove that the nanofiber membrane prepared by the antibacterial modification method is excellent in antibacterial performance, and the antibacterial rate of the nanofiber membrane on gram-negative escherichia coli, gram-positive staphylococcus aureus strains and other bacteria can reach 85-95%. Meanwhile, the nanofiber membrane after bacteriostatic modification is more stable in structure and higher in adsorption capacity. The nanofiber membranes prepared in accordance with the present invention are particularly useful for the extraction of noble/heavy metal ions, including but not limited to UO 2 (CO 3 ) 3 4- 、Pb 2+ 、Ni 2+ 、Co 2+ 、Ce 3+ 、Cr 6+ 、Au + 、Cu 2+ 、K + 、Ca 2+ 、Mg 2+ 、Na + 、Fe 2+ 、Fe 3+ The method can be used in the fields of heavy metal adsorption, rare and precious metal recovery, medical treatment, water treatment and the like, and has great economic and social values.
Drawings
Fig. 1 is a flow chart illustrating an exemplary method for modifying the bacteriostatic activity of the nanofiber membrane provided by the invention.
Fig. 2 is a schematic structural diagram illustrating an exemplary bacteriostatic modifying device for a nanofiber membrane provided in the invention.
Description of the element reference numerals
11 antibiotic liquid proportioning tank
12 charging pump
13 antibacterial modification tank
14 circulation pump
15 distributor
16 stop valve
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1-2. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
In the prior art, due to the existence of microorganisms in the use environment, the activity of the adsorption active groups is lost and the strength of the base material is reduced after the nanofiber membrane material is attached by the microorganisms, so that the adsorption capacity is easily reduced greatly and the reuse rate is low after the nanofiber membrane adsorbs metal ions for a period of time, and the preparation process of the existing antibacterial membrane material is complex. In order to solve the problems, the invention provides a bacteriostatic modification method of a nanofiber membrane.
Specifically, as shown in fig. 1, the bacteriostatic modification method provided by the invention comprises the following steps:
s1: mixing the antibacterial agent and the diluent in proportion to prepare the antibacterial liquid, such as mixing two antibacterial raw materials in an antibacterial liquid batching tank; the antibacterial agent comprises one or more of silver, silver oxide, titanium oxide, zirconium oxide, aluminum oxide, magnesium oxide and copper oxide nano particles;
s2: placing the prepared antibacterial liquid into an antibacterial modification tank, for example, conveying the prepared antibacterial liquid from an antibacterial liquid batching tank to the antibacterial modification tank through a charging pump;
s3: placing the nanofiber membrane to be subjected to bacteriostatic modification treatment into an antibacterial modification tank for circulating bacteriostatic modification treatment, for example, connecting the antibacterial modification tank with a distributor and a circulating pump to form a circulating system, soaking the nanofiber membrane to be treated in antibacterial liquid in the antibacterial modification tank, conveying the antibacterial liquid in the antibacterial modification tank to the distributor through the circulating pump, and conveying the antibacterial liquid back to the antibacterial modification tank through the distributor again to perform sufficient bacteriostatic modification treatment on the nanofiber membrane so as to improve the antibacterial performance of the prepared nanofiber membrane;
s4: and drying the nanofiber membrane subjected to the antibacterial modification treatment, for example, drying in a dryer by using warm air.
The antibacterial modification method of the nanofiber membrane provided by the invention is simple in process and very easy to implement, so that the cost of the antibacterial nanofiber membrane material can be greatly reduced. Experiments prove that the nanofiber membrane prepared by the bacteriostasis modification method has very excellent antibacterial performance, such as gram-negative escherichia coli and gram-positive golden yellow glucanThe bacteriostasis rate of staphylococcus and other fungi can reach 85-95%. Meanwhile, the nanofiber membrane after bacteriostatic modification is more stable in structure and higher in adsorption capacity. The nanofiber membranes prepared in accordance with the present invention are particularly useful for the extraction of noble/heavy metal ions, including but not limited to UO 2 (CO 3 ) 3 4- 、Pb 2+ 、Ni 2 + 、Co 2+ 、Ce 3+ 、Cr 6+ 、Au + 、Cu 2+ 、K + 、Ca 2+ 、Mg 2+ 、Na + 、Fe 2+ 、Fe 3+ The method can be used in the fields of heavy metal adsorption, rare and precious metal recovery, medical treatment, water treatment and the like, and has great economic and social values.
In one example, in step S1, the diluent includes, but is not limited to, one or more of water, methanol, and ethanol. The raw materials are easy to obtain, cheap and easy to recycle, and contribute to reducing the production cost and reducing the environmental pollution.
In one example, in step S1, the weight ratio of the antibacterial agent to the diluent is 0.5:100 to 5:100 (unless otherwise specified, all values representing the endpoints including both sides when the description relates to the numerical range in the present specification). More preferably 1: 100-3: 100, which is beneficial to the full and uniform distribution of effective components in the antibacterial liquid and improves the antibacterial performance. The two raw materials can be fully stirred after being added so as to lead the effective components to be uniformly dispersed and avoid the agglomeration of particles. An activating agent (such as hydrochloric acid), and/or a dispersing agent may be added as necessary.
In one example, in step S1, the two raw materials are mixed for 0.5 to 2 hours at a temperature of 5 to 80 ℃.
In one example, the nanofiber membrane includes either or both of a membrane sheet and a roll-up membrane module, that is, the nanofiber membrane may be a single membrane sheet, or a roll-up membrane module prepared from a membrane sheet by using a roll-up membrane machine, thereby preparing an antibacterial nanofiber membrane sheet or module.
The nanofiber membrane is preferably prepared by an electrostatic spinning process, so that the nanofiber membrane has the outstanding advantages of high specific surface area, high porosity, an internally communicated open pore structure and the like, and the nanofiber membrane shows good adsorption performance and recycling performance in the aspect of adsorption and separation of metal ions.
In one example, the time for performing the cyclic antibacterial modification treatment in step S3 is 0.5 to 600 minutes, and more preferably 5 to 60 minutes, such as 5 minutes, 10 minutes, 15 minutes, 60 minutes, or any time duration therebetween, so as to ensure sufficient antibacterial modification treatment.
In one example, the drying temperature in step S4 is 30 to 90 ℃, more preferably 50 to 80 ℃, such as 50 ℃, 55 ℃, 60 ℃, 80 ℃ or any temperature in this interval, to ensure the bacteriostatic modification effect; the drying time is 0.1 to 4 hours, preferably 1 to 2 hours.
In one example, the modifying treatment of the nanofiber membrane further comprises one or more of heat treatment, acid treatment, alkali treatment and functional modification treatment. For example, before the nanofiber membrane is placed in the antibacterial modification tank, the nanofiber membrane to be treated is subjected to heat treatment to enhance the mechanical strength of the nanofiber membrane, and after the modification treatment is completed, the nanofiber membrane is subjected to acid treatment and/or alkali treatment to improve the acid and alkali resistance of the nanofiber membrane, so that the service life of the nanofiber membrane is further prolonged.
The invention also provides a nanofiber membrane prepared by the bacteriostatic modification method in any one of the schemes, the nanofiber membrane is used for extracting metal ions, and the metal ions comprise UO 2 (CO 3 ) 3 4 、Pb 2+ 、Ni 2+ 、Co 2+ 、Ce 3+ 、Cr 6+ 、Au + 、Cu 2+ 、K + 、Ca 2+ 、Mg 2+ 、Na + 、Fe 2+ And Fe 3+ One or more of (a). The nanofiber membrane can be used in the fields of heavy metal adsorption, rare and precious metal recovery, medical treatment, water treatment and the like, and has great economic and social values.
As shown in fig. 2, the present invention further provides a bacteriostatic modifying device for nanofiber membranes, which can be used to implement the bacteriostatic modifying method for nanofiber membranes as described in any of the above embodiments, but may also have other uses. Or the bacteriostatic modification method of the nanofiber membrane can be realized based on the bacteriostatic modification device of the embodiment, and certainly can also be realized based on other devices. In this embodiment, antibacterial modified device includes antibiotic liquid proportioning bins 11, charge pump 12, antibiotic modified tank 13, circulating pump 14 and distributor 15, charge pump 12 connect in antibiotic liquid proportioning bins 11 with between the antibiotic modified tank 13, antibiotic modified tank 13 with circulating pump 14 is connected, distributor 15 is located in antibiotic modified tank 13, and with circulating pump 14 is linked together. Specifically, the raw materials are added into the antibacterial liquid batching tank 11 and mixed according to a predetermined proportion to prepare antibacterial liquid, then the antibacterial liquid is conveyed into the antibacterial modification tank 13 through the feeding pump 12, the nanofiber membrane to be subjected to antibacterial modification treatment is placed into the antibacterial modification tank 13 and can be soaked in the antibacterial liquid, the nanofiber membrane is placed in the antibacterial modification tank 13 and is circulated through the circulating pump 14, the circulated antibacterial liquid enters the antibacterial modification tank 13 through the distributor to be subjected to antibacterial modification of the nanofiber membrane or the component, and the nanofiber membrane after being subjected to the circulated modification treatment has excellent antibacterial performance and a more stable structure.
In one example, the distributor 15 is a porous liquid distributor with a hole diameter of 1-8 mm to improve the distribution uniformity of the antibacterial liquid
In one example, a stop valve 16 is disposed on a communication pipeline between the feed pump and the antibacterial modification tank, and the stop valve 16 can be opened as required to supplement the raw materials into the antibacterial modification tank 13. Control valves can be arranged between the antibacterial modification tank and the circulating pump, between the circulating pump and the distributor, and between the antibacterial liquid batching tank and the charging pump as required. The bacteriostatic modification device can also be provided with a control module connected with the stop valve and/or the control valve, and the control module opens and/or closes the corresponding valve according to a preset program to execute corresponding operation, so that the automation level of the device is improved.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the description of the present specification. The invention is capable of other embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit of the invention.
It should be noted that, in the related test related to the present embodiment,
(1) the method for testing the adsorption capacity comprises the following steps: q ═ C 0 -C t )*V/M
Wherein Q is adsorption capacity mg/g; c 0 Is the original concentration of metal ions; c t Is the concentration of the metal ion after t times of adsorption, V is the volume of the metal ion solution; m is the mass of the adsorbent.
(2) The bacteriostatic rate of the adsorbent is measured according to GB/T20944.3-2008.
Example 1
The antibacterial liquid batching tank is internally provided with water to prepare the titanium dioxide nano antibacterial liquid with the concentration of 1 percent. The method comprises the steps of using a PAN nanofiber membrane with the molecular weight of 20 ten thousand, carrying out oximation with amidoamine, activating with hydrochloric acid with the concentration of 1%, placing the activated membrane into a modification tank, starting a feeding pump to add antibacterial liquid into the modification tank, closing the feeding pump, starting a circulating pump, carrying out modification treatment for 1 hour, and drying with warm air at 60 ℃ for 2 hours. The obtained nanofiber membrane is used as an adsorbent, the inhibition rate of the nanofiber membrane on escherichia coli is 85%, the inhibition rate of the nanofiber membrane on staphylococcus aureus is 90%, and the adsorption capacity of uranium in the actual marine environment is 5.2 mg/g. Under the same condition, the inhibition rate of the nanofiber membrane without titanium dioxide treatment on escherichia coli is 50%, the inhibition rate on staphylococcus aureus is 55%, and the adsorption capacity of uranium in the actual marine environment is 0.5 mg/g.
Example 2
The antibacterial liquid batching tank is internally provided with silver oxide nano antibacterial liquid with the concentration of 1 percent by using water. The PAN nanofiber membrane is used, the molecular weight is 20 ten thousand, after amidoximization, hydrochloric acid with the concentration of 1% is used for activation, after activation, the PAN nanofiber membrane is placed in a modification tank, a feeding pump is started to enable antibacterial liquid to be added into the modification tank, the feeding pump is closed, a circulating pump is started, modification treatment is carried out for 1 hour, and the PAN nanofiber membrane is dried for 2 hours by warm air at the temperature of 60 ℃. The obtained nanofiber membrane as an adsorbent has 88% inhibition rate on escherichia coli, 93% inhibition rate on staphylococcus aureus and 150.5mg/g adsorption capacity on gold in the gold pregnant solution under actual working conditions. Under the same condition, the nano-fiber membrane without being treated by the silver oxide has the inhibition rate of 50 percent on escherichia coli, the inhibition rate of 55 percent on staphylococcus aureus and the gold adsorption capacity of 5.2mg/g in the gold pregnant solution under the actual working condition.
Example 3
The antibacterial liquid batching tank is internally provided with 1 percent silver/silver oxide nano composite antibacterial liquid by water, wherein the proportion of silver and silver oxide respectively accounts for 50 percent. Using a PAN nano-fiber membrane component with the molecular weight of less than 22 ten thousand, carrying out oximation by amidoamine, then carrying out activation treatment by using 2% hydrochloric acid, placing the activated product into a modification tank, starting a charging pump to add the antibacterial liquid into the modification tank, closing the charging pump, starting a circulating pump, carrying out modification treatment for 2h, and drying for 3h by using warm air at 80 ℃. The obtained nanofiber membrane is used as an adsorbent, the inhibition rate of the nanofiber membrane on escherichia coli is 90%, the inhibition rate of the nanofiber membrane on staphylococcus aureus is 95%, and the adsorption capacity of uranium in the actual marine environment is 7.2 mg/g. Under the same condition, the inhibition rate of the nanofiber membrane without being treated by silver/silver oxide on escherichia coli is only 50%, the inhibition rate on staphylococcus aureus is 55%, and the adsorption capacity of uranium in the actual marine environment is 0.5 mg/g.
Example 4
Preparing titanium dioxide/copper oxide nano composite antibacterial liquid with the concentration of 3% by using water in an antibacterial liquid batching tank, wherein the ratio of titanium dioxide to copper oxide is 4: 1. using a PAN nano-fiber membrane component with the molecular weight of 22 ten thousand, carrying out oximation by amidoamine, then activating by 2% hydrochloric acid, placing into a modification tank after activation, starting a charging pump to add the antibacterial liquid into the modification tank, closing the charging pump, starting a circulating pump, carrying out modification treatment for 2h, and drying by 60 ℃ warm air for 3 h. The obtained nanofiber membrane adsorbent has the inhibition rate of 86% on escherichia coli and 87% on staphylococcus aureus, and the adsorption capacity of iron in the gold-precious liquid under the actual working condition is 40.5 mg/g. Under the same condition, the inhibition rate of the nanofiber membrane which is not treated by titanium dioxide and copper oxide in the gold pregnant solution under the actual working condition to escherichia coli is 50%, the inhibition rate to staphylococcus aureus is 55%, and the adsorption capacity to iron is 8.2 mg/g.
The experiments fully prove that the nanofiber membrane treated by the antibacterial modification method has excellent antibacterial and ion adsorption properties.
In summary, the invention provides a bacteriostatic modification method and device for a nanofiber membrane. The bacteriostatic modification method comprises the following steps of S1: mixing an antibacterial agent and the diluent in proportion to prepare an antibacterial solution, wherein the antibacterial agent comprises one or more of silver, silver oxide, titanium oxide, zirconium oxide, aluminum oxide, magnesium oxide and copper oxide nanoparticles; s2: placing the prepared antibacterial liquid into an antibacterial modification tank; s3: placing the nanofiber membrane to be subjected to bacteriostatic modification treatment into a bacteriostatic modification tank for circulating bacteriostatic modification treatment; s4: and drying the nanofiber membrane subjected to the antibacterial modification treatment. The antibacterial modification method of the nanofiber membrane provided by the invention is simple in process and very easy to implement, and the cost can be greatly reduced. Experiments prove that the nanofiber membrane prepared by the antibacterial modification method is excellent in antibacterial performance, and the antibacterial rate of the nanofiber membrane on gram-negative escherichia coli, gram-positive staphylococcus aureus strains and other bacteria can reach 85-95%. Meanwhile, the nanofiber membrane after bacteriostatic modification is more stable in structure and higher in adsorption capacity. The nanofiber membranes prepared in accordance with the present invention are particularly useful for the extraction of noble/heavy metal ions, including but not limited to UO 2 (CO 3 ) 3 4- 、Pb 2+ 、Ni 2+ 、Co 2+ 、Ce 3+ 、Cr 6+ 、Au + 、Cu 2+ 、K + 、Ca 2+ 、Mg 2+ 、Na + 、Fe 2+ 、Fe 3+ And the method can be used in the fields of heavy metal adsorption, rare and precious metal recovery, medical treatment, water treatment and the like, and has great economic and social values. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A bacteriostatic modification method of a nanofiber membrane is characterized by comprising the following steps:
s1: mixing an antibacterial agent and the diluent in proportion to prepare an antibacterial solution, wherein the antibacterial agent comprises one or more of silver, silver oxide, titanium oxide, zirconium oxide, aluminum oxide, magnesium oxide and copper oxide nanoparticles;
s2: placing the prepared antibacterial liquid into an antibacterial modification tank;
s3: placing the nanofiber membrane to be subjected to bacteriostatic modification treatment into a bacteriostatic modification tank for circulating bacteriostatic modification treatment;
s4: and drying the nanofiber membrane subjected to the antibacterial modification treatment.
2. The bacteriostatic modification method according to claim 1, wherein in step S1, the diluent comprises one or more of water, methanol and ethanol; the weight ratio of the antibacterial agent to the diluent is 0.5: 100-5: 100, the mixing time is 0.5-2 hours, and the mixing temperature is 5-80 ℃.
3. The bacteriostasis modification method according to claim 1, wherein the nanofiber membrane comprises any one or two of a membrane sheet and a roll-type membrane component, and the nanofiber membrane is prepared by an electrostatic spinning process.
4. The bacteriostasis modification method according to claim 1, wherein the time for the cyclic bacteriostasis modification treatment in the step S3 is 0.5-600 minutes, the drying temperature in the step S4 is 30-90 ℃, and the drying time is 0.1-4 hours.
5. The bacteriostasis modification method according to claim 4, wherein the time of the cyclic bacteriostasis modification treatment in the step S3 is 5-60 minutes, the drying temperature in the step S4 is 50-80 ℃, and the drying time is 1-2 hours.
6. A bacteriostatic modification method according to any one of claims 1-5, wherein the nanofiber membrane is subjected to one or more of heat treatment, acid treatment, alkali treatment and functional modification treatment before and/or after the modification treatment.
7. A nanofiber membrane, which is prepared by the bacteriostatic modification method according to any one of claims 1-6, and is used for extracting metal ions, wherein the metal ions comprise UO 2 (CO 3 ) 3 4- 、Pb 2+ 、Ni 2+ 、Co 2+ 、Ce 3+ 、Cr 6+ 、Au + 、Cu 2+ 、K + 、Ca 2+ 、Mg 2+ 、Na + 、Fe 2+ And Fe 3+ One or more of (a).
8. The utility model provides an antibacterial device that modifies of nanofiber membrane, its characterized in that, antibacterial device that modifies includes antibiotic liquid proportioning tank, charge pump, antibiotic modified tank, circulating pump and distributor, the charge pump connect in antibiotic liquid proportioning tank with between the antibiotic modified tank, antibiotic modified tank with the circulating pump is connected, the distributor is located in the antibiotic modified tank, and with the circulating pump is linked together.
9. A bacteriostatic modifying device according to claim 8, wherein the distributor is a porous liquid distributor with pores of 1-8 mm in diameter.
10. The bacteriostasis modification device of claim 8, wherein a stop valve is arranged on a communication pipeline between the charging pump and the antibiosis modification tank.
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