CN111495172A - Preparation method of composite nanofiber filtering membrane - Google Patents
Preparation method of composite nanofiber filtering membrane Download PDFInfo
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- CN111495172A CN111495172A CN201910089419.1A CN201910089419A CN111495172A CN 111495172 A CN111495172 A CN 111495172A CN 201910089419 A CN201910089419 A CN 201910089419A CN 111495172 A CN111495172 A CN 111495172A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
- B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
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Abstract
The invention relates to a preparation method of a composite nanofiber filtering membrane, which is characterized by comprising the following steps of 1) dissolving a polymer in a solvent to prepare a polymer solution at 40-80 ℃, carrying out electrostatic spinning on the surface of a non-woven fabric by using the polymer solution to form a nanofiber membrane layer on the surface of the non-woven fabric to obtain a filtering membrane substrate, 2) dissolving manganese salt and metal salt in deionized water to prepare a solution A, wherein the concentration of the manganese salt in the solution A is 0.03-0.6 mol/L, the concentration of the metal salt is 0-0.06 mol/L, dissolving potassium permanganate in the deionized water, uniformly stirring to prepare a solution B with the concentration of 0.03-0.6 mol/L, and 3) soaking the filtering membrane substrate prepared in the step 1 in the solution A for 3-10min, drying at 50 ℃, then soaking in the solution B for 3-10min, and drying at 50 ℃ to obtain the functional composite nanofiber filtering membrane.
Description
Technical Field
The invention relates to the field of air purification, in particular to a preparation method of a composite nanofiber filtering membrane.
Background
CN201310309595.4 discloses an electrostatic spinning preparation method of manganese dioxide/polyacrylonitrile-based oxidative decomposition formaldehyde type nanofiber membrane, which comprises the following steps: (1) preparing nano manganese dioxide by using potassium permanganate and cyclohexanol through a hydrothermal method, wherein the diameter of the nano manganese dioxide is 50-600 nm; (2) mixing Polyacrylonitrile (PAN) and nano Manganese Dioxide (MD), dissolving in N-N Dimethylformamide (DMF), and stirring to obtain uniformly dispersed electrostatic spinning solution; wherein the mass ratio of MD to PAN is 0.01-0.5: 1; (3) and (3) performing electrostatic spinning by using the prepared electrostatic spinning solution to obtain the manganese dioxide/polyacrylonitrile (MD/PAN) based formaldehyde oxidative decomposition type nanofiber membrane. The nanofiber membrane has the function of oxidizing and decomposing formaldehyde.
However, in the nanofiber membrane, the nano manganese dioxide is directly added into the spinning solution, so that the spinnability of the original spinning solution is reduced, and a part of Mn ions are wrapped in the inside of the fiber, so that the effective utilization rate is reduced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a composite nanofiber filtering membrane which has high effective utilization rate and can remove particles and decompose ozone in the current situation of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a composite nanofiber filtering membrane is characterized by comprising the following steps:
1) dissolving a polymer in a solvent to prepare a polymer solution with the concentration of 5-20 wt% and the viscosity of 200-2000mPa & s at 40-80 ℃;
carrying out electrostatic spinning on the surface of the non-woven fabric by using the polymer solution to form a nanofiber membrane layer on the surface of the non-woven fabric to obtain a filter membrane substrate;
the polymer is selected from at least one of polyacrylonitrile, polyvinylidene fluoride, nylon, polycarbonate and polyether sulfone;
the organic solvent is at least one selected from dimethylformamide, dimethylacetamide and acetone;
2) preparation of ozone catalyst precursor
Dissolving manganese salt and metal salt in deionized water to prepare a solution A, wherein the concentration of the manganese salt in the solution A is 0.03-0.6 mol/L, and the concentration of the metal salt is 0-0.06 mol/L;
the manganese salt is selected from at least one of manganese nitrate, manganese acetate, manganese sulfate, manganese chloride and manganese carbonate; the metal salt is at least one selected from silver nitrate, cobalt nitrate, ferric nitrate, silver acetate, cobalt acetate and ferric acetate;
dissolving potassium permanganate in deionized water, and uniformly stirring to prepare a solution B with the concentration of 0.03-0.6 mol/L;
3) and (3) soaking the filter membrane substrate prepared in the step (1) in the solution A for 3-10min, and drying at 50 ℃. And soaking the membrane in the solution B for 3-10min, and drying at 50 ℃ to obtain the functional composite nanofiber filtering membrane.
Preferably, the concentration of the metal salt is 0.01-0.06 mol/L.
Preferably, the electrospinning conditions are as follows:
the electrostatic spinning voltage is 7-26kv, the distance between the needle end of the injector and the collector is 5-25cm, the injection speed is 5-100ul/min, the rotating speed of the collector is 300-;
the non-woven fabric is wrapped on the collector.
Further, a non-woven fabric protective layer may be combined with the electrospun membrane.
Preferably, the non-woven fabric protective layer is bonded with the periphery of the electrostatic spinning membrane through a hot melt net membrane.
Preferably, the non-woven fabric protective layer is a PP non-woven fabric.
The hot melt net film is preferably selected from an ethylene-vinyl acetate copolymer hot melt net film, a polyamide hot melt net film or a polyurethane hot melt net film.
Compared with the prior art, the manganese oxide is attached to the outer surface of the prepared fiber of the nanofiber filtering membrane, catalyst particles are exposed outside, the effective utilization rate of the catalyst is high, and ineffective catalyst particles are avoided; the membrane is prepared into a membrane shape, so that particles can be filtered and removed, and ozone can be decomposed.
Drawings
FIG. 1 is a scanning electron micrograph of PAN nanofibers on which catalyst particles are supported in example 1 of the present invention
Fig. 2 is a partially enlarged view of fig. 1.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1
Spinning nano-fiber, namely adding 6.59g of Polyacrylonitrile (PAN) into 50m L N, N-Dimethylformamide (DMF), stirring for 2h at 60 ℃ at the rotating speed of 300r/min to prepare 12% PAN solution, wherein the solution is light yellow, defoaming or standing for 12h before spinning, then injecting the prepared solution into an injector for spinning, wherein the spinning parameter temperature is 25 ℃, the humidity is 50%, the distance from the tip of a spray head to a receiving end is 15cm, non-woven fabric is wrapped on a collector, the rotating speed of the collector is 500rpm, the injection speed is 10ul/min, the voltage is 9.5KV, and the PAN nano-fiber is obtained after spinning for 1 h.
2.6g of manganese acetate is dissolved in 500ml of deionized water and evenly stirred to prepare a solution A.
Dissolving 1.58g of potassium permanganate in 500ml of deionized water, uniformly stirring to prepare a 0.04 mol/L potassium permanganate solution, and then dripping nitric acid until the pH value is 3 to prepare a solution B.
And soaking the PAN nanofiber membrane in the solution A for 5min, and then drying in an oven at 50 ℃. And soaking the nanofiber membrane in the solution B for 5min, and drying the nanofiber membrane at 50 ℃.
Covering a layer of thin PP non-woven fabric on the surface of the nanofiber membrane, and fixing the periphery of the nanofiber membrane by using an EVA (ethylene vinyl acetate) hot-melt net membrane through hot pressing to obtain the composite nanofiber membrane.
The prepared composite nanofiber membrane is subjected to electron microscope scanning, as shown in fig. 1 and 2.
Wherein, fig. 1 is a whole macroscopic view of PAN nano fiber loaded with ozone catalyst, which shows that the fiber surface is full of point-like substances, and fig. 2 is a partial enlarged view, which shows that a single nano fiber is full of manganese oxide particles with the size of dozens of nanometers, and the specific surface area of the nano fiber is very large, so compared with the traditional carrier, the loading amount of the ozone catalyst is greatly increased. It can be seen from fig. 1 that the ozone catalyst particles are much smaller than the diameter and pore size of the nanofibers and therefore do not affect the filtration performance.
The composite nanofiber filtration membranes prepared in the examples were subjected to performance tests.
Firstly, the filtering performance of composite nanofiber membrane particles is as follows:
the filtering performance of the composite nanofiber membrane is tested by adopting a TSI 8130 type automatic filter material tester, the sample size is 15cm × 15cm, NaCl aerosol with the mass median diameter of particle particles of 0.26um is generated, and the air flow speed is 32L/min.
Through testing the concentration of the particles at two ends of the membrane, the penetration rate k of the particles is obtained, and then the filtration efficiency η is obtained
C1 for downstream aerosol concentration and C2 for upstream aerosol concentration
Secondly, ozone catalytic performance, namely, loading about 0.2g of nanofiber loaded with an ozone catalyst into a quartz tube, wherein the gas flow of the system is 1.05L/min (mass space velocity 315L/g.h), the ozone inlet concentration c0 is 100ppm, the relative humidity is 55%, detecting the ozone concentration c at the outlet of the pipeline by using a Model 202 Serial ozone analyzer, detecting the outlet stable concentration, and calculating the ozone removal rate according to the following formula:
the performance test result shows that when the space velocity is 315L/g.h and the inlet concentration is 93ppm, the catalytic ozone decomposition efficiency of the sample is 75 percent, the filtering efficiency for PM0.3 particulate matter is 76.95 percent, and the pressure drop is 94 pa.
Example 2:
spinning nano-fiber, namely adding 4.2g of polyacrylonitrile (PAN4) into 50m L N, N-Dimethylformamide (DMF) water, stirring for 2h at 60 ℃ at the rotating speed of 300r/min to prepare 8% PAN solution, wherein the solution is light yellow, then adding 0.5g L iCl, stirring uniformly, defoaming or standing for 12h before spinning, then injecting the prepared solution into an injector for spinning, wherein the spinning parameter temperature is 25 ℃, the humidity is 50%, the distance from the tip of a spray head to a receiving end is 10cm, non-woven fabric is wrapped on a collector, the rotating speed of the collector is 500rpm, the injection speed is 10ul/min, the voltage is 7.5KV, and the PAN nano-fiber is obtained after spinning for 1 h.
Dissolving 4.33g of manganese acetate in 500ml of deionized water, uniformly stirring, adding 0.105 g of silver nitrate into the solution, and uniformly stirring to prepare a solution A, wherein the ratio of Mn: ag 40:1 (weight ratio).
3.16g of potassium permanganate is dissolved in 500ml of deionized water, the mixture is stirred uniformly to prepare a 0.06 mol/L potassium permanganate solution, and then nitric acid is dropped until the pH value is 3 to prepare a solution B.
Soaking the PAN nanofiber membrane in the solution A for 10min, and drying at 50 ℃. Drying, soaking in solution B for 10min, and drying at 50 deg.C.
And finally, covering a layer of thin PP non-woven fabric on the surface of the nanofiber membrane, and fixing the periphery of the nanofiber membrane by using a hot-melt net membrane made of materials such as TPU polyurethane through hot pressing to obtain the composite nanofiber membrane.
The performance test result shows that when the space velocity is 315L/g.h and the inlet concentration is 93ppm, the catalytic ozone decomposition efficiency of the sample is 81 percent, the filtration efficiency for PM0.3 particles is 95.39 percent, and the pressure drop is 109 pa.
Example 3:
spinning nano fibers:
adding 10.62g of polyvinylidene fluoride PVDFF into 50m L N, N-dimethylformamide DMF, stirring for 4h at 80 ℃ at the rotating speed of 300rpm to prepare a PVDF solution with the concentration of 18%, wherein the solution is light yellow and is uniformly stirred, defoaming or standing for 12h before spinning, then injecting the prepared solution into an injector for spinning, wherein the spinning parameter temperature is 25 ℃, the humidity is 50%, the distance from a spray head tip to a receiving end is 20cm, a non-woven fabric is wrapped on a collector, the rotating speed of the collector is 500rpm, the injection speed is 150ul/min, the voltage is 12KV, and spinning is carried out for 1h to obtain the PVDF nanofiber.
4.9g of tetrahydrate manganese acetate is dissolved in 500ml of deionized water and uniformly stirred, then 0.58g of cobalt nitrate hexahydrate is added into the solution and uniformly stirred to prepare a solution A, wherein the molar ratio of Mn: co 10: 1.
2.37g of potassium permanganate is dissolved in 500ml of deionized water, the mixture is stirred uniformly to prepare a 0.03 mol/L potassium permanganate solution, and then nitric acid is dropped until the pH value is 3 to prepare a solution B.
And soaking the PVDF nano-fiber membrane in the solution A for 10min, and drying at 50 ℃. Then soaked in solution B for 10min, and dried at 50 deg.C.
And finally, covering a thin PP non-woven fabric layer on the surface of the nanofiber membrane, and fixing the periphery of the nanofiber membrane by using an EVA (ethylene vinyl acetate) hot-melt net membrane through hot pressing to obtain the composite nanofiber membrane.
The performance test shows that when the space velocity is 315L/g.h and the inlet concentration is 93ppm, the catalytic ozone decomposition efficiency of the sample is 86 percent, the filtering efficiency for PM0.3 particulate matter is 99.86 percent, and the pressure drop is 91 pa.
Claims (7)
1. A preparation method of a composite nanofiber filtering membrane is characterized by comprising the following steps:
1) dissolving a polymer in a solvent to prepare a polymer solution with the concentration of 5-20 wt% and the viscosity of 200-2000mPa & s at 40-80 ℃;
carrying out electrostatic spinning on the surface of the non-woven fabric by using the polymer solution to form a nanofiber membrane layer on the surface of the non-woven fabric to obtain a filter membrane substrate;
the polymer is selected from at least one of polyacrylonitrile, polyvinylidene fluoride, nylon, polycarbonate and polyether sulfone;
the organic solvent is at least one selected from dimethylformamide, dimethylacetamide and acetone;
2) preparation of ozone catalyst precursor
Dissolving manganese salt and metal salt in deionized water to prepare a solution A, wherein the concentration of the manganese salt in the solution A is 0.03-0.6 mol/L, and the concentration of the metal salt is 0-0.06 mol/L;
the manganese salt is selected from at least one of manganese nitrate, manganese acetate, manganese sulfate, manganese chloride and manganese carbonate; the metal salt is at least one selected from silver nitrate, cobalt nitrate, ferric nitrate, silver acetate, cobalt acetate and ferric acetate;
dissolving potassium permanganate in deionized water, and uniformly stirring to prepare a solution B with the concentration of 0.03-0.6 mol/L;
3) and (2) soaking the filter membrane substrate prepared in the step (1) in the solution A for 3-10min, drying at 50 ℃, soaking in the solution B for 3-10min, and drying at 50 ℃ to obtain the functional composite nanofiber filter membrane.
2. The method for preparing a composite nanofiber filtration membrane according to claim 1, wherein the concentration of the metal salt is 0.01 to 0.06 mol/L.
3. The method for the production of a composite nanofibrous filtration membrane according to claim 1 or 2, characterised in that the conditions of the electrostatic spinning are:
the electrostatic spinning voltage is 7-26kv, the distance between the needle end of the injector and the collector is 5-25cm, the injection speed is 5-100ul/min, the rotating speed of the collector is 300-;
the non-woven fabric is wrapped on the collector.
4. The method of preparing a composite nanofiber filtration membrane as claimed in claim 3, wherein the electrospun membrane is compounded with a non-woven fabric protective layer.
5. The method for preparing a composite nanofiber filtration membrane as claimed in claim 4, wherein the non-woven fabric protective layer is bonded to the periphery of the electrospun membrane through a hot-melt net membrane.
6. The method for preparing a composite nanofiber filtration membrane according to claim 5, characterized in that the non-woven fabric protective layer is a PP non-woven fabric.
7. The method for preparing a composite nanofiber filter membrane according to claim 6, wherein the hot melt net film is selected from an ethylene vinyl acetate copolymer hot melt net film, a polyamide hot melt net film or a polyurethane hot melt net film.
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Cited By (2)
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CN114471196A (en) * | 2021-12-20 | 2022-05-13 | 中国科学院新疆生态与地理研究所 | Preparation method of multifunctional nanofiber water purification membrane |
CN114795664A (en) * | 2021-01-27 | 2022-07-29 | 宁波方太厨具有限公司 | Sanitary nursing product and preparation method thereof |
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CN109224874A (en) * | 2018-11-05 | 2019-01-18 | 南京工业大学 | A kind of catalytic membrane and preparation method thereof for air cleaning |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114795664A (en) * | 2021-01-27 | 2022-07-29 | 宁波方太厨具有限公司 | Sanitary nursing product and preparation method thereof |
CN114471196A (en) * | 2021-12-20 | 2022-05-13 | 中国科学院新疆生态与地理研究所 | Preparation method of multifunctional nanofiber water purification membrane |
CN114471196B (en) * | 2021-12-20 | 2023-11-14 | 中国科学院新疆生态与地理研究所 | Preparation method of multifunctional nanofiber water purification membrane |
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