CN104607072A - Chitosan-modified mesoporous silica-filled hybrid membrane as well as preparation and application thereof - Google Patents
Chitosan-modified mesoporous silica-filled hybrid membrane as well as preparation and application thereof Download PDFInfo
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- CN104607072A CN104607072A CN201510008419.6A CN201510008419A CN104607072A CN 104607072 A CN104607072 A CN 104607072A CN 201510008419 A CN201510008419 A CN 201510008419A CN 104607072 A CN104607072 A CN 104607072A
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Abstract
The invention discloses a chitosan-modified mesoporous silica-filled hybrid membrane which is composed of a polyoxyethylene-polycaprolactam block copolymer and chitosan-modified mesoporous silica. A preparation process comprises the following steps: preparing chitosan-modified mesoporous silica; preparing a polyoxyethylene-polycaprolactam block copolymer solution; adding the chitosan-modified mesoporous silica into the polyoxyethylene-polycaprolactam block copolymer solution to prepare a membrane casting solution, and finally preparing the chitosan-modified mesoporous silica-filled hybrid membrane. According to the invention, the hybrid membrane has excellent membrane separation performance; the preparation method is easy to operate; the used membrane materials are low in price; when the hybrid membrane is used for separating CO2/CH4 gas mixture, the CO2 flux is 1835barrer, and the CO2/CH4 separation factor is 36; when the hybrid membrane is used for separating CO2/N2 gas mixture, the flux is 1943barrer, and the CO2/N2 separation factor is 85.
Description
Technical field
The present invention relates to a kind of gas separation membrane, particularly relate to a kind of chitosan-modified mesoporous silicon oxide and fill hybridized film and preparation method and application.
Background technology
Due to greenhouse gases CO
2the series of environmental problems that brings of discharge, efficient carbon capture method has caused the extensive concern of countries in the world.Compared to gas separating methods such as traditional absorption process, absorption method and cryogenic separations, membrane separating method is as a kind of novel gas separating method, high with its separative efficiency, energy consumption is low, technique is flexible, equipment is simple, the features such as operation, environmental friendliness that are easy to are at CO
2trapping field has potential advantage.The kind of current gas separation membrane is mainly divided into polymeric membrane, inoranic membrane and hybrid organic-inorganic film.For polymeric membrane, its infiltration coefficient and selective " tradeoff " effect that is subject to restrict, and namely infiltration coefficient increase can cause optionally declining, and vice versa.For inoranic membrane, usually can obtain high infiltration coefficient and high selective, but this membrane material is more crisp, easily produce defect, expensive and be difficult to realize industrialization.And select inorganic particulate as decentralized photo, polymer matrix prepares hybrid organic-inorganic film as continuous phase, combines the advantage of polymeric membrane and inoranic membrane, obtains the hybridized film of high osmosis and high selectivity while being expected to overcome " tradeoff " effect.Inorganic particulate conventional at present comprises: the organic knot framework of zeolite, CNT, mesoporous silicon oxide, metal etc.Wherein, mesoporous silicon oxide contains great amount of hydroxy group, larger specific area (>1000m with its surface
2/ g), orderly pore passage structure (1.5-10nm), larger pore volume (>0.7cm
3/ g) and good mechanical strength and heat endurance and obtain extensive concern.
But preparation hybridized film easily produces the problem such as boundary defect and particle aggregation, have impact on the gas separating property of film.Therefore, usually need to modify to surface of inorganic particles the compatibility improved between inorganic particulate and polymer matrix.Shitosan is as a kind of native biopolymer, and polymer matrix has good compatibility; Can as CO containing the amino functional group that waits on its chain
2carrier; In addition, shitosan is a kind of superabsorbent hydrogel, can absorb a large amount of water and water insoluble, and the raising of water content can increase CO
2dissolubility in film.Based on this, select shitosan as the dressing agent of mesoporous silicon oxide, be expected to the interface compatibility, the raising CO that improve between polymer matrix and inorganic particulate
2the water content of film is improved while vector contg.
Summary of the invention
For prior art, the invention provides a kind of chitosan-modified mesoporous silicon oxide and fill hybridized film, shitosan is selected to modify mesoporous silicon oxide as boiomacromolecule, and the mesoporous silicon oxide after modifying is filled in polyoxyethylene-polycaprolactam block copolymer and prepares hybridized film, obtain the CO of Thief zone coefficient and high selectivity
2diffusion barrier.The preparation process of this hybridized film provided by the invention is simple, and the chitosan-modified mesoporous silicon oxide prepared is filled hybridized film and be may be used for separation of C O
2/ CH
4and CO
2/ N
2gaseous mixture, under unstripped gas and sweep gas humidified condition, has high osmosis and high separation factor.
The chitosan-modified mesoporous silicon oxide of the one that the present invention proposes fills hybridized film, this hybridized film thickness 70-105 μm, and be that the polyoxyethylene-polycaprolactam block copolymer of 60-98% and chitosan-modified mesoporous silicon oxide form by mass fraction, in described polyoxyethylene-polycaprolactam block copolymer, polyoxyethylene segment accounts for the 55-60% of block copolymer mass fraction, and polycaprolactam segment accounts for the 40-45% of block copolymer mass fraction.
Above-mentioned chitosan-modified mesoporous silicon oxide fills the preparation method of hybridized film, comprises the following steps:
The preparation of step 1, chitosan-modified mesoporous silicon oxide:
Step 1-1, in a container, add the g softex kw solution that mass concentration is 0.002g/mL, then the sodium hydroxide solution of 2.0mol/L is dropwise added, the concentration of NaOH is made to be 0.014mol/L, treat that oil bath reaches 80 DEG C and continues to stir 40min, slow dropping ethyl orthosilicate, ethyl orthosilicate is 1.43 times of added NaOH volume, stops reaction after reacting 3h under keeping 80 DEG C of conditions; Suction filtration is carried out to gained solution, first spends deionized water 3 times, then wash 1 time with ethanol and obtain solid product; Gained solid product is put into cuvette, dry 48h in the vacuum drying chamber of 40 DEG C, obtain the mesoporous silicon oxide being with template;
Step 1-2, the mesoporous silicon oxide taking the band template of step 1-1 gained add in a container, then concentrated hydrochloric acid and methyl alcohol is added, the volume ratio of concentrated hydrochloric acid and methyl alcohol is 1: 0.06, the meso-porous titanium dioxide silicon concentration obtaining being with template is the solution of 0.009mg/mL, and at temperature 65 DEG C, condensing reflux stirs 48h; Carry out centrifugation to gained solution afterwards, wash 3 times, absolute ethyl alcohol washes 1 time, after putting into vacuum drying chamber inner drying 48h, obtains mesoporous silicon oxide;
Step 1-3, take a certain amount of shitosan, this shitosan being dissolved in mass fraction is in the glacial acetic acid solution of 5%, and room temperature mechanical stirs 24h, and obtaining mass fraction is the chitosan solution of 1%; Take the mesoporous silicon oxide of step 1-2 gained, by this mesoporous silicon oxide powder dispersion in ethanolic solution, obtain the mesoporous silicon oxide mixture that mass fraction is 1%, ultrasonic 15min, and with the glacial acetic acid of pH=4.8, described mesoporous silicon oxide mixture to be adjusted to pH be 3.5-4.5; Then add rapidly and form mixture A with the γ of the quality such as mesoporous silicon oxide-glycidyl ether oxygen propyl trimethoxy silicane, room temperature continues to stir 3h; Be that the chitosan solution of 2 times, mesoporous silicon oxide mixture adds in mixture A by volume ratio, stirring at room temperature 24h, centrifugal washing 3 times, ethanol washs 1 time, after putting into vacuum drying chamber inner drying 48h, obtains chitosan-modified mesoporous silicon oxide;
The preparation of step 2, polyoxyethylene-polycaprolactam block copolymer solution: in mass ratio 1: (10-50), it is in the ethanol of 65-75% that polyoxyethylene-polycaprolactam block copolymer is added mass fraction, at temperature 75-80 DEG C, reflux heating more than 75 DEG C, stir 0.5-4h, polyoxyethylene-polycaprolactam block copolymer is dissolved completely, and obtaining mass fraction is 2-7% polyoxyethylene-polycaprolactam block copolymer solution;
Step 3, chitosan-modified mesoporous silicon oxide fill the preparation of hybridized film: in mass ratio 1: the ratio of (100-300), the chitosan-modified mesoporous silicon oxide of gained in step 1 is added in the obtained polyoxyethylene-polycaprolactam block copolymer solution of step 2, in stirred at ambient temperature 5-10h, the casting solution of gained is poured on curtain coating on clean glass plate, dry under room temperature, then put into vacuum drying oven and remove residual solvent, obtain chitosan-modified mesoporous silicon oxide and fill hybridized film.
Chitosan-modified mesoporous silicon oxide described above is filled hybridized film for separating of CO
2/ CH
4mixture, its CO
2flux is 450-1835barrer, CO
2/ CH
4separation factor is 15-36.This hybridized film also can be used for separation of C O
2/ N
2mixture, its flux is 460-1943barrer, CO
2/ N
2separation factor is 49-85.
Compared with prior art, preparation method of the present invention is easy to operation, and membrane material used is cheap, and membrane separating property is excellent.Chitosan-modified mesoporous silicon oxide is filled in film and can improves interface compatibility between polymer matrix and inorganic particulate significantly, improve CO in film
2the content of carrier the water content that improve in film, thus permeability of the membrane and separation selectivity are significantly improved.Other can also be selected CO for chitosan-modified dose used
2the functional polymer hydrogel material of carrier, as gelatin, hyaluronic acid and sodium alginate etc.
Accompanying drawing explanation
The chitosan-modified mesoporous silicon oxide of Fig. 1 obtained by embodiment 1 fills the SEM sectional drawing of hybridized film;
The chitosan-modified mesoporous silicon oxide of Fig. 2 obtained by embodiment 2 fills the SEM sectional drawing of hybridized film;
The chitosan-modified mesoporous silicon oxide of Fig. 3 obtained by embodiment 3 fills the SEM sectional drawing of hybridized film;
The chitosan-modified mesoporous silicon oxide of Fig. 4 obtained by embodiment 4 fills the SEM sectional drawing of hybridized film;
The not chitosan-containing of Fig. 5 obtained by comparative example modifies the SEM sectional drawing that mesoporous silicon oxide fills hybridized film.
Detailed description of the invention
Tell about detailed content of the present invention by the following examples, provide embodiment to be convenience in order to understand, is never restriction the present invention.
Embodiment 1: prepare chitosan-modified mesoporous silicon oxide and fill hybridized film.
The thickness of this hybridized film is 85 μm, be that the polyoxyethylene-polycaprolactam block copolymer of 4% and the chitosan-modified mesoporous silicon oxide of 0.05g form by 12.5g mass fraction, in described polyoxyethylene-polycaprolactam block copolymer, polyoxyethylene segment accounts for 60% of block copolymer mass fraction, polycaprolactam segment accounts for 40% of block copolymer mass fraction, and the preparation process of this hybridized film is as follows:
The preparation of step 1, chitosan-modified mesoporous silicon oxide:
Step 1-1, measure 480ml deionized water, add 1.0g softex kw, after liquid agitation becomes homogeneous phase, dropwise add the NaOH solution 3.5ml of 2.0mol/L.Treat that oil bath reaches 80 DEG C and continues to stir 40min, slowly drip the ethyl orthosilicate of 5ml, under keeping 80 DEG C of conditions, stop after reaction 3h.After carrying out suction filtration to gained solution, first with the washing of 500ml deionized water, then obtain solid product with the washing of 250ml ethanol.Solid product is put into cuvette, dry 48h in the vacuum drying chamber of 40 DEG C, obtain the mesoporous silicon oxide being with template;
Step 1-2, the mesoporous silicon oxide of band template taking 5.25g add in container, then add concentrated hydrochloric acid and the 560ml methyl alcohol of 31.5ml, and at temperature 65 DEG C, condensing reflux stirs 48h.Afterwards centrifugation is carried out to gained solution, after washing wash 1 time with absolute ethyl alcohol again 3 times, after putting into vacuum drying chamber inner drying 48h, obtain mesoporous silicon oxide;
Step 1-3, take the shitosan of 2.0g, the mass fraction being dissolved in 200mL is in 5% glacial acetic acid solution, and room temperature mechanical stirs 24h.Obtain the chitosan solution of 1%.Take the meso-porous titanium dioxide Si powder of the above-mentioned acquisition of 0.1g, be dispersed in the ethanolic solution of 10mL, ultrasonic 15min, be adjusted between 3.5-4.5 with glacial acetic acid (PH=4.8).Then add rapidly the γ-glycidyl ether oxygen propyl trimethoxy silicane of 0.1g, room temperature continues to stir 3h.Add in mixture by the chitosan solution of 20mL, stirring at room temperature 24h, centrifugal washing 3 times, ethanol washs 1 time, after putting into vacuum drying chamber inner drying 48h, obtains chitosan-modified mesoporous silicon oxide;
Step 2, take 0.5g polyoxyethylene-polycaprolactam block copolymer (commodity are called Pebax 1657), 3.6g deionized water and 8.4g absolute ethyl alcohol and add in container, be placed in the water bath with thermostatic control of 80 DEG C, reflux under stirring 2h, block copolymer is all dissolved, is then cooled to room temperature for subsequent use.
Step 3, chitosan-modified mesoporous silicon oxide fill the preparation of hybridized film: take the chitosan-modified mesoporous silicon oxide of 0.025g and add above-mentioned 12.5g polyoxyethylene-polycaprolactam block copolymer solution, stir 6h, the casting solution of gained is poured on curtain coating on clean polyfluortetraethylene plate, dry more than 24h under room temperature, then at 45 DEG C, dry 24h under vacuum condition, obtaining thickness is 85 μm of hybridized film.Fig. 1 is the SEM sectional drawing of the hybridized film that embodiment 1 prepares.
Under room temperature, 1bar condition, by this hybridized film for separating of CO
2volume fraction is the CO of 30%
2/ CH
4mixed gas separation is tested, its CO
2infiltration coefficient is 710barrer, CO
2/ CH
4separation factor is 20; By this hybridized film for separating of CO
2volume fraction is the CO of 10%
2/ N
2mixed gas separation is tested, its CO
2infiltration coefficient is 770barrer, CO
2/ N
2separation factor is 57.
Embodiment 2: prepare chitosan-modified mesoporous silicon oxide and fill hybridized film.
The thickness of this hybridized film is 89 μm, be that the polyoxyethylene-polycaprolactam block copolymer of 4% and the chitosan-modified mesoporous silicon oxide of 0.05g form by 12.5g mass fraction, in described polyoxyethylene-polycaprolactam block copolymer, polyoxyethylene segment accounts for 60% of block copolymer mass fraction, polycaprolactam segment accounts for 40% of block copolymer mass fraction, the difference of its preparation method and above-described embodiment 1 is only: in step 3, chitosan-modified mesoporous silicon oxide consumption is become 0.05g from 0.025g, finally obtain the chitosan-modified mesoporous silicon oxide filling hybridized film that thickness is 89 μm of homogeneous.Fig. 2 is the SEM sectional drawing of the hybridized film that embodiment 2 prepares.
Under room temperature, 1bar condition, by this hybridized film for separating of CO
2volume fraction is the CO of 30%
2/ CH
4mixed gas separation is tested, its CO
2infiltration coefficient is 990barrer, CO
2/ CH
4separation factor is 24; By this hybridized film for separating of CO
2volume fraction is the CO of 10%
2/ N
2mixed gas separation is tested, its CO
2infiltration coefficient is 1082barrer, CO
2/ N
2separation factor is 68.
Embodiment 3: prepare chitosan-modified mesoporous silicon oxide and fill hybridized film.
The thickness of this hybridized film is 96 μm, be that the polyoxyethylene-polycaprolactam block copolymer of 4% and the chitosan-modified mesoporous silicon oxide of 0.075g form by 12.5g mass fraction, in described polyoxyethylene-polycaprolactam block copolymer, polyoxyethylene segment accounts for 60% of block copolymer mass fraction, polycaprolactam segment accounts for 40% of block copolymer mass fraction, the difference of its preparation method and above-described embodiment 1 is only: in step 3, sulfonic acid funtionalized hollow Nano hydrogel consumption is become 0.075g from 0.025g, finally obtain the chitosan-modified mesoporous silicon oxide filling hybridized film that thickness is 96 μm of homogeneous.Fig. 3 is the SEM sectional drawing of the hybridized film that embodiment 3 prepares.
Under room temperature, 1bar condition, by this hybridized film for separating of CO
2volume fraction is the CO of 30%
2/ CH
4mixed gas separation is tested, its CO
2infiltration coefficient is 1420barrer, CO
2/ CH
4separation factor is 29; By this hybridized film for separating of CO
2volume fraction is the CO of 10%
2/ N
2mixed gas separation is tested, its CO
2infiltration coefficient is 1561barrer, CO
2/ N
2separation factor is 79.
Embodiment 4: prepare chitosan-modified mesoporous silicon oxide and fill hybridized film.
The thickness of this hybridized film is 105 μm, be that the polyoxyethylene-polycaprolactam block copolymer of 4% and the functionalization hollow Nano hydrogel of 0.1g form by 12.5g mass fraction, in described polyoxyethylene-polycaprolactam block copolymer, polyoxyethylene segment accounts for 60% of block copolymer mass fraction, polycaprolactam segment accounts for 40% of block copolymer mass fraction, the difference of its preparation method and above-described embodiment 1 is only: in step 3, chitosan-modified mesoporous silicon oxide consumption is become 0.1g from 0.025g, finally obtain the chitosan-modified mesoporous silicon oxide filling hybridized film that thickness is 105 μm of homogeneous.Fig. 4 is the SEM sectional drawing of the hybridized film that embodiment 4 prepares.
Under room temperature, 1bar condition, by this hybridized film for separating of CO
2volume fraction is the CO of 30%
2/ CH
4mixed gas separation is tested, its CO
2infiltration coefficient is 1835barrer, CO
2/ CH
4separation factor is 36; By this hybridized film for separating of CO
2volume fraction is the CO of 10%
2/ N
2mixed gas separation is tested, its CO
2infiltration coefficient is 1943barrer, CO
2/ N
2separation factor is 85.
Comparative example: prepare not chitosan-containing and modify mesoporous silicon oxide filling
1657 pure films.
The thickness of this film is 70 μm.Its preparation method is: (commodity are called to take 0.5g polyoxyethylene-polycaprolactam block copolymer
1657), 3.6g deionized water and 8.4g absolute ethyl alcohol add in container, is placed in the water bath with thermostatic control of 80 DEG C, and 500r/min refluxes under stirring 2h, block copolymer is all dissolved, is then cooled to room temperature for subsequent use.Be poured into by above-mentioned Polymer Solution in clean glass plate, dry more than 24h under room temperature, then at 45 DEG C, dry 24h under vacuum condition, obtaining thickness is 70 μm
1657 pure films, Fig. 5 is the SEM sectional drawing of this film.
Under room temperature, 1bar condition, by this hybridized film for separating of CO
2volume fraction is the CO of 30%
2/ CH
4mixed gas separation is tested, its CO
2infiltration coefficient is 450barrer, CO
2/ CH
4separation factor is 15; By this hybridized film for separating of CO
2volume fraction is the CO of 10%
2/ N
2mixed gas separation is tested, its CO
2infiltration coefficient is 460barrer, CO
2/ N
2separation factor is 49.
To sum up, can show that prepared chitosan-modified mesoporous silicon oxide is filled hybridized film and had high osmosis and high separation factor according to above-described embodiment 1-4 and comparative example, mainly because chitosan-modified mesoporous silicon oxide improves compatibility between polymer matrix and inorganic particulate, improves CO
2vector contg and the water content added in film.Modify compared to not chitosan-containing that mesoporous silicon oxide fills
1657 pure films, chitosan-modified mesoporous silicon oxide fills hybridized film at CO
2/ CH
4cO in gaseous mixture
2flux improves 4 times, CO
2/ CH
4separation factor improves 2.4 times; At CO
2/ N
2cO in gaseous mixture
2flux improves 4.2 times, CO
2/ N
2separation factor improves 1.73 times.
Although invention has been described by reference to the accompanying drawings above; but the present invention is not limited to above-mentioned detailed description of the invention; above-mentioned detailed description of the invention is only schematic; instead of it is restrictive; those of ordinary skill in the art is under enlightenment of the present invention; when not departing from present inventive concept, can also make a lot of distortion, these all belong within protection of the present invention.
Claims (4)
1. a chitosan-modified mesoporous silicon oxide fills hybridized film, it is characterized in that: this hybridized film thickness 70-105 μm, and be that the polyoxyethylene-polycaprolactam block copolymer of 60-98% and chitosan-modified mesoporous silicon oxide form by mass fraction, in described polyoxyethylene-polycaprolactam block copolymer, polyoxyethylene segment accounts for the 55-60% of block copolymer mass fraction, and polycaprolactam segment accounts for the 40-45% of block copolymer mass fraction.
2. chitosan-modified mesoporous silicon oxide fills the preparation method of hybridized film according to claim 1, it is characterized in that: comprise the following steps:
The preparation of step 1, chitosan-modified mesoporous silicon oxide:
Step 1-1, in a container, add the g softex kw solution that mass concentration is 0.002g/mL, then the sodium hydroxide solution of 2.0mol/L is dropwise added, the concentration of NaOH is made to be 0.014mol/L, treat that oil bath reaches 80 DEG C and continues to stir 40min, slow dropping ethyl orthosilicate, ethyl orthosilicate is 1.43 times of added NaOH volume, stops reaction after reacting 3h under keeping 80 DEG C of conditions; Suction filtration is carried out to gained solution, first spends deionized water 3 times, then wash 1 time with ethanol and obtain solid product; Gained solid product is put into cuvette, dry 48h in the vacuum drying chamber of 40 DEG C, obtain the mesoporous silicon oxide being with template;
Step 1-2, the mesoporous silicon oxide taking the band template of step 1-1 gained add in a container, then concentrated hydrochloric acid and methyl alcohol is added, the volume ratio of concentrated hydrochloric acid and methyl alcohol is 1: 0.06, the meso-porous titanium dioxide silicon concentration obtaining being with template is the solution of 0.009mg/mL, and at temperature 65 DEG C, condensing reflux stirs 48h; Carry out centrifugation to gained solution afterwards, wash 3 times, absolute ethyl alcohol washes 1 time, after putting into vacuum drying chamber inner drying 48h, obtains mesoporous silicon oxide;
Step 1-3, take a certain amount of shitosan, this shitosan being dissolved in mass fraction is in the glacial acetic acid solution of 5%, and room temperature mechanical stirs 24h, and obtaining mass fraction is the chitosan solution of 1%; Take the mesoporous silicon oxide of step 1-2 gained, by this mesoporous silicon oxide powder dispersion in ethanolic solution, obtain the mesoporous silicon oxide mixture that mass fraction is 1%, ultrasonic 15min, and with the glacial acetic acid of pH=4.8, described mesoporous silicon oxide mixture to be adjusted to pH be 3.5-4.5; Then add rapidly and form mixture A with the γ of the quality such as mesoporous silicon oxide-glycidyl ether oxygen propyl trimethoxy silicane, room temperature continues to stir 3h; Be that the chitosan solution of 2 times, mesoporous silicon oxide mixture adds in mixture A by volume ratio, stirring at room temperature 24h, centrifugal washing 3 times, ethanol washs 1 time, after putting into vacuum drying chamber inner drying 48h, obtains chitosan-modified mesoporous silicon oxide;
The preparation of step 2, polyoxyethylene-polycaprolactam block copolymer solution:
In mass ratio 1: (10-50), it is in the ethanol of 65-75% that polyoxyethylene-polycaprolactam block copolymer is added mass fraction, at temperature 75-80 DEG C, reflux heating more than 75 DEG C, stir 0.5-4h, polyoxyethylene-polycaprolactam block copolymer is dissolved completely, and obtaining mass fraction is 2-7% polyoxyethylene-polycaprolactam block copolymer solution;
Step 3, chitosan-modified mesoporous silicon oxide fill the preparation of hybridized film:
In mass ratio 1: the ratio of (100-300), the chitosan-modified mesoporous silicon oxide of gained in step 1 is added in the obtained polyoxyethylene-polycaprolactam block copolymer solution of step 2, in stirred at ambient temperature 5-10h, the casting solution of gained is poured on curtain coating on clean glass plate, dry under room temperature, then put into vacuum drying oven and remove residual solvent, obtain chitosan-modified mesoporous silicon oxide and fill hybridized film.
3. chitosan-modified mesoporous silicon oxide fills the application of hybridized film according to claim 1, by this hybridized film for separating of CO
2/ CH
4mixture, its CO
2flux is 450-1835barrer, CO
2/ CH
4separation factor is 15-36.
4. chitosan-modified mesoporous silicon oxide fills the application of hybridized film according to claim 1, by this hybridized film for separating of CO
2/ N
2mixture, its flux is 460-1943barrer, CO
2/ N
2separation factor is 49-85.
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| CN110339726A (en) * | 2019-07-10 | 2019-10-18 | 浙江海印数码科技有限公司 | A kind of hydridization polyether sulfone filtering film that polystyrene microsphere/carbon nanotube is composite modified and preparation method thereof, application |
| CN110339726B (en) * | 2019-07-10 | 2021-09-07 | 浙江海印数码科技有限公司 | Polystyrene microsphere/carbon nanotube composite modified hybrid polyethersulfone nanofiltration membrane as well as preparation method and application thereof |
| CN112007426A (en) * | 2020-07-08 | 2020-12-01 | 山东联科科技股份有限公司 | Preparation method of high-performance mesoporous silica-chitosan composite antibacterial filter sheet |
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