CN110193289A - The method that one pot a kind of, in-situ method prepares bielement nano material codope mixed substrate membrane containing nano-grade molecular sieve - Google Patents
The method that one pot a kind of, in-situ method prepares bielement nano material codope mixed substrate membrane containing nano-grade molecular sieve Download PDFInfo
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- CN110193289A CN110193289A CN201910329661.1A CN201910329661A CN110193289A CN 110193289 A CN110193289 A CN 110193289A CN 201910329661 A CN201910329661 A CN 201910329661A CN 110193289 A CN110193289 A CN 110193289A
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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
- B01D53/22—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 by diffusion
- B01D53/228—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 by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
- B01D69/10—Supported membranes; Membrane supports
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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
- B01D71/06—Organic material
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
Abstract
The present invention provides the method that one pot a kind of, in-situ method prepares bielement nano material codope mixed substrate membrane containing nano-grade molecular sieve, includes the following steps: that (1) mixes polymerizable oil-phase medium, polymerizable surfactants and water, constructs reverse micelle microemulsion；Then nano material-I is added, adds the presoma of nano material-II after being dispersed with stirring again, stirs, must include the reverse micelle microemulsion of nano material-I, nano material-II；(2) initiator is added, carries out home position polymerization reaction, obtains codope polymer latex；(3) preparation liquid is stood to obtain after adjusting viscosity；(4) preparation liquid is coated uniformly on support membrane, it is thermally treated to obtain the final product." one pot " of the present invention, bielement nano material codope mixed-matrix membrane preparation method in situ are easy, economical, environmental-friendly.Mixed substrate membrane containing nano-grade molecular sieve provided by the present invention is significantly improved due to nano material-I, the synergistic effect of nano material-II, gas separating property or infiltration evaporation performance.
Description
Technical field
The present invention relates to technical field of membrane separation, and in particular to " one pot ", in-situ method prepare bielement nano material codope
Mixed substrate membrane containing nano-grade molecular sieve and application.
Background technique
Mixed substrate membrane containing nano-grade molecular sieve is the hydridization for being doped in continuous polymer phase inorganic nano material as dispersed phase and preparing
Film, the film combine the respective excellent properties of organic and inorganic materials, and pass through regulation nothing on the basis of traditional polymer film
Machine nanometer material structure and property strengthen the performance of mixed substrate membrane containing nano-grade molecular sieve.The preparation method of mixed substrate membrane containing nano-grade molecular sieve mainly has physics at present
Blending method and situ aggregation method, common inorganic nano material have metal nanoparticle (including metal simple-substance, metal oxide,
The nanoparticles such as metal halide, metal sulfide), low-dimensional carbon nanomaterial (graphene, carbon nanotube) etc..
China applies for a patent CN201410301851.X and discloses a kind of sulfonated polyether-ether-ketone-amino acid modification graphite oxide
Alkene hybridized film, the hybridized film are made of sulfonated polyether-ether-ketone and amino acid modification graphene oxide.Its preparation process includes:
Graphite flake oxidation is prepared into graphene oxide first, then adds graphene oxide into the methylol first containing dopamine
In alkane-HCl solution, the modified graphene oxide of dopamine is obtained through chelatropic reaction；The modified graphene oxide of dopamine is added
Enter graft reaction in cysteine solution and obtains amino acid modification graphene oxide；Then by amino acid modification graphene oxide with
Sulfonated polyether-ether-ketone solution blending obtains casting solution, obtains the hybridized film through film.Invention sulfonated polyether-ether-ketone/the amino acid is repaired
It adorns graphene oxide hybridized film and is used for CO2/CH4The separation of mixed gas, selectivity and permeability with higher.
China, which applies for a patent CN201510726253.1 and discloses a kind of polyimides containing trifluoromethyl/carboxyl multi wall carbon, to be received
Mitron gas separates mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof.The invention is more by the polyimides addition carboxyl that will contain trifluoromethyl
Wall carbon nano tube and form mixed substrate membrane containing nano-grade molecular sieve, the interaction using the two polar groups makes carbon nanotube in mixed substrate membrane containing nano-grade molecular sieve
In can be uniformly dispersed, while make two-phase interface have good bonding force, to make the gas permeability of mixed substrate membrane containing nano-grade molecular sieve
It is improved with selectivity.
China applies for a patent CN201810589354.2 and discloses a kind of sulfonated polyether-ether-ketone of doping carbon quantum dot in situ
Mixed substrate membrane containing nano-grade molecular sieve and its preparation method and application.Using polyvinyl alcohol, polyether-ether-ketone as raw material, it is added in the concentrated sulfuric acid, after reaction,
Obtained original position is doped with the sulfonated polyether-ether-ketone composite material of carbon quantum dot；In deionized water by composite material dissolution, match
Casting solution is made, functional layer is prepared in microporous membrane surface by cladding process, forms the sulfonated polyether of doping carbon quantum dot in situ
Ether ketone mixed substrate membrane containing nano-grade molecular sieve.Prepared functional membrane can be applied to CO2/N2Gas separation, has higher CO2Permeability and separation because
Son.
China applies for a patent CN201710326631.6, and to disclose a kind of Nano carbon balls-polyimides binary gas separation mixed
Matrix membrane and preparation method thereof is closed, includes the following steps: (1) under ultrasonication, Nano carbon balls is dispersed in N, N '-two
In methylacetamide, 4,4 '-diaminodiphenyl ethers are added later, 3,3 ', 4,4 '-biphenyl four are slowly added to after it is completely dissolved
Formic acid dianhydride, sealing stirring reaches 100~300mPas to system viscosity after being all added, and obtains casting solution；(2) by casting film
Liquid knifing on a glass is cooled to room temperature after loading chaffy glass plate heat treatment, receives after demoulding is handled up to carbon
Rice ball-polyimides binary gas separates mixed substrate membrane containing nano-grade molecular sieve.The invention obtains having the Nano carbon balls-that excellent release can be stable
Polyimides binary gas separates mixed substrate membrane containing nano-grade molecular sieve.
China applies for a patent CN201710096026.4 and discloses one kind based on dopen Nano Cu2In the visible light catalytic of O
Fibre ultrafiltration film and preparation method.By polysulfones or polyether sulfone, pore-foaming agent, surfactant, dopen Nano Cu2O and solvent are pressed
It is added in dissolving tank, stirs to being completely dissolved, casting solution is made in standing and defoaming according to certain sequence；Using traditional dry-wet
Method spinning technique prepares visible light catalytic hollow fiber ultrafiltration membrane.Ultrafiltration membrane prepared by the invention has good antifouling property
With visible light catalytic performance.
Summary of the invention
The present invention provides a kind of new preparation process of bielement nano material codope mixed substrate membrane containing nano-grade molecular sieve, using " one pot ", original
Position method preparation.
A kind of preparation method of bielement nano material codope mixed substrate membrane containing nano-grade molecular sieve, includes the following steps:
(1) polymerizable oil-phase medium and polymerizable surfactants are mixed, constructs reverse micelle microemulsion；To gained
Nano material-I is added in reverse micelle microemulsion, adds the presoma of nano material-II after being dispersed with stirring again, is stirred；Must include
There is the reverse micelle microemulsion of nano material-I, nano material-II；
The nano material-I is low-dimensional carbon nanomaterial；The nano material-II is water-soluble transition metal salt；
(2) to include nano material-I, nano material-II reverse micelle microemulsion in be added initiator, carry out in situ
Polymerization reaction obtains nano material-I ,-II codope polymer latex of nano material；
(3) bielement nano is obtained after adjusting nano material-I, the viscosity of-II codope polymer latex of nano material and standing
Material is co-doped with heteropolymer preparation liquid；
(4) bielement nano material heteropolymer preparation liquid is co-doped with to be coated uniformly on support membrane, it is thermally treated to obtain binary
Nano material codope mixed substrate membrane containing nano-grade molecular sieve.
When preparing mixed substrate membrane containing nano-grade molecular sieve using metal nanoparticle, low-dimensional carbon nanomaterial doping, metal nanoparticle, low-dimensional
Carbon nanomaterial structure is to determine one of the key factor of mixed-matrix film properties.And by situ on low-dimensional carbon nanomaterial
Metal nanoparticle is grown, the metal nanoparticle with three-dimensional structure/carbon nanomaterial compound can be obtained, this is a kind of new
The inorganic nano composite material of type has broad application prospects in seperation film field.
The present invention selects polymerizable type oil-phase medium and polymerizable type surfactant to construct reverse micelle microemulsion, using anti-
Micelle microemulsion liquid growth in situ nano material-II in nano material-I.Then being obtained again by micro-emulsion polymerization includes to receive
Rice material-I, nano material-II bielement nano material be co-doped with heteropolymer preparation liquid.Coating, heat treatment method are finally used,
Bielement nano material codope mixed substrate membrane containing nano-grade molecular sieve is obtained, CO is applied to2/N2Deng admixture of gas separation or benzene/cyclohexane
The infiltration evaporation of the organic mixtures such as equal aromatic hydrocarbons/cycloalkane, olefin/paraffin.
The forming process of the preparation liquid of step (1)~(3) of the present invention carries out in the same reactor (" one pot "), in
Between not product separation, purifying, the also not generation and discharge of by-product, i.e. mixed substrate membrane containing nano-grade molecular sieve preparation liquid are in " one pot "
It is formed.
It include nano material-I, 3 kinds of nano material-II, polymer materials in mixed substrate membrane containing nano-grade molecular sieve.Nano material-I is directly thrown
It is added in reactor, nano material-II is generated by the precursor mixture fabricated in situ being added in reactor, and polymer is logical
Cross can the in-situ polymerization of oil-phase medium and surfactant generate, i.e., mixed-matrix membrane material is formed in situ in " one pot "
's.
Preferably, the polymerizable oil-phase medium is the mixture of phenylethylene or phenylethylene and acrylate；Institute
State polymerizable surfactants be styrene dodecyl dimethyl ammonium chloride, styrene dodecyldimethylamine ammonium chloride,
Styrene hexadecyldimethyl benzyl ammonium ammonium chloride or styrene octadecyldimethyl ammonium chloride.Oil-phase medium and polymerizable surface are living
Property agent is all made of commercial goods.
Preferably, polymerizable surfactants, polymerizable oil-phase medium, the mass ratio between water three are 1g:10
~15g:0.01~0.05g.Further preferably 1g:11.5~12.5g:0.02~0.03g.
Preferably, the mass ratio of the dosage of nano material-I and reverse micelle microemulsion is 1mg:6.0~8.5g.Further
Preferably 1mg:7.0~7.5g.
Preferably, the mass ratio of the presoma dosage Yu reverse micelle microemulsion of nano material-II is 1mg:1~6g.Into
One step is preferably 1mg:2.5~4.5g.
Preferably, the low-dimensional carbon nanomaterial is graphene oxide, amination graphene, chloride graphene, carbonoxide
Nanotube, amination carbon nanotube or acyl chlorides carbon nano tube.
Preferably, the water-soluble transition metal salt is water-soluble cobalt salt, zinc salt, mantoquita, titanium salt, silver salt or manganese
Salt.
Preferably, the initiator is azodiisobutyronitrile.Dosage is oil-phase medium and surfactant gross mass
0.3%.
Preferably, the home position polymerization reaction time is 2~4 hours.
Preferably, adjust nano material-I, the viscosity of-II codope polymer latex of nano material be 250~
350mPa·s；Time of repose is 4~6 hours.
Preferably, the support membrane is the polysulfone ultrafiltration membrane of molecular cut off 2~40,000；Heat treatment temperature is 60~80 DEG C,
Heat treatment time is 8~12 hours.
The present invention also provides a kind of bielement nano material codope mixed substrate membrane containing nano-grade molecular sieves that the preparation method is prepared.
The present invention also provides a kind of applications of bielement nano material codope mixed substrate membrane containing nano-grade molecular sieve.
The present invention prepares low-dimensional carbon nanomaterial by " one pot ", in-situ method, transition metal nanoparticles adulterate mixed base
Plasma membrane.It is embodied in a reactor (" one pot "), is given birth in situ on low-dimensional carbon nanomaterial using reverse micelle microemulsion
Long transition metal nanoparticles, then bielement nano material is obtained by microemulsion in-situ polymerization and is co-doped with heteropolymer preparation liquid.Most
Afterwards using coating and heat treatment process, low-dimensional carbon nanomaterial, transition metal nanoparticles bielement nano material codope are obtained
Mixed substrate membrane containing nano-grade molecular sieve.
Compared with prior art, the present invention has following advantage and characteristic:
Low-dimensional carbon nanomaterial, transition metal nanoparticles bielement nano material codope mixed substrate membrane containing nano-grade molecular sieve " one pot " legal system
Standby, method is easy, economical, environmental-friendly.
Low-dimensional carbon nanomaterial provided by the invention, transition metal nanoparticles bielement nano material codope mixed-matrix
Film, due to the synergistic effect of low-dimensional carbon nanomaterial and transition metal nanoparticles, mixed substrate membrane containing nano-grade molecular sieve is in CO2/N2Deng gas it is mixed
Isolating and purifying in application for the organic mixtures such as aromatic hydrocarbons/cycloalkane, the olefin/paraffin such as the separation of conjunction object or benzene/cyclohexane, shows
Excellent permeability and permselective property out.
Specific embodiment
It is further illustrated below by way of specific embodiment using how the present invention prepares low-dimensional carbon nanomaterial, transition gold
Belong to the CO of nanoparticle bielement nano material codope mixed substrate membrane containing nano-grade molecular sieve and its prepared film2、N2Infiltration and permselective property, or
The Pervaporation Separation of benzene/cyclohexane mixture.
The gas infiltration of low-dimensional carbon nanomaterial, transition metal nanoparticles bielement nano material codope mixed substrate membrane containing nano-grade molecular sieve
Performance evaluation: mixed substrate membrane containing nano-grade molecular sieve being put into the continuous filter of gas permeation test device, and the effective area of film is 19.6cm2, film
Upstream side gas (CO2Or N2) pressure be 0.15Mpa, film downstream lateral pressure be 0.1Mpa.The flux of air penetrating film is by penetrating film
Gas flow calculating measure.It is thought poorly of in unit time through the gas permeation volume (under standard state) of per membrane area
Tie up the gas permeability of carbon nanomaterial, transition metal nanoparticles codope mixed substrate membrane containing nano-grade molecular sieve.
Low-dimensional carbon nanomaterial, transition metal nanoparticles bielement nano material codope mixed substrate membrane containing nano-grade molecular sieve benzene/ring
The infiltration evaporation performance evaluation of alkane mixture system: mixed substrate membrane containing nano-grade molecular sieve being put into the continuous filter of vaporization performance testing device,
The effective area of film is 19.6cm2, seeped using benzene/cyclohexane mixture system of 30 DEG C, 50wt% to evaluate mixed substrate membrane containing nano-grade molecular sieve
Vaporization performance (permeation flux J, separation factor α thoroughlyBenzene/cyclohexane), film downstream lateral pressure is controlled in 100 ± 10Pa.
Embodiment 1
In 30 DEG C of water-baths, 3g styrene dodecyl dimethyl ammonium chloride, 36.4g styrene, 0.08g water are mixed, stirred
Dissolution is mixed, the graphene oxide of 5mg is then added, is dispersed with stirring, then slowly adds the zinc chloride of 10mg, is stirred, formation includes
There is the reverse micelle microemulsion of graphene, zinc nanoparticle.
1.2g azodiisobutyronitrile is added into the reverse micelle microemulsion of formation, it is small to carry out polymerization reaction 3 under normal temperature and pressure
When, acquisition includes the latex of graphene, zinc nanoparticle.The latex viscosity of acquisition is adjusted to 250mPa.s or so, after standing
Coated on ultrafiltration support membrane, 80 μm of coating thickness or so, then drying 12 hours under the conditions of temperature is 80 DEG C, obtain thickness
Graphene, the zinc nanoparticle codope mixed substrate membrane containing nano-grade molecular sieve of 17 μm of degree.
The CO of graphene prepared by the present embodiment, zinc nanoparticle codope mixed substrate membrane containing nano-grade molecular sieve2、 N2Permeance property is shown in Table
1。
Embodiment 2
In 30 DEG C of water-baths, by 3g styrene dodecyl dimethyl ammonium chloride, 21.8g (40mL) styrene, 15.1g
(16mL) methyl methacrylate, the mixing of 0.08g water, stirring and dissolving, then add the amination carbon nanotube of 5mg, stirring point
It dissipates, then slowly adds the copper acetate of 14.7mg, stir, formation includes the reverse micelle microemulsion of carbon nanotube, copper nano-particle.
1.2g azodiisobutyronitrile is added into the reverse micelle microemulsion of formation, is carried out polymerization reaction under normal temperature and pressure, is obtained
It must include the latex of graphene, copper nano-particle compound.The latex viscosity of acquisition is adjusted to 250mPa.s or so, after standing
Coated on ultrafiltration support membrane, 80 μm of coating thickness or so, then drying 12 hours under the conditions of temperature is 80 DEG C, obtain thickness
The carbon nanotube of 17 μm of degree, copper nano-particle codope mixed substrate membrane containing nano-grade molecular sieve.
The CO of carbon nanotube prepared by the present embodiment, copper nano-particle codope mixed substrate membrane containing nano-grade molecular sieve2、 N2Permeance property is shown in
Table 1.
Embodiment 3
In 30 DEG C of water-baths, by 3g styrene dodecyldimethylamine ammonium chloride, 21.8g (24mL) styrene, 15.1g
(16mL) methyl methacrylate, the mixing of 0.08g water, stirring and dissolving, then add the amination graphene of 5mg, are dispersed with stirring,
The silver nitrate of 12.4mg is slowly added again, is stirred, formation includes the reverse micelle microemulsion of graphene, Nano silver grain.
1.2g azodiisobutyronitrile is added into the reverse micelle microemulsion of formation, carries out polymerization reaction, acquisition includes stone
The latex of black alkene, Nano silver grain.The latex viscosity of acquisition is adjusted to 250mPa.s or so, ultrafiltration is coated in after standing and supports
On film, 80 μm of coating thickness or so, then dry 12 hours under the conditions of temperature is 80 DEG C, obtain 17 μm of thickness graphene,
Nano silver grain codope mixed substrate membrane containing nano-grade molecular sieve.
Benzene/thiacyclohexane mixture infiltration of graphene prepared by the present embodiment, Nano silver grain codope mixed substrate membrane containing nano-grade molecular sieve
Vaporization performance is shown in Table 2 thoroughly.
Embodiment 4
In 30 DEG C of water-baths, by 3g styrene dodecyldimethylamine ammonium chloride, 21.8g styrene, 15.1g metering system
Sour methyl esters, the mixing of 0.08g water, stirring and dissolving, then add the acyl chlorides carbon nano tube of 5mg, are dispersed with stirring, then slowly add
The cobalt nitrate of 13.4mg, stirring, formation includes the reverse micelle microemulsion of carbon nanotube, cobalt nanometer particle.
1.2g azodiisobutyronitrile is added into the reverse micelle microemulsion of formation, carries out polymerization reaction, acquisition includes stone
The latex of black alkene, cobalt nanometer particle.The latex viscosity of acquisition is adjusted to 250mPa.s or so, ultrafiltration is coated in after standing and supports
It is 80 μm of coating thickness or so, then 12 hours dry under the conditions of temperature is 80 DEG C on film, obtain 17 μm of thickness of carbon nanometer
Pipe, cobalt nanometer particle codope mixed substrate membrane containing nano-grade molecular sieve.
Benzene/thiacyclohexane mixture of carbon nanotube prepared by the present embodiment, cobalt nanometer particle codope mixed substrate membrane containing nano-grade molecular sieve
Infiltration evaporation performance is shown in Table 2.
Low-dimensional carbon nanomaterial prepared by 1. embodiment of the present invention of table, transition metal nanoparticles codope mixed-matrix
The CO of film2、N2Permeance property.
Low-dimensional carbon nanomaterial prepared by 2. embodiment of the present invention of table, transition metal nanoparticles codope mixed-matrix
The benzene of film/thiacyclohexane mixture infiltration evaporation performance
The foregoing is merely the specific implementation cases of the invention patent, but the technical characteristic of the invention patent is not limited to
This, within the field of the present invention, made changes or modifications all cover of the invention special any those skilled in the relevant art
Among sharp range.
Claims (9)
1. a kind of preparation method of bielement nano material codope mixed substrate membrane containing nano-grade molecular sieve, which comprises the steps of:
(1) polymerizable oil-phase medium, polymerizable surfactants and water are mixed, constructs reverse micelle microemulsion；To gained
Nano material-I is added in reverse micelle microemulsion, adds the presoma of nano material-II after being dispersed with stirring again, is stirred；Must include
There is the reverse micelle microemulsion of nano material-I, nano material-II；
The nano material-I is low-dimensional carbon nanomaterial；The nano material-II is water-soluble transition metal salt；
(2) to include nano material-I, nano material-II reverse micelle microemulsion in be added initiator, carry out in-situ polymerization
Reaction, obtains nano material-I ,-II codope polymer latex of nano material；
(3) bielement nano material is obtained after adjusting nano material-I, the viscosity of-II codope polymer latex of nano material and standing
It is co-doped with heteropolymer preparation liquid；
(4) bielement nano material heteropolymer preparation liquid is co-doped with to be coated uniformly on support membrane, it is thermally treated to obtain bielement nano
Material codope mixed substrate membrane containing nano-grade molecular sieve.
2. preparation method according to claim 1, which is characterized in that polymerizable surfactants, polymerizable oil are mutually situated between
Mass ratio between matter, water three is 1g:10~15g:0.01~0.05g.
3. preparation method according to claim 1, which is characterized in that the dosage of nano material-I and reverse micelle microemulsion
Mass ratio is 1mg:6.0~8.5g.
4. preparation method according to claim 1, which is characterized in that the presoma dosage and reverse micelle of nano material-II
The mass ratio of microemulsion is 1mg:1~6g.
5. preparation method according to claim 1, which is characterized in that the low-dimensional carbon nanomaterial is graphene oxide, amine
Graphite alkene, chloride graphene, oxide/carbon nanometer tube, amination carbon nanotube or acyl chlorides carbon nano tube.
6. preparation method according to claim 1, which is characterized in that the water-soluble transition metal salt is water-soluble cobalt
Salt, zinc salt, mantoquita, titanium salt, silver salt or manganese salt.
7. preparation method according to claim 1, which is characterized in that adjusting nano material-I, nano material-II are co-doped with heteromeric
The viscosity for closing object latex is 250~350mPas；Time of repose is 4~6 hours.
8. preparation method according to claim 1, which is characterized in that the support membrane is the polysulfones of molecular cut off 2~40,000
Ultrafiltration membrane；Heat treatment temperature is 60~80 DEG C, and heat treatment time is 8~12 hours.
9. a kind of bielement nano material that the preparation method as described in any one of claim 1~8 claim is prepared is co-doped with
Miscellaneous mixed substrate membrane containing nano-grade molecular sieve.
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| WO2021091485A1 (en) * | 2019-11-08 | 2021-05-14 | National University Of Singapore | Low temperature separation method using 2d material-based nanocomposite coating |
| CN113813798A (en) * | 2021-09-28 | 2021-12-21 | 浙江工商大学 | Cobalt @ iron bimetallic hydroxide nanoparticle-doped mixed matrix ultrafiltration membrane and preparation method thereof |
| CN113813801A (en) * | 2021-09-28 | 2021-12-21 | 浙江工商大学 | Mixed matrix ultrafiltration membrane doped with ZIFs @ polyion liquid compound and preparation method thereof |
| CN113813801B (en) * | 2021-09-28 | 2023-06-06 | 浙江工商大学 | Mixed matrix ultrafiltration membrane doped with ZIFs@polyionic liquid compound and preparation method thereof |
| CN113813798B (en) * | 2021-09-28 | 2023-11-14 | 浙江工商大学 | Mixed matrix ultrafiltration membrane doped with cobalt@iron double metal hydroxide nanoparticles and preparation method thereof |
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