CN110354684A - A kind of reverse osmosis membrane of low energy consumption and its preparation method and application - Google Patents
A kind of reverse osmosis membrane of low energy consumption and its preparation method and application Download PDFInfo
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- CN110354684A CN110354684A CN201910762196.0A CN201910762196A CN110354684A CN 110354684 A CN110354684 A CN 110354684A CN 201910762196 A CN201910762196 A CN 201910762196A CN 110354684 A CN110354684 A CN 110354684A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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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
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses reverse osmosis membrane of a kind of low energy consumption and its preparation method and application, which includes polysulfone porous supporting layer and the polyamide desalination layer that is formed on supporting layer, doped with polyurethane particles inside the polyamide desalination layer.Reverse osmosis membrane provided by the invention can be used for the fields such as wastewater treatment, sea water desalination, pure water manufacture, have lower energy consumption in counter-infiltration system operation.
Description
Technical field
The present invention relates to water-treatment technology field, in particular to a kind of reverse osmosis membrane of low energy consumption and preparation method thereof and answer
With.
Background technique
Aromatic polyamide complex reverse osmosis membrane is current most widely used reverse osmosis membrane materials, one in preparation process
As interface polycondensation reaction carried out in polysulfones support film surface using m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride form polyamide desalination layer.
The type reverse osmosis membrane has been widely used for wastewater treatment, Treated sewage reusing, pure water manufacture and field of seawater desalination.With the whole world
Energy shortage, the non-renewable resources such as fossil energy gradually exhaust, and reducing counter-infiltration system operation energy consumption becomes reverse osmosis technology
Mainstream research direction.
In order to reduce the energy consumption of reverse osmosis membrane, solution is usually to improve the flux of reverse osmosis membrane.High reverse osmosis membrane
Flux can reduce the energy consumption of counter-infiltration system compared with the production water for obtaining phase homogenous quantities under ow operating pressure.It discloses at present
Patent mainly uses the flux for preparing mixed-matrix reverse osmosis membrane, improving film in modes such as reverse osmosis membrane surface modifications, also
It is the reverse osmosis membrane for obtaining low energy consumption.In terms of wherein preparing mixed-matrix reverse osmosis membrane, patent CN105457494B discloses one kind
The preparation method of the mixed-matrix reverse osmosis membrane of natural nano crystal doping, by adulterating Cellulose nanocrystal in reverse osmosis membrane
Body or chitin nanocrystal, realize the promotion of flux.Patent CN108114614A discloses a kind of ZSM-5 zeolite nanometer
Grain doping mixed-matrix reverse osmosis membrane, this reverse osmosis membrane by the way that nano particle is added in oil-phase solution, preparation it is anti-
Infiltration is to realize the promotion of flux.Patent CN102527254A, which is disclosed, is added to a kind of sericin in aqueous phase solution,
And then high-flux reverse osmosis membrane method is prepared by interfacial polymerization.In terms of reverse osmosis membrane surface modification, patent
CN102527254A discloses a kind of reverse osmosis membrane surface that will be prepared and aoxidizes, and makes to improve reverse osmosis membrane after its hydrophiling logical
The method of amount.
Although having formed some reverse osmosis membranes high-throughput about preparation in the prior art, that is, reduce reverse osmosis membrane energy consumption
Technical solution, but these technical solutions are continuing to improve reverse osmosis membrane flux, need in terms of the energy consumption for reducing reverse osmosis membrane further
Improve.
Summary of the invention
The purpose of the present invention is to provide reverse osmosis membranes of a kind of low energy consumption and preparation method thereof, can have higher
Water flux, to reduce reduction operating pressure, energy saving.
Another object of the present invention is to provide the application of the reverse osmosis membrane, which are mainly applied to water treatment fields.
In order to achieve the above objectives, The technical solution adopted by the invention is as follows:
First aspect present invention provides a kind of reverse osmosis membrane of low energy consumption, the reverse osmosis membrane include polysulfone porous supporting layer and
The polyamide desalination layer being formed on supporting layer, wherein doped with polyurethane particles inside polyamide desalination layer.
The reverse osmosis membrane of low energy consumption of the invention, the partial size of the polyurethane particles are less than the thickness of polyamide desalination layer,
Preferably, the partial size of the polyurethane particles is 0.001-0.2 μm, more preferably 0.01-0.1 μm
The reverse osmosis membrane of low energy consumption of the invention, the polyurethane particles are aliphatic or aromatic urethane particle, example
Such as aliphatic or aromatic waterborne polyurethane dispersion, preferably water-based aliphaic polyurethane dispersion, the aliphatic is aqueous to gather
Urethane dispersion is preferably Wan Hua company1629、1630A、1630B、
1633、1637 HesOne of 1645 or a variety of.
The reverse osmosis membrane of low energy consumption of the invention, in a kind of preferred embodiment, the porous support layer is shape
At in the polysulfones support membrane on non-woven fabrics.The existing well-known technique system in this field can be used in the preparation of the polysulfones support membrane
, this is not particularly limited.In one kind preferably specific embodiment, preparing in the formula of polysulfones support membrane can contain
The glycol monoethyl ether of the polysulfone resin of 16.0wt%~20.0wt%, 10.0wt%~15.0wt%, these components are dissolved in
Polysulfones casting solution is obtained in polar solvent；The polysulfones casting solution for filtering deaeration painting is scraped in non-woven fabrics (such as non-woven polyester later
Cloth etc.) on；It forms a film subsequently into water through inversion of phases, obtains polysulfones support after cleaning (main to remove solvent and additive etc.)
Film；The polar solvent preferably includes in N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone
It is one or more.
The reverse osmosis membrane of low energy consumption of the invention, in a kind of preferred embodiment, the desalination layer is to be formed in
Polyamide desalination layer on polysulfones support membrane.The preparation of the polyamide desalination layer can be used the existing well-known technique in this field into
Row is made, and is not particularly limited to this.In a kind of preferred embodiment, polyamide desalination layer is aromatic polyamide, preferably
The crosslinked aromatic polyamide formed by m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride by interface polycondensation reaction.
Second aspect of the present invention provides the preparation method of the reverse osmosis membrane of low energy consumption of the invention, and preparation method includes following
Step:
(1) polyurethane particles aqueous solution is added in the aqueous phase solution containing m-phenylene diamine (MPD), is stirred at room temperature to being completely dissolved,
Form the m-phenylene diamine (MPD) aqueous phase solution containing polyurethane particles；
(2) polysulfone porous supporting layer is contacted with the m-phenylene diamine (MPD) aqueous phase solution, remove excess surface water phase, then with equal benzene
The organic phase solution of three formyl chlorides contacts, and interfacial polycondensation occurs for m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride, in polysulfone porous supporting layer
Polyamide desalination layer is adulterated in upper formation, obtains the reverse osmosis membrane of nascent state；
(3) it is heat-treated the reverse osmosis membrane of nascent state.
The preparation method of the reverse osmosis membrane of low energy consumption of the invention, in a kind of preferred embodiment, the step
(1) also contain camphorsulfonic acid and triethylamine in aqueous phase solution.
The preparation method of the reverse osmosis membrane of low energy consumption of the invention, in a kind of preferred embodiment, step (1) is obtained
Aqueous phase solution in, the mass percents of polyurethane particles is 0.01wt%~1.0wt%, preferably 0.02wt%~
0.5wt%；In solution, the mass percent of m-phenylene diamine (MPD) is 1.2wt%~6.0wt%, it is preferred that the matter of the camphorsulfonic acid
Amount percentage is 2.3wt%~6.5wt%, and the mass percent of triethylamine is 1.1wt%~3.5wt%.
The preparation method of the reverse osmosis membrane of low energy consumption of the invention, in a kind of preferred embodiment, in step (2)
Pyromellitic trimethylsilyl chloride concentration is 0.05wt%~0.2wt%, the organic phase solution and polysulfone porous supporting layer of pyromellitic trimethylsilyl chloride
Time of contact be 10~30s, the time of contact of polysulfone porous supporting layer and m-phenylene diamine (MPD) aqueous phase solution is 10s~360s, excellent
It is selected as 20s~120s.Organic phase solvent can choose isoparaffin, such as Mobil Corporation isopar G, isopar E；Also it may be selected
The linear paraffins such as n-hexane, normal heptane, n-decane.
The preparation method of the reverse osmosis membrane of low energy consumption of the invention, in a kind of preferred embodiment, the step
(3) heat treatment mode are as follows: it puts it into baking oven, it is dry, to remove organic phase solvent, finally obtained reverse osmosis membrane is soaked
It ducks in drink.The preparation method of the reverse osmosis membrane of low energy consumption of the invention, in a kind of preferred embodiment, step (3)
Middle drying condition is dry in 80~130 DEG C of hot-air oven.
Third aspect present invention provides the application of the reverse osmosis membrane, the reverse osmosis membrane of low energy consumption described above or institute above
Reverse osmosis membrane made from the preparation method stated, the reverse osmosis membrane as low energy consumption are applied in water treatment component or device, and/or
Applied in method for treating water.The water treatment component or device can be arbitrary the peace that can be applied in water treatment procedure
Component or device equipped with antipollution polyamide reverse osmose membrane of the invention." being applied in the water treatment component or device " packet
The component or device product for being applied to be equipped with low energy consumption polyamide reverse osmose membrane of the invention are included, also includes being applied to prepare this
Kind component or device product.The component for example can be spiral membrane module and dish tubular plate membrane module etc..The dress
Setting for example can be reverse osmosis with household/commercialization reverse osmosis water purifier, industrial boiler water-supply reverse osmosis water purifier, Reuse of Industrial Reclaimed Water
Device and desalination plant etc..The method for treating water for example may is that drinking water manufacture, waste water recycling, sea water desalination,
The methods of beverage concentration.
Present inventor it was unexpectedly observed that for the interface polycondensation reaction that m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride occur,
When adding polyurethane particles in m-phenylene diamine (MPD) aqueous phase solution, when especially adding aliphatic polyurethane class polyurethane particles,
It is more preferable with the affinity of hydrone due to containing a large amount of RNH-COOR ' structures in polyurethane particles, hydrone is more advantageous to anti-
Transmission in permeable membrane.Therefore, under identical counter-infiltration system operating pressure, hydrone is easier to penetrate reverse osmosis membrane, into
And keep the reverse osmosis membrane flux using polyurethane particles doping higher.Secondly as polyurethane class high molecular nano particle molecule
Special-NH-COO- structure in structure can form hydrogen bond with polyamide-NH-CO- structure in reverse osmosis membrane, therefore adulterate polyamides
The crystallization stereochemical structure of amine film is unaffected, therefore its salt rejection rate will not reduce.Due to polyamide desalination in reverse osmosis membrane
Layer is usually at 0.2 μm, and the size of aqueous polyurethane particle is less than the thickness of polyamide in reverse osmosis membrane, especially when aqueous poly- ammonia
When the size of polymeric particles is less than 0.1 μm in ester dispersion, the more uniform distribution in reverse osmosis membrane may be implemented, it will not be right
Polyamide desalination layer in reverse osmosis membrane causes to run through, and influences separating property.
Technical solution provided by the invention has the following beneficial effects:
(1) polyamide reverse osmose membrane provided by the invention has the characteristics that high throughput, in industry well known processing
Under test condition under 2000ppm sodium chloride bitter, 1.55MPa, permeation flux can reach 80~90L/ (m2H), chlorination
Sodium salt rejection rate can be applied to the water process necks such as drinking water manufacture, waste water recycling, sea water desalination, beverage concentration 99.5% or so
Domain.
(2) preparation method of the reverse osmosis membrane of low energy consumption provided by the invention improves the flux of reverse osmosis membrane, therefore,
In the case where identical water yield, the specific energy consumption of counter-infiltration system can be reduced about 30~45%.Preparation method of the invention also has
There is the features such as easy to operate, easy to industrialized production.
Specific embodiment
Technical solution for a better understanding of the present invention, below with reference to the embodiment content that the present invention is further explained,
But the contents of the present invention are not limited only to following embodiment.If raw material used in following embodiment or comparative example is not special
Illustrate, be commercially available technical grade conventional raw material, primary raw material information see the table below.
The method used or may used in the embodiment of the present invention or comparative example is illustrated below:
1. the evaluation of salt rejection rate and permeation flux
Salt rejection rate and permeation flux are two important parameters for evaluating reverse osmosis membrane separation performance.The present invention is according to GB/T
32373-2015 " reverse osmosis membrane test method " carries out separating property evaluation to reverse osmosis membrane.
Salt rejection rate (R) is defined as: under certain operating conditions, feeding liquid salinity (Cf) with penetrating fluid in salinity
(Cp) difference, then divided by feeding liquid salinity (Cf), such as formula (1).
Permeation flux (F) is defined as: under certain operating conditions, through the body of the water of per membrane area in the unit time
Product, unit are L/ (m2·h)。
The operating condition that reverse osmosis membrane separation performance measurement uses in the present invention are as follows: feeding liquid is the sodium chloride of 2000ppm
Aqueous solution, pH value of solution are 7.0 ± 0.5, and operating pressure 1.55MPa, feeding liquid temperature is 25 DEG C.The representation method of specific energy consumption
Are as follows: standard testing pressure (P=1.55MPa)/permeation flux.
Comparative example 1~3
The preparation of polysulfones support membrane: prepared in N,N-dimethylformamide polysulfone resin containing 16.5wt%,
The polysulfones casting solution 25g that the glycol monoethyl ether of 10.0wt% and the lauryl sodium sulfate of 0.1wt% are dissolved in；Then it incited somebody to action
Polysulfones casting solution painting after filter deaeration is scraped on polyester non-woven fabric；It subsequently enters in water and forms a film through inversion of phases, then cleaned obtain
Polysulfones support membrane, film is having a size of 16cm × 12cm.
The preparation of aromatic polyamide desalination layer: water phase A of the preparation containing m-phenylene diamine (MPD), camphorsulfonic acid and triethylamine first is molten
Liquid 25g；Then water phase solution A is contacted with the polysulfones support membrane of hygrometric state, polysulfones support membrane can be completely covered in solution A；Remove table
After the extra moisture in face, then it is contacted instead with organic phase B solution (isopar G isoparaffin) 25g containing pyromellitic trimethylsilyl chloride
It answers, polysulfones support membrane can be completely covered in B solution, and interfacial polycondensation forms polyamide composite film；Composite membrane subsequently enters 90 DEG C of baking ovens
Middle heat treatment 4 minutes；It is to be measured in deionized water that crosslinking aromatic polyamides reverse osmosis membrane immersion will finally be obtained.Different formulations column
In table 1.
Salt rejection rate, permeation flux performance evaluation are carried out to the reverse osmosis membrane, are as a result reported in Table 2 below.
Embodiment 1~13
Polysulfones support membrane is prepared using the method in comparative example 1.
Aromatic polyamide desalination layer, is prepared using following steps:
(1) aqueous solution containing m-phenylene diamine (MPD), camphorsulfonic acid and triethylamine is prepared first, then adds Wan Hua company in the solution
The polyurethane nano particle aqueous solution of the different trades mark of production, is stirred at room temperature and makes it completely dissolved, obtain pbz polymer nanometer
The water phase solution A of grain.Water-based aliphaic polyurethane nano particle additive amount is listed in Table 1 below；
(2) polysulfone porous supporting layer is contacted with the m-phenylene diamine (MPD) water phase solution A, remove excess surface water phase, then with
Interface contracting occurs for three formyl chloride organic phase B solution of benzene (isopar G isoparaffin) contact, m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride
It is poly-, doping polyamide desalination layer is formed on polysulfone porous supporting layer, the polyamide for obtaining the biopolymer nanoparticles containing doping is de-
The reverse osmosis membrane of salt deposit；
(3) reverse osmosis membrane is put into 90 DEG C-baking oven and is heat-treated 4 minutes, obtain the poly- of doping biopolymer nanoparticles
Amide reverse osmosis membrane impregnates to be measured in deionized water.Technological condition is listed in Table 1 below.
Salt rejection rate, permeation flux, specific energy consumption are carried out to the reverse osmosis membrane that different embodiments obtain, the results are shown in Table 2.
The doping component and process conditions of 1 embodiment of table and comparative example
The evaluation result of 2 embodiment of table and comparative example
In conjunction with the experimental result of Tables 1 and 2, polyurethane nano particle is added in m-phenylene diamine (MPD) water phase solution A, it is obtained to mix
The reverse osmosis membrane of heteromeric urethane nano particle has significantly higher flux, thus has lower specific energy consumption, and desalination
Rate does not reduce.
It will be understood by those skilled in the art that under the introduction of this specification, the present invention can be made some modifications or
Adjustment.These modifications or adjustment should also be as within the scope of the claims in the present invention.
Claims (10)
1. a kind of reverse osmosis membrane of low energy consumption, which is characterized in that the reverse osmosis membrane includes polysulfone porous supporting layer and is formed in branch
The polyamide desalination layer on layer is supportted, wherein doped with polyurethane particles inside polyamide desalination layer.
2. reverse osmosis membrane according to claim 1, which is characterized in that the partial size of the polyurethane particles is de- less than polyamide
The thickness of salt deposit, it is preferred that the partial size of the polyurethane particles is 0.001-0.2 μm, more preferably 0.01-0.1 μm.
3. reverse osmosis membrane according to claim 1 or 2, which is characterized in that the polyurethane particles are aliphatic or fragrance
Race's polyurethane particles, such as aliphatic or aromatic waterborne polyurethane dispersion, preferably water-based aliphaic polyurethane dispersion,
The water-based aliphaic polyurethane dispersion is preferably Wan Hua company1629、1630A、
1630B、1633、1637 HesOne of 1645 or a variety of.
4. reverse osmosis membrane according to claim 1, which is characterized in that the polyamide desalination layer is aromatic polyamide,
It is preferred that the crosslinked aromatic polyamide formed by m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride by interface polycondensation reaction.
5. the preparation method of reverse osmosis membrane according to any one of claims 1 to 3, which comprises the following steps:
(1) polyurethane particles aqueous solution is added in the aqueous phase solution containing m-phenylene diamine (MPD), stirring is formed to being completely dissolved containing poly-
The m-phenylene diamine (MPD) aqueous phase solution of urethane particle；
(2) polysulfone porous supporting layer is contacted with the m-phenylene diamine (MPD) aqueous phase solution, remove excess surface water phase, then with equal benzene front three
The organic phase solution of acyl chlorides contacts, and interfacial polycondensation, the shape on polysulfone porous supporting layer occur for m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride
At doping polyamide desalination layer, the reverse osmosis membrane of nascent state is obtained；
(3) it is heat-treated the reverse osmosis membrane of nascent state.
6. preparation method according to claim 5, which is characterized in that also contain camphor tree in the aqueous phase solution of the step (1)
Brain sulfonic acid and triethylamine.
7. preparation method according to claim 5 or 6, which is characterized in that the m-phenylene diamine (MPD) aqueous phase solution that step (1) obtains
In, the mass percent of polyurethane particles is 0.01wt%~1.0wt%, preferably 0.02wt%~0.5wt%；In solution,
The mass percent of m-phenylene diamine (MPD) is 1.2wt%~6.0wt%, it is preferred that the mass percent of the camphorsulfonic acid is
2.3wt%~6.5wt%, the mass percent of triethylamine are 1.1wt%~3.5wt%.
8. preparation method according to claim 5, which is characterized in that pyromellitic trimethylsilyl chloride concentration is in step (2)
0.05wt%~0.2wt%, the organic phase solution of pyromellitic trimethylsilyl chloride and polysulfone porous supporting layer time of contact are 10~30s,
The time of contact of polysulfone porous supporting layer and m-phenylene diamine (MPD) aqueous phase solution is 10s~360s, preferably 20s~120s.
9. preparation method according to claim 5, which is characterized in that the heat treatment mode of the step (3) are as follows: will come into being
The reverse osmosis membrane of state is put into baking oven, dry, finally impregnates obtained reverse osmosis membrane in water；
Preferably, the drying condition in step (3) is to dry the solution of film surface i.e. in 80~130 DEG C of hot-air oven
It can.
10. preparation method system described in any one of reverse osmosis membrane of any of claims 1-4 or claim 5-9
The application of the reverse osmosis membrane obtained, the reverse osmosis membrane as low energy consumption is applied in water treatment component or device, and/or is applied to water
In processing method.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110917907A (en) * | 2019-12-12 | 2020-03-27 | 万华化学集团股份有限公司 | High-flux reverse osmosis membrane and preparation method and application thereof |
| CN114950150A (en) * | 2022-07-19 | 2022-08-30 | 湖南沁森高科新材料有限公司 | Extremely-low-pressure reverse osmosis membrane and preparation method thereof |
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| CN107281940A (en) * | 2016-03-30 | 2017-10-24 | 天津工业大学 | A kind of polymer/polymer hollow microsphere hybridized film and application |
| CN110052170A (en) * | 2019-05-09 | 2019-07-26 | 万华化学集团股份有限公司 | A kind of reverse osmosis membrane and its preparation method and application of acid and alkali-resistance cleaning |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101462025A (en) * | 2008-08-13 | 2009-06-24 | 贵阳时代汇通膜科技有限公司 | Double-layer polyamide surface layer composite reverse osmosis membrane and preparation method thereof |
| CN107281940A (en) * | 2016-03-30 | 2017-10-24 | 天津工业大学 | A kind of polymer/polymer hollow microsphere hybridized film and application |
| CN110052170A (en) * | 2019-05-09 | 2019-07-26 | 万华化学集团股份有限公司 | A kind of reverse osmosis membrane and its preparation method and application of acid and alkali-resistance cleaning |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110917907A (en) * | 2019-12-12 | 2020-03-27 | 万华化学集团股份有限公司 | High-flux reverse osmosis membrane and preparation method and application thereof |
| CN110917907B (en) * | 2019-12-12 | 2022-03-08 | 万华化学集团股份有限公司 | High-flux reverse osmosis membrane and preparation method and application thereof |
| CN114950150A (en) * | 2022-07-19 | 2022-08-30 | 湖南沁森高科新材料有限公司 | Extremely-low-pressure reverse osmosis membrane and preparation method thereof |
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