CN114259885A - Double-sided polyamide reverse osmosis composite membrane, preparation process and reverse osmosis membrane preparation device - Google Patents
Double-sided polyamide reverse osmosis composite membrane, preparation process and reverse osmosis membrane preparation device Download PDFInfo
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- CN114259885A CN114259885A CN202111616566.3A CN202111616566A CN114259885A CN 114259885 A CN114259885 A CN 114259885A CN 202111616566 A CN202111616566 A CN 202111616566A CN 114259885 A CN114259885 A CN 114259885A
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- reverse osmosis
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- polyamide
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- 239000012528 membrane Substances 0.000 title claims abstract description 107
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 57
- 239000004952 Polyamide Substances 0.000 title claims abstract description 45
- 229920002647 polyamide Polymers 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004744 fabric Substances 0.000 claims abstract description 32
- 239000012074 organic phase Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000004698 Polyethylene Substances 0.000 claims abstract description 24
- -1 polyethylene Polymers 0.000 claims abstract description 24
- 229920000573 polyethylene Polymers 0.000 claims abstract description 24
- 238000003618 dip coating Methods 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000011033 desalting Methods 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 238000005096 rolling process Methods 0.000 claims abstract description 9
- 238000003466 welding Methods 0.000 claims abstract description 9
- 239000012071 phase Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000004026 adhesive bonding Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims description 19
- 239000008346 aqueous phase Substances 0.000 claims description 17
- 238000012695 Interfacial polymerization Methods 0.000 claims description 14
- 238000004804 winding Methods 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000012696 Interfacial polycondensation Methods 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003851 corona treatment Methods 0.000 claims description 2
- 238000009832 plasma treatment Methods 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- 229920002492 poly(sulfone) Polymers 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000010926 purge Methods 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a double-sided polyamide reverse osmosis composite membrane, a preparation process and a reverse osmosis membrane preparation device. The double-sided polyamide reverse osmosis composite membrane consists of a water production diversion cloth in the middle, polyethylene porous layers and polyamide desalting layers on two sides; the formed composite reverse osmosis membrane and the concentrated water diversion cloth are wound to manufacture the membrane element with an improved structure. The composite process of double-sided reverse osmosis composite polyamide membrane includes ultrasonic welding, heat welding or adhesive bonding of porous polyethylene layer to water producing flow guiding cloth, and one-step in-situ interface polymerization of polyamide desalting layer on the porous polyethylene layer. A process for preparing a polyamide membrane comprising: the method comprises the steps that a double-sided polyethylene porous layer combined with water-producing guide cloth is subjected to surface modification, water-phase monomer solution dip-coating, solvent removal, organic-phase monomer solution dip-coating and solvent removal in sequence; and washing, drying and rolling.
Description
Technical Field
The invention belongs to the technical field of membranes, and particularly relates to a double-sided polyamide reverse osmosis composite membrane, a preparation process thereof, a reverse osmosis membrane preparation device and a novel membrane element structure.
Background
The existing commercial reverse osmosis membrane element is composed of a single-sided reverse osmosis membrane, concentrated water guide cloth, pure water guide cloth, a central tube, an externally wound adhesive tape and the like, and the single-sided membrane is cut, laminated and wound to form the membrane element. Wherein the single-sided reverse osmosis membrane is also a three-layer composite material and is respectively a polyester non-woven fabric, a polysulfone porous layer and a polyamide desalting layer from bottom to top. The traditional reverse osmosis membrane is firstly prepared into a polysulfone porous membrane by coating and phase separation on a polyester non-woven fabric, then interfacial polymerization is carried out to form a polyamide desalting layer on the polysulfone side, so that a single-sided reverse osmosis membrane is obtained, a layer of single-sided reverse osmosis membrane is respectively superposed on two sides of a pure water guide cloth, and then the membrane element is obtained by winding the membrane with a concentrated water flow passage cloth and the like. The method has the defects that multiple processes of preparing a polysulfone porous layer, preparing a polyamide desalting layer, combining a membrane and a guide cloth and rolling the element are required to be sequentially carried out from a single-side membrane to a membrane element, and each step involves a complicated operation flow. For example, the polysulfone porous layer needs to be repeatedly rinsed and generates waste water, and the composite polyamide membrane and the flow guide cloth need to be cut one by one and then combined, and then the element can be rolled. The complex process not only impairs the production efficiency of the membrane element, but also increases the quality control points of the membrane element, resulting in the increase of defective rate.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a double-sided polyamide reverse osmosis composite membrane (bag) containing water production diversion cloth, which can be directly combined with concentrated water diversion cloth (grid) to be wound to prepare a membrane element. Another object of the present invention is to provide a combined process of a double-sided polyamide reverse osmosis composite membrane, which can greatly reduce the processes from the preparation of reverse osmosis membrane sheets to the preparation of membrane elements, greatly reduce the thickness of membrane bags (a membrane rolling basic unit comprising two membrane sheets and one pure water guide cloth), and improve the packing density of the membrane elements. The invention further aims to provide a one-step double-sided interfacial polymerization process of the double-sided polyamide reverse osmosis membrane composite membrane, which ensures the time for double sides of the polyethylene porous membrane to contact the aqueous phase solution and the organic phase monomer solution, realizes double-sided interfacial polymerization and direct winding of the composite membrane (bag) in one step, further realizes direct preparation of the membrane element with a novel structure, and does not need to relate to the later cutting and bonding of the composite membrane and the produced water guide cloth. The fourth purpose of the invention is to provide a reverse osmosis membrane preparation device which shortens the reverse osmosis membrane element manufacturing process, reduces the cost, realizes the industrial production of reverse osmosis membrane in batches and improves the production efficiency.
The technical scheme of the invention is that the double-sided polyamide reverse osmosis composite membrane is characterized by comprising a water production diversion cloth arranged in the middle, and a polyethylene porous layer and a polyamide desalting layer which are respectively arranged on two sides of the water production diversion cloth; and winding the formed composite reverse osmosis membrane and the concentrated water guide cloth to prepare the membrane element.
The other technical scheme of the invention is a combination process of the double-sided polyamide reverse osmosis composite membrane, which is characterized in that the polyethylene porous layer is compounded with the water-producing flow guide cloth through ultrasonic welding, thermal welding or adhesive bonding, and then the polyethylene porous layer is subjected to surface modification; the polyamide desalting layer is polymerized on the surface of the polyethylene porous layer through one-step in-situ interface.
The invention also discloses a technical scheme of a one-step double-sided interfacial polymerization process of the double-sided polyamide reverse osmosis composite membrane, which is characterized by comprising the following steps of:
the surface modification of the polyethylene porous layer comprises: surfactant treatment, surface corona treatment, surface plasma treatment and surface chemical treatment.
The fourth technical scheme of the invention is a one-step double-sided interfacial polymerization process of the double-sided polyamide reverse osmosis composite membrane, which is characterized by comprising the following steps of:
the method comprises the steps that a double-sided polyethylene porous layer after being compounded with water-producing diversion cloth is subjected to surface modification, water-phase monomer solution dip-coating, solvent removal, dip-coating of organic-phase monomer solution and solvent removal;
and washing, drying and rolling.
Preferably, the method comprises the following steps: the interfacial polymerization is an interfacial polycondensation reaction of a water phase monomer and an organic phase monomer, wherein the water phase monomer comprises polyamine, polyhydric phenol and polyhydric alcohol, and the organic phase monomer comprises polybasic acyl chloride.
The fifth technical solution of the present invention is the reverse osmosis membrane preparation apparatus, which is characterized by comprising an unwinding shaft, an aqueous phase monomer solution dip-coating tank, an organic phase monomer solution dip-coating tank, a cleaning tank, an oven and a winding shaft, which are sequentially arranged from left to right, wherein rollers are respectively installed at the bottoms and two sides of an upper end opening of the aqueous phase monomer solution dip-coating tank, the organic phase monomer solution dip-coating tank and the cleaning tank, and a membrane roll on the unwinding shaft sequentially bypasses each roller, then passes through the oven and is connected to the winding shaft.
Preferably, the method comprises the following steps: the device comprises a cleaning tank, a water phase monomer solution dipping tank, an organic phase solvent removing chamber, rollers and a control system.
Preferably, the method comprises the following steps: the cleaning tank is internally provided with a plurality of cleaning chambers, the bottom of each cleaning chamber and the two sides of the upper end opening are respectively provided with a roller, and the film roll sequentially enters the oven after passing through each cleaning chamber.
Compared with the prior art, the invention has the beneficial effects that:
the process from reverse osmosis membrane preparation to membrane element preparation is greatly reduced, the thickness of a membrane bag (a membrane rolling basic unit comprising two layers of membranes and one layer of pure water guide cloth) is greatly reduced, and the filling density of the membrane element is improved;
the invention can simplify the preparation process of the reverse osmosis membrane element and reduce the defective rate of products.
Drawings
FIG. 1 is a schematic structural view of a double-sided polyamide reverse osmosis composite membrane according to the present invention;
FIG. 2 is a schematic view of the interfacial polymerization process of the double-sided polyamide reverse osmosis composite membrane of the present invention.
Detailed Description
The invention will be described in more detail below with reference to the accompanying drawings:
referring to fig. 1, the double-sided polyamide reverse osmosis composite membrane (bag) includes a polyamide desalination layer, and the composite reverse osmosis membrane is composed of a polyethylene porous layer respectively compounded on two surfaces of a pure water diversion cloth and a polyamide desalination layer generated in situ on two surfaces in situ; and winding the formed composite reverse osmosis membrane and the concentrated water guide cloth to prepare the membrane element.
The composite process of double-sided reverse osmosis composite polyamide membrane includes ultrasonic welding, heat welding or adhesive bonding of porous polyethylene layer to water producing flow guiding cloth, and one-step in-situ interface polymerization of polyamide desalting layer on the porous polyethylene layer.
Referring to fig. 2, the reverse osmosis membrane preparation apparatus includes an unwinding shaft, an aqueous phase monomer solution dip-coating tank, an organic phase monomer solution dip-coating tank, a cleaning tank, an oven, and a winding shaft, which are sequentially arranged from left to right, wherein rollers are respectively installed at the bottoms and the two sides of the upper end openings of the aqueous phase monomer solution dip-coating tank, the organic phase monomer solution dip-coating tank, and the cleaning tank, and a membrane roll on the unwinding shaft sequentially bypasses the rollers, then passes through the oven, and then is connected to the winding shaft.
In this embodiment, an aqueous phase solvent removing chamber is provided between the aqueous phase monomer solution dip coating tank and the organic phase monomer solution dip coating tank, an organic phase solvent removing chamber is provided between the organic phase monomer solution dip coating tank and the cleaning tank, and rollers are provided at the bottom and both sides of an opening at the upper end of the aqueous phase solvent removing chamber and the organic phase solvent removing chamber.
In this embodiment, be equipped with a plurality of purge chambers in the washing tank, the bottom and the upper end opening both sides of every purge chamber all are equipped with the gyro wheel, and the membrane is rolled up and is got into the oven behind every purge chamber in proper order.
Referring to fig. 2, a one-step double-sided interfacial polymerization process for a double-sided polyamide reverse osmosis composite membrane includes the following steps:
the method comprises the steps that a double-sided polyethylene porous layer combined with water-producing guide cloth is subjected to surface modification, water-phase monomer solution dip-coating, solvent removal, organic-phase monomer solution dip-coating and solvent removal in sequence;
and washing, drying and rolling.
The combination and preparation of a double-sided polyamide reverse osmosis composite membrane is illustrated in detail by the following examples, which are presented only to further illustrate the features and advantages of the present invention and are not intended to limit the claims of the present invention.
In the following examples, the thickness of the water-generating cloth used to prepare the double-sided polyamide reverse osmosis composite membrane was about 0.30mm, the thickness of the polyethylene porous layer was about 10um, and the pore size was about 0.1 um. The thickness of the concentrated water grid used for preparing the membrane element is about 0.35 mm.
Example 1: the water-producing flow guide cloth and the polyethylene porous layer are subjected to ultrasonic welding of two edges and surface modification treatment, and then one-step interfacial polymerization of the double-sided polyamide reverse osmosis composite membrane is carried out on equipment with a continuous membrane preparation process shown in figure 2. The aqueous phase solution was 1.0% wt piperazine in water and the membrane residence time was 1min, and the organic phase was 0.25% wt trimesoyl chloride in n-hexane or isopar series and the membrane residence time was 1 min. Drying and cleaning, and directly rolling.
Example 2: the water-producing flow guide cloth and the polyethylene porous layer are bonded at two edges through an adhesive and subjected to surface modification treatment, and then the one-step interfacial polymerization of the double-sided polyamide reverse osmosis composite membrane is carried out on equipment with a continuous membrane preparation process shown in figure 2. The aqueous phase solution is 2.0 wt% metaphenylene diamine aqueous solution, the residence time of the membrane therein is 1min, the organic phase is 0.1 wt% trimesoyl chloride solution of n-hexane or isopar series, and the residence time of the membrane therein is 1 min. Drying and cleaning, and directly rolling.
The double-sided polyamide reverse osmosis composite membrane of the above two examples was combined with a dense water grid and rolled into a 1812 type membrane element.
The performance of the double-sided polyamide reverse osmosis composite membrane and the element in the above two examples are tested as follows:
TABLE 1 Performance of the double-sided Polyamide reverse osmosis composite membranes and elements thereof
Note: the test solution is 250mg/L sodium chloride solution, the test pressure is 0.41MPa, the membrane surface flow rate of the membrane is 0.45m/s, and the recovery rate of the element is 50%.
The table shows that the double-sided polyamide reverse osmosis composite membrane and element have good water production flux and desalting performance.
The above-mentioned embodiments are only preferred embodiments of the present invention, and all equivalent changes and modifications made within the scope of the claims of the present invention should be covered by the claims of the present invention.
Claims (8)
1. The double-sided polyamide reverse osmosis composite membrane is characterized by comprising a water production flow guide cloth in the middle, and a polyethylene porous layer and a polyamide desalting layer which are respectively arranged on two sides of the water production flow guide cloth; and winding the formed composite reverse osmosis membrane and the concentrated water guide cloth to prepare the membrane element.
2. The combined process of the double-sided polyamide reverse osmosis composite membrane is characterized in that the polyethylene porous layer is compounded with the water-producing flow guide cloth through ultrasonic welding, thermal welding or adhesive bonding, and then the polyethylene porous layer is subjected to surface modification; the polyamide desalting layer is polymerized on the surface of the polyethylene porous layer through one-step in-situ interface.
3. A one-step double-sided interfacial polymerization process for a double-sided polyamide reverse osmosis membrane composite membrane is characterized in that the surface modification of a polyethylene porous layer comprises the following steps: surfactant treatment, surface corona treatment, surface plasma treatment and surface chemical treatment.
4. A one-step double-sided interfacial polymerization process of a double-sided polyamide reverse osmosis composite membrane is characterized by comprising the following steps of:
the method comprises the steps that a double-sided polyethylene porous layer after being compounded with water-producing diversion cloth is subjected to surface modification, water-phase monomer solution dip-coating, solvent removal, dip-coating of organic-phase monomer solution and solvent removal;
and washing, drying and rolling.
5. The process for one-step double-sided interfacial polymerization of a double-sided polyamide reverse osmosis membrane composite membrane according to claim 4, wherein the interfacial polymerization is interfacial polycondensation of an aqueous phase monomer and an organic phase monomer, the aqueous phase monomer comprises polyamine, polyhydric phenol and polyhydric alcohol, and the organic phase monomer comprises polyacyl chloride.
6. The reverse osmosis membrane preparation device is characterized by comprising an unwinding shaft, an aqueous phase monomer solution dip-coating groove, an organic phase monomer solution dip-coating groove, a cleaning groove, an oven and a winding shaft which are sequentially arranged from left to right, wherein rollers are respectively arranged at the bottoms and the two sides of an opening at the upper end of the aqueous phase monomer solution dip-coating groove, the bottom and the two sides of an opening at the upper end of the organic phase monomer solution dip-coating groove and the cleaning groove, and a membrane roll on the unwinding shaft sequentially bypasses the rollers and then passes through the oven to be connected to the winding shaft.
7. A device for preparing a reverse osmosis membrane according to claim 6, wherein an aqueous phase solvent removing chamber is arranged between the aqueous phase monomer solution dipping tank and the organic phase monomer solution dipping tank, an organic phase solvent removing chamber is arranged between the organic phase monomer solution dipping tank and the cleaning tank, and rollers are arranged at the bottom and two sides of an opening at the upper end of each of the aqueous phase solvent removing chamber and the organic phase solvent removing chamber.
8. A reverse osmosis membrane preparation apparatus according to claim 6, wherein: the cleaning tank is internally provided with a plurality of cleaning chambers, the bottom of each cleaning chamber and the two sides of the upper end opening are respectively provided with a roller, and the film roll sequentially enters the oven after passing through each cleaning chamber.
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| CN202111616566.3A CN114259885A (en) | 2021-12-27 | 2021-12-27 | Double-sided polyamide reverse osmosis composite membrane, preparation process and reverse osmosis membrane preparation device |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101732997A (en) * | 2008-11-25 | 2010-06-16 | 中国石油天然气股份有限公司 | Sealing method of spiral rolled membrane module by acetone benzol solvent recovery |
| US20190366269A1 (en) * | 2016-07-07 | 2019-12-05 | Sk Innovation Co., Ltd. | Reverse osmosis membrane |
| CN111203105A (en) * | 2020-02-04 | 2020-05-29 | 厦门江天智能仿生科技有限公司 | Preparation method of multilayer reverse osmosis composite membrane |
| CN212549041U (en) * | 2020-03-20 | 2021-02-19 | 北京碧水源膜科技有限公司 | Production equipment of reverse osmosis membrane |
| CN214159179U (en) * | 2020-10-14 | 2021-09-10 | 追觅创新科技(苏州)有限公司 | Reverse osmosis membrane assembly, filter element with same and water purifier |
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- 2021-12-27 CN CN202111616566.3A patent/CN114259885A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101732997A (en) * | 2008-11-25 | 2010-06-16 | 中国石油天然气股份有限公司 | Sealing method of spiral rolled membrane module by acetone benzol solvent recovery |
| US20190366269A1 (en) * | 2016-07-07 | 2019-12-05 | Sk Innovation Co., Ltd. | Reverse osmosis membrane |
| CN111203105A (en) * | 2020-02-04 | 2020-05-29 | 厦门江天智能仿生科技有限公司 | Preparation method of multilayer reverse osmosis composite membrane |
| CN212549041U (en) * | 2020-03-20 | 2021-02-19 | 北京碧水源膜科技有限公司 | Production equipment of reverse osmosis membrane |
| CN214159179U (en) * | 2020-10-14 | 2021-09-10 | 追觅创新科技(苏州)有限公司 | Reverse osmosis membrane assembly, filter element with same and water purifier |
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