CN117138605B - Ultralow-pressure reverse osmosis membrane and preparation method thereof - Google Patents
Ultralow-pressure reverse osmosis membrane and preparation method thereof Download PDFInfo
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- CN117138605B CN117138605B CN202311402855.2A CN202311402855A CN117138605B CN 117138605 B CN117138605 B CN 117138605B CN 202311402855 A CN202311402855 A CN 202311402855A CN 117138605 B CN117138605 B CN 117138605B
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- 239000012528 membrane Substances 0.000 title claims abstract description 53
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000008346 aqueous phase Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000005266 casting Methods 0.000 claims abstract description 35
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 28
- 239000012071 phase Substances 0.000 claims abstract description 27
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 21
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 229920002113 octoxynol Polymers 0.000 claims abstract description 16
- 229940066429 octoxynol Drugs 0.000 claims abstract description 16
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 230000008961 swelling Effects 0.000 claims abstract description 11
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 73
- 239000000178 monomer Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000001723 curing Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000013007 heat curing Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 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 claims description 5
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 5
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 4
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000007602 hot air drying Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012971 dimethylpiperazine Substances 0.000 claims description 3
- -1 isopar L Chemical compound 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 9
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 238000010612 desalination reaction Methods 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 4
- 230000004907 flux Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004952 Polyamide Substances 0.000 description 7
- 229920002647 polyamide Polymers 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of membrane separation, in particular to an ultra-low pressure reverse osmosis membrane and a preparation method thereof. The preparation method comprises the following steps: coating an aqueous phase solution on a base film, then coating an oil phase solution, performing interfacial polymerization reaction, and performing heat treatment to obtain an ultra-low pressure reverse osmosis membrane; the base film is prepared by compounding a film casting solution and non-woven fabrics; the casting film liquid comprises a component a, octoxynol and a first solvent; the component a comprises polysulfone. In the invention, octabenyl alcohol is added into a polysulfone/polyacrylonitrile casting film liquid system, the hydrophilicity of the base film is regulated and controlled through the proportion of polysulfone and polyacrylonitrile, and the pore diameter structure of the base film is regulated and controlled through the addition amount of octabenyl alcohol. And immersing the base membrane into an organic solvent dimethylacetamide solution, and increasing the porosity of the base membrane through swelling and shrinkage of polymer chains to obtain the base membrane with uniform pore diameter. The ultra-low pressure reverse osmosis membrane prepared by the invention has higher water flux and better desalination rate.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to an ultra-low pressure reverse osmosis membrane and a preparation method thereof.
Background
Reverse Osmosis (RO) membrane separation technology has become an effective means for solving the water resource shortage at the present stage due to the advantages of high efficiency, low consumption, high quality of produced water and the like. Further improving the permselectivity of RO membranes is beneficial to reducing the cost of produced water and improving the quality of produced water, so the preparation of RO membranes with high permselectivity has been the focus of research in the membrane field. The formation of a thin layer composite structure by interfacial polymerization to produce a Polyamide (PA) separation layer on a porous base membrane is an important technical process for preparing reverse osmosis membranes. Since the polyamide separation layer determines the separation and water permeation characteristics of the composite membrane, a great deal of research has been focused on improving the performance of the PA layer. However, during interfacial polymerization, the base film has a critical impact on the formation of the polyamide separation layer. The structure (pore size, porosity) and surface properties (hydrophilicity, surface charge, etc.) of the base film can affect the amount of aqueous phase carried, the interaction of the base film with the aqueous phase solution, the diffusion rate of the aqueous phase monomer into the organic phase, and the spreading state of the aqueous phase solution within the base film, thereby affecting the degree of crosslinking, thickness, and separation performance of the PA separation layer.
In the prior art, polyether sulfone (PES) and Polyacrylonitrile (PAN) are used as membrane materials, a metallic compound and a hydrophilic high molecular polymer are added to blend to form a casting solution, and the structure and performance of a base membrane are regulated and controlled by regulating the total mass fraction, the mass ratio and the mass fraction of an additive.
Currently, polysulfone (PSF) ultrafiltration membranes are the most widely used base membranes in laboratories and enterprises for preparing reverse osmosis membranes because of their good mechanical strength, thermal stability, wide pH operating range, and relatively low manufacturing cost. However, the polysulfone-based membrane surface has relatively small pore size, low porosity, and polysulfone has natural hydrophobicity. After the hydrophobic base film with small pore diameter and low porosity is soaked in the aqueous phase solution, the carried aqueous phase solution is less, the degree of interfacial polymerization reaction is low, the crosslinking degree of the generated PA separation layer is low, and the thickness is relatively thin. In addition, the existing reverse osmosis membrane base membranes are mostly prepared by a phase inversion method, the pore size of the base membrane is distributed in a relatively wide range, and the pore size of the base membrane is difficult to accurately regulate by changing the casting conditions or other modification methods.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an ultra-low pressure reverse osmosis membrane and a preparation method thereof, wherein the desalination rate of the ultra-low pressure reverse osmosis membrane is better.
The invention provides a preparation method of an ultralow-pressure reverse osmosis membrane, which comprises the following steps:
coating an aqueous phase solution on a base film, then coating an oil phase solution, performing interfacial polymerization reaction, and performing heat treatment to obtain an ultra-low pressure reverse osmosis membrane;
the base film is prepared by compounding a film casting solution and non-woven fabrics; the casting film liquid comprises a component a, octoxynol and a first solvent; the component a comprises polysulfone.
Preferably, said component a further comprises polyacrylonitrile;
in the film casting liquid, the mass content of the component a is 15% -25%, and the mass content of the octoxynol is 10% -20%;
the mass ratio of the polysulfone to the polyacrylonitrile is 8-10: 0-2;
the first solvent comprises dimethylacetamide;
the preparation method of the casting film liquid comprises the following steps:
and dissolving and uniformly mixing polysulfone, polyacrylonitrile, octoxynol and a first solvent at 70-90 ℃, and then defoaming and cooling to obtain the membrane casting solution.
Preferably, the preparation method of the base film comprises the following steps:
and (3) coating the casting solution on one side surface of the non-woven fabric, curing, rinsing, immersing in DMAc aqueous solution for swelling, and then performing heat curing to obtain the base film.
Preferably, the coating method is slot extrusion;
the method of curing includes: the phase inversion was performed in a gel tank filled with RO water at 15 ℃. The curing time is 0.5-2 min;
the rinsing temperature is 5-55 ℃ and the rinsing time is 1-5 min;
the mass concentration of the DMAc aqueous solution is 10% -30%, and the swelling time is 10-60 s;
the water temperature of the heat curing is 7-95 ℃ and the time is 0.5-3 min.
Preferably, the aqueous phase solution comprises: an aqueous monomer, an acid acceptor, and an acidic material;
the aqueous phase monomer comprises m-phenylenediamine;
in the aqueous phase solution, the mass content of the aqueous phase monomer is 0.5% -10.0%;
the acid acceptor comprises at least one of triethylamine, N-dimethyl piperazine, sodium carbonate and sodium hydroxide;
the acidic substance includes at least one of camphorsulfonic acid, acetic acid and methanesulfonic acid.
Preferably, the aqueous solution further comprises an additive;
the additive comprises at least one of glycerol, dimethyl sulfoxide and sodium dodecyl sulfate;
in the aqueous phase solution, the mass content of the additive is 0.005% -20.0%;
the pH value of the aqueous phase solution is 4.0-11.0.
Preferably, the oil phase solution comprises an organic phase monomer and a second solvent;
the organic phase monomer comprises trimesic acid chloride;
in the oil phase solution, the mass content of the organic phase monomer is 0.015% -2.5%;
the second solvent includes at least one of Isopar G, isopar L, and n-hexane.
Preferably, after the aqueous phase solution is coated on the base film, the method further comprises:
removing excessive water from the coated base film, and then carrying out vacuum water absorption and drying;
the pressure of the vacuum water absorption is-1 to-55 KPa;
the drying includes: carrying out hot air drying on the back surface of the base film through a hot air system until the surface of the water phase of the base film is dry; the temperature of the hot air is 30-70 ℃.
Preferably, the temperature of the interfacial polymerization reaction is 30-70 ℃ and the time is 5-30 s;
the temperature of the heat treatment is 60-80 ℃ and the time is 1.5-2.5 min.
The invention also provides an ultralow-pressure reverse osmosis membrane prepared by the preparation method.
The invention provides a preparation method of an ultralow-pressure reverse osmosis membrane, which comprises the following steps: coating an aqueous phase solution on a base film, then coating an oil phase solution, performing interfacial polymerization reaction, and performing heat treatment to obtain an ultra-low pressure reverse osmosis membrane; the base film is prepared by compounding a film casting solution and non-woven fabrics; the casting film liquid comprises a component a, octoxynol and a first solvent; the component a comprises polysulfone. In the invention, octabenyl alcohol is added into a polysulfone/polyacrylonitrile casting film liquid system, the hydrophilicity of the base film is regulated and controlled through the proportion of polysulfone and polyacrylonitrile, and the pore diameter structure of the base film is regulated and controlled through the addition amount of octabenyl alcohol. And immersing the base membrane into an organic solvent dimethylacetamide solution, and increasing the porosity of the base membrane through swelling and shrinkage of polymer chains to obtain the base membrane with uniform pore diameter. The ultra-low pressure reverse osmosis membrane prepared by the invention has higher water flux and better desalination rate. In addition, in the preparation method provided by the invention, the adopted raw materials are low in cost, the additive belongs to a low-irritation substance, the method is high in operability, and the preparation method can be used for industrial production.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of an ultralow-pressure reverse osmosis membrane, which comprises the following steps:
coating an aqueous phase solution on a base film, then coating an oil phase solution, performing interfacial polymerization reaction, and performing heat treatment to obtain an ultra-low pressure reverse osmosis membrane;
the base film is prepared by compounding a film casting solution and non-woven fabrics; the casting film liquid comprises a component a, octoxynol and a first solvent; the component a includes Polysulfone (PSF).
In certain embodiments of the present invention, the component a further comprises Polyacrylonitrile (PAN).
In some embodiments of the present invention, the mass content of the component a in the film casting solution is 15% -25%, such as 18%; the mass content of the octoxynol is 10% -20%, such as 10% and 15%. The mass ratio of the polysulfone to the polyacrylonitrile is 8-10: 0-2. In certain embodiments, the polysulfone and polyacrylonitrile have a mass ratio of 8: 2. 9:1. 10:0.
the first solvent includes dimethylacetamide (DMAc).
In certain embodiments of the present invention, the method of preparing the casting solution comprises the steps of:
and dissolving and uniformly mixing polysulfone, polyacrylonitrile, octoxynol and a first solvent at 70-90 ℃, and then defoaming and cooling to obtain the membrane casting solution.
The time for dissolving and mixing is 2-4 hours.
The defoaming and cooling time is 24-48 h, and the defoaming and cooling are performed in a degassing tank.
In certain embodiments of the present invention, the method of preparing the base film comprises the steps of:
and (3) coating the casting solution on one side surface of the non-woven fabric, curing, rinsing, immersing in DMAc aqueous solution for swelling, and then performing heat curing to obtain the base film.
The coating method is slit extrusion.
The method of curing includes: the phase inversion was performed in a gel tank filled with RO water at 15 ℃. The curing time is 0.5-2 min; such as 1 min.
The rinsing temperature is 5-55 ℃, such as 30 ℃; the time is 1-5 min; such as 2 minutes. The mass concentration of the DMAc aqueous solution is 10% -30%, such as 30% and 10%; swelling time is 10-60 s; such as 30 s. The water temperature for heat curing is 7-95 ℃, such as 70 ℃; the time is 0.5-3 min, such as 1.5 min.
In certain embodiments of the invention, the aqueous phase solution comprises: an aqueous monomer, an acid acceptor, and an acidic material. The aqueous monomer comprises at least one of aromatic amine and aliphatic amine, preferably m-phenylenediamine. In the aqueous phase solution, the mass content of the aqueous phase monomer is 0.5% -10.0%, such as 2%.
The acid acceptor includes at least one of triethylamine, N-dimethylpiperazine, sodium carbonate, and sodium hydroxide. The acidic substance includes at least one of camphorsulfonic acid, acetic acid and methanesulfonic acid.
In certain embodiments of the invention, the aqueous solution further comprises an additive. The additive comprises at least one of glycerol, dimethyl sulfoxide and sodium dodecyl sulfate. The mass content of the additive in the aqueous phase solution is 0.005% -20.0%, such as 6.1%.
The pH value of the aqueous phase solution is 4.0-11.0, such as 8.0.
The aqueous phase solution is prepared by uniformly mixing raw materials comprising an aqueous phase monomer, an acid acceptor, an acidic substance and an additive.
In certain embodiments of the invention, the oil phase solution includes an organic phase monomer and a second solvent. The organic phase monomer comprises trimesoyl chloride. In the oil phase solution, the mass content of the organic phase monomer is 0.015% -2.5%, such as 0.2%. The second solvent includes at least one of Isopar G, isopar L, and n-hexane.
In certain embodiments of the invention, the oil phase solution is obtained by mixing well a feedstock comprising an organic phase monomer and a second solvent.
In certain embodiments of the invention, applying the aqueous phase solution on the base film comprises: coating 10-30 g/m on the front surface of the base film 2 Is a solution of (1) in water; such as 20 g/m 2 。
In certain embodiments of the present invention, after applying the aqueous phase solution to the base film, further comprising:
and removing redundant aqueous phase solution from the coated base film, and then carrying out vacuum water absorption and drying.
The coated base film was passed through a wiper blade to remove excess aqueous solution.
The vacuum water absorption comprises: and (5) carrying out vacuum water absorption on the back surface of the coated base film. The pressure of the vacuum water absorption is-1 to-55 KPa; such as-10 KPa.
The drying includes: carrying out hot air drying on the back surface of the base film through a hot air system until the surface of the water phase of the base film is dry; the temperature of the hot air is 30-70 ℃; such as 38 deg.c.
In some embodiments of the invention, the oil phase solution has a coating amount of 5-15 g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Such as 10 g/m 2 。
In some embodiments of the present invention, the interfacial polymerization reaction is performed at a temperature of 30 to 70 ℃, such as 50 ℃; the time is 5-30 s, such as 30 s.
In some embodiments of the invention, the temperature of the heat treatment is 60-80 ℃, such as 75 ℃; the time is 1.5-2.5 min, specifically 2 min. The heat treatment serves to rapidly remove the solvent from the surface of the base film and promote further progress of the polycondensation reaction.
The invention also provides an ultralow-pressure reverse osmosis membrane prepared by the preparation method.
In some embodiments of the present invention, the ultra-low pressure reverse osmosis membrane is suitable for a pressure of 1.03-4.14 MPa, such as 1.03 MPa.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
In order to further illustrate the present invention, the following examples are provided to describe an ultra-low pressure reverse osmosis membrane and a preparation method thereof in detail, but the present invention is not to be construed as being limited to the scope of protection.
The reagents used in the following examples and comparative examples are all commercially available.
Example 1
1. Preparing a casting solution:
dissolving polysulfone, polyacrylonitrile, octoxynol and dimethylacetamide (DMAc) at 80 ℃ and uniformly mixing the materials for 3 h, and then defoaming and cooling the materials in a degassing tank for 24 h to obtain a casting solution;
the mass ratio of the polysulfone to the polyacrylonitrile is 8:2;
in the casting film liquid, the mass content of polysulfone and polyacrylonitrile is 18%, and the mass content of octoxynol is 10%.
2. Preparing an aqueous phase solution:
uniformly mixing m-phenylenediamine, an acid acceptor (sodium hydroxide), an acidic substance (camphorsulfonic acid), dimethyl sulfoxide and sodium dodecyl sulfate to obtain a water phase solution;
in the aqueous phase solution, the mass content of m-phenylenediamine is 2%, the mass content of dimethyl sulfoxide is 6%, and the mass content of sodium dodecyl sulfate is 0.1%; the pH of the aqueous solution was 8.0.
3. Preparing an oil phase solution:
uniformly mixing trimesoyl chloride and Isopar G to obtain an oil phase solution;
in the oil phase solution, the mass content of trimesic acid chloride is 0.2%.
4. Preparation of a base film:
coating the casting solution on one side surface of the non-woven fabric by a slit extrusion method, and placing the non-woven fabric in a gel tank filled with RO water at 15 ℃ for phase inversion for 1min; rinsing in hot water at 30deg.C for 2min; then immersing in DMAc solution with the mass concentration of 30%, and swelling for 30 seconds; and then thermally curing the mixture for 1.5min at 70 ℃ with hot water to obtain the base film.
5. Preparation of an ultralow-pressure reverse osmosis membrane:
coating 20 g/m on the front side of the base film 2 Removing excessive aqueous phase solution from the coated base film through a wiper blade, then carrying out vacuum water absorption on the back surface of the base film, wherein the vacuum water absorption pressure is-10 KPa, and then carrying out hot air drying on the back surface of the base film through a hot air system until the surface of the base film is dry, wherein the hot air temperature is 38 ℃;
the front surface of the base film after the surface drying of the water phase is coated with an oil phase solution (the coating amount of the oil phase solution is 10 g/m) 2 ) And (3) carrying out interfacial polymerization reaction at 50 ℃ for 30 seconds, and then sending the mixture into an oven for heat treatment, wherein the heat treatment temperature is 75 ℃ and the time is 2 minutes, so as to obtain the ultra-low pressure reverse osmosis membrane.
Example 2
The difference from example 1 is that:
the mass ratio of polysulfone to polyacrylonitrile is controlled to be 9:1.
example 3
The difference from example 1 is that:
the mass ratio of polysulfone to polyacrylonitrile is controlled to be 10:0.
example 4
The difference from example 1 is that:
in the film casting liquid, the mass content of the octoxynol is 15%.
Example 5
The difference from example 1 is that:
in the preparation of the base film, a DMAc solution with a mass concentration of 10% was immersed.
Comparative example 1
The difference from example 1 is that:
in the film casting liquid, the mass content of the octoxynol is 0%.
Comparative example 2
The difference from example 1 is that:
the mass ratio of polysulfone to polyacrylonitrile is controlled to be 5:5.
comparative example 3
The difference from example 1 is that:
the base film was prepared without a step of swelling in a DMAc solution having a mass concentration of 30% for 30 s.
Comparative example 4
The difference from example 1 is that:
in the film casting liquid, the mass content of the octoxynol is 2%.
Comparative example 5
The difference from example 1 is that:
in the preparation of the base film, a DMAc solution with a mass concentration of 50% was immersed.
Comparative example 6
The difference from example 5 is that:
1. preparing a casting solution:
weighing 1.75% of polysulfone resin with the brand name of P7304 (with the intrinsic viscosity of 0.45) produced by Dalian polysulfone plastic Co., ltd., 13.5% of polyvinyl chloride resin with the brand name of DG-1000 produced by Tianjin Dagu chemical Co., ltd., 1.75% of thermoplastic polyurethane resin with the brand name of WHT-14 produced by Jiujia Wanhua polyurethane Co., ltd., 12% of polyvinylpyrrolidone with the brand name of K-30 produced by Boai New open source pharmaceutical Co., ltd., 1788 produced by Anhui Wanjia Gao material Co., ltd., and 63% of dimethylformamide with the brand name of 1788 produced by Temmin diamond (Nanjing) in sequence, and stirring the materials in a reaction kettle at 90 ℃ for 48 hours to obtain a casting film liquid.
The ultra-low pressure reverse osmosis membranes prepared in examples 1 to 5 and comparative examples 1 to 6 were tested for water flux and desalination rate, and the results are shown in table 1. Diaphragm performance test conditions: and under the pressure of 1.03MPa, testing by using a sodium chloride aqueous solution with the pH value of 7.5-8.0 and the concentration of 1500ppm at the testing temperature of 25+/-0.5 ℃ and the testing flow of 1.1GPM.
Table 1 Water flux and desalination Rate of ultra-low pressure reverse osmosis membranes prepared in examples 1 to 5 and comparative examples 1 to 6
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the ultra-low pressure reverse osmosis membrane comprises the following steps:
coating an aqueous phase solution on a base film, then coating an oil phase solution, performing interfacial polymerization reaction, and performing heat treatment to obtain an ultra-low pressure reverse osmosis membrane;
the base film is prepared by immersing the base film into a dimethylacetamide solution for swelling after the film casting solution and the non-woven fabric are compounded; the film casting solution consists of a component a, octoxynol and a first solvent; the component a is polysulfone and polyacrylonitrile, and the mass ratio of the polysulfone to the polyacrylonitrile is 8-10: 0-2;
in the film casting liquid, the mass content of the component a is 15% -25%, and the mass content of the octoxynol is 10% -20%;
the mass concentration of the dimethylacetamide solution is 10% -30%.
2. The method according to claim 1, wherein,
the first solvent comprises dimethylacetamide;
the preparation method of the casting film liquid comprises the following steps:
and (3) dissolving and uniformly mixing the component a, the octoxynol and the first solvent at 70-90 ℃, and then defoaming and cooling to obtain the casting film liquid.
3. The method of producing according to claim 1, wherein the method of producing the base film comprises the steps of:
and (3) coating the casting solution on one side surface of the non-woven fabric, curing, rinsing, immersing in DMAc aqueous solution for swelling, and then performing heat curing to obtain the base film.
4. A method of manufacture according to claim 3, wherein the method of coating is slot extrusion;
the method of curing includes: placing in a gel tank filled with RO water at 15 ℃ for phase inversion; the curing time is 0.5-2 min;
the rinsing temperature is 5-55 ℃ and the rinsing time is 1-5 min;
the mass concentration of the DMAc aqueous solution is 10% -30%, and the swelling time is 10-60 s;
the water temperature of the heat curing is 7-95 ℃ and the time is 0.5-3 min.
5. The method of claim 1, wherein the aqueous phase solution comprises: an aqueous monomer, an acid acceptor, and an acidic material;
the aqueous phase monomer comprises m-phenylenediamine;
in the aqueous phase solution, the mass content of the aqueous phase monomer is 0.5% -10.0%;
the acid acceptor comprises at least one of triethylamine, N-dimethyl piperazine, sodium carbonate and sodium hydroxide;
the acidic substance includes at least one of camphorsulfonic acid, acetic acid and methanesulfonic acid.
6. The method of claim 5, wherein the aqueous solution further comprises an additive;
the additive comprises at least one of glycerol, dimethyl sulfoxide and sodium dodecyl sulfate;
in the aqueous phase solution, the mass content of the additive is 0.005% -20.0%;
the pH value of the aqueous phase solution is 4.0-11.0.
7. The method of claim 1, wherein the oil phase solution comprises an organic phase monomer and a second solvent;
the organic phase monomer comprises trimesic acid chloride;
in the oil phase solution, the mass content of the organic phase monomer is 0.015% -2.5%;
the second solvent includes at least one of Isopar G, isopar L, and n-hexane.
8. The method according to claim 1, further comprising, after the aqueous phase solution is applied to the base film:
removing excessive water from the coated base film, and then carrying out vacuum water absorption and drying;
the pressure of the vacuum water absorption is-1 to-55 KPa;
the drying includes: carrying out hot air drying on the back surface of the base film through a hot air system until the surface of the water phase of the base film is dry; the temperature of the hot air is 30-70 ℃.
9. The preparation method according to claim 1, wherein the interfacial polymerization reaction is carried out at a temperature of 30-70 ℃ for 5-30 s;
the temperature of the heat treatment is 60-80 ℃ and the time is 1.5-2.5 min.
10. The ultra-low pressure reverse osmosis membrane produced by the production method according to any one of claims 1 to 9.
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