CN112844077A - Reverse osmosis membrane with PE microporous membrane as base material and preparation method thereof - Google Patents
Reverse osmosis membrane with PE microporous membrane as base material and preparation method thereof Download PDFInfo
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- CN112844077A CN112844077A CN202011569683.4A CN202011569683A CN112844077A CN 112844077 A CN112844077 A CN 112844077A CN 202011569683 A CN202011569683 A CN 202011569683A CN 112844077 A CN112844077 A CN 112844077A
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- microporous membrane
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- reverse osmosis
- polyvinyl alcohol
- graphene oxide
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- 239000012528 membrane Substances 0.000 title claims abstract description 112
- 239000012982 microporous membrane Substances 0.000 title claims abstract description 99
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000004952 Polyamide Substances 0.000 claims abstract description 32
- 229920002647 polyamide Polymers 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000004698 Polyethylene Substances 0.000 claims description 112
- 239000000243 solution Substances 0.000 claims description 103
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 93
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 93
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 78
- 229910021389 graphene Inorganic materials 0.000 claims description 78
- 239000007864 aqueous solution Substances 0.000 claims description 62
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 239000004970 Chain extender Substances 0.000 claims description 24
- 238000005266 casting Methods 0.000 claims description 24
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 24
- 239000010954 inorganic particle Substances 0.000 claims description 24
- 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 21
- 238000004132 cross linking Methods 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- 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 18
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 18
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 18
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- HJLHTTJLVALHOP-UHFFFAOYSA-N hexane;hydron;chloride Chemical compound Cl.CCCCCC HJLHTTJLVALHOP-UHFFFAOYSA-N 0.000 claims description 16
- 238000012695 Interfacial polymerization Methods 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000006136 alcoholysis reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical group CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- 238000009998 heat setting Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims 2
- 229960001153 serine Drugs 0.000 claims 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 7
- 230000004907 flux Effects 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 37
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- 238000000605 extraction Methods 0.000 description 9
- 239000004745 nonwoven fabric Substances 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D71/26—Polyalkenes
-
- 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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a reverse osmosis membrane taking a PE microporous membrane as a base material and a preparation method thereof, wherein the reverse osmosis membrane comprises the PE microporous membrane, a polysulfone layer coated on the PE microporous membrane and a polyamide layer coated on the polysulfone layer; the PE microporous membrane has the pore diameter of 0.01-10 mu m, the porosity of 70-95% and the thickness of 20-120 mu m. The PE microporous membrane is small in pore diameter and excellent in homogeneity, the polysulfone layer is coated on the surface of the PE microporous membrane, and due to the fact that DMF, DMAc, NMP or DMSO and other organic solvents are adopted when polysulfone is coated, the PE microporous membrane is easily dissolved in the solvents, so that the PE microporous membrane can be subjected to permeation etching, and the pore diameter of the surface of the polysulfone layer is reduced and is more uniform. Because the pore diameter of the polysulfone layer is more uniform, the defects of the polyamide layer are reduced in the polymerization process, the polyamide layer is more uniform, and the performance is more excellent. The reverse osmosis membrane prepared by the invention has excellent water flux and rejection rate.
Description
Technical Field
The invention belongs to the field of reverse osmosis membranes, and particularly relates to a reverse osmosis membrane with a PE microporous membrane as a base material and a preparation method thereof.
Background
Reverse osmosis is an efficient water purification method, has the advantages of high efficiency, low cost, no phase change, easy integration, modularization, automation and the like, and is widely applied to the fields of high-purity water preparation, medical water preparation, seawater desalination, brackish water desalination, sewage recycling and the like in the electronic industry. With the shortage of fresh water resources and the increasing water pollution, reverse osmosis technology plays an increasingly important role in water purification.
However, the pore size distribution of the base membrane of the existing reverse osmosis membrane is not uniform, so that the pore size on the surface of the reverse osmosis membrane is not uniform in the reaction process of the polyamide membrane, and the flux and rejection rate of the reverse osmosis membrane are finally influenced.
Disclosure of Invention
In order to solve the technical problems, the invention provides the reverse osmosis membrane with the PE microporous membrane as the base material and the preparation method thereof, the polysulfone layer and the polyamide layer have uniform pore diameter and more excellent performance, and the water flux and the rejection rate of the reverse osmosis membrane can be improved.
The technical scheme of the invention is realized as follows:
a reverse osmosis membrane taking a PE microporous membrane as a base material comprises the PE microporous membrane, a polysulfone layer coated on the PE microporous membrane and a polyamide layer coated on the polysulfone layer;
the PE microporous membrane has the pore diameter of 0.01-10 mu m, the porosity of 70-95% and the thickness of 20-120 mu m.
Further, the PE microporous membrane comprises high density PE, a chain extender, a hydrophilic polymer, and inorganic particles; the mass ratio of the high-density PE to the chain extender to the hydrophilic polymer to the inorganic particles is 2: 1: 2: 1.
further, the hydrophilic polymer is polyvinyl alcohol, polyethylene glycol, polymethyl pyrrolidone and polyacrylic acid.
Further, the inorganic particles are silica, sodium chloride, calcium carbonate or titanium dioxide.
Further, the chain extender is phthalic anhydride or polyisodiol.
The invention also provides a preparation method of the reverse osmosis membrane with the PE microporous membrane as the base material, which comprises the following steps:
1) coating a polysulfone membrane casting solution on the surface of the PE microporous membrane, and curing to obtain the PE microporous membrane coated with a polysulfone layer;
2) adding m-phenylenediamine, triethylamine and camphorsulfonic acid into deionized water, and magnetically stirring to obtain an aqueous solution; adding trimesoyl chloride into n-hexane, and stirring until the trimesoyl chloride is dissolved to obtain a trimesoyl chloride-n-hexane oil phase solution; immersing the PE microporous membrane coated with the polysulfone layer obtained in the step 1) into a water phase solution, taking out the PE microporous membrane, removing the solvent, immersing the PE microporous membrane into a prepared trimesoyl chloride-n-hexane oil phase solution for interfacial polymerization reaction to form a polyamide layer, taking out the polyamide layer, and removing the solvent n-hexane to obtain the nascent state polyamide reverse osmosis membrane;
3) dissolving polyvinyl alcohol in deionized water, and mechanically stirring to obtain a polyvinyl alcohol aqueous solution; dissolving graphene oxide in deionized water, magnetically stirring, and ultrasonically dispersing to obtain a graphene oxide aqueous solution; mixing the graphene oxide aqueous solution with a polyvinyl alcohol aqueous solution to obtain a polyvinyl alcohol aqueous solution containing graphene oxide; adding glutaraldehyde, levoserine and hydrochloric acid into a polyvinyl alcohol aqueous solution containing graphene oxide to obtain a polyvinyl alcohol crosslinking reaction solution containing graphene oxide, coating the polyvinyl alcohol crosslinking reaction solution containing graphene oxide on the surface of the nascent reverse osmosis membrane obtained in the step 1), and drying to obtain the reverse osmosis membrane.
Further, the preparation method of the PE microporous membrane comprises the following steps:
1) uniformly mixing the high-density PE, the chain extender, the hydrophilic polymer and the inorganic particles, pouring the mixture into a screw extruder for melt extrusion, wherein the traction ratio of a melt extrusion base film is 10-100;
2) annealing, stretching and heat setting the base membrane obtained in the step 1), wherein the annealing temperature is 100-150 ℃, and the stretching ratio is 60-150%, so as to obtain the PE microporous membrane for the water treatment membrane substrate.
Furthermore, the mass concentration of m-phenylenediamine in the aqueous phase solution is 5.9 percent, the mass concentration of triethylamine is 3.4 percent, and the mass concentration of camphorsulfonic acid is 5.9 percent; the mass concentration of trimesoyl chloride in the oil phase solution is 0.3 percent;
furthermore, the polymerization degree of the polyvinyl alcohol is 1000, and the alcoholysis degree is 99%; the mass ratio of the graphene oxide to the polyvinyl alcohol in the polyvinyl alcohol aqueous solution containing the graphene oxide is 1: 20-50;
furthermore, the mass concentration of polyvinyl alcohol in the polyvinyl alcohol crosslinking reaction solution containing graphene oxide is 3.8%, the mass concentration of glutaraldehyde is 0.38%, the mass concentration of levoserine is 0.19%, and the mass concentration of hydrochloric acid is 0.1%.
The invention provides a reverse osmosis membrane taking a PE microporous membrane as a base material and a preparation method thereof, and the reverse osmosis membrane has the following advantages:
1) the PE microporous membrane has small pore diameter and excellent homogeneity, the polysulfone layer is coated on the surface of the PE microporous membrane, and the PE microporous membrane is easily dissolved in DMF, DMAc, NMP or DMSO and other organic solvents when the polysulfone layer is coated, so that the PE microporous membrane is subjected to permeation etching, the pore diameter of the surface of the polysulfone layer is reduced, and the polysulfone layer is more uniform.
2) Because the pore diameter of the polysulfone layer is more uniform, the defects of the polyamide layer are reduced in the polymerization process, the polyamide layer is more uniform, and the performance is more excellent.
3) The reverse osmosis membrane prepared by the invention has excellent water flux and rejection rate.
Detailed Description
For better understanding of the essence of the present invention, the following embodiments of the present invention are given only for illustrating how the present invention can be carried into effect and not for limiting the present invention to be carried into effect only by the following embodiments, and the modifications, substitutions and structural modifications of the present invention are made on the basis of understanding the technical solution of the present invention and the scope of the present invention is covered by the claims and the equivalents thereof.
The invention discloses a reverse osmosis membrane taking a PE microporous membrane as a base material, which comprises the PE microporous membrane, a polysulfone layer coated on the PE microporous membrane and a polyamide layer coated on the polysulfone layer;
the PE microporous membrane has the pore diameter of 0.01-10 mu m, the porosity of 70-95% and the thickness of 20-120 mu m.
The PE microporous membrane is small in pore size and excellent in homogeneity, the polysulfone layer is coated on the surface of the PE microporous membrane, and due to the fact that DMF, DMAc, NMP or DMSO and other organic solvents are adopted when polysulfone is coated, the PE microporous membrane is easily dissolved in the solvents, so that the PE microporous membrane can be subjected to permeation etching, and the pore size of the surface of the polysulfone layer is reduced and is more uniform. Because the pore diameter of the polysulfone layer is more uniform, the defects of the polyamide layer are reduced in the polymerization process, the polyamide layer is more uniform, and the performance is more excellent.
Further, the PE microporous membrane comprises high density PE, a chain extender, a hydrophilic polymer, and inorganic particles; the mass ratio of the high-density PE to the chain extender to the hydrophilic polymer to the inorganic particles is 2: 1: 2: 1.
further, the hydrophilic polymer is polyvinyl alcohol, polyethylene glycol, polymethyl pyrrolidone and polyacrylic acid.
Further, the inorganic particles are silica, sodium chloride, calcium carbonate or titanium dioxide.
Further, the chain extender is phthalic anhydride or polyisodiol.
The invention also provides a preparation method of the reverse osmosis membrane with the PE microporous membrane as the base material, which comprises the following steps:
1) coating a polysulfone membrane casting solution on the surface of the PE microporous membrane, and curing to obtain the PE microporous membrane coated with a polysulfone layer;
2) adding m-phenylenediamine, triethylamine and camphorsulfonic acid into deionized water, and magnetically stirring to obtain an aqueous solution; adding trimesoyl chloride into n-hexane, and stirring until the trimesoyl chloride is dissolved to obtain a trimesoyl chloride-n-hexane oil phase solution; immersing the PE microporous membrane coated with the polysulfone layer obtained in the step 1) into a water phase solution, taking out the PE microporous membrane, removing the solvent, immersing the PE microporous membrane into a prepared trimesoyl chloride-n-hexane oil phase solution for interfacial polymerization reaction to form a polyamide layer, taking out the polyamide layer, and removing the solvent n-hexane to obtain the nascent state polyamide reverse osmosis membrane;
3) dissolving polyvinyl alcohol in deionized water, and mechanically stirring to obtain a polyvinyl alcohol aqueous solution; dissolving graphene oxide in deionized water, magnetically stirring, and ultrasonically dispersing to obtain a graphene oxide aqueous solution; mixing the graphene oxide aqueous solution with a polyvinyl alcohol aqueous solution to obtain a polyvinyl alcohol aqueous solution containing graphene oxide; adding glutaraldehyde, levoserine and hydrochloric acid into a polyvinyl alcohol aqueous solution containing graphene oxide to obtain a polyvinyl alcohol crosslinking reaction solution containing graphene oxide, coating the polyvinyl alcohol crosslinking reaction solution containing graphene oxide on the surface of the nascent reverse osmosis membrane obtained in the step 1), and drying to obtain the reverse osmosis membrane.
The method is characterized in that a polysulfone membrane casting solution is coated on the surface of the PE microporous membrane with small pore diameter and excellent homogeneity, the polysulfone membrane casting solution is organic solvents such as DMF, DMAc, NMP, DMSO and the like, PE materials are easy to dissolve in the solvents, and in the process of coating the membrane casting solution on the PE microporous membrane serving as a substrate, the PE microporous membrane is subjected to permeation etching by the membrane casting solution, so that the pore diameter of the surface of the membrane after the membrane casting solution is formed is reduced and the membrane casting solution is more uniform. The pore diameter of the polysulfone layer base membrane is more uniform, so that the defects of the polyamide layer are reduced in the polymerization process, the polyamide layer membrane is more uniform, and the performance is more excellent.
Further, the preparation method of the PE microporous membrane comprises the following steps:
1) uniformly mixing the high-density PE, the chain extender, the hydrophilic polymer and the inorganic particles, pouring the mixture into a screw extruder for melt extrusion, wherein the traction ratio of a melt extrusion base film is 10-100;
2) annealing, stretching and heat setting the base membrane obtained in the step 1), wherein the annealing temperature is 100-150 ℃, and the stretching ratio is 60-150%, so as to obtain the PE microporous membrane for the water treatment membrane substrate.
The PE microporous membrane prepared by the method has small aperture, high porosity and excellent homogeneity, and can improve the flux and rejection rate of the reverse osmosis membrane when being used as a base membrane of the reverse osmosis membrane.
Furthermore, the mass concentration of m-phenylenediamine in the aqueous phase solution is 5.9 percent, the mass concentration of triethylamine is 3.4 percent, and the mass concentration of camphorsulfonic acid is 5.9 percent; the mass concentration of trimesoyl chloride in the oil phase solution is 0.3 percent;
furthermore, the polymerization degree of the polyvinyl alcohol is 1000, and the alcoholysis degree is 99%; the mass ratio of the graphene oxide to the polyvinyl alcohol in the polyvinyl alcohol aqueous solution containing the graphene oxide is 1: 20-50;
furthermore, the mass concentration of polyvinyl alcohol in the polyvinyl alcohol crosslinking reaction solution containing graphene oxide is 3.8%, the mass concentration of glutaraldehyde is 0.38%, the mass concentration of levoserine is 0.19%, and the mass concentration of hydrochloric acid is 0.1%.
To further illustrate the technical solution of the present invention, the following examples are specifically illustrated.
Example 1
The reverse osmosis membrane with the PE microporous membrane as a base material comprises the PE microporous membrane, a polysulfone layer coated on the PE microporous membrane and a polyamide layer coated on the polysulfone layer; the PE microporous membrane has the aperture of 0.01-10 mu m, the porosity of 70-95% and the thickness of 20-120 mu m;
the PE microporous membrane comprises high-density PE, a chain extender, a hydrophilic polymer and inorganic particles; the mass ratio of the high-density PE to the chain extender to the hydrophilic polymer to the inorganic particles is 2: 1: 2: 1. the hydrophilic polymer is polyacrylic acid; the inorganic particles are titanium dioxide; the chain extender is phthalic anhydride;
the preparation method of the reverse osmosis membrane with the PE microporous membrane as the base material comprises the following steps:
1) and (2) mixing the following components in mass ratio: 1: 2: 1, uniformly mixing the high-density PE, the chain extender, the hydrophilic polymer and the inorganic particles, pouring the mixture into a screw extruder for melt extrusion, wherein the traction ratio of a melt extrusion base film is 10-100; annealing, biaxially stretching and heat setting the base film, wherein the annealing temperature is 100-150 ℃, and the stretching ratio is 60-150%, so as to obtain a PE microporous film with the thickness of 100 mu m;
2) coating a polysulfone membrane casting solution on the surface of the PE microporous membrane, wherein the solvent used by the polysulfone membrane casting solution is DMAC (dimethylacetamide), the mass concentration of polysulfone is 10%, and curing to obtain the PE microporous membrane coated with a 50-micron polysulfone layer;
3) 70g of m-phenylenediamine, 40g of triethylamine and 70g of camphorsulfonic acid are added into 1000ml of deionized water, magnetically stirring for 5min to obtain water phase solution (containing m-phenylenediamine 5.9 wt%, triethylamine 3.4 wt%, and camphorsulfonic acid 5.9%), adding trimesoyl chloride 3g into 1000ml n-hexane, stirring until dissolving to obtain trimesoyl chloride-n-hexane oil phase solution (mass concentration of trimesoyl chloride in the oil phase solution is 0.3%), immersing the PE microporous membrane coated with the polysulfone layer obtained in the step 1) into the water phase solution, the immersion time is 25s, the solvent is removed after the extraction, the extraction solution is immersed into the prepared trimesoyl chloride-normal hexane oil phase solution for interfacial polymerization reaction to form a polyamide layer, the interfacial polymerization reaction time is 50s, and the solvent normal hexane is removed after the extraction to obtain the nascent state polyamide reverse osmosis membrane;
4) 40g of polyvinyl alcohol with the polymerization degree of 1000 and the alcoholysis degree of 99 percent is dissolved in 900ml of deionized water at the temperature of 80 ℃, and the mechanical stirring is carried out for 15min to obtain a polyvinyl alcohol aqueous solution; dissolving 0.8g of graphene oxide in 100ml of deionized water, magnetically stirring for 10min, and ultrasonically dispersing for 2h to obtain a graphene oxide aqueous solution; mixing the graphene oxide aqueous solution with a polyvinyl alcohol aqueous solution, magnetically stirring for 10min, and ultrasonically dispersing for 30min to obtain a polyvinyl alcohol aqueous solution containing graphene oxide (the mass ratio of the graphene oxide to the polyvinyl alcohol is 1: 50); adding 4g of glutaraldehyde, 2g of levoserine and 1g of hydrochloric acid into a polyvinyl alcohol aqueous solution containing graphene oxide, magnetically stirring for 10min to obtain a polyvinyl alcohol crosslinking reaction solution containing graphene oxide (the mass concentration of polyvinyl alcohol in the solution is 3.8%, the mass concentration of glutaraldehyde is 0.38%, the mass concentration of levoserine is 0.19% and the mass concentration of hydrochloric acid is 0.1%), coating the polyvinyl alcohol crosslinking reaction solution containing graphene oxide on the ecological surface of the primary reverse osmosis membrane obtained in the step 1), and placing the primary reverse osmosis membrane in a drying oven at 100 ℃ for reaction for 10min to obtain the reverse osmosis membrane.
Example 2
The reverse osmosis membrane with the PE microporous membrane as a base material comprises the PE microporous membrane, a polysulfone layer coated on the PE microporous membrane and a polyamide layer coated on the polysulfone layer; the PE microporous membrane has the aperture of 0.01-10 mu m, the porosity of 70-95% and the thickness of 20-120 mu m;
the PE microporous membrane comprises high-density PE, a chain extender, a hydrophilic polymer and inorganic particles; the mass ratio of the high-density PE to the chain extender to the hydrophilic polymer to the inorganic particles is 2: 1: 2: 1. the hydrophilic polymer is polyacrylic acid; the inorganic particles are titanium dioxide; the chain extender is phthalic anhydride;
the preparation method of the reverse osmosis membrane with the PE microporous membrane as the base material comprises the following steps:
1) and (2) mixing the following components in mass ratio: 1: 2: 1, uniformly mixing the high-density PE, the chain extender, the hydrophilic polymer and the inorganic particles, pouring the mixture into a screw extruder for melt extrusion, wherein the traction ratio of a melt extrusion base film is 10-100; annealing, biaxially stretching and heat setting the base film, wherein the annealing temperature is 100-150 ℃, and the stretching ratio is 60-150%, so as to obtain a PE microporous film with the thickness of 100 mu m;
2) coating a polysulfone membrane casting solution on the surface of the PE microporous membrane, wherein the solvent used by the polysulfone membrane casting solution is DMAC (dimethylacetamide), the mass concentration of polysulfone is 10%, and curing to obtain the PE microporous membrane coated with a 50-micron polysulfone layer;
3) 70g of m-phenylenediamine, 40g of triethylamine and 70g of camphorsulfonic acid are added into 1000ml of deionized water, magnetically stirring for 5min to obtain water phase solution (containing m-phenylenediamine 5.9 wt%, triethylamine 3.4 wt%, and camphorsulfonic acid 5.9%), adding trimesoyl chloride 3g into 1000ml n-hexane, stirring until dissolving to obtain trimesoyl chloride-n-hexane oil phase solution (mass concentration of trimesoyl chloride in the oil phase solution is 0.3%), immersing the PE microporous membrane coated with the polysulfone layer obtained in the step 1) into the water phase solution, the immersion time is 25s, the solvent is removed after the extraction, the extraction solution is immersed into the prepared trimesoyl chloride-normal hexane oil phase solution for interfacial polymerization reaction to form a polyamide layer, the interfacial polymerization reaction time is 50s, and the solvent normal hexane is removed after the extraction to obtain the nascent state polyamide reverse osmosis membrane;
4) 40g of polyvinyl alcohol with the polymerization degree of 1000 and the alcoholysis degree of 99 percent is dissolved in 900ml of deionized water at the temperature of 80 ℃, and the mechanical stirring is carried out for 15min to obtain a polyvinyl alcohol aqueous solution; dissolving 1.33g of graphene oxide in 100ml of deionized water, magnetically stirring for 10min, and ultrasonically dispersing for 2h to obtain a graphene oxide aqueous solution; mixing the graphene oxide aqueous solution with a polyvinyl alcohol aqueous solution, magnetically stirring for 10min, and ultrasonically dispersing for 30min to obtain a polyvinyl alcohol aqueous solution containing graphene oxide (the mass ratio of the graphene oxide to the polyvinyl alcohol is 1: 30); adding 4g of glutaraldehyde, 2g of levoserine and 1g of hydrochloric acid into a polyvinyl alcohol aqueous solution containing graphene oxide, magnetically stirring for 10min to obtain a polyvinyl alcohol crosslinking reaction solution containing graphene oxide (the mass concentration of polyvinyl alcohol in the solution is 3.8%, the mass concentration of glutaraldehyde is 0.38%, the mass concentration of levoserine is 0.19% and the mass concentration of hydrochloric acid is 0.1%), coating the polyvinyl alcohol crosslinking reaction solution containing graphene oxide on the ecological surface of the primary reverse osmosis membrane obtained in the step 1), and placing the primary reverse osmosis membrane in a drying oven at 100 ℃ for reaction for 10min to obtain the reverse osmosis membrane.
Example 3
The reverse osmosis membrane with the PE microporous membrane as a base material comprises the PE microporous membrane, a polysulfone layer coated on the PE microporous membrane and a polyamide layer coated on the polysulfone layer; the PE microporous membrane has the aperture of 0.01-10 mu m, the porosity of 70-95% and the thickness of 20-120 mu m;
the PE microporous membrane comprises high-density PE, a chain extender, a hydrophilic polymer and inorganic particles; the mass ratio of the high-density PE to the chain extender to the hydrophilic polymer to the inorganic particles is 2: 1: 2: 1. the hydrophilic polymer is polyacrylic acid; the inorganic particles are titanium dioxide; the chain extender is phthalic anhydride;
the preparation method of the reverse osmosis membrane with the PE microporous membrane as the base material comprises the following steps:
1) and (2) mixing the following components in mass ratio: 1: 2: 1, uniformly mixing the high-density PE, the chain extender, the hydrophilic polymer and the inorganic particles, pouring the mixture into a screw extruder for melt extrusion, wherein the traction ratio of a melt extrusion base film is 10-100; annealing, biaxially stretching and heat setting the base film, wherein the annealing temperature is 100-150 ℃, and the stretching ratio is 60-150%, so as to obtain a PE microporous film with the thickness of 100 mu m;
2) coating a polysulfone membrane casting solution on the surface of the PE microporous membrane, wherein the solvent used by the polysulfone membrane casting solution is DMAC (dimethylacetamide), the mass concentration of polysulfone is 10%, and curing to obtain the PE microporous membrane coated with a 50-micron polysulfone layer;
3) 70g of m-phenylenediamine, 40g of triethylamine and 70g of camphorsulfonic acid are added into 1000ml of deionized water, magnetically stirring for 5min to obtain water phase solution (containing m-phenylenediamine 5.9 wt%, triethylamine 3.4 wt%, and camphorsulfonic acid 5.9%), adding trimesoyl chloride 3g into 1000ml n-hexane, stirring until dissolving to obtain trimesoyl chloride-n-hexane oil phase solution (mass concentration of trimesoyl chloride in the oil phase solution is 0.3%), immersing the PE microporous membrane coated with the polysulfone layer obtained in the step 1) into the water phase solution, the immersion time is 25s, the solvent is removed after the extraction, the extraction solution is immersed into the prepared trimesoyl chloride-normal hexane oil phase solution for interfacial polymerization reaction to form a polyamide layer, the interfacial polymerization reaction time is 50s, and the solvent normal hexane is removed after the extraction to obtain the nascent state polyamide reverse osmosis membrane;
4) 40g of polyvinyl alcohol with the polymerization degree of 1000 and the alcoholysis degree of 99 percent is dissolved in 900ml of deionized water at the temperature of 80 ℃, and the mechanical stirring is carried out for 15min to obtain a polyvinyl alcohol aqueous solution; dissolving 2g of graphene oxide in 100ml of deionized water, magnetically stirring for 10min, and ultrasonically dispersing for 2h to obtain a graphene oxide aqueous solution; mixing the graphene oxide aqueous solution with a polyvinyl alcohol aqueous solution, magnetically stirring for 10min, and ultrasonically dispersing for 30min to obtain a polyvinyl alcohol aqueous solution containing graphene oxide (the mass ratio of the graphene oxide to the polyvinyl alcohol is 1: 20); adding 4g of glutaraldehyde, 2g of levoserine and 1g of hydrochloric acid into a polyvinyl alcohol aqueous solution containing graphene oxide, magnetically stirring for 10min to obtain a polyvinyl alcohol crosslinking reaction solution containing graphene oxide (the mass concentration of polyvinyl alcohol in the solution is 3.8%, the mass concentration of glutaraldehyde is 0.38%, the mass concentration of levoserine is 0.19% and the mass concentration of hydrochloric acid is 0.1%), coating the polyvinyl alcohol crosslinking reaction solution containing graphene oxide on the ecological surface of the primary reverse osmosis membrane obtained in the step 1), and placing the primary reverse osmosis membrane in a drying oven at 100 ℃ for reaction for 10min to obtain the reverse osmosis membrane.
Comparative example 1
1) Taking a PET non-woven fabric as a base material, producing the non-woven fabric by the PET non-woven fabric through a pressing process, coating a polysulfone membrane casting solution on the surface, wherein a solvent used by the polysulfone membrane casting solution is DMAC, the mass concentration of polysulfone is 10%, the thickness is controlled to be 50 mu m, the polysulfone membrane casting solution is prepared for later use after being solidified in water, adding 70g of m-phenylenediamine, 40g of triethylamine and 70g of camphorsulfonic acid into 1000ml of deionized water, magnetically stirring for 5min to prepare a water phase solution (the mass concentration of m-phenylenediamine in the water phase solution is 5.9%, the mass concentration of triethylamine is 3.4% and the mass concentration of camphorsulfonic acid is 5.9%), adding 3g of trimesoyl chloride into 1000ml of n-hexane, stirring until being dissolved to prepare a trimesoyl chloride-n-hexane oil phase solution (the mass concentration of trimesoyl chloride in the oil phase solution is 0.3%), immersing a polysulfone support membrane into the water phase solution for 25s, the interfacial polymerization reaction time is 50s, and the solvent n-hexane is removed after the interfacial polymerization reaction time is taken out, so that the nascent state reverse osmosis membrane is obtained;
2) 40g of polyvinyl alcohol with the polymerization degree of 1000 and the alcoholysis degree of 99 percent is dissolved in 900ml of deionized water at the temperature of 80 ℃, and the mechanical stirring is carried out for 15min to obtain a polyvinyl alcohol aqueous solution;
3) dissolving 0.8g of graphene oxide in 100ml of deionized water, magnetically stirring for 10min, and ultrasonically dispersing for 2h to obtain a graphene oxide aqueous solution;
4) mixing the graphene oxide aqueous solution with a polyvinyl alcohol aqueous solution, magnetically stirring for 10min, and ultrasonically dispersing for 30min to obtain a polyvinyl alcohol aqueous solution containing graphene oxide (the mass ratio of the graphene oxide to the polyvinyl alcohol is 1: 50); adding 4g of glutaraldehyde, 2g of levoserine and 1g of hydrochloric acid into a polyvinyl alcohol aqueous solution containing graphene oxide, magnetically stirring for 10min to obtain a polyvinyl alcohol crosslinking reaction solution containing graphene oxide (the mass concentration of polyvinyl alcohol in the solution is 3.8%, the mass concentration of glutaraldehyde is 0.38%, the mass concentration of levoserine is 0.19% and the mass concentration of hydrochloric acid is 0.1%), coating the polyvinyl alcohol crosslinking reaction solution containing graphene oxide on the surface of a nascent state reverse osmosis membrane, and placing the nascent state reverse osmosis membrane in a drying oven at 100 ℃ for reaction for 10min to obtain the reverse osmosis membrane.
Comparative example 2:
1) taking a PET non-woven fabric as a base material, producing the non-woven fabric by the PET non-woven fabric through a pressing process, coating a polysulfone membrane casting solution on the surface, wherein a solvent used by the polysulfone membrane casting solution is DMAC, the mass concentration of polysulfone is 10%, the thickness is controlled to be 50 mu m, the polysulfone membrane casting solution is prepared for later use after being solidified in water, adding 70g of m-phenylenediamine, 40g of triethylamine and 70g of camphorsulfonic acid into 1000ml of deionized water, magnetically stirring for 5min to prepare a water phase solution (the mass concentration of m-phenylenediamine in the water phase solution is 5.9%, the mass concentration of triethylamine is 3.4% and the mass concentration of camphorsulfonic acid is 5.9%), adding 3g of trimesoyl chloride into 1000ml of n-hexane, stirring until being dissolved to prepare a trimesoyl chloride-n-hexane oil phase solution (the mass concentration of trimesoyl chloride in the oil phase solution is 0.3%), immersing a polysulfone support membrane into the water phase solution for 25s, the interfacial polymerization reaction time is 50s, and the solvent n-hexane is removed after the interfacial polymerization reaction time is taken out, so that the nascent state reverse osmosis membrane is obtained;
2) 40g of polyvinyl alcohol with the polymerization degree of 1000 and the alcoholysis degree of 99 percent is dissolved in 900ml of deionized water at the temperature of 80 ℃, and the mechanical stirring is carried out for 15min to obtain a polyvinyl alcohol aqueous solution;
3) dissolving 1.33g of graphene oxide in 100ml of deionized water, magnetically stirring for 10min, and ultrasonically dispersing for 2h to obtain a graphene oxide aqueous solution;
4) mixing the graphene oxide aqueous solution with a polyvinyl alcohol aqueous solution, magnetically stirring for 10min, and ultrasonically dispersing for 30min to obtain a polyvinyl alcohol aqueous solution containing graphene oxide (the mass ratio of the graphene oxide to the polyvinyl alcohol is 1: 30); adding 4g of glutaraldehyde, 2g of levoserine and 1g of hydrochloric acid into a polyvinyl alcohol aqueous solution containing graphene oxide, magnetically stirring for 10min to obtain a polyvinyl alcohol crosslinking reaction solution containing graphene oxide (the mass concentration of polyvinyl alcohol in the solution is 3.8%, the mass concentration of glutaraldehyde is 0.38%, the mass concentration of levoserine is 0.19% and the mass concentration of hydrochloric acid is 0.1%), coating the polyvinyl alcohol crosslinking reaction solution containing graphene oxide on the surface of a nascent state reverse osmosis membrane, and placing the nascent state reverse osmosis membrane in a drying oven at 100 ℃ for reaction for 10min to obtain the reverse osmosis membrane.
Comparative example 3:
1) taking a PET non-woven fabric as a base material, producing the non-woven fabric by a pressing process for the PET non-woven fabric, coating a polysulfone membrane casting solution on the surface, coating the polysulfone membrane casting solution on the surface, adding 70g of m-phenylenediamine, 40g of triethylamine and 70g of camphorsulfonic acid into 1000ml of deionized water for later use after the polysulfone membrane casting solution is solidified in water, magnetically stirring for 5min to obtain an aqueous phase solution (the mass concentration of the m-phenylenediamine in the aqueous phase solution is 5.9%, the mass concentration of the triethylamine in the aqueous phase solution is 3.4% and the mass concentration of the camphorsulfonic acid is 5.9%), adding 3g of trimesoyl chloride into 1000ml of n-hexane, stirring until the mixture is dissolved to obtain a trimesoyl chloride-n-hexane oil phase solution (the mass concentration of the trimesoyl chloride in the oil phase solution is 0.3%), immersing a polysulfone support membrane into the aqueous phase solution for 25s, then immersing the membrane into a prepared trimesoyl chloride-n-hexane oil phase solution for interfacial polymerization reaction, wherein the interfacial polymerization reaction time is 50s, and removing the solvent n-hexane after taking out to obtain the nascent state reverse osmosis membrane;
2) 40g of polyvinyl alcohol with the polymerization degree of 1000 and the alcoholysis degree of 99 percent is dissolved in 900ml of deionized water at the temperature of 80 ℃, and the mechanical stirring is carried out for 15min to obtain a polyvinyl alcohol aqueous solution;
3) dissolving 2g of graphene oxide in 100ml of deionized water, magnetically stirring for 10min, and ultrasonically dispersing for 2h to obtain a graphene oxide aqueous solution;
4) mixing the graphene oxide aqueous solution with a polyvinyl alcohol aqueous solution, magnetically stirring for 10min, and ultrasonically dispersing for 30min to obtain a polyvinyl alcohol aqueous solution containing graphene oxide (the mass ratio of the graphene oxide to the polyvinyl alcohol is 1: 20); adding 4g of glutaraldehyde, 2g of levoserine and 1g of hydrochloric acid into a polyvinyl alcohol aqueous solution containing graphene oxide, magnetically stirring for 10min to obtain a polyvinyl alcohol crosslinking reaction solution containing graphene oxide (the mass concentration of polyvinyl alcohol in the solution is 3.8%, the mass concentration of glutaraldehyde is 0.38%, the mass concentration of levoserine is 0.19% and the mass concentration of hydrochloric acid is 0.1%), coating the polyvinyl alcohol crosslinking reaction solution containing graphene oxide on the surface of a nascent state reverse osmosis membrane, and placing the nascent state reverse osmosis membrane in a drying oven at 100 ℃ for reaction for 10min to obtain the reverse osmosis membrane.
The reverse osmosis membranes prepared in examples 1 to 3 and comparative examples 1 to 3 were placed in water, and the water flux and salt rejection were measured after the membranes had been stably operated for 30min under test conditions of 25 c, 150psi pressure, 2000ppm aqueous solution of sodium chloride, and the test results are shown in table 1.
TABLE 1 test results of examples 1 to 3 and comparative examples 1 to 3
As can be seen from Table 1, the reverse osmosis prepared according to the present invention has higher water flux and salt rejection than those of comparative examples 1 to 3.
In conclusion, the above embodiments are merely intended to illustrate the technical solution of the present invention and not to limit, although the present invention has been described by referring to certain preferred embodiments thereof, it should be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (10)
1. A reverse osmosis membrane taking a PE microporous membrane as a base material is characterized by comprising the PE microporous membrane, a polysulfone layer coated on the PE microporous membrane and a polyamide layer coated on the polysulfone layer;
the PE microporous membrane has the pore diameter of 0.01-10 mu m, the porosity of 70-95% and the thickness of 20-120 mu m.
2. A reverse osmosis membrane having a PE microporous membrane as a substrate according to claim 1, wherein the PE microporous membrane comprises high-density PE, a chain extender, a hydrophilic polymer, and inorganic particles; the mass ratio of the high-density PE to the chain extender to the hydrophilic polymer to the inorganic particles is 2: 1: 2: 1.
3. a reverse osmosis membrane based on PE microporous membrane according to claim 2 wherein the hydrophilic polymer is polyvinyl alcohol, polyethylene glycol, polymethyl pyrrolidone, polyacrylic acid.
4. A reverse osmosis membrane having a PE microporous membrane as a substrate according to claim 2, wherein the inorganic particles are silica, sodium chloride, calcium carbonate or titanium dioxide.
5. A reverse osmosis membrane having a PE microporous membrane as a substrate according to claim 2, wherein the chain extender is phthalic anhydride or polyisodiol.
6. A method for preparing a reverse osmosis membrane using a PE microporous membrane as a substrate according to any one of claims 1 to 5, comprising the steps of:
1) coating a polysulfone membrane casting solution on the surface of the PE microporous membrane, and curing to obtain the PE microporous membrane coated with a polysulfone layer;
2) adding m-phenylenediamine, triethylamine and camphorsulfonic acid into deionized water, and magnetically stirring to obtain an aqueous solution; adding trimesoyl chloride into n-hexane, and stirring until the trimesoyl chloride is dissolved to obtain a trimesoyl chloride-n-hexane oil phase solution; immersing the PE microporous membrane coated with the polysulfone layer obtained in the step 1) into a water phase solution, taking out the PE microporous membrane, removing the solvent, immersing the PE microporous membrane into a prepared trimesoyl chloride-n-hexane oil phase solution for interfacial polymerization reaction to form a polyamide layer, taking out the polyamide layer, and removing the solvent n-hexane to obtain the nascent state polyamide reverse osmosis membrane;
3) dissolving polyvinyl alcohol in deionized water, and mechanically stirring to obtain a polyvinyl alcohol aqueous solution; dissolving graphene oxide in deionized water, magnetically stirring, and ultrasonically dispersing to obtain a graphene oxide aqueous solution; mixing the graphene oxide aqueous solution with a polyvinyl alcohol aqueous solution to obtain a polyvinyl alcohol aqueous solution containing graphene oxide; adding glutaraldehyde, levoserine and hydrochloric acid into a polyvinyl alcohol aqueous solution containing graphene oxide to obtain a polyvinyl alcohol crosslinking reaction solution containing graphene oxide, coating the polyvinyl alcohol crosslinking reaction solution containing graphene oxide on the surface of the nascent reverse osmosis membrane obtained in the step 1), and drying to obtain the reverse osmosis membrane.
7. The method for preparing a reverse osmosis membrane using a PE microporous membrane as a substrate according to claim 6, wherein the method for preparing the PE microporous membrane comprises the following steps:
1) uniformly mixing the high-density PE, the chain extender, the hydrophilic polymer and the inorganic particles, pouring the mixture into a screw extruder for melt extrusion, wherein the traction ratio of a melt extrusion base film is 10-100;
2) annealing, stretching and heat setting the base membrane obtained in the step 1), wherein the annealing temperature is 100-150 ℃, and the stretching ratio is 60-150%, so as to obtain the PE microporous membrane for the water treatment membrane substrate.
8. A method for preparing a reverse osmosis membrane based on a PE microporous membrane according to claim 6, wherein the aqueous solution contains m-phenylenediamine 5.9% by mass, triethylamine 3.4% by mass and camphorsulfonic acid 5.9% by mass; the mass concentration of trimesoyl chloride in the oil phase solution is 0.3 percent.
9. A preparation method of a reverse osmosis membrane using a PE microporous membrane as a base material according to claim 6, wherein the polymerization degree of polyvinyl alcohol is 1000, and the alcoholysis degree is 99%; the mass ratio of the graphene oxide to the polyvinyl alcohol in the polyvinyl alcohol aqueous solution containing the graphene oxide is 1: 20-50.
10. A method for preparing a reverse osmosis membrane using a PE microporous membrane as a base material according to claim 6, wherein the polyvinyl alcohol crosslinking reaction solution containing graphene oxide comprises 3.8% by mass of polyvinyl alcohol, 0.38% by mass of glutaraldehyde, 0.19% by mass of L-serine, and 0.1% by mass of hydrochloric acid.
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| CN111389238A (en) * | 2020-03-20 | 2020-07-10 | 北京碧水源膜科技有限公司 | Composite nanofiltration membrane based on modified polyolefin microporous substrate and preparation method thereof |
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| CN107638805A (en) * | 2017-11-03 | 2018-01-30 | 宁波日新恒力科技有限公司 | A kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol |
| CN111389238A (en) * | 2020-03-20 | 2020-07-10 | 北京碧水源膜科技有限公司 | Composite nanofiltration membrane based on modified polyolefin microporous substrate and preparation method thereof |
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