CN115090118B - Formula and coating process of reverse osmosis membrane functional layer solution - Google Patents
Formula and coating process of reverse osmosis membrane functional layer solution Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 61
- 238000000576 coating method Methods 0.000 title claims abstract description 55
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 48
- 239000002346 layers by function Substances 0.000 title claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 69
- 239000010410 layer Substances 0.000 claims abstract description 53
- 239000011248 coating agent Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002253 acid Substances 0.000 claims abstract description 35
- 239000006247 magnetic powder Substances 0.000 claims abstract description 27
- 239000012071 phase Substances 0.000 claims abstract description 22
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 13
- 239000008346 aqueous phase Substances 0.000 claims abstract description 12
- 239000011241 protective layer Substances 0.000 claims abstract description 12
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 11
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002861 polymer material Substances 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 8
- 229920000768 polyamine Polymers 0.000 claims abstract description 7
- 125000002252 acyl group Chemical group 0.000 claims abstract description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 5
- 239000002033 PVDF binder Substances 0.000 claims abstract description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 43
- 238000005507 spraying Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000007605 air drying Methods 0.000 claims description 11
- 238000005554 pickling Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000012695 Interfacial polymerization Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 230000005389 magnetism Effects 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 4
- 235000013980 iron oxide Nutrition 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 2
- 230000035515 penetration Effects 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010612 desalination reaction Methods 0.000 abstract description 13
- 230000004907 flux Effects 0.000 abstract description 13
- 239000002131 composite material Substances 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241001125929 Trisopterus luscus Species 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- ONRYXFFHIXYZMZ-UHFFFAOYSA-N xenon oxytetrafluoride Chemical compound F[Xe](F)(F)(F)=O ONRYXFFHIXYZMZ-UHFFFAOYSA-N 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- 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)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a reverse osmosis membrane functional layer solution comprising: base layer liquid, aqueous phase liquid, oil phase liquid and protective layer liquid; according to the mass parts, 10-12 parts of polysulfone, 2-4 parts of magnetic powder with the diameter of 5-10 um, 100-150 parts of dimethylacetamide and 10-12 parts of polyvinylpyrrolidone; 120-160 parts of water, 3-5 parts of polyamine and 0.5-1 part of polyalcohol in parts by mass; 1-3 parts of acyl oxyhalide and 100-200 parts of triethanolamine by mass; 50-100 parts of dimethylacetamide and 5-10 parts of acid-resistant hydrophilic polymer material; wherein the acid-resistant hydrophilic polymer material is one or a mixture of more of polyvinylidene fluoride, N-dimethylacrylamide and butyl methacrylate. The invention can conveniently and accurately control the coating thickness of the base layer liquid, control the final porous structure form of the base layer liquid, and realize high reverse osmosis water flux, high desalination rate and high acid resistance.
Description
Technical Field
The invention relates to the field of reverse osmosis membrane production, in particular to a reverse osmosis membrane functional layer solution formula and a coating process.
Background
Conventional reverse osmosis membranes generally consist of a nonwoven fabric, a support layer (porous polysulfone layer) sprayed on the nonwoven fabric, and a desalination layer disposed on the support layer. The reverse osmosis membrane prepared by selecting different layers of membranes (formula) has great differences in water flux, desalination rate, water pressure and applicable environment.
The porous structure in the support layer of the conventional reverse osmosis membrane is formed by only using polysulfone materials after gel washing, and the porosity and the pore size of the conventional reverse osmosis membrane are difficult to realize accurate control, so that the performance of the reverse osmosis membrane is greatly restricted.
The coating mode of the reverse osmosis membrane coating mainly comprises knife coating, roller coating, ultrasonic spraying and slit coating. The doctor blade coating mode is not easy to control the doctor blade coating thickness, namely, a larger error value is easy to appear; the coating is easy to be uneven in the rolling coating mode; the ultrasonic spraying mode has high manufacturing cost and high debugging difficulty; the slit coating mode belongs to a closed loop system, has very high requirements on the stability of a production system, and the spraying modes are complicated in adjustment of the spraying thickness.
The application number is CN201710046486.6, the preparation method of the reverse osmosis composite membrane and the reverse osmosis composite membrane disclose that partial hydrolysis of the surface of a polyacrylonitrile support membrane under alkaline conditions is utilized to convert partial nitrile groups into carboxyl groups or amide groups, and the hydrophilicity of the support membrane is improved, so that the water flux of the prepared reverse osmosis composite membrane is improved.
The application number of CN201811191069.1 is a preparation method of a high-flux composite polyamide reverse osmosis membrane, which provides the thought of adding different substances into two phases (aqueous phase and oil phase) of interfacial polymerization reaction to improve the water flux of the polyamide reverse osmosis membrane, changing the structure or performance of a membrane desalination layer and improving the water flux of the polyamide reverse osmosis membrane, and improving the structural performance of a support layer to improve the membrane flux and the removal rate of sodium chloride.
The application number is CN201010129173.5, namely an acid-resistant composite reverse osmosis membrane, a polymer desalting layer is compounded on a porous support membrane, and an acid-resistant hydrophilic polymer functional material layer is arranged on the polymer desalting layer, so that the acid-resistant purpose of the reverse osmosis membrane is realized.
All three patents realize water flux, desalination rate and acid-resistant environment by changing the components of different membrane casting solutions on the reverse osmosis membrane, but the three main technical points are mutually independent, namely, the water flux, the desalination rate and the acid-resistant environment are not integrated together.
Huang Zhengqing A doctor paper (the university of science and technology, 2006, university of China, university of medical science and technology, guo Xingpeng) discloses the idea that a PAN-Fe_3O_4 ultrafiltration membrane is prepared by using an immersion precipitation phase inversion method with or without a magnetic field by selecting a magnetic substance (Fe_3O_4) as an inorganic filler, and the influence of different arrangement modes of magnetism under the magnetic field on the performance of a reverse osmosis membrane is tested.
The published main paper of Chen Kun (structure, performance and influence of orthogonal magnetic field of polysulfone-ferroferric oxide ultrafiltration membrane) (the university of Hubei industry, 2008 guide: huang Zhengqing) suggests that the inorganic filler added in the research of organic-inorganic ultrafiltration membrane mainly comprises SiO_2, al_2O_3, zrO_2, tiO_2 and the like, and the research of taking Fe_3O_4 as the filler is not seen; fe_3o_4 has not only good hydrophilicity but also magnetism, and if a magnetic field is introduced during the film formation process, the alignment state of fe_3o_4 is changed, thereby affecting the structure and performance of the film.
The papers all propose that the magnetic material is used as the filler of the reverse osmosis membrane, the property of the reverse osmosis membrane is changed by changing the arrangement mode of the magnetic field, and the magnetic material is always in the reverse osmosis membrane.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a formulation and a coating process for a solution of a reverse osmosis membrane functional layer, which can control the coating thickness of a base layer solution more conveniently and accurately, control the final form of a porous structure of the base layer solution, and realize high water flux, high desalination rate and high acid resistance of reverse osmosis.
The aim of the invention is realized by the following technical scheme:
the reverse osmosis membrane functional layer solution comprises a base layer solution, a water phase solution, an oil phase solution and a protective layer solution;
the base layer liquid comprises, by mass, 10-12 parts of polysulfone, 2-4 parts of 5-10 um diameter magnetic powder, 100-150 parts of dimethylacetamide and 10-12 parts of polyvinylpyrrolidone;
the aqueous phase liquid comprises 120-160 parts of water, 3-5 parts of polyamine and 0.5-1 part of polyol according to parts by weight;
the oil phase liquid comprises 1-3 parts of acyl oxyhalide and 100-200 parts of triethanolamine according to parts by weight;
the protective layer liquid comprises 50-100 parts of dimethylacetamide and 5-10 parts of acid-resistant hydrophilic polymer material according to the parts by weight, wherein the acid-resistant hydrophilic polymer material is one or a mixture of more of polyvinylidene fluoride, N-dimethylacrylamide and butyl methacrylate.
Further, the base layer liquid comprises, by mass, 11 parts of polysulfone, 3 parts of 5-10 um diameter magnetic powder, 130 parts of dimethylacetamide and 11 parts of polyvinylpyrrolidone;
the aqueous phase liquid comprises 140 parts of water, 4 parts of polyamine and 0.8 part of polyalcohol according to parts by weight;
the oil phase liquid comprises 2 parts of acyl oxyhalide and 160 parts of triethanolamine according to parts by weight;
the protective layer liquid comprises, by mass, 95 parts of dimethylacetamide and 7 parts of acid-resistant hydrophilic polymer material, wherein the acid-resistant hydrophilic polymer material comprises, by mass, 2-5 parts of tetrafluoroethylene, 1-2 parts of N, N-dimethylacrylamide and 2-3 parts of butyl methacrylate.
The coating process of the reverse osmosis membrane functional layer solution comprises the following steps:
s1, polysulfone powder is made into particles with the diameter smaller than 10um, and polysulfone, magnetic powder, polyvinylpyrrolidone and dimethylacetamide are fully mixed and dissolved to form base layer liquid;
s2, arranging the non-woven fabric on a substrate with magnetism, atomizing and spraying base layer liquid to the non-woven fabric, and coating the base layer liquid on the non-woven fabric under the action of a magnetic field;
s3, after the non-woven fabric is dried, cleaning by using pure water, pickling the non-woven fabric by using an acid solution, reacting the acid solution with the magnetic powder, and cleaning by using the pure water after pickling the acid solution;
s4, sequentially coating water phase liquid on the non-woven fabric washed by the pure water, then air-drying, coating oil phase liquid after air-drying, then air-drying, pickling after air-drying, performing interfacial polymerization reaction, and washing by using the pure water after the interfacial polymerization reaction;
and S5, coating protective layer liquid on the non-woven fabric, drying by hot air after coating, rinsing by pure water after drying, and drying.
Further, in the step S2, after the non-woven fabric is sprayed with the base layer liquid, the non-woven fabric is moved out of the spraying area, and a magnetic field is applied to the non-woven fabric on the opposite surface of the base layer liquid, so that the magnetic powder is uniformly distributed in the base layer liquid.
Further, the magnetic powder in step S3 is a mixture of one or more of iron oxides; the product salt of the acidic solution used in step S3 after reaction with the magnetic powder is a water-soluble salt.
Further, the total amount of the magnetic powder remaining after the acid washing in step S3 is not more than 20%;
in step S2, spraying is performed in a vacuum environment by using multiple spray nozzles, wherein magnetic plates are respectively arranged on two sides of the non-woven fabric, and the magnetic poles of the magnetic plates facing the side surface of the non-woven fabric are the same as the magnetic poles of the magnetic substrate facing the non-woven fabric.
Further, in the step S3, the acid solution is washed by pure water after being washed, so that the front surface of the non-woven fabric is pressurized for infiltration washing and then rinsed.
Further, the thickness of the base layer liquid coated in the step S2 is 30-40 um, and the drying temperature in the step S3 is 50-65 ℃; in the step S4, a multilayer coating mode is adopted when aqueous phase liquid is coated, the total coating thickness is 120-125 nm, vacuum environment ultrasonic vibration is adopted for removing bubbles after each layer of coating, and in the step S5, vacuum environment ultrasonic vibration is adopted for removing bubbles after the coating of oil phase liquid is finished, wherein the coating thickness of the oil phase liquid is 110-115 nm.
A coating process of reverse osmosis membrane functional layer solution, wherein base layer solution is coated on non-woven fabric base material by magnetic control spraying.
Due to the adoption of the technical scheme, the invention has the following advantages:
1. magnetic powder is added into the base layer liquid, so that the base layer liquid can be driven under a magnetic field, and a magnetic force control mode can be selected for coating during coating, thereby realizing more accurate and convenient adjustment of coating thickness and coating area.
2. After the magnetic powder is coated, the magnetic powder can be reacted through acid washing, and holes are formed at the original magnetic powder, so that the control of the void structure on the base layer liquid is realized.
3. The reverse osmosis membrane is sequentially coated with the aqueous phase liquid, the oil phase liquid and the acid-resistant protective layer liquid, the water flux, the desalination rate and the acid resistance of the reverse osmosis membrane are controlled, and the three properties can be comprehensively blended to the greatest extent.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
The drawings of the present invention are described as follows:
FIG. 1 is an electron micrograph of a cross section of a reverse osmosis membrane obtained in Experimental example 7.
FIG. 2 is an electron micrograph of the front surface of the reverse osmosis membrane obtained in Experimental example 7.
FIG. 3 is an electron micrograph of the front surface of the reverse osmosis membrane obtained in Experimental example 7.
Detailed Description
The invention is further described below with reference to the drawings and examples.
Examples:
according to research and development experience of reverse osmosis membrane manufacturing, 12 experimental examples are respectively prepared according to components in four casting membrane liquids of base layer liquid, aqueous phase liquid, oil phase liquid and protective layer liquid, and the weight parts of the materials are as follows:
the magnetic powder may be selected from those which do not produce precipitates after reaction with an acid, such as iron oxides, etc., and in this embodiment, iron oxide is selected as the magnetic powder; as the polyhydric alcohol, dipropylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, 1, 4-butanediol, etc. are specifically selected, and trimethylolpropane is selected in this example; the polyamine is used as a part of interfacial polymerization reaction, and specifically one or more of o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, piperazine, triethylamine, ethylenediamine, diphenylmethane diamine and hexamethylenetetramine can be selected, and m-phenylenediamine is selected in the embodiment; the polyamide is prepared by reacting acyl oxyhalide with polyamine, and specifically one or more of tetrafluoro-xenon monoxide, sulfuryl chloride, thionyl chloride, trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride can be selected, and trimesoyl chloride is selected in the embodiment.
The prepared base layer liquid, aqueous phase liquid, oil phase liquid and protective layer liquid are subjected to experiments according to the following steps, as shown in fig. 1, specifically:
s1, polysulfone powder is made into particles with the diameter smaller than 5um, and polysulfone, magnetic powder, polyvinylpyrrolidone and dimethylacetamide are fully mixed and dissolved to form base layer liquid;
s2, arranging the non-woven fabric on a substrate with magnetism, wherein magnetic plates are respectively arranged on two sides of the non-woven fabric, and magnetic poles of the magnetic plates, which are opposite to the side surfaces of the non-woven fabric, are identical to those of the substrate with magnetism, which is opposite to the non-woven fabric; so that the spray nozzles are outwards uniformly dispersed, and the base layer liquid finally falling onto the non-woven fabric is more uniform;
spraying is carried out in a vacuum environment, spraying is carried out by adopting a plurality of spray nozzles side by side, the base layer liquid is sprayed to the non-woven fabric in an atomizing way, the base layer liquid is coated on the non-woven fabric under the action of a magnetic field, and the thickness of the coated base layer liquid is 35um;
after the non-woven fabric is sprayed with the base layer liquid, the non-woven fabric is moved out of the spraying area, and a magnetic field is applied to the opposite surface of the non-woven fabric, so that the magnetic powder is uniformly distributed in the base layer liquid.
S3, after the non-woven fabric is dried, the drying temperature is 55 ℃, pure water is used for cleaning after the non-woven fabric is dried, then an acid solution (a solution containing hydrochloric acid) is used for pickling the non-woven fabric, the acid solution reacts with the magnetic powder, the total amount of the magnetic powder remained on the non-woven fabric after the reaction is 5-8% of the original amount, and the non-woven fabric is subjected to permeation cleaning after the acid solution is pickled, namely the front surface of the non-woven fabric is pressurized by the pure water for rinsing;
s4, coating aqueous phase liquid on the non-woven fabric cleaned by pure water in a multi-layer coating mode, removing bubbles by ultrasonic vibration in a vacuum environment after each layer of coating, and air-drying the non-woven fabric;
coating oil phase liquid after air drying, removing bubbles by adopting vacuum environment ultrasonic vibration after coating, wherein the total coating thickness is 112nm, pickling after air drying of the oil phase liquid, carrying out interfacial polymerization reaction on a pickling solution by adopting citric acid solution, and cleaning by using pure water after the interfacial polymerization reaction;
and S5, coating protective layer liquid on the non-woven fabric, drying by hot air after coating, rinsing by pure water after drying, and drying.
The reverse osmosis membrane prepared according to the steps is subjected to experiments, and the experimental results are as follows:
the water flux (water flux) refers to the volume of water per unit of pressure, per unit of time through a unit of membrane area, abbreviated: PWP, unit is: liter/square meter/pressure/hour, i.e., the flow of water through the membrane per unit area of membrane at a unit pressure; PWP = water flow per unit time temperature correction factor/TMP/membrane area; wherein the membrane penetration pressure tmp= (pin+pout)/2-Pp, i.e. the average of the inlet pressure plus the outlet pressure minus the permeate pressure.
Desalination rate (rate of desalination) refers to the percentage of the original amount removed during the removal of anions and cations from water by chemical or ion exchange methods. In practical application, the salt removal rate of the reverse osmosis system is generally referred to as the following calculation formula: desalination rate = (total feed water salt content-total produced water salt content)/total feed water salt content x 100%.
The acid resistance index refers to the time for which the desalination rate of a reverse osmosis membrane immersed in an acidic solution having a pH of 2 decreases by 1%.
According to the experimental results of the table, the best technical scheme is achieved by combining three numerical values of water flux, desalination rate and acid resistance, wherein the performance of experimental example 7 is the most balanced.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (9)
1. The coating process of the reverse osmosis membrane functional layer solution is characterized by comprising the following steps of:
s1, polysulfone powder is made into particles with the diameter smaller than 10um, and polysulfone, magnetic powder, polyvinylpyrrolidone and dimethylacetamide are fully mixed and dissolved to form base layer liquid;
s2, arranging the non-woven fabric on a substrate with magnetism, atomizing and spraying base layer liquid to the non-woven fabric, and coating the base layer liquid on the non-woven fabric under the action of a magnetic field;
s3, after the non-woven fabric is dried, cleaning by using pure water, pickling the non-woven fabric by using an acid solution, reacting the acid solution with the magnetic powder, and cleaning by using the pure water after pickling the acid solution;
s4, sequentially coating water phase liquid on the non-woven fabric washed by the pure water, then air-drying, coating oil phase liquid after air-drying, then air-drying, pickling after air-drying, performing interfacial polymerization reaction, and washing by using the pure water after the interfacial polymerization reaction;
s5, coating protective layer liquid on the non-woven fabric, drying by hot air after coating, rinsing by pure water after drying, and drying;
the base layer liquid comprises, by mass, 10-12 parts of polysulfone, 2-4 parts of 5-10 um diameter magnetic powder, 100-150 parts of dimethylacetamide and 10-12 parts of polyvinylpyrrolidone;
the aqueous phase liquid comprises 120-160 parts of water, 3-5 parts of polyamine and 0.5-1 part of polyalcohol in parts by mass;
the oil phase liquid comprises, by mass, 1-3 parts of acyl oxyhalide and 100-200 parts of triethanolamine;
the protective layer liquid comprises 50-100 parts of dimethylacetamide and 5-10 parts of acid-resistant hydrophilic polymer material according to parts by weight, wherein the acid-resistant hydrophilic polymer material is one or more of polyvinylidene fluoride, N-dimethylacrylamide and butyl methacrylate.
2. The process for coating a solution of a reverse osmosis membrane functional layer according to claim 1, wherein in the step S2, after spraying the base layer solution onto the nonwoven fabric, the nonwoven fabric is moved out of the spraying area, and a magnetic field is applied to the nonwoven fabric on the opposite side of the base layer solution, so that the magnetic powder is uniformly distributed in the base layer solution.
3. The process for coating a solution of a reverse osmosis membrane functional layer according to claim 1, wherein the magnetic powder in step S3 is a mixture of one or more of iron oxides; the product salt of the acidic solution used in step S3 after reaction with the magnetic powder is a water-soluble salt.
4. The process for coating a solution for a reverse osmosis membrane functional layer according to claim 1, wherein the total amount of the magnetic powder remaining after the acid washing in step S3 is not more than 20%.
5. The process for coating a solution of a reverse osmosis membrane functional layer according to claim 1, wherein in step S2, spraying is performed under vacuum environment by using a plurality of spray nozzles for spraying side by side, magnetic plates are respectively arranged on two sides of the non-woven fabric, and magnetic poles of the magnetic plates facing the side of the non-woven fabric are the same as magnetic poles of the magnetic substrate facing the non-woven fabric.
6. The process for coating a solution of a reverse osmosis membrane functional layer according to any one of claims 1 to 5, wherein the acidic solution in step S3 is washed with pure water after pickling to perform penetration washing on the front surface of the nonwoven fabric under pressure, and then rinsed.
7. The process for coating a solution of a reverse osmosis membrane functional layer according to any one of claims 1 to 5, wherein the thickness of the base layer solution coated in step S2 is 30 to 40 μm, and the drying temperature in step S3 is 50 to 65 ℃; and in the step S4, a multilayer coating mode is adopted when the aqueous phase liquid is coated, the total coating thickness is 120-125 nm, vacuum environment ultrasonic vibration is adopted for removing bubbles after each layer of coating, and in the step S5, vacuum environment ultrasonic vibration is adopted for removing bubbles after the oil phase liquid coating is finished, wherein the oil phase liquid coating thickness is 110-115 nm.
8. The coating process of the reverse osmosis membrane functional layer solution according to claim 1, wherein the base layer solution comprises, by mass, 11 parts of polysulfone, 3 parts of 5-10 um diameter magnetic powder, 130 parts of dimethylacetamide and 11 parts of polyvinylpyrrolidone;
the aqueous phase liquid comprises 140 parts of water, 4 parts of polyamine and 0.8 part of polyalcohol according to parts by weight;
the oil phase liquid comprises 2 parts of acyl oxyhalide and 160 parts of triethanolamine according to parts by weight;
the protective layer liquid comprises, by mass, 95 parts of dimethylacetamide and 7 parts of acid-resistant hydrophilic polymer material, wherein the acid-resistant hydrophilic polymer material comprises, by mass, 2-5 parts of tetrafluoroethylene, 1-2 parts of N, N-dimethylacrylamide and 2-3 parts of butyl methacrylate.
9. The process for coating a solution of a reverse osmosis membrane functional layer according to claim 1, wherein the base layer solution is coated on the nonwoven fabric substrate by means of magnetic control spraying.
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