CN112191112A - Polyamide reverse osmosis membrane with acid resistance and preparation method thereof - Google Patents
Polyamide reverse osmosis membrane with acid resistance and preparation method thereof Download PDFInfo
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- CN112191112A CN112191112A CN202011029401.1A CN202011029401A CN112191112A CN 112191112 A CN112191112 A CN 112191112A CN 202011029401 A CN202011029401 A CN 202011029401A CN 112191112 A CN112191112 A CN 112191112A
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- 239000012528 membrane Substances 0.000 title claims abstract description 75
- 239000004952 Polyamide Substances 0.000 title claims abstract description 43
- 229920002647 polyamide Polymers 0.000 title claims abstract description 43
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 35
- 239000002253 acid Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 238000005266 casting Methods 0.000 claims description 43
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- 229920002492 poly(sulfone) Polymers 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 18
- 229920000768 polyamine Polymers 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 230000001112 coagulating effect Effects 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000008346 aqueous phase Substances 0.000 claims description 13
- 239000012074 organic phase Substances 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000007790 scraping Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 150000001263 acyl chlorides Chemical class 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims 1
- YHKLGNXLHZWOQF-UHFFFAOYSA-N CC(C=CC=C1)=C1N(CCNC1)C1(N)N Chemical compound CC(C=CC=C1)=C1N(CCNC1)C1(N)N YHKLGNXLHZWOQF-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000000108 ultra-filtration 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
- 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
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- 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
- B01D71/50—Polycarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides an acid-resistant polyamide reverse osmosis membrane which is characterized by comprising a polyamide separation layer, wherein a double-layer supporting layer which is tightly attached is arranged on the same side of the separation layer, the double-layer supporting layer comprises a small hole supporting layer which is close to the polyamide separation layer and a large hole supporting layer which is adjacent to the small hole supporting layer, the hole diameter of the small hole supporting layer is about 5-20nm, the hole diameter of the large hole supporting layer is about 50-500nm, and the small hole supporting layer contains an all-silicon molecular sieve.
Description
Technical Field
The invention relates to a polyamide membrane, in particular to a polyamide reverse osmosis membrane with acid resistance.
Background
In recent years, the reverse osmosis membrane separation technology has more and more remarkable advantages in the aspects of comprehensive energy consumption, resource cost and the like, and plays a significant role in the sea water desalination and sewage treatment industries. The membrane polyamide membrane is the most used reverse osmosis membrane at present, and has the advantages of higher flux and salt rejection rate, larger operation temperature and pH value adjustment range and convenient operation.
The polyamide membrane is usually prepared by an interfacial polymerization method, namely, polyamine and polyacyl chloride are contacted on a porous support body at one time to be polymerized into a polyamide layer on the surface interface of the porous support body. The porous support body mostly adopts a microfiltration membrane or an ultrafiltration membrane specially prepared for the polyamide reverse osmosis, and the porous support layer is required to enable an aqueous phase solution to be uniformly spread on the surface of the porous support body, so that a defect-free polyamide membrane layer can be further prepared. For porous support layers, requirements are generally made both in terms of pore size and hydrophilicity. Regarding the pore size, generally speaking, the larger the pore size of the porous support, the smaller the water molecule passing obstruction, the larger the water flux of the reverse osmosis membrane, but the too large pore size leads to the penetration of water phase into the pore during the polyamide preparation process, and the applicant has found that the pore size of about 10nm is most suitable for the preparation of the polyamide membrane. For hydrophilicity and hydrophobicity, the hydrophilicity and hydrophobicity of the porous support layer influence the interfacial polymerization process of polyamide, and good hydrophilicity is favorable for spreading of a water phase on the porous support layer. In order to improve the hydrophilicity of the supporting layer, the applicant tries to dope a hydrophilic molecular sieve, such as NaA molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve, etc., in the porous supporting layer, but on one hand, the framework structure containing aluminum inevitably causes the membrane to be acid-intolerant, which limits the application process, and on the other hand, the higher hydrophilicity also causes the water phase to be continuously adsorbed and transferred by NaA molecular sieve and to be difficult to spread on the porous supporting surface.
Disclosure of Invention
In order to overcome the technical problems, the invention improves the supporting layer of the existing polyamide reverse osmosis membrane, so that the polyamide reverse osmosis membrane has good performance in the aspects of pore diameter and hydrophilicity and hydrophobicity, which is beneficial to spreading of aqueous phase solution.
The acid-resistant polyamide reverse osmosis membrane is characterized by comprising a polyamide separation layer, wherein a double-layer supporting layer which is tightly attached is arranged on the same side of the separation layer, the double-layer supporting layer comprises a small hole supporting layer which is close to the polyamide separation layer and a large hole supporting layer which is adjacent to the small hole supporting layer, the hole diameter of the small hole supporting layer is about 5-20nm, the hole diameter of the large hole supporting layer is about 50-500nm, and the small hole supporting layer contains an all-silicon molecular sieve.
The macroporous supporting layer and the small pore supporting layer are prepared from the same high polymer material.
The polymer material is one of polysulfone, polyethersulfone, polyacrylonitrile, polytetrafluoroethylene and polyvinylidene fluoride.
The macroporous supporting layer is formed by dissolving calcium carbonate into inorganic acid to form pores, and the small pore supporting layer takes lithium chloride as a pore-forming agent.
The all-silicon molecular sieve is a Silicalite-1 molecular sieve.
A method of making the acid resistant reverse osmosis membrane described above, comprising:
(1) preparation of a double-layer support layer
(a) Preparing a casting solution: mixing polysulfone, lithium chloride, an all-silicon molecular sieve and a solvent, heating, stirring, standing and defoaming to form a first membrane casting solution, mixing the polysulfone, the solvent and calcium carbonate particles, heating, stirring, standing and defoaming to form a second membrane casting solution;
(b) preparing a primary film: at room temperature, uniformly scraping the first casting solution on a clean glass plate by using a scraper, and then transferring the first casting solution into a coagulating bath to perform phase conversion into a small-hole supporting layer; taking the small-hole supporting layer out of the coagulating bath, continuously scraping the second casting solution on the small-hole supporting layer by using a scraper, and then transferring the second casting solution into the coagulating bath to convert the second casting solution into a large-hole supporting layer so as to form a supporting layer embryonic membrane;
(c) and (3) post-treatment: completely soaking the support layer embryonic membrane in 0.05-0.1mol/L inorganic acid solution for 2-6 min; washing with clear water, soaking for 2-4h to form a double-layer supporting layer;
(2) preparation of polyamide reverse osmosis membrane
And (2) taking the double-layer supporting layer prepared in the step (1) as a supporting body to sequentially contact the polyamine aqueous phase solution and the polyacylchloride organic phase solution so as to realize the polymerization of the surface interface of the small-hole supporting layer of the double-layer supporting layer into the polyamide reverse osmosis membrane.
The multifunctional amine solution is one or more of m-phenylenediamine, p-phenylenediamine, piperazine, o-phenylenediamine, diaminotoluene and 2, 5-dimethylpiperazine, and the multifunctional acyl chloride is one or more of trimesoyl chloride, terephthaloyl chloride, phthaloyl chloride and isophthaloyl chloride.
The method of claim 6, wherein the size of the all-silica molecular sieve is 10-50 nm.
The first membrane casting solution contains 10-30wt% of polysulfone, 0.3-2wt% of lithium chloride, 0.2-1wt% of all-silicon molecular sieve and the balance of solvent; the content of polysulfone in the second membrane casting solution is 10-30wt%, the content of calcium carbonate particles is 2-5wt%, and the balance is solvent.
The aqueous polyamine solution comprises 0.1-4.0wt% polyamine, 0.005-1.0wt.% surfactant and pH adjusting agent, and has a pH range of 10-12; the polybasic acyl chloride organic phase solution contains 0.01-2wt% of polybasic acyl chloride, and the organic solvent is one of cyclohexane, hexane, n-heptane and octane.
Compared with the prior art, the water phase supporting layer is formed by combining the large pore supporting layer and the small pore supporting layer, on one hand, the large pore supporting layer can ensure good water flux, and the small pore supporting layer can ensure proper pore diameter to be beneficial to water phase spreading, on the other hand, the invention also improves the hydrophilicity of the supporting layer by hybridizing the all-silicon molecular sieve in the small pore supporting layer, avoids the situation of acid corrosion in the preparation process of the supporting layer and improves the integral acid resistance of the reverse osmosis membrane.
Detailed Description
Example 1
The polyamide reverse osmosis membrane prepared in this example was prepared by the following procedure
(1) Preparation of a double-layer support layer
(a) Preparing a casting solution: mixing polysulfone, lithium chloride, silicalite-1 molecular sieve and dimethylformamide, heating, stirring, standing and defoaming to form a first membrane casting solution, wherein the content of the polysulfone in the first membrane casting solution is 20 wt%, the content of the lithium chloride is 0.5 wt%, the content of the silicalite-1 molecular sieve is 0.5 wt%, and the balance is solvent dimethylformamide; mixing polysulfone, a solvent and calcium carbonate particles, heating, stirring, standing and defoaming to form a second membrane casting solution, wherein the content of polysulfone in the second membrane casting solution is 20 wt%, the content of calcium carbonate particles is 2wt%, and the balance is the solvent.
(b) Preparing a primary film: at room temperature, uniformly scraping the first casting solution on a clean glass plate by using a scraper, and then transferring the first casting solution into a coagulating bath to perform phase conversion into a small-hole supporting layer; taking the small-hole supporting layer out of the coagulating bath, continuously scraping the second casting solution on the small-hole supporting layer by using a scraper, and then transferring the second casting solution into the coagulating bath to convert the second casting solution into a large-hole supporting layer so as to form a supporting layer embryonic membrane;
(c) and (3) post-treatment: completely soaking the support layer embryonic membrane in 0.1mol/L hydrochloric acid solution for 5 min; washing with clear water, soaking for 4h to form a double-layer supporting layer;
(2) preparation of polyamide reverse osmosis membrane
Mixing 2.0 wt% of m-phenylenediamine, 0.05 wt% of surfactant sodium dodecyl sulfate and pH regulator sodium hydroxide in pure water to prepare a polyamine aqueous phase solution with the pH value of 11; adding 0.1 wt% of trimesoyl chloride into cyclohexane to form a polybasic acyl chloride organic phase solution;
and (2) taking the double-layer supporting layer prepared in the step (1) as a supporting body, firstly contacting the polyamine aqueous phase solution for 120s, taking out the supporting layer, removing the surface solution, and then continuously immersing the supporting layer into the polyacyl chloride organic phase solution for 60s to realize the polymerization of the surface interface of the small-hole supporting layer of the double-layer supporting layer into the polyamide reverse osmosis membrane.
Comparative example 1
(1) Preparation of the supporting layer
Mixing polysulfone, lithium chloride and dimethylformamide, heating, stirring, standing and defoaming to form a membrane casting solution, wherein the content of polysulfone in the membrane casting solution is 20 wt%, the content of lithium chloride is 0.5 wt%, and the balance is solvent dimethylformamide; at room temperature, uniformly scraping the casting solution on a clean glass plate by using a scraper, and then transferring the glass plate into a coagulating bath to perform phase conversion into a supporting layer;
(2) preparation of polyamide reverse osmosis membrane
Mixing 2.0 wt% of m-phenylenediamine, 0.05 wt% of surfactant sodium dodecyl sulfate and pH regulator sodium hydroxide in pure water to prepare a polyamine aqueous phase solution with the pH value of 11; adding 0.1 wt% of trimesoyl chloride into cyclohexane to form a polybasic acyl chloride organic phase solution;
and (2) taking the support layer prepared in the step (1) as a support body, firstly contacting the polyamine aqueous phase solution for 120s, taking out the support layer, removing the surface solution, and then continuously immersing the support layer into the polyacyl chloride organic phase solution for 60s to realize the polymerization of the surface interface of the support layer into the polyamide reverse osmosis membrane.
Comparative example 2
(1) Preparation of the supporting layer
Mixing polysulfone, a solvent and calcium carbonate particles, heating, stirring, standing and defoaming to form a membrane casting solution; at room temperature, uniformly scraping the membrane liquid on a clean glass plate by using a scraper, and then transferring the membrane liquid into a coagulating bath to perform phase conversion into a supporting layer embryonic membrane; completely soaking the support layer embryonic membrane in 0.1mol/L hydrochloric acid solution for 5 min; washing with clear water, and soaking for 4h to form a supporting layer;
(2) preparation of polyamide reverse osmosis membrane
Mixing 2.0 wt% of m-phenylenediamine, 0.05 wt% of surfactant sodium dodecyl sulfate and pH regulator sodium hydroxide in pure water to prepare a polyamine aqueous phase solution with the pH value of 11; adding 0.1 wt% of trimesoyl chloride into cyclohexane to form a polybasic acyl chloride organic phase solution;
and (2) taking the support layer prepared in the step (1) as a support body, firstly contacting the polyamine aqueous phase solution for 120s, taking out the support layer, removing the surface solution, and then continuously immersing the support layer into the polyacyl chloride organic phase solution for 60s to realize the polymerization of the surface interface of the support layer into the polyamide reverse osmosis membrane.
Comparative example 3
(1) Preparation of the supporting layer
(a) Preparing a casting solution: mixing polysulfone, lithium chloride and dimethylformamide, heating, stirring, standing and defoaming to form a first membrane casting solution, wherein the content of the polysulfone in the first membrane casting solution is 20 wt%, the content of the lithium chloride is 0.5 wt%, and the balance is solvent dimethylformamide; mixing polysulfone, a solvent and calcium carbonate particles, heating, stirring, standing and defoaming to form a second membrane casting solution;
(b) preparing a primary film: at room temperature, uniformly scraping the first casting solution on a clean glass plate by using a scraper, and then transferring the first casting solution into a coagulating bath to perform phase conversion into a small-hole supporting layer; taking the small-hole supporting layer out of the coagulating bath, continuously scraping the second casting solution on the small-hole supporting layer by using a scraper, and then transferring the second casting solution into the coagulating bath to convert the second casting solution into a large-hole supporting layer so as to form a supporting layer embryonic membrane;
(c) and (3) post-treatment: completely soaking the support layer embryonic membrane in 0.1mol/L hydrochloric acid solution for 5 min; washing with clear water, soaking for 4h to form a double-layer supporting layer;
(2) preparation of polyamide reverse osmosis membrane
Mixing 2.0 wt% of m-phenylenediamine, 0.05 wt% of surfactant sodium dodecyl sulfate and pH regulator sodium hydroxide in pure water to prepare a polyamine aqueous phase solution with the pH value of 11; adding 0.1 wt% of trimesoyl chloride into cyclohexane to form a polybasic acyl chloride organic phase solution;
and (2) taking the double-layer supporting layer prepared in the step (1) as a supporting body, firstly contacting the polyamine aqueous phase solution for 120s, taking out the supporting layer, removing the surface solution, and then continuously immersing the supporting layer into the polyacyl chloride organic phase solution for 60s to realize the polymerization of the surface interface of the small-hole supporting layer of the double-layer supporting layer into the polyamide reverse osmosis membrane.
The polyamide reverse osmosis membrane samples prepared in example 1 and comparative examples 1 to 3 above were tested for initial performance of the membrane using 2000ppm of aqueous sodium chloride solution at 30 ℃ under 1MPa pressure, and the test results are shown in the following table:
| sample (I) | Salt rejection (%) | Water flux (L/m)2.h) |
| Example 1 | 98.9 | 62.1 |
| Comparative example 1 | 99.2 | 32.4 |
| Comparative example 2 | 58.2 | 79.3 |
| Comparative example 3 | 95.2 | 56.3 |
As can be seen from the data, the polyamide reverse osmosis membrane sample prepared by the embodiment maintains higher levels in the aspects of salt rejection rate and water flux, and proves that the polyamide reverse osmosis membrane sample is beneficial to spreading of aqueous phase solution on the surface of a support and subsequent interfacial polymerization reaction.
The above is the embodiment of the present invention. It should be noted that, for a person skilled in the art, several modifications and adaptations can be made without departing from the basic inventive concept and are therefore considered to be within the scope of the present invention.
Claims (10)
1. An acid-resistant polyamide reverse osmosis membrane is characterized in that the reverse osmosis membrane is provided with a polyamide separation layer, a double-layer supporting layer which is tightly attached is arranged on the same side of the separation layer, the double-layer supporting layer comprises a small hole supporting layer adjacent to the polyamide separation layer and a large hole supporting layer adjacent to the small hole supporting layer, the hole diameter of the small hole supporting layer is about 5-20nm, the hole diameter of the large hole supporting layer is about 50-500nm, and the small hole supporting layer contains an all-silicon molecular sieve.
2. The polyamide reverse osmosis membrane of claim 1, wherein the macroporous support layer and the microporous support layer are made of the same polymeric material.
3. The polyamide permeable membrane according to claim 2, wherein the polymer material is one of polysulfone, polyethersulfone, polyacrylonitrile, polytetrafluoroethylene, and polyvinylidene fluoride.
4. The polyamide reverse osmosis membrane of claim 1, wherein the macroporous support layer is formed by dissolving calcium carbonate in an inorganic acid to form pores, and the small pore support layer is formed by using lithium chloride as a pore-forming agent.
5. The polyamide reverse osmosis membrane of claim 1, characterized in that said all-silica molecular sieve is Silicalite-1 molecular sieve.
6. A method of making an acid resistant reverse osmosis membrane according to any one of claims 1-5, characterized in that said method comprises:
(1) preparation of a double-layer support layer
(a) Preparing a casting solution: mixing polysulfone, lithium chloride, an all-silicon molecular sieve and a solvent, heating, stirring, standing and defoaming to form a first membrane casting solution, mixing the polysulfone, the solvent and calcium carbonate particles, heating, stirring, standing and defoaming to form a second membrane casting solution;
(b) preparing a primary film: at room temperature, uniformly scraping the first casting solution on a clean glass plate by using a scraper, and then transferring the first casting solution into a coagulating bath to perform phase conversion into a small-hole supporting layer; taking the small-hole supporting layer out of the coagulating bath, continuously scraping the second casting solution on the small-hole supporting layer by using a scraper, and then transferring the second casting solution into the coagulating bath to convert the second casting solution into a large-hole supporting layer so as to form a supporting layer embryonic membrane;
(c) and (3) post-treatment: completely soaking the support layer embryonic membrane in 0.05-0.1mol/L inorganic acid solution for 2-6 min; washing with clear water, soaking for 2-4h to form a double-layer supporting layer;
(2) preparation of polyamide reverse osmosis membrane
And (2) taking the double-layer supporting layer prepared in the step (1) as a supporting body to sequentially contact the polyamine aqueous phase solution and the polyacylchloride organic phase solution so as to realize the polymerization of the surface interface of the small-hole supporting layer of the double-layer supporting layer into the polyamide reverse osmosis membrane.
7. The method according to claim 6, wherein the polyamine solution is one or more of m-phenylenediamine, p-phenylenediamine, diaminotolylpiperazine, and o-phenylenediamine, and the poly-acid chloride is one or more of trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride, and phthaloyl chloride.
8. The method of claim 6, wherein the size of the all-silica molecular sieve is 10-50 nm.
9. The method according to claim 6, wherein the first membrane casting solution comprises 10 to 30wt% of polysulfone, 0.3 to 2wt% of lithium chloride, 0.2 to 1wt% of all-silicon molecular sieve, and the balance of solvent; the content of polysulfone in the second membrane casting solution is 10-30wt%, the content of calcium carbonate particles is 2-5wt%, and the balance is solvent.
10. The process according to claim 6, characterized in that the aqueous polyamine solution comprises 0.1-4.0 wt.% polyamine, 0.005-1.0wt.% surfactant and pH adjusting agent, the pH range being 10-12; the polybasic acyl chloride organic phase solution contains 0.01-2wt% of polybasic acyl chloride, and the organic solvent is one of cyclohexane, hexane, n-heptane and octane.
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