CN115445456B - Preparation method of high-flux reverse osmosis composite membrane - Google Patents
Preparation method of high-flux reverse osmosis composite membrane Download PDFInfo
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- CN115445456B CN115445456B CN202211209732.2A CN202211209732A CN115445456B CN 115445456 B CN115445456 B CN 115445456B CN 202211209732 A CN202211209732 A CN 202211209732A CN 115445456 B CN115445456 B CN 115445456B
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- 239000012528 membrane Substances 0.000 title claims abstract description 111
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 37
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 37
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims abstract description 32
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims abstract description 32
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims abstract description 32
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000017 hydrogel Substances 0.000 claims abstract description 28
- 239000008346 aqueous phase Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000004952 Polyamide Substances 0.000 claims abstract description 24
- 229920002647 polyamide Polymers 0.000 claims abstract description 24
- 238000011033 desalting Methods 0.000 claims abstract description 17
- 239000012071 phase Substances 0.000 claims abstract description 17
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 16
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 15
- 238000001879 gelation Methods 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 49
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000010612 desalination reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 14
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 10
- 230000004907 flux Effects 0.000 claims description 10
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- 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 7
- 230000029087 digestion Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 65
- 239000000543 intermediate Substances 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 229920002492 poly(sulfone) Polymers 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002346 layers by function Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000002352 surface water Substances 0.000 description 6
- 238000001728 nano-filtration Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
Abstract
The invention belongs to the technical field of reverse osmosis membrane preparation, and particularly relates to a preparation method of a high-flux reverse osmosis composite membrane, which adopts polyacrylic acid and hydroxypropyl methyl cellulose as pH sensitive in-situ gelation liquid medium, wherein a base membrane is soaked in an alkaline aqueous phase solution containing polyacrylic acid and an aqueous phase solution containing hydroxypropyl methyl cellulose in sequence to generate a hydrogel intermediate layer on the surface of the base membrane and in membrane holes, and then a membrane is soaked in an oil phase solution containing acyl chloride to enable the surface of the base membrane to undergo interfacial polymerization reaction to generate a polyamide desalting layer, and meanwhile, the hydrogel intermediate layer is digested in the interfacial polymerization reaction process to obtain the high-flux reverse osmosis composite membrane with a non-woven fabric, a base membrane layer and a polyamide desalting layer structure from bottom to top.
Description
Technical Field
The invention belongs to the technical field of reverse osmosis membrane preparation, and particularly relates to a preparation method of a high-flux reverse osmosis composite membrane.
Background
In the application process of nanofiltration membrane and reverse osmosis membrane water treatment technology, the water flux of the membrane is improved when the membrane is operated under the condition of fixed pressure, and the method has great significance for saving energy consumption of the technology. The membrane operation water flux is mainly influenced by the effective thickness of the membrane functional layer, so that the preparation of the membrane with the ultrathin desalting layer becomes a hot spot in the research of preparing the high-flux nanofiltration membrane and the reverse osmosis membrane. The "ultrathin desalting layer" of the nanofiltration membrane and the reverse osmosis membrane can be obtained in various ways, for example: modifying the base film to influence the interfacial polymerization reaction degree on the surface of the base film, changing the concentration of water phase and oil phase monomers in the interfacial polymerization reaction process, preparing a functional layer by realizing the crosslinking reaction through the photocatalytic reaction, coating the nano material on the surface of the base film or introducing a reaction intermediate layer for changing the interfacial polymerization reaction miscible area, and the like.
In the prior art, a reaction intermediate layer or a regulating layer is introduced between a base membrane and a functional layer in the membrane covering process of preparing the nanofiltration membrane and the reverse osmosis membrane, so that the aim of improving the performance of the membrane in a certain aspect can be fulfilled. While some of the intermediate layer or the regulating layer is remained between the base film and the functional layer, and some of the intermediate layer or the regulating layer is digested in the reaction process. The purpose of introducing an intermediate layer or a regulating layer is to change the structure of the functional layer prepared by interfacial polymerization, wherein the purpose is to improve the high flux of the membrane (for example, patent CN109847586B, CN111992039B, CN 114642986A), and the purpose is to change the structure of the blade on the surface of the functional layer to influence desalination (for example, patent CN 114130225A). The intermediate layer in many technical schemes is obtained by coating or reacting a layer of nano material intermediate layer on the surface of a base film, and then coating the surface of the base film to obtain the composite nanofiltration or reverse osmosis film. However, coating or reacting on the surface of the base film to form a nano material intermediate layer has the following technical defects: 1. the nano material needs to be prepared in advance, and the preparation process of the nano material is complicated and the preparation cost is high; 2. the nano material has insufficient adhesive mechanical strength on the surface of the base film, and is easy to fall off partially before the film coating process is carried out after the intermediate layer is formed on the surface of the base film.
Disclosure of Invention
The invention provides a preparation method of a high-flux reverse osmosis composite membrane aiming at the defects of the prior art.
The method is realized by the following technical scheme:
the preparation method of the high-flux reverse osmosis composite membrane comprises the steps of taking polyacrylic acid and hydroxypropyl methyl cellulose as pH sensitive in-situ gelation liquid medium, soaking a base membrane in an alkaline aqueous solution containing polyacrylic acid and an aqueous solution containing hydroxypropyl methyl cellulose in sequence to generate a hydrogel intermediate layer on the surface of the base membrane and in membrane holes, soaking the membrane in an oil phase solution containing acyl chloride to enable the surface of the base membrane to undergo interfacial polymerization reaction to generate a polyamide desalting layer, and digesting the hydrogel intermediate layer in the interfacial polymerization reaction process to obtain the high-flux reverse osmosis composite membrane with a non-woven fabric, a base membrane layer and a polyamide desalting layer structure from bottom to top.
The preparation method of the high-flux reverse osmosis composite membrane comprises the following steps:
1) Immersing a base film in an alkaline aqueous solution containing polyacrylic acid, fully contacting for 1-20s, taking out the base film and removing water drops on the surface of the base film, wherein the alkaline aqueous solution containing polyacrylic acid consists of polyacrylic acid, m-diphenylamine, camphorsulfonic acid and triethylamine;
2) Immersing the base film obtained in the step 1) into an aqueous phase solution containing hydroxypropyl methyl cellulose at room temperature for 3-5min to generate a layer of hydrogel on the surface of the base film;
3) Immersing the membrane obtained in the step 2) into an oil phase solution containing acyl chloride, fully contacting for 1-20s to form a polyamide desalting layer, taking out, washing with citric acid solution, removing residual hydrogel digestion residual substances on the surface of the membrane, and finally drying.
The alkaline aqueous solution containing polyacrylic acid consists of the following substances in percentage by mass: 0.1 to 5.0 percent of polyacrylic acid, 1.0 to 10 percent of m-phenylenediamine, 1 to 10 percent of camphorsulfonic acid, 0.5 to 5 percent of triethylamine and the balance of water.
The room temperature was 25 ℃.
The mass concentration of the hydroxypropyl methylcellulose in the aqueous phase solution containing the hydroxypropyl methylcellulose is 0.05-2.5%.
The acyl chloride-containing oil phase solution consists of the following substances in percentage by mass: 0.1-1.0% oxalyl chloride, 0.1-1.0% trimesoyl chloride, and the balance ethylcyclohexane.
The mass concentration of the citric acid solution is 12%.
The water washing time is 1-2min, and the temperature is 70 ℃.
The thickness of the polyamide desalting layer is 20-100nm.
The thickness of the polyamide desalting layer is 30-60nm, and the polyamide desalting layer has a thinner desalting layer compared with the thickness of the polyamide desalting layer of a conventional reverse osmosis composite membrane.
The preparation of the hydrogel adopts polyacrylic acid and hydroxypropyl methyl cellulose as pH sensitive in-situ gelation liquid medium, and a base film is soaked in alkaline aqueous solution containing polyacrylic acid and m-phenylenediamine reaction monomers, and then soaked in the aqueous solution containing hydroxypropyl methyl cellulose, so that a very thin hydrogel layer is generated on the surface of the base film in alkaline environment, and part of the hydrogel layer is sunk into film holes of the base film.
The hydrogel formed by the polyacrylic acid and the hydroxypropyl methyl cellulose has strong water absorption, so that the film hole and the surface hole of the base film contain aqueous phase reaction solution which can participate in reaction, at the moment, the base film is soaked in organic phase solution containing a little oxalyl chloride and trimesoyl chloride, the aqueous phase monomer enters into the organic phase to undergo interfacial polymerization reaction, so that the sufficiency of the interfacial polymerization reaction is ensured, meanwhile, oxalic acid and hydrochloric acid generated by the interfacial polymerization reaction and reaction heat released by the reaction enable the hydrogel layer to be digested, so that the finally-formed reverse osmosis composite film structure is sequentially a non-woven fabric, a base film layer and a polyamide desalination layer, and the polyamide desalination layer generated on the surface of the base film slowly releases the adsorbed aqueous phase monomer in the interfacial polymerization process, so that the polyamide desalination layer generated by the reaction in the reaction miscible area has a very thin layer with the thickness of about 20-100nm, and the polyamide desalination layer has an ultrathin structure.
The hydroxypropyl methylcellulose is selected to have strong hydrogel property, and the polyacrylic acid participating in copolymerization and crosslinking has strong pH sensitivity, so that the pH value has great influence on the equilibrium swelling rate of the hydrogel, and the polyacrylic acid adopting copolymerization and crosslinking of hydroxypropyl methylcellulose and polyacrylic acid with certain content can be rapidly hydrogel-immobilized on the surface of the base film and rapidly dissociated under certain pH change conditions.
The beneficial effects are that:
according to the invention, the adsorption rate of the aqueous phase monomer is increased by introducing the hydrogel intermediate layer, so that the sufficiency and effectiveness of the interfacial polymerization reaction are ensured, the aqueous phase monomer can be slowly released when the aqueous phase monomer contacts with the organic phase by utilizing the strong adsorption force of the hydrogel, the thickness of a reaction miscible area in the interfacial polymerization process is ensured to be thinner, and the thickness of a generated polyamide desalting layer is ensured to be thinner.
Drawings
FIG. 1 is a schematic structural view of a reverse osmosis composite membrane of the present invention.
Detailed Description
The following detailed description of the invention is provided in further detail, but the invention is not limited to these embodiments, any modifications or substitutions in the basic spirit of the present examples, which still fall within the scope of the invention as claimed.
Example 1
The preparation method of the high-flux reverse osmosis composite membrane comprises the following steps:
1) Immersing a polysulfone base membrane supporting layer with the average pore diameter of 10nm on the surface of the porous supporting layer into an alkaline aqueous phase solution containing polyacrylic acid, contacting for 20s, and removing surface water drops; then immersing in an aqueous phase solution containing hydroxypropyl methyl cellulose, immersing for 5min at 25 ℃ to generate a layer of hydrogel on the surface of the base film; the alkaline aqueous solution containing polyacrylic acid consists of the following substances in percentage by mass: 0.5% polyacrylic acid, 3.0% m-phenylenediamine, 4% camphorsulfonic acid, 2% triethylamine and the balance of water; the mass concentration of the hydroxypropyl methylcellulose in the aqueous phase solution containing the hydroxypropyl methylcellulose is 0.25%;
2) Taking out the membrane obtained in the step 1), immersing the membrane in an oil phase solution containing acyl chloride, contacting for 20s to form a polyamide desalination layer with the thickness of about 45nm, taking out the membrane, washing the membrane with a citric acid solution with the mass concentration of 12% at 70 ℃ for 1min, removing residual hydrogel digestion residual substances on the surface of the membrane, and drying the membrane at 70 ℃ to obtain the reverse osmosis composite membrane; the acyl chloride-containing oil phase solution consists of the following substances in percentage by mass: 0.5% oxalyl chloride, 0.15% trimesoyl chloride, and the balance ethylcyclohexane;
comparative example 1
1) Contacting the porous support layer with an aqueous solution below a polysulfone base membrane support layer with the surface average pore diameter of 10nm for 20s to remove surface water drops; the aqueous phase solution consists of the following substances in percentage by mass: 3.0% of m-phenylenediamine, 4% of camphorsulfonic acid, 2% of triethylamine and the balance of water;
2) Step 2) of example 1;
comparative example 2
On the basis of example 1, the difference from example 1 is that: directly on the basis of the base film, under the same formulation conditions, the polyamide film is covered, and the post-introduction intermediate layer (namely the hydrogel layer) in the example 1 is not performed; the method specifically comprises the following steps:
1) Immersing a polysulfone base membrane supporting layer with the average pore diameter of 10nm on the surface of the porous supporting layer into an alkaline aqueous phase solution containing polyacrylic acid, contacting for 20s, and removing surface water drops; the alkaline aqueous solution containing polyacrylic acid consists of the following substances in percentage by mass: 0.5% polyacrylic acid, 3.0% m-phenylenediamine, 4% camphorsulfonic acid, 2% triethylamine and the balance of water;
2) Step 2) of example 1;
comparative example 3
1) Immersing a polysulfone base membrane supporting layer with the average pore diameter of 10nm on the surface of the porous supporting layer into an aqueous phase solution containing hydroxypropyl methyl cellulose, and immersing for 5min at 25 ℃; the aqueous phase solution containing hydroxypropyl methyl cellulose consists of the following substances in percentage by mass: the mass concentration of the hydroxypropyl methylcellulose is 0.25 percent, 3.0 percent of m-phenylenediamine, 4 percent of camphorsulfonic acid, 2 percent of triethylamine and the balance of water;
2) Step 2) of example 1;
performance comparative test:
comparative examples 1, 2, 3 were compared with the membrane of example 1 for membrane performance. Diaphragm performance test 1: the desalination rate and flux of the two sets of membranes were tested with 1500ppm aqueous NaCl at an operating pressure of 1.0MPa and a temperature of 25 ℃.
The test results in NaCl solution are shown in Table 1 below (concentrate cycle):
TABLE 1
Diaphragm performance test 2: the desalination rate and flux of the two groups of diaphragms are tested under the conditions that the operation pressure is 1.0MPa and the temperature is 25 ℃; wherein the preparation of the water-soluble solution is as follows: 11.10g CaCl was added to 40L pure water 2 、10.75g NaHCO 3 2.00g of NaCl, and then 40ml of hypochlorous acid solution, which is obtained by diluting 6-8ml of hypochlorous acid dissolved in 1L of pure water, was added.
The results of the test in the aqueous solution are shown in table 2 below (concentrate cycle):
TABLE 2
As can be seen from tables 1 and 2, a high flux reverse osmosis composite membrane incorporating an intermediate layer via one of example 1: when the salt-removing agent runs in NaCl solution, the flux is greatly improved from about 36GFD to about 54GFD, the desalination rate is reduced from 99.0% to 98.8%, and the salt-removing agent can stably run for a long time; when the desalination device operates in the water-effect solution, the flux is greatly improved from about 34GFD to about 50GFD, and the desalination rate is almost unchanged and is kept at about 96.5%. In addition, the desalted layers of comparative examples 1 to 3 each had a thickness of more than 100nm.
Example 2
The preparation method of the high-flux reverse osmosis composite membrane comprises the following steps:
1) Immersing a polysulfone base membrane supporting layer with the average pore diameter of 10nm on the surface of the porous supporting layer into an alkaline aqueous phase solution containing polyacrylic acid, contacting for 1s, and removing surface water drops; then immersing in an aqueous phase solution containing hydroxypropyl methyl cellulose, immersing for 3min at 25 ℃ to generate a layer of hydrogel on the surface of the base film; the alkaline aqueous solution containing polyacrylic acid consists of the following substances in percentage by mass: 0.2% polyacrylic acid, 3.0% m-phenylenediamine, 4% camphorsulfonic acid, 2% triethylamine and the balance of water; the mass concentration of the hydroxypropyl methylcellulose in the aqueous phase solution containing the hydroxypropyl methylcellulose is 0.1 percent;
2) Taking out the membrane obtained in the step 1), immersing the membrane in an oil phase solution containing acyl chloride, contacting for 20s to form a polyamide desalting layer, taking out the membrane, washing the membrane with a citric acid solution with the mass concentration of 12% at 70 ℃ for 1min, removing residual hydrogel digestion residual substances on the surface of the membrane, and drying the membrane at 70 ℃ to obtain the reverse osmosis composite membrane; the acyl chloride-containing oil phase solution consists of the following substances in percentage by mass: 0.5% oxalyl chloride, 0.15% trimesoyl chloride, and the balance ethylcyclohexane.
Example 3
The preparation method of the high-flux reverse osmosis composite membrane comprises the following steps:
1) Immersing a polysulfone base membrane supporting layer with the average pore diameter of 10nm on the surface of the porous supporting layer into an alkaline aqueous phase solution containing polyacrylic acid, contacting for 15s, and removing surface water drops; then immersing in an aqueous phase solution containing hydroxypropyl methyl cellulose, immersing for 5min at 25 ℃ to generate a layer of hydrogel on the surface of the base film; the alkaline aqueous solution containing polyacrylic acid consists of the following substances in percentage by mass: 0.8% polyacrylic acid, 3% m-phenylenediamine, 4% camphorsulfonic acid, 2% triethylamine and the balance of water; the mass concentration of the hydroxypropyl methylcellulose in the aqueous phase solution containing the hydroxypropyl methylcellulose is 0.4%;
2) Taking out the membrane obtained in the step 1), immersing the membrane in an oil phase solution containing acyl chloride, contacting for 20s to form a polyamide desalting layer, taking out the membrane, washing the membrane with a citric acid solution with the mass concentration of 12% at 70 ℃ for 2min, removing residual hydrogel digestion residual substances on the surface of the membrane, and drying the membrane at 70 ℃ to obtain the reverse osmosis composite membrane; the acyl chloride-containing oil phase solution consists of the following substances in percentage by mass: 0.5% oxalyl chloride, 0.15% trimesoyl chloride, and the balance ethylcyclohexane.
Example 4
The preparation method of the high-flux reverse osmosis composite membrane comprises the following steps:
1) Immersing a polysulfone base membrane supporting layer with the average pore diameter of 10nm on the surface of the porous supporting layer into an alkaline aqueous phase solution containing polyacrylic acid, contacting for 15s, and removing surface water drops; then immersing the membrane in an aqueous phase solution containing hydroxypropyl methyl cellulose, and immersing the membrane for 4min at 25 ℃ to generate a layer of hydrogel on the surface of the base membrane; the alkaline aqueous solution containing polyacrylic acid consists of the following substances in percentage by mass: 0.5% polyacrylic acid, 3% m-phenylenediamine, 6% camphorsulfonic acid, 3% triethylamine and the balance of water; the mass concentration of the hydroxypropyl methylcellulose in the aqueous phase solution containing the hydroxypropyl methylcellulose is 0.25%;
2) Taking out the membrane obtained in the step 1), immersing the membrane in an oil phase solution containing acyl chloride, contacting for 20s to form a polyamide desalting layer, taking out the membrane, washing the membrane with a citric acid solution with the mass concentration of 12% at 70 ℃ for 1.5min, removing residual hydrogel digestion residual substances on the surface of the membrane, and drying the membrane at 70 ℃ to obtain the reverse osmosis composite membrane; the acyl chloride-containing oil phase solution consists of the following substances in percentage by mass: 1.0% oxalyl chloride, 0.15% trimesoyl chloride, and the balance ethylcyclohexane;
the reverse osmosis composite membranes obtained in examples 2-4 were tested according to example 1 and the results are shown in Table 3:
TABLE 3 Table 3
Claims (9)
1. A preparation method of a high-flux reverse osmosis composite membrane is characterized in that polyacrylic acid and hydroxypropyl methyl cellulose are adopted as pH sensitive in-situ gelation liquid medium, a base membrane is soaked in an alkaline aqueous solution containing polyacrylic acid and an aqueous solution containing hydroxypropyl methyl cellulose in sequence to generate a hydrogel intermediate layer on the surface and in membrane holes of the base membrane, aqueous reaction solution capable of participating in reaction is contained in the membrane holes and surface holes of the base membrane, then the membrane is soaked in an oil phase solution containing acyl chloride to enable the surface of the base membrane to undergo interfacial polymerization reaction to generate a polyamide desalination layer, and meanwhile, the hydrogel intermediate layer is digested in the interfacial polymerization reaction process to obtain the high-flux reverse osmosis composite membrane with a non-woven fabric, a base membrane layer and a polyamide desalination layer structure from bottom to top.
2. The method for preparing a high flux reverse osmosis composite membrane according to claim 1, comprising the steps of:
1) Immersing a base film in an alkaline aqueous solution containing polyacrylic acid, fully contacting for 1-20s, taking out the base film and removing water drops on the surface of the base film, wherein the alkaline aqueous solution containing polyacrylic acid consists of polyacrylic acid, m-diphenylamine, camphorsulfonic acid and triethylamine;
2) Immersing the base film obtained in the step 1) into an aqueous phase solution containing hydroxypropyl methyl cellulose at room temperature for 3-5min to generate a layer of hydrogel on the surface of the base film;
3) Immersing the membrane obtained in the step 2) into an oil phase solution containing acyl chloride, fully contacting for 1-20s to form a polyamide desalting layer, taking out, washing with citric acid solution, removing residual hydrogel digestion residual substances on the surface of the membrane, and finally drying.
3. The method for preparing a high-flux reverse osmosis composite membrane according to claim 1 or 2, wherein the aqueous alkaline solution containing polyacrylic acid comprises the following substances in mass fraction: 0.1 to 5.0 percent of polyacrylic acid, 1.0 to 10 percent of m-phenylenediamine, 1 to 10 percent of camphorsulfonic acid, 0.5 to 5 percent of triethylamine and the balance of water.
4. The method for preparing a high-flux reverse osmosis composite membrane according to claim 1 or 2, wherein the mass concentration of hydroxypropyl methylcellulose in the aqueous solution containing hydroxypropyl methylcellulose is 0.05-2.5%.
5. The preparation method of the high-flux reverse osmosis composite membrane according to claim 1 or 2, wherein the oil phase solution containing the acyl chloride comprises the following substances in percentage by mass: 0.1-1.0% oxalyl chloride, 0.1-1.0% trimesoyl chloride, and the balance ethylcyclohexane.
6. The method for preparing a high-flux reverse osmosis composite membrane according to claim 2, wherein the mass concentration of the citric acid solution is 12%.
7. The method for preparing a high flux reverse osmosis composite membrane according to claim 2, wherein the water washing time is 1-2min and the temperature is 70 ℃.
8. The method for preparing a high-flux reverse osmosis composite membrane according to claim 1 or 2, wherein the polyamide desalination layer has a thickness of 20-100nm.
9. The method for preparing a high-flux reverse osmosis composite membrane according to claim 8, wherein the polyamide desalination layer has a thickness of 30-60nm.
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