CN108654399A - A kind of preparation method of high-flux composite reverse osmosis membrane - Google Patents
A kind of preparation method of high-flux composite reverse osmosis membrane Download PDFInfo
- Publication number
- CN108654399A CN108654399A CN201810506390.8A CN201810506390A CN108654399A CN 108654399 A CN108654399 A CN 108654399A CN 201810506390 A CN201810506390 A CN 201810506390A CN 108654399 A CN108654399 A CN 108654399A
- Authority
- CN
- China
- Prior art keywords
- reverse osmosis
- osmosis membrane
- membrane
- open support
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 68
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 27
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 26
- 210000004379 membrane Anatomy 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000009835 boiling Methods 0.000 claims abstract description 17
- 239000012071 phase Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000008346 aqueous phase Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003368 amide group Chemical group 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- -1 o-phthaloyl chloride Chemical compound 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 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
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 claims description 2
- 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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 238000007765 extrusion coating Methods 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 2
- 239000005711 Benzoic acid Substances 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000002346 layers by function Substances 0.000 abstract description 5
- 230000018044 dehydration Effects 0.000 abstract description 3
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000010148 water-pollination Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 230000004907 flux Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of preparation methods of high-flux composite reverse osmosis membrane, include the following steps：Open support basement membrane is contacted with the aqueous phase solution of the compound containing two or more amidos；2) the extra aqueous phase solution of the open support membrane surface after aqueous phase solution infiltrates is removed；3) pass through step 2) treated that open support basement membrane is contacted with the oil-phase solution of the compound containing two or more acid chloride groups；4) in the aqueous solution of the certain density high boiling hydrophilic organic molecule of diaphragm backside coating by step 3) processing；5) it is heat-treated and the complex reverse osmosis membrane is made.The present invention is after the formation of complex reverse osmosis membrane dense functional layer; before heat treatment; in the aqueous solution of the high boiling hydrophily organic molecule of the backside coating of complex reverse osmosis membrane; the pore structure of basement membrane will not be shunk and collapse because of dehydration in composite film heat processing procedure in protection composite membrane, and the complex reverse osmosis membrane prepared according to this has high-throughput and high rejection.
Description
Technical field
The present invention relates to membrane separation techniques, furtherly, are related to a kind of preparation method of high-flux composite reverse osmosis membrane.
Background technology
Compound reverse osmosis technology, application is very extensive, including seawater and brackish water desalination, water softening, at industrial wastewater
Prepared by reason, ultra-pure water, the wide range of areas such as household water-purifying machine.Complex reverse osmosis membrane is the core of compound reverse osmosis technology, compound anti-
The performance of permeable membrane directly influences production cost and application range.
The technical process of complex reverse osmosis membrane is described in United States Patent (USP) US4277344A, i.e., is first coated in polysulfones
The micropore counterdie formed by phase inversion on polyester non-woven fabric, is immersed in diamines or polyamines aqueous solution, then drenched by wind,
The methods of roll-in shows extra amine aqueous solution except striping, then is immersed in the chloride compounds containing two or more acid chloride groups
Interface polymerization reaction occurs with acyl chlorides in organic non-polar solution, to form the fine and close polyamides with separation function on surface
Amine ultra-thin separating layer after film forming, then carries out heat cure, washing and post-processing, prepares our required complex reverse osmosis membranes.
Wherein, it is the development trend of membrane for water treatment to prepare while having the high-throughput complex reverse osmosis membrane with high rejection
It is growth requirement.It is attempted by different research, it has been found that increase the method for water flux mainly by compound reverse osmosis
Thickness, density, hydrophily, roughness and surface charge of desalination functional layer etc. is controlled in film film forming procedure to realize.Such as China
In patent CN105080352B, the aqueous solution soaking support membrane of the solvent by can dissolve open support basement membrane material, to support
Basement membrane is handled, to prepare high-flux composite reverse osmosis membrane.In order to increase the hydrophily of complex reverse osmosis membrane, people attempt will
With hydrophilic group such as sulfonic group, carboxyl or other hydrophilic polymers are introduced into aromatic polyamides.In interfacial polymerization
The method that different additives is introduced in step is also attempted, by the way that camphor tree is added in water phase in Chinese patent CN101569836B
Brain sulfonic acid, water-soluble additives, surfactant realize the promotion of complex reverse osmosis membrane flux and salt-stopping rate.And in an another piece
In state patent CN103111191B, the flux of complex reverse osmosis membrane is improved by adding plasticizer into oil phase.In addition also have
By the post-processing to reverse osmosis membrane to increase flux and salt-stopping rate.
In addition, in the heat treatment process of reverse osmosis composite membrane composite membrane-forming, due to the loss of hydrone in basement membrane hole, make
It collapses, shrink at basement membrane hole, seriously reduce the water permeability of entire complex reverse osmosis membrane, therefore plug-hole is added in the water phase of amine
Agent becomes required.It is right in heat treatment process to realize by the way that amine salt is added in water phase first such as United States Patent (USP) US4872984A
The protection in basement membrane hole improves the water flux of composite membrane.The present invention does not heat after complex reverse osmosis membrane forms dense functional layer
Before solidification, in the aqueous solution of the certain density higher boiling organic molecule of composite membrane backside coating, higher boiling organic molecule is compound
Still stayed in hole in the heat treatment process of film forming, protect the pore structure of basement membrane in composite membrane in composite membrane heating process not
It can shrink and collapse because of dehydration, the complex reverse osmosis membrane prepared according to this has high-throughput and high rejection.
Invention content
To solve the problem in the prior art, the present invention provides a kind of preparation sides of high-flux composite reverse osmosis membrane
Method.Open support basement membrane by the compound containing two or more amidos and is contained into two or more acid chloride groups
Chloride compounds interfacial polymerization formed dense functional layer, by the complex reverse osmosis membrane back side preliminarily formed apply last layer protection
Liquid, the protection liquid are the aqueous solution of high boiling hydrophilic organic molecule, and the complex reverse osmosis membrane of coating protection liquid is added
Heat treatment obtains high-throughput and high rejection complex reverse osmosis membrane.
Technical scheme is as follows for lifting implementation：A kind of preparation method of high-flux composite reverse osmosis membrane, feature
It is：Include the following steps：
1) open support basement membrane is contacted with the aqueous phase solution of the compound containing two or more amidos；
2) the extra aqueous phase solution of the open support membrane surface after aqueous phase solution infiltrates is removed；
3) pass through step 2) treated open support basement membrane and the compound containing two or more acid chloride groups
Oil-phase solution contacts；
4) in the water-soluble of the certain density high boiling hydrophilic organic molecule of diaphragm backside coating by step 3) processing
Liquid；
5) complex reverse osmosis membrane is made in heating and drying processing.
The open support basement membrane is polysulfone porous support basement membrane, sulfonated polysulfone open support basement membrane, the porous branch of polyether sulfone
One kind in support group film, sulfonated polyether sulfone open support basement membrane；
The compound containing two or more amidos is m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, 1,3,5-
Three amido benzene, 1,2,4- tri- amido benzene, 3,5- diamines yl benzoic acid 2,4- toluenediamines, 2,4-, bis- amido methyl phenyl ethers anisoles, Ah meter
At least one of phenol；
It is described containing two or more acid chloride groups be paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride,
At least one of biphenyl dimethyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride；
The organic solvent of the oil-phase solution is n-hexane, hexamethylene, trifluorotrichloroethane, normal heptane, normal octane, first
One or more of benzene, ethylbenzene, ISOPAR solvents.
The aqueous solution of high boiling hydrophilic organic molecule described in step 4) is glycerine, polyvinyl alcohol (PVA), polyethylene glycol
(PEG), the aqueous solutions of polyethylene pyrrole network alkanone (PVP), the one or more of polyacrylic acid (PAA), polyethylene glycol oxide (PEO).
The coating method includes spraying, blade coating, slot coated, Extrusion Coating and dip-coating.
The mass fraction of the compound containing two or more amidos is 0.1-5%；
The mass fraction of the compound containing two or more acid chloride groups is 0.1-3% in the oil-phase solution；
The mass fraction of the aqueous solution of the high boiling hydrophilic organic molecule is 0.1-20%；
Time of contact in the step 1) and step 3) is 10-150 seconds.
Step 5) the heat treatment is 1-10 minutes dry at 30-120 DEG C.
Beneficial effects of the present invention：The present invention is after complex reverse osmosis membrane forms dense functional layer, before not being heating and curing,
The aqueous solution of the certain density higher boiling organic molecule of composite membrane backside coating, higher boiling organic molecule is at the warm of composite membrane-forming
It is still stayed in hole during reason, protects the pore structure of basement membrane in composite membrane will not be because of during composite membrane is heating and drying
Dehydration and shrink and collapse, the complex reverse osmosis membrane prepared according to this has high-throughput and high rejection.
Specific implementation mode
The present invention is illustrated with reference to embodiment.
Examples 1 to 3：
In this group of embodiment, the aqueous solution using the high boiling hydrophilic organic molecule of various concentration is listed to porous branch
Support group film handle the test performance of obtained reverse osmosis membrane.In this group of embodiment, before complex reverse osmosis membrane is heating and curing,
The concentration of polymer solution handled compound back of the membrane is 10%, and preparation method is that the reagent selected by accurate measure is placed in appearance
Then deionized water is added to scale in measuring bottle.Specially 1~embodiment of embodiment 3 selects glycerine respectively, polyethylene glycol (PEG),
The solution that the mass concentration that polyacrylic acid (PAA) is configured to is 10%.The solution prepared is put into watering can preserves (22 at room temperature
℃)。
It is using homemade polysulfone porous support membrane, this membrane surface is molten for 3% m-phenylene diamine (MPD) water phase with mass concentration
Liquid wetting contact 60 seconds after outwelling extra aqueous phase solution later, is done film surface roller with clean rubber rollers.Then by film and quality
The hexane solution front face of a concentration of 0.15% pyromellitic trimethylsilyl chloride 20 seconds, removes extra oil-phase solution, then uses
The aqueous solution of macromolecular is uniformly sprayed to compound back of the membrane by watering can.Composite membrane is placed in 110 DEG C of baking oven again and handles 3min,
Then it is rinsed 10 minutes in 25 DEG C of water, obtains complex reverse osmosis membrane, the complex reverse osmosis membrane prepared is stored in deionization
In water.
Reference examples
Its operating method of reference examples is removed with step and does not spray the water-soluble of high boiling hydrophilic organic molecule at the composite membrane back side
It is same as Example 1 outside liquid, i.e., the step of directly carrying out contacting water phase and oil phase successively to open support basement membrane, and in water
Flux also uses identical condition with the experiment of salt-stopping rate test with embodiment 1.Test result is shown in Table 1.
Reverse osmosis membrane made from Examples 1 to 3 and reference examples is subjected to reverse osmosis operation experiments, tests corresponding retention
Rate and water flux.
The present invention test condition be：The sodium chloride solution of a concentration of 200ppm, operating pressure 0.6Mpa, operation temperature are
25℃。
Table 1
| Higher boiling organic molecule solution and its mass concentration | Water flux (L/m2*h) | Rejection (%) | |
| Embodiment 1 | 10% glycerine | 25.3 | 99.0 |
| Embodiment 2 | 10% polyethylene glycol | 28.1 | 98.0 |
| Embodiment 3 | 10% polyacrylic acid | 25.1 | 98.5 |
| Reference examples | Nothing | 16.5 | 97.0 |
Wherein, water flux (F, L/m2* it h) is defined as at certain temperature and operating pressure, is penetrated in the unit interval (t)
The water volume (V) of per membrane area (S), calculation formula are：F=V/ (S*t).Rejection (R) be defined as in certain temperature and
Under operating pressure, the difference of salinity (Cp) in feeding liquid salinity (Cf) and permeate, then divided by feeding liquid concentration (Cf).It calculates
Formula is：R=(1-Cp/Cf) * 100%.
From the test result of table 1 show embodiment prepare by high boiling hydrophilic organic molecular solution spraying after
The complex reverse osmosis membrane of reason is under the selected test condition of experiment, and water flux has increased significantly, and salt rejection rate also has one
Fixed promotion.
Embodiment 4~6
In this group of embodiment, list using compound anti-obtained by different polyethylene glycol (PEG) concentration preprocessing solution
The test performance of permeable membrane.In this group of embodiment, selected open support basement membrane, experimental procedure and method, test condition are equal
It is identical as described in Examples 1 to 3.
Complex reverse osmosis membrane test result is shown in Table 2：
Table 2
| Polyethylene glycol | Water flux (L/m2*h) | Rejection (%) | |
| Embodiment 4 | 2% | 20.3 | 97.2 |
| Embodiment 5 | 5% | 27.5 | 97.5 |
| Embodiment 1 | 10% | 28.1 | 98.0 |
| Embodiment 6 | 15% | 28.3 | 97.3 |
| Embodiment 7 | 20% | 28.4 | 97.1 |
| Reference examples | Nothing | 16.5 | 97.0 |
Show from the test result of table 2 using compound reverse osmosis prepared after the PEG aqueous solutions processing basement membrane of various concentration
The water flux of permeable membrane increases than reference examples, while the salt-stopping rate of film is also improved than reference examples, is specifically using a concentration of 10%
PEG treatment fluids when reach highest numerical value.
The above embodiments are only a part of the embodiment of the present invention, and do not limit the embodiments.For affiliated
For the those of ordinary skill in field, the variation of other different forms or variation that can be made based on the present invention.Here it is not necessarily to
All embodiments can not be exhaustive.And the obvious changes or variations thus amplified are still in the present invention's
In protection domain.
Claims (7)
1. a kind of preparation method of high-flux composite reverse osmosis membrane, it is characterised in that：Include the following steps：
1) open support basement membrane is contacted with the aqueous phase solution of the compound containing two or more amidos；
2) the extra aqueous phase solution of the open support membrane surface after aqueous phase solution infiltrates is removed；
3) pass through the oil phase of step 2) treated open support basement membrane and the compound containing two or more acid chloride groups
Solution contacts；
4) in the aqueous solution of the certain density high boiling hydrophilic organic molecule of diaphragm backside coating by step 3) processing；
5) it is heat-treated and the complex reverse osmosis membrane is made.
2. a kind of preparation method of high-flux composite reverse osmosis membrane according to claim 1, it is characterised in that：
The open support basement membrane is polysulfone porous support basement membrane, sulfonated polysulfone open support basement membrane, polyether sulfone open support base
One kind in film, sulfonated polyether sulfone open support basement membrane；
The compound containing two or more amidos is m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, 1,3,5- triamines
Base benzene, 1,2,4- tri- amido benzene, 3,5- diamines yl benzoic acid 2, in 4- toluenediamines, 2,4-, bis- amido methyl phenyl ethers anisoles, amidol
At least one；
It is described containing two or more acid chloride groups be paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl
At least one of dimethyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride；
The organic solvent of the oil-phase solution is n-hexane, hexamethylene, trifluorotrichloroethane, normal heptane, normal octane, toluene, second
One or more of benzene, ISOPAR solvents.
3. a kind of preparation method of high-flux composite reverse osmosis membrane according to claim 1, it is characterised in that：Institute in step 4)
The aqueous solution for stating high boiling hydrophilic organic molecule is glycerine, polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyethylene pyrrole network alkane
One or more of aqueous solutions of ketone (PVP), polyacrylic acid (PAA), polyethylene glycol oxide (PEO).
4. a kind of preparation method of high-flux composite reverse osmosis membrane according to claim 1, it is characterised in that：The coating side
Formula includes spraying, blade coating, slot coated, Extrusion Coating and dip-coating.
5. a kind of preparation method of high-flux composite reverse osmosis membrane according to claim 1, it is characterised in that：Containing there are two or
The mass fraction of the compound of more than two amidos is 0.1-5%；
The compound quality score containing two or more acid chloride groups is 0.1-3% in the oil-phase solution；
The mass fraction of the aqueous solution of the high boiling hydrophilic organic molecule is 0.1-20%.
6. a kind of preparation method of high-flux composite reverse osmosis membrane according to claim 1, it is characterised in that：The step 1)
It it is 10-150 seconds with the time of contact in step 3).
7. a kind of preparation method of high-flux composite reverse osmosis membrane according to claim 1, it is characterised in that：The step 5)
Heat treatment process is 1-10 minutes dry at 30-120 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810506390.8A CN108654399A (en) | 2018-05-16 | 2018-05-16 | A kind of preparation method of high-flux composite reverse osmosis membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810506390.8A CN108654399A (en) | 2018-05-16 | 2018-05-16 | A kind of preparation method of high-flux composite reverse osmosis membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108654399A true CN108654399A (en) | 2018-10-16 |
Family
ID=63776470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810506390.8A Pending CN108654399A (en) | 2018-05-16 | 2018-05-16 | A kind of preparation method of high-flux composite reverse osmosis membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108654399A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1451465A (en) * | 2002-04-12 | 2003-10-29 | 四川大学 | Method for making composite membrane for separation of polymer fluid |
| CN103071404A (en) * | 2013-01-28 | 2013-05-01 | 中国科学院化学研究所 | Composite reverse osmosis membrane and preparation method thereof |
| CN104667759A (en) * | 2013-11-29 | 2015-06-03 | 贵阳时代沃顿科技有限公司 | Preparation method of high-throughput anti-pollution composite nanofiltration membrane |
| CN105561801A (en) * | 2015-12-19 | 2016-05-11 | 杭州水处理技术研究开发中心有限公司 | Preparation method of high-performance reverse-osmosis anti-pollution film |
-
2018
- 2018-05-16 CN CN201810506390.8A patent/CN108654399A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1451465A (en) * | 2002-04-12 | 2003-10-29 | 四川大学 | Method for making composite membrane for separation of polymer fluid |
| CN103071404A (en) * | 2013-01-28 | 2013-05-01 | 中国科学院化学研究所 | Composite reverse osmosis membrane and preparation method thereof |
| CN104667759A (en) * | 2013-11-29 | 2015-06-03 | 贵阳时代沃顿科技有限公司 | Preparation method of high-throughput anti-pollution composite nanofiltration membrane |
| CN105561801A (en) * | 2015-12-19 | 2016-05-11 | 杭州水处理技术研究开发中心有限公司 | Preparation method of high-performance reverse-osmosis anti-pollution film |
Non-Patent Citations (1)
| Title |
|---|
| 岳鑫业;林泽;陈可可;潘巧明;: "聚酰胺反渗透干膜的研究" * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108671755A (en) | A kind of preparation method of complex reverse osmosis membrane | |
| JP4936438B2 (en) | Method for producing dry composite semipermeable membrane | |
| CN105080352B (en) | A kind of complex reverse osmosis membrane and preparation method | |
| EP2857088B1 (en) | Method for manufacturing a reverse osmosis membrane | |
| JP2008093544A (en) | Composite semipermeable membrane and manufacturing method thereof | |
| EP2883600B1 (en) | Manufacturing of polyamide-based water-treatment separation membrane | |
| CN109304106B (en) | Janus forward osmosis membrane and preparation method and application thereof | |
| CN108636118A (en) | A kind of preparation method of complex reverse osmosis membrane | |
| CN109453674A (en) | The preparation method of ultra-thin composite membrane | |
| CN106310972A (en) | Hollow fiber nanofiltration membrane and preparation method thereof | |
| CN106621849B (en) | Polyamide hollow fiber nanofiltration membrane and preparation method | |
| CN104289116A (en) | Composite reverse osmosis membrane and preparation method thereof | |
| CN107486041B (en) | Ultra-low pressure composite reverse osmosis membrane and preparation method thereof | |
| KR20090127186A (en) | Manufacturing method of composite semipermeable membrane | |
| JP2006102594A (en) | Method for manufacturing composite semipermeable membrane | |
| Lang et al. | Preparation and testing of polyvinyl alcohol composite membranes for reverse osmosis | |
| CN108654399A (en) | A kind of preparation method of high-flux composite reverse osmosis membrane | |
| KR101779889B1 (en) | Composite membrane comprising polyamide coating layer and preparation method thereof | |
| KR102072877B1 (en) | Method for manufacturing water-treatment membrane, water-treatment membrane manufactured by thereof, and water treatment module comprising membrane | |
| CN106621829A (en) | Composite reverse osmosis membrane preparation method and composite reverse osmosis membrane | |
| CN111036094B (en) | Chlorine-resistant composite reverse osmosis membrane, and preparation method and application thereof | |
| CN102210982B (en) | Method for preparing polyamide reverse osmosis composite membrane | |
| CN102188915A (en) | Method for optimizing property of polyamide composite membrane | |
| KR102041657B1 (en) | Method for manufacturing water-treatment membrane, water-treatment membrane manufactured by thereof, and water treatment module comprising membrane | |
| CN112642303A (en) | Composite reverse osmosis membrane and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181016 |