CN108452684A - A kind of metal organic frame reverse osmosis membrane and preparation method thereof - Google Patents
A kind of metal organic frame reverse osmosis membrane and preparation method thereof Download PDFInfo
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- CN108452684A CN108452684A CN201810231771.XA CN201810231771A CN108452684A CN 108452684 A CN108452684 A CN 108452684A CN 201810231771 A CN201810231771 A CN 201810231771A CN 108452684 A CN108452684 A CN 108452684A
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- metal organic
- organic frame
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- 239000012528 membrane Substances 0.000 title claims abstract description 76
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 65
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 61
- 239000002184 metal Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000010410 layer Substances 0.000 claims abstract description 82
- 239000002346 layers by function Substances 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 200
- 239000000243 solution Substances 0.000 claims description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 72
- 239000012071 phase Substances 0.000 claims description 41
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 33
- 239000008346 aqueous phase Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 24
- 238000010612 desalination reaction Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- 238000002604 ultrasonography Methods 0.000 claims description 20
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 19
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 19
- 239000002086 nanomaterial Substances 0.000 claims description 19
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 19
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 19
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 239000004745 nonwoven fabric Substances 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 230000001112 coagulating effect Effects 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 claims description 7
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical group [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 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 5
- 230000008569 process Effects 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 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 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- -1 ether sulfone Chemical class 0.000 claims description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 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 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000002159 nanocrystal Substances 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000013049 sediment Substances 0.000 claims 1
- 239000013535 sea water Substances 0.000 abstract description 23
- 238000005265 energy consumption Methods 0.000 abstract description 16
- 230000004907 flux Effects 0.000 abstract description 13
- 150000003839 salts Chemical class 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 235000011187 glycerol Nutrition 0.000 description 15
- 239000007788 liquid Substances 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229920006393 polyether sulfone Polymers 0.000 description 5
- 230000002000 scavenging effect Effects 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 239000002090 nanochannel Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 102000010637 Aquaporins Human genes 0.000 description 1
- 108010063290 Aquaporins Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004941 mixed matrix membrane Substances 0.000 description 1
- 238000000877 multi-layer micromoulding Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009711 regulatory function Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FZGRPBJBMUNMQH-UHFFFAOYSA-N trimethyl-$l^{3}-chlorane Chemical compound CCl(C)C FZGRPBJBMUNMQH-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- 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
- B01D69/107—Organic support material
-
- 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
- B01D69/107—Organic support material
- B01D69/1071—Woven, non-woven or net mesh
-
- 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
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- 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
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
- B01D71/441—Polyvinylpyrrolidone
-
- 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
-
- 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
-
- 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 present invention relates to reverse osmosis membrane technical field of modification, especially a kind of metal organic frame reverse osmosis membrane and preparation method thereof, metal organic frame and polymers function layer are combined by the present invention, pass through the preparation processes such as polymeric support layer, metal organic frame nano-particle, seawater film functional layer, and adjust the technological parameter in preparation process, can be obtained a kind of reverse osmosis membrane thickness 100nm or so high-throughput low energy consumption seawater film.The presence of metal organic frame is not only that functional layer provides a large amount of hydrogen bond, and can also carry out crosslinking condensation with the amino to dissociate in functional layer and polymerize, to improve the crosslinking degree of reverse osmosis membrane.The seawater reverse osmosis membrane has thinner diaphragm thickness, and cost of manufacture is greatly saved, it is often more important that, membrane flux can be greatly improved under the premise of not influencing salt rejection rate to reduce the operation energy consumption of seawater film, be a kind of low energy consumption seawater film of superior performance.
Description
Technical field
The present invention relates to reverse osmosis membrane technical field of modification, especially a kind of metal organic frame reverse osmosis membrane and its preparation
Method.
Background technology
Water is that Source of life, the even more mankind and animals and plants are depended on for existence conditio sune qua non.Seawater and hardship are salty on the earth
Water occupies 97.4% of global total water or more, how to desalinize seawater as the most direct effective hand of water resource shortage is solved
Section.Currently, desalination technology in the world is broadly divided into Re Fa and embrane method, hot method includes mainly multistage flash distillation (MSF), multiple-effect
Distill (MED) and gas phase compression distillation (VCD)；Embrane method mainly has reverse osmosis (RO) and nanofiltration (NF).Wherein Membrane seawater desalination
Technology especially seawater reverse osmosis membrane desalination technology is at low cost, performance is stable, provides high-quality water under the conditions of low energy consumption
The advantages that be referred to as " green " pure water making system, occupied Global Seawater desalination market 60% or so, but its height operation pressure
The high energy consumption issues that power is brought so that always sea water desalination cost is high, and perplex the bottleneck of embrane method popularization and application.
The cost of sea water desalination is down to 1/5th by sea-water reverse osmose embrane method, but energy saving is that the whole world follows up always
Eternal topic, how to reduce embrane method cost is always the direction that numerous scientific and technical personnel make great efforts, due to taking of consuming of energy consumption in embrane method
With the 50-60% for accounting for total cost, therefore, how to reduce the energy consumption of seawater embrane method becomes the breach of cost-effective most critical
(Zarzo et al.,Desalination,2018,427,1-9).For example, the membrane component for developing larger diameter realizes million
Tonne mega project；Feed water by reverse osmosis is carried out by the devices such as the reverse osmosis combination of nanofiltration-or electrodialysis-reverse osmosis combination pre-
Processing；It will be the effective ways for reducing seawater cost to prepare energy recycle device etc. all.
Core of the reverse osmosis membrane as sea water desalination embrane method, energy consumption will be substantially reduced by promoting the flux of film.It is reported that if
The flux of reverse osmosis membrane is improved to more than the three times of existing PA membrane, then can reduce by 44% pressure vessel to reduce
Desalination energy consumption (David et al., the Energy Environ.Sci., 2014,7,1134- of 15% seawater reverse osmosis membrane
1141).Therefore, the flux that diaphragm how is improved in the case where ensureing effluent characteristics, by high yield water and the organic knot of low energy consumption
It closes, is always the target that global polyamide composite reverse osmosis membrane worker pursues, many companies also develop numerous low pressure in succession
The reverse osmosis membrane product of low energy consumption.But all the time, the flux of diaphragm and salt rejection rate are usually shifting, it is difficult to it is satisfactory to both parties, because
This how to be greatly improved under the premise of ensureing effluent characteristics membrane flux have been a hot spot of research (Park et al.,
Science,2017,356,1137).Therefore, advanced membrane material is also developing always in improvement, for example prepares containing aquaporin
The modification of the materials such as albumen, Nano-size Porous Graphite alkene, covalent triazine frame, molybdenum dioxide, Porous-Organic cage, zeolite nanometer sheet is anti-
Permeable membrane material (CN105457494, CN102438736, Alireza et al., J Membr.Sci., 2017,531,59-
67), on the one hand prepare thinner polyamide reverse osmose membrane functional layer, make its pore structure arrangement it is more regular, on the other hand certain
Reverse osmosis membrane after a little material modifications can provide size controllable intake tunnel.Therefore, how to the material of reverse osmosis membrane into
Row improves, and then optimizes performance by regulatory function layer structure so that maintains to greatly improve while equipment with high desalinization reverse osmosis
The flux of film is current preparation low pressure low energy consumption reverse osmosis membrane field one of major issue urgently to be resolved hurrily.
Invention content
In order to solve the problems, such as seawater embrane method high energy consumption, the present invention is intended to provide a kind of high throughput low energy consumption sea water desalination is anti-
Permeable membrane and its preparation method.Advanced mixed-matrix can be obtained in blended cross linking metal-organic framework material in reverse osmosis membrane functional layer
On the one hand film (MMMs), the introduction of the material improve the thermal stability and mechanical performance of film, the controllable size of another aspect
Metal organic frame nanochannel provides selective intake tunnel, which on the one hand can shape
Increase the hydrophily of film surface at a large amount of hydrogen bonds, on the other hand its intrinsic carboxylate radical can be formed with acyl chlorides progress condensation polymerization
Covalent bond increases the degree of cross linking of film functional layer, therefore the introducing of the material can significantly carry under conditions of not losing film salt rejection rate
The flux of high film.In addition, this patent prepares thinner seawater film by controlling process conditions, and it is on the one hand cost-effective, it is another
Aspect also improves the water flux of film.It has the system energy consumption caused by flux is low of the reverse osmosis membrane in the solution prior art
The feature of high technical problem.
It is achieved especially by following technical scheme：
A kind of metal organic frame reverse osmosis membrane, which is characterized in that supporting layer is closed by polymer and active hydrophilic stabilizer
At aqueous phase solution includes catalyst and aqueous phase monomers, and oil-phase solution includes metal organic frame nano material and oil phase monomer, position
It is that interface polymerization reaction of the supporting layer through aqueous phase solution, oil-phase solution is formed with crosslinking nano crystalline substance in the desalination layer on supporting layer
The functional layer of volume grid structure.
The polymer is one kind in polysulfones or polyether sulfone, in the solution for preparing supporting layer a concentration of 16wt%~
20wt%.
The active hydrophilic stabilizer is polyvinylpyrrolidone, a concentration of in the solution for preparing supporting layer
0.15wt%~5wt%.
The solution for preparing supporting layer, solvent are n,N-Dimethylformamide (DMF), polymer and active hydrophilic
The remainder of stabilizer is supplemented to 100wt% by N,N-dimethylformamide (DMF).
The catalyst is the mixture of phase transfer catalyst and acid binding agent；Wherein, phase transfer catalyst is the tetrabutyl
One of which in ammonium chloride, triethylamine hydrochloride, benzyltriethylammoinium chloride, dodecyl trimethyl ammonium chloride, in water phase
A concentration of 0.5wt%~5.0wt% in solution；Acid binding agent is triethylamine, a concentration of 0.5wt% in aqueous phase solution~
5.0wt%.
The aqueous phase monomers are m-phenylene diamine (MPD), a concentration of 0.5wt%~5.0wt% in aqueous phase solution.
The metal organic frame nano material is made of silver ion and trimesic acid, mass ratio 1:1, activity
Functional group is carboxyl, a concentration of 0.02wt%~0.1wt% in oil-phase solution.
The oil phase monomer is o-phthaloyl chloride, paraphthaloyl chloride, m-phthaloyl chloride, 4,4'- biphenyl diformazans
One kind in acyl chlorides, pyromellitic trimethylsilyl chloride, a concentration of 0.005wt%~3wt% in oil-phase solution.
The oil-phase solution, solvent are n-hexane, hexamethylene, normal heptane, the one of which in Isopar G or several
Kind.
A kind of preparation method of metal organic frame reverse osmosis membrane, includes the following steps：
(1) preparation of metal organic frame：According to mass ratio it is 1 by silver nitrate and N,N-dimethylformamide (DMF):38
Ultrasonic disperse 10min is carried out, trimesic acid is 1 according to mass ratio with n,N-Dimethylformamide (DMF):38 carry out ultrasound point
10min is dissipated, the two mixes ultrasound 1h, centrifuges and filter, mixture (the V water of obtained solid object water and ethyl alcohol:V ethyl alcohol
=1:1) rinse 3~5 times, at 60 DEG C it is dry for 24 hours, gained metal organic frame nano material retain in vacuum desiccator to
It uses；
(2) preparation of supporting layer：By the polyvinylpyrrolidone and N,N-dimethylformamide of 0.15wt%~5wt%
(DMF) carry out mixing dispersion, and use mixing speed for 60-90r/min stir process so that polyvinylpyrrolidone in N,
It is uniformly dispersed in dinethylformamide (DMF) solution, mixing speed is maintained to be warming up to 90 DEG C, mass concentration is added thereto is
The polymer of 16wt%~20wt%, remainder are supplemented to 100% by n,N-Dimethylformamide (DMF), obtain preparing branch
The solution of layer is supportted, then is filtered after carrying out vacuum defoamation processing at -80kPa, is cooled to room temperature, by the solution coating in non-woven fabrics
On base material and enter coagulating bath, places it in deionized water after handling 200s, obtain supporting layer；
(3) preparation of desalination layer：The supporting layer prepared in step (2) is impregnated into 30min in deionized water, from go from
Take out supporting layer in sub- water, and with contain 0.5wt%~5wt% m-phenylene diamine (MPD)s, 0.5wt%~5wt% triethylamines, 0.5wt%
The aqueous phase solution of~5wt% phase transfer catalysts contacts 40s~60s, and aqueous phase solution is made to penetrate into inside supporting layer hole；It was filtered dry
The aqueous phase droplets of the aqueous solution of amount, membrane surface are removed with rubber rollers are rolled；Diaphragm is immersed and contains 0.02wt%~0.1wt%
Metal organic frame nano material, 0.005wt%~3wt% o-phthaloyl chlorides, paraphthaloyl chloride, m-phthaloyl chloride,
Biphenyl dimethyl chloride, pyromellitic trimethylsilyl chloride oil-phase solution 30s~60s after, take out diaphragm clean 5min with dilute hydrochloric acid, in glycerine
5min is infiltrated in aqueous solution, be put into 30 DEG C~90 DEG C baking ovens dry to get.
The step (3), supporting layer liquid compatible with water, oil-phase solution preparation ratio be 100g：4~6L：4~6L.
The ultrasound, power 24kHz, output and pulse are respectively 80w and 0.6.
The oven temperature is 30 DEG C~90 DEG C, preferably 80 DEG C.
The coagulating bath is N,N-dimethylformamide (DMF) aqueous solution that mass fraction is 1.0%.
The mass concentration of the dilute hydrochloric acid, hydrogen chloride is 2%.
The mass concentration of the glycerine water solution, glycerine is 8%.
Compared with prior art, the present invention has the following advantages：
The speed that phase transfer catalyst improves polymerisation is added in the present invention in water phase, makes the polyamide reverse osmosis of preparation
Permeable membrane has more regular, finer and close hole, it is often more important that is added to metal organic frame nano material in oil phase, prepares
Reverse osmosis membrane it is thinner, additionally provide additional intake tunnel, the nanochannel of controllable size will not influence the desalination of film
Rate.Generally speaking, the method for the nano-material modified polyamide seawater film functional layer of this metal organic frame is not influencing seawater
The flux of film, and easy to operate and low manufacture cost are greatly improved under the premise of film salt rejection rate.In addition, being prepared by adjusting
Technological parameter in the process, and metal organic frame and polymers function layer are combined, the presence of metal organic frame
It is not only that functional layer provides a large amount of hydrogen bond, and can also carry out crosslinking condensation with the amino to dissociate in functional layer and polymerize to be formed
Covalent bond, the reverse osmosis membrane thickness of manufacture is in 100nm or so.
Specific implementation mode
Further solution is made to the technical solution of the invention with reference to specific embodiment and experimental example
It releases and illustrates, in order to which those skilled in the art fully understand the invention, but the explanation and illustration, it is not to this
The further restriction of innovation and creation technical solution, on the basis of the innovation and creation, the replacement for the simple numerical value made and
The improved technical solution of general adjustment, belongs to the protection domain of the invention.
Supplementary explanation：
The mass percent of polysulfones, polyether sulfone, polyvinylpyrrolidone in this specification is prepare supporting layer molten
Mass percent in liquid.
Tetrabutylammonium chloride, triethylamine hydrochloride, benzyltriethylammoinium chloride, trimethyl chlorine in this specification
The mass percent for changing ammonium, triethylamine, m-phenylene diamine (MPD), is the mass percent in aqueous phase solution.
Metal organic frame nano material, o-phthaloyl chloride, paraphthaloyl chloride, phenyl-diformyl in this specification
The mass percent of chlorine, 4,4'- biphenyl dimethyl chloride, pyromellitic trimethylsilyl chloride, n-hexane, hexamethylene, normal heptane, Isopar G,
It is the mass percent in oil-phase solution.
Embodiment 1
A kind of preparation method of metal organic frame reverse osmosis membrane, includes the following steps：
(1) preparation of metal organic frame：According to mass ratio it is 1 by silver nitrate and N,N-dimethylformamide (DMF):38
Ultrasonic disperse 10min is carried out, trimesic acid is 1 according to mass ratio with n,N-Dimethylformamide (DMF):38 carry out ultrasound point
10min is dissipated, the two mixes ultrasound 1h, centrifuges and filter, mixture (the V water of obtained solid object water and ethyl alcohol:V ethyl alcohol
=1:1) rinse 3 times, at 60 DEG C it is dry for 24 hours, gained metal organic frame nano material retains in vacuum desiccator to making
With.
(2) preparation of supporting layer：0.15wt% polyvinylpyrrolidone and N,N-dimethylformamide (DMF) are carried out
Mixing dispersion, uses mixing speed to be stirred for 60r/min so that polyvinylpyrrolidone is in N, N- dimethyl methyls
It is uniformly dispersed in amide (DMF) solution, mixing speed is maintained to be warming up to 90 DEG C, 16wt% polysulfones, remainder are added thereto
100wt% is supplemented to by n,N-Dimethylformamide (DMF), obtains the solution for preparing supporting layer, then carried out very at -80kPa
It filters, is cooled to room temperature after empty deaeration processing, be uniformly coated on non-woven fabrics base material and entered in coagulating bath using doctor blade system,
Coagulating bath is the DMF aqueous solutions that mass fraction is 1.0%, and temperature is 20 DEG C；By the solution coating on non-woven fabrics base material, by it
It is placed in deionized water, adjustment temperature is 20 DEG C, after handling 200s, obtains supporting layer.
(3) preparation of desalination layer：The supporting layer prepared in step (2) is impregnated into 30min in deionized water, from go from
Take out supporting layer in sub- water, and with contain 0.5wt% m-phenylene diamine (MPD)s, 0.5wt% triethylamines, 0.5wt% tetrabutylammonium chlorides
Aqueous phase solution contacts 40s, and aqueous phase solution is made to penetrate into inside supporting layer hole；It is filtered dry excessive aqueous solution, the water phase of membrane surface
Drop is removed with rubber rollers are rolled；Diaphragm is immersed using Isopar G as solvent and contains 0.02wt% metal organic frame nanometers
Material, 0.005wt% o-phthaloyl chlorides oil-phase solution 30s after, take out diaphragm carried out at cleaning with the dilute hydrochloric acid of 2.0wt%
Reason, scavenging period 5min are subsequently placed in the glycerine water solution of 8.0wt%, glycerine temperature 60 C, infiltrating time 5min, finally,
Prepared metal organic frame reverse osmosis membrane is dried in 60 DEG C of baking ovens to get SWRO-MOFs-1 reverse osmosis membranes.
The step (3), supporting layer liquid compatible with water, oil-phase solution preparation ratio be 100g：4L：4L.
The ultrasound, power 24kHz, output and pulse are respectively 80w and 0.6.
Embodiment 2
A kind of preparation method of metal organic frame reverse osmosis membrane, includes the following steps：
(1) preparation of metal organic frame：According to mass ratio it is 1 by silver nitrate and N,N-dimethylformamide (DMF):38
Ultrasonic disperse 10min is carried out, trimesic acid is 1 according to mass ratio with n,N-Dimethylformamide (DMF):38 carry out ultrasound point
10min is dissipated, the two mixes ultrasound 1h, centrifuges and filter, mixture (the V water of obtained solid object water and ethyl alcohol:V ethyl alcohol
=1:1) rinse 4 times, at 60 DEG C it is dry for 24 hours, gained metal organic frame nano material retains in vacuum desiccator to making
With.
(2) preparation of supporting layer：1wt% polyvinylpyrrolidone and N,N-dimethylformamide (DMF) are mixed
Dispersion is closed, uses mixing speed to be stirred for 70r/min so that polyvinylpyrrolidone is in N, N- dimethyl formyls
Be uniformly dispersed in amine (DMF) solution, maintain mixing speed be warming up to 90 DEG C, thereto be added 17wt% polysulfones, remainder by
N,N-Dimethylformamide (DMF) is supplemented to 100wt%, obtains the solution for preparing supporting layer, then vacuum is carried out at -80kPa
It filters, is cooled to room temperature after deaeration processing, be uniformly coated on non-woven fabrics base material using doctor blade system and enter in coagulating bath, coagulate
Gu bath is the DMF aqueous solutions that mass fraction is 1.0%, temperature is 20 DEG C；By the solution coating on non-woven fabrics base material, set
In deionized water, adjustment temperature is 20 DEG C, after handling 200s, obtains supporting layer.
(3) preparation of desalination layer：The supporting layer prepared in step (2) is impregnated into 30min in deionized water, from go from
Take out supporting layer in sub- water, and with it is molten containing 1wt% m-phenylene diamine (MPD)s, 1wt% triethylamines, the water phase of 1wt% triethylamine hydrochlorides
Liquid contacts 45s, and aqueous phase solution is made to penetrate into inside supporting layer hole；It is filtered dry excessive aqueous solution, the aqueous phase droplets of membrane surface are used
Rubber rollers are rolled to remove；By diaphragm immerse using Isopar G as solvent, and containing 0.04wt% metal organic frames nano material,
After the oil-phase solution 40s of 0.5wt% paraphthaloyl chlorides, takes out diaphragm and started the cleaning processing with the dilute hydrochloric acid of 2.0wt%, cleaned
Time 5min, is subsequently placed in the glycerine water solution of 8.0wt%, glycerine temperature 60 C, and infiltrating time 5min is finally, prepared
Metal organic frame reverse osmosis membrane dried to get SWRO-MOFs-2 reverse osmosis membranes in 70 DEG C of baking ovens.
The step (3), supporting layer liquid compatible with water, oil-phase solution preparation ratio be 100g：4L：5L.
The ultrasound, power 24kHz, output and pulse are respectively 80w and 0.6.
Embodiment 3
A kind of preparation method of metal organic frame reverse osmosis membrane, includes the following steps：
(1) preparation of metal organic frame：According to mass ratio it is 1 by silver nitrate and N,N-dimethylformamide (DMF):38
Ultrasonic disperse 10min is carried out, trimesic acid is 1 according to mass ratio with n,N-Dimethylformamide (DMF):38 carry out ultrasound point
10min is dissipated, the two mixes ultrasound 1h, centrifuges and filter, mixture (the V water of obtained solid object water and ethyl alcohol:V ethyl alcohol
=1:1) rinse 4 times, at 60 DEG C it is dry for 24 hours, gained metal organic frame nano material retains in vacuum desiccator to making
With.
(2) preparation of supporting layer：2.5wt% polyvinylpyrrolidone and N,N-dimethylformamide (DMF) are carried out
Mixing dispersion, uses mixing speed to be stirred for 75r/min so that polyvinylpyrrolidone is in N, N- dimethyl methyls
It is uniformly dispersed in amide (DMF) solution, mixing speed is maintained to be warming up to 90 DEG C, 18wt% polyether sulfones, remainder are added thereto
Divide and 100wt% is supplemented to by n,N-Dimethylformamide (DMF), obtains the solution for preparing supporting layer, then carried out at -80kPa
It filters, is cooled to room temperature after vacuum defoamation processing, be uniformly coated on non-woven fabrics base material using doctor blade system and enter coagulating bath
In, coagulating bath is the DMF aqueous solutions that mass fraction is 1.0%, and temperature is 20 DEG C；By the solution coating on non-woven fabrics base material,
It places it in deionized water, adjustment temperature is 20 DEG C, after handling 200s, obtains supporting layer.
(3) preparation of desalination layer：The supporting layer prepared in step (2) is impregnated into 30min in deionized water, from go from
Take out supporting layer in sub- water, and with contain 2.5wt% m-phenylene diamine (MPD)s, 2.5wt% triethylamines, 2.5wt% benzyl triethyl ammonium chlorinations
The aqueous phase solution of ammonium contacts 50s, and aqueous phase solution is made to penetrate into inside supporting layer hole；It is filtered dry excessive aqueous solution, membrane surface
Aqueous phase droplets are removed with rubber rollers are rolled；Diaphragm is immersed with n-hexane, hexamethylene mass ratio 1：1 is solvent, and is contained
0.06wt% metal organic frames nano material, 1wt% m-phthaloyl chlorides oil-phase solution 45s after, take out diaphragm use
The dilute hydrochloric acid of 2.0wt% starts the cleaning processing, and scavenging period 5min is subsequently placed in the glycerine water solution of 8.0wt%, glycerine temperature
Degree 60 DEG C, infiltrating time 5min, finally, prepared metal organic frame reverse osmosis membrane dried in 75 DEG C of baking ovens to get
SWRO-MOFs-3 reverse osmosis membranes.
The step (3), supporting layer liquid compatible with water, oil-phase solution preparation ratio be 100g：5L：5L.
The ultrasound, power 24kHz, output and pulse are respectively 80w and 0.6.
Embodiment 4
A kind of preparation method of metal organic frame reverse osmosis membrane, includes the following steps：
(1) preparation of metal organic frame：According to mass ratio it is 1 by silver nitrate and N,N-dimethylformamide (DMF):38
Ultrasonic disperse 10min is carried out, trimesic acid is 1 according to mass ratio with n,N-Dimethylformamide (DMF):38 carry out ultrasound point
10min is dissipated, the two mixes ultrasound 1h, centrifuges and filter, mixture (the V water of obtained solid object water and ethyl alcohol:V ethyl alcohol
=1:1) rinse 5 times, at 60 DEG C it is dry for 24 hours, gained metal organic frame nano material retains in vacuum desiccator to making
With.
(2) preparation of supporting layer：4wt% polyvinylpyrrolidone and N,N-dimethylformamide (DMF) are mixed
Dispersion is closed, uses mixing speed to be stirred for 80r/min so that polyvinylpyrrolidone is in N, N- dimethyl formyls
It is uniformly dispersed in amine (DMF) solution, mixing speed is maintained to be warming up to 90 DEG C, 19wt% polyether sulfones, remainder are added thereto
100wt% is supplemented to by n,N-Dimethylformamide (DMF), obtains the solution for preparing supporting layer, then carried out very at -80kPa
It filters, is cooled to room temperature after empty deaeration processing, be uniformly coated on non-woven fabrics base material and entered in coagulating bath using doctor blade system,
Coagulating bath is the DMF aqueous solutions that mass fraction is 1.0%, and temperature is 20 DEG C；By the solution coating on non-woven fabrics base material, by it
It is placed in deionized water, adjustment temperature is 20 DEG C, after handling 200s, obtains supporting layer.
(3) preparation of desalination layer：The supporting layer prepared in step (2) is impregnated into 30min in deionized water, from go from
Take out supporting layer in sub- water, and with contain 4wt% m-phenylene diamine (MPD)s, 4wt% triethylamines, 4wt% dodecyl trimethyl ammonium chloride
Aqueous phase solution contact 55s, so that aqueous phase solution is penetrated into inside supporting layer hole；It is filtered dry excessive aqueous solution, the water of membrane surface
Phase drop is removed with rubber rollers are rolled；Diaphragm is immersed with hexamethylene, normal heptane mass ratio 1：1 is solvent, and contains 0.8wt%
Metal organic frame nano material, 2wt%4 after the oil-phase solution 50s of 4'- biphenyl dimethyl chlorides, take out diaphragm 2.0wt%
Dilute hydrochloric acid start the cleaning processing, scavenging period 5min is subsequently placed in the glycerine water solution of 8.0wt%, glycerine temperature 60 C,
Infiltrating time 5min, finally, prepared metal organic frame reverse osmosis membrane are dried in 80 DEG C of baking ovens to get SWRO-MOFs-
4 reverse osmosis membranes.
The step (3), supporting layer liquid compatible with water, oil-phase solution preparation ratio be 100g：6L：5L.
The ultrasound, power 24kHz, output and pulse are respectively 80w and 0.6.
Embodiment 5
A kind of preparation method of metal organic frame reverse osmosis membrane, includes the following steps：
(1) preparation of metal organic frame：According to mass ratio it is 1 by silver nitrate and N,N-dimethylformamide (DMF):38
Ultrasonic disperse 10min is carried out, trimesic acid is 1 according to mass ratio with n,N-Dimethylformamide (DMF):38 carry out ultrasound point
10min is dissipated, the two mixes ultrasound 1h, centrifuges and filter, mixture (the V water of obtained solid object water and ethyl alcohol:V ethyl alcohol
=1:1) rinse 5 times, at 60 DEG C it is dry for 24 hours, gained metal organic frame nano material retains in vacuum desiccator to making
With.
(2) preparation of supporting layer：5wt% polyvinylpyrrolidone and N,N-dimethylformamide (DMF) are mixed
Dispersion is closed, uses mixing speed to be stirred for 90r/min so that polyvinylpyrrolidone is in N, N- dimethyl formyls
It is uniformly dispersed in amine (DMF) solution, mixing speed is maintained to be warming up to 90 DEG C, 20wt% polyether sulfones, remainder are added thereto
100wt% is supplemented to by n,N-Dimethylformamide (DMF), obtains the solution for preparing supporting layer, then carried out very at -80kPa
It filters, is cooled to room temperature after empty deaeration processing, be uniformly coated on non-woven fabrics base material and entered in coagulating bath using doctor blade system,
Coagulating bath is the DMF aqueous solutions that mass fraction is 1.0%, and temperature is 20 DEG C；By the solution coating on non-woven fabrics base material, by it
It is placed in deionized water, adjustment temperature is 20 DEG C, after handling 200s, obtains supporting layer.
(3) preparation of desalination layer：The supporting layer prepared in step (2) is impregnated into 30min in deionized water, from go from
Take out supporting layer in sub- water, and with it is molten containing 5wt% m-phenylene diamine (MPD)s, 5wt% triethylamines, the water phase of 5wt% tetrabutylammonium chlorides
Liquid contacts 60s, and aqueous phase solution is made to penetrate into inside supporting layer hole；It is filtered dry excessive aqueous solution, the aqueous phase droplets of membrane surface are used
Rubber rollers are rolled to remove；Diaphragm is immersed with n-hexane, normal heptane, Isopar G mass ratioes 1：1：1 is solvent, and is contained
0.1wt% metal organic frames nano material, 3wt% pyromellitic trimethylsilyl chlorides oil-phase solution 60s after, take out diaphragm use
The dilute hydrochloric acid of 2.0wt% starts the cleaning processing, and scavenging period 5min is subsequently placed in the glycerine water solution of 8.0wt%, glycerine temperature
Degree 60 DEG C, infiltrating time 5min, finally, prepared metal organic frame reverse osmosis membrane dried in 90 DEG C of baking ovens to get
SWRO-MOFs-5 reverse osmosis membranes.
The step (3), supporting layer liquid compatible with water, oil-phase solution preparation ratio be 100g：6L：6L.
The ultrasound, power 24kHz, output and pulse are respectively 80w and 0.6.
Embodiment 6
A kind of preparation method of metal organic frame reverse osmosis membrane, includes the following steps：
(1) preparation of supporting layer：5wt% polyvinylpyrrolidone and N,N-dimethylformamide (DMF) are mixed
Dispersion is closed, uses mixing speed to be stirred for 90r/min so that polyvinylpyrrolidone is in N, N- dimethyl formyls
Be uniformly dispersed in amine (DMF) solution, maintain mixing speed be warming up to 90 DEG C, thereto be added 18wt% polysulfones, remainder by
N,N-Dimethylformamide (DMF) is supplemented to 100wt%, obtains the solution for preparing supporting layer, then vacuum is carried out at -80kPa
It filters, is cooled to room temperature after deaeration processing, be uniformly coated on non-woven fabrics base material using doctor blade system and enter in coagulating bath, coagulate
Gu bath is the DMF aqueous solutions that mass fraction is 1.0%, temperature is 20 DEG C；By the solution coating on non-woven fabrics base material, set
In deionized water, adjustment temperature is 20 DEG C, after handling 200s, obtains supporting layer.
(2) preparation of desalination layer：The supporting layer prepared in step (1) is impregnated into 30min in deionized water, from go from
Take out supporting layer in sub- water, and with the water containing 3wt% m-phenylene diamine (MPD)s, 4wt% triethylamines, 2wt% benzyltriethylammoinium chlorides
Phase solution contacts 40s, and aqueous phase solution is made to penetrate into inside supporting layer hole；It is filtered dry excessive aqueous solution, the water phase liquid of membrane surface
Drop is removed with rubber rollers are rolled；Diaphragm is immersed using Isopar G as solvent, and the oil phase containing 3wt% pyromellitic trimethylsilyl chlorides is molten
After liquid 60s, takes out diaphragm and started the cleaning processing with the dilute hydrochloric acid of 2.0wt%, scavenging period 5min is subsequently placed in 8.0wt%'s
In glycerine water solution, glycerine temperature 60 C, infiltrating time 5min, finally, prepared metal organic frame reverse osmosis membrane is 80
Drying is to get SWRO reverse osmosis membranes in DEG C baking oven.
The step (3), supporting layer liquid compatible with water, oil-phase solution preparation ratio be 100g：5L：5L.
The ultrasound, power 24kHz, output and pulse are respectively 80w and 0.6.
Test example
SWRO-MOFs-1, SWRO-MOFs-2, SWRO-MOFs-3, SWRO-MOFs-4, SWRO- of Example 1-6
MOFs-5 and SWRO is placed on the test of reverse osmosis membrane monitor station, 15min is rinsed under the pressure that operating pressure is 500psi with pure water
After switch to 32000ppm NaCl aqueous solutions as raw water, temperature control 25 DEG C, pH be 6.4~7.3, pressure 800psi
Under conditions of test reverse osmosis membrane performance after operation 30min, and record the thickness of each reverse osmosis membrane, the results are shown in Table 1.
Table 1. is modified SWRO-MOFs diaphragms and is compared with unmodified reverse osmosis membrane performance
From the point of view of the data shown by upper table 1, the present invention is logical compared with the water of the seawater desalination reverse osmosis film of prior art preparation
Amount is greatly improved, and salt rejection rate is almost unchanged, and increasing substantially for flux reduces in reverse osmosis membrane application process
Energy consumption extends the service life of reverse osmosis membrane, and the present invention reduces diaphragm flux and salt rejection rate to a certain extent
The behavior of trade-off has significant progress and essential characteristics outstanding.
Claims (10)
1. a kind of metal organic frame reverse osmosis membrane, which is characterized in that supporting layer is synthesized by polymer and active hydrophilic stabilizer,
Aqueous phase solution includes catalyst and aqueous phase monomers, and oil-phase solution includes metal organic frame nano material and oil phase monomer, is located at
Desalination layer on supporting layer is that interface polymerization reaction of the supporting layer through aqueous phase solution, oil-phase solution is formed with crosslinking nano crystal
The functional layer of network structure.
2. metal organic frame reverse osmosis membrane as described in claim 1, which is characterized in that the polymer is polysulfones or gathers
One kind in ether sulfone, a concentration of 16wt%~20wt% in the solution for preparing supporting layer.
3. metal organic frame reverse osmosis membrane as described in claim 1, which is characterized in that the active hydrophilic stabilizer is
Polyvinylpyrrolidone, a concentration of 0.15wt%~5wt% in the solution for preparing supporting layer.
4. such as Claims 2 or 3 any one of them metal organic frame reverse osmosis membrane, which is characterized in that the preparation branch
Support the solution of layer, solvent is n,N-Dimethylformamide (DMF), the remainder of polymer and active hydrophilic stabilizer by N,
Dinethylformamide (DMF) is supplemented to 100wt%.
5. metal organic frame reverse osmosis membrane as described in claim 1, which is characterized in that the catalyst is urged for phase transfer
The mixture of agent and acid binding agent；Wherein, phase transfer catalyst is tetrabutylammonium chloride, triethylamine hydrochloride, benzyl triethyl ammonium
One of which in ammonium chloride, dodecyl trimethyl ammonium chloride, a concentration of 0.5wt%~5.0wt% in aqueous phase solution；
Acid binding agent is triethylamine, a concentration of 0.5wt%~5.0wt% in aqueous phase solution.
6. metal organic frame reverse osmosis membrane as described in claim 1, which is characterized in that the aqueous phase monomers are isophthalic two
Amine, a concentration of 0.5wt%~5.0wt% in aqueous phase solution.
7. metal organic frame reverse osmosis membrane as described in claim 1, which is characterized in that the metal organic frame nanometer
Material is made of silver ion and trimesic acid, mass ratio 1:1, activity functional groups are carboxyl, in oil-phase solution
A concentration of 0.02wt%~0.1wt%.
8. metal organic frame reverse osmosis membrane as described in claim 1, which is characterized in that the oil phase monomer is adjacent benzene two
One kind in formyl chloride, paraphthaloyl chloride, m-phthaloyl chloride, 4,4'- biphenyl dimethyl chloride, pyromellitic trimethylsilyl chloride, in oil
A concentration of 0.005wt%~3wt% in phase solution.
9. metal organic frame reverse osmosis membrane as described in claim 1, which is characterized in that the oil-phase solution, solvent
For one of which in n-hexane, hexamethylene, normal heptane, Isopar G or several.
10. a kind of preparation method of metal organic frame reverse osmosis membrane, which is characterized in that include the following steps：
(1) preparation of metal organic frame：According to mass ratio it is 1 by silver nitrate and N,N-dimethylformamide (DMF):38 carry out
Ultrasonic disperse 10min, trimesic acid are 1 according to mass ratio with n,N-Dimethylformamide (DMF):38 carry out ultrasonic disperse
10min, the two mix ultrasound 1h, centrifuge and filter, mixture (the V water of gained sediment water and ethyl alcohol:V ethyl alcohol=
1:1) rinse 3~5 times, at 60 DEG C it is dry for 24 hours, gained metal organic frame nano material retains in vacuum desiccator to making
With；
(2) preparation of supporting layer：By the polyvinylpyrrolidone and N,N-dimethylformamide of 0.15wt%~5wt%
(DMF) carry out mixing dispersion, and use mixing speed for 60-90r/min stir process so that polyvinylpyrrolidone in N,
It is uniformly dispersed in dinethylformamide (DMF) solution, mixing speed is maintained to be warming up to 90 DEG C, mass concentration is added thereto is
The polymer of 16wt%~20wt%, remainder are supplemented to 100% by n,N-Dimethylformamide (DMF), obtain preparing branch
The solution of layer is supportted, then is filtered after carrying out vacuum defoamation processing at -80kPa, is cooled to room temperature, by the solution coating in non-woven fabrics
On base material and enter coagulating bath, places it in deionized water after handling 200s, obtain supporting layer；
(3) preparation of desalination layer：The supporting layer prepared in step (2) is impregnated into 30min in deionized water, from deionized water
Middle taking-up supporting layer, and with containing 0.5wt%~5wt% m-phenylene diamine (MPD)s, 0.5wt%~5wt% triethylamines, 0.5wt%~
The aqueous phase solution of 5wt% phase transfer catalysts contacts 40s~60s, and aqueous phase solution is made to penetrate into inside supporting layer hole；It is filtered dry excess
Aqueous solution, the aqueous phase droplets of membrane surface remove with rubber rollers are rolled；Diaphragm is immersed containing 0.02wt%~0.1wt% gold
Belong to organic frame nano material, 0.005wt%~3wt% o-phthaloyl chlorides, paraphthaloyl chloride, m-phthaloyl chloride, connection
Phthalyl chloride, pyromellitic trimethylsilyl chloride oil-phase solution 30s~60s after, take out diaphragm clean 5min with dilute hydrochloric acid, in glycerol liquor
5min is infiltrated in solution, be put into 30 DEG C~90 DEG C baking ovens dry to get.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126480A (en) * | 2018-09-04 | 2019-01-04 | 同济大学 | Modified forward osmosis membrane of a kind of metal organic frame nanometer sheet and its preparation method and application |
| CN109847586A (en) * | 2018-12-20 | 2019-06-07 | 时代沃顿科技有限公司 | High-flux reverse osmosis membrane and its preparation method and application |
| WO2019179082A1 (en) * | 2018-03-20 | 2019-09-26 | 时代沃顿科技有限公司 | Metal organic frame reverse osmosis membrane and preparation method therefor |
| CN111013398A (en) * | 2019-12-23 | 2020-04-17 | 同济大学 | Janus nano-channel leading nanofiltration membrane for selectively removing charged drugs and preparation method thereof |
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| WO2019179082A1 (en) * | 2018-03-20 | 2019-09-26 | 时代沃顿科技有限公司 | Metal organic frame reverse osmosis membrane and preparation method therefor |
| CN109126480A (en) * | 2018-09-04 | 2019-01-04 | 同济大学 | Modified forward osmosis membrane of a kind of metal organic frame nanometer sheet and its preparation method and application |
| CN109126480B (en) * | 2018-09-04 | 2021-06-01 | 同济大学 | Metal organic framework nanosheet modified forward osmosis membrane and preparation method and application thereof |
| CN109847586A (en) * | 2018-12-20 | 2019-06-07 | 时代沃顿科技有限公司 | High-flux reverse osmosis membrane and its preparation method and application |
| CN111013398A (en) * | 2019-12-23 | 2020-04-17 | 同济大学 | Janus nano-channel leading nanofiltration membrane for selectively removing charged drugs and preparation method thereof |
| CN113318616A (en) * | 2021-06-30 | 2021-08-31 | 西安建筑科技大学 | rGO/ZIF-8 composite nano material as middle layer modified nanofiltration membrane and preparation method thereof |
| CN113318616B (en) * | 2021-06-30 | 2022-05-31 | 西安建筑科技大学 | rGO/ZIF-8 composite nano material as middle layer modified nanofiltration membrane and preparation method thereof |
| CN113880317A (en) * | 2021-11-17 | 2022-01-04 | 青岛延晖环保科技有限公司 | Biological desalination method in seawater desalination process |
| CN115477579A (en) * | 2022-11-11 | 2022-12-16 | 吉林中科研伸科技有限公司 | Ligand for preparing metal organic framework material, film and application of film |
| CN115477579B (en) * | 2022-11-11 | 2023-02-14 | 吉林中科研伸科技有限公司 | Ligand for preparing metal organic framework material, film and application of film |
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| CN108452684B (en) | 2020-04-24 |
| WO2019179082A1 (en) | 2019-09-26 |
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