CN108325399A - A kind of preparation method of graphene polyamide reverse osmose membrane - Google Patents
A kind of preparation method of graphene polyamide reverse osmose membrane Download PDFInfo
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- CN108325399A CN108325399A CN201810031464.7A CN201810031464A CN108325399A CN 108325399 A CN108325399 A CN 108325399A CN 201810031464 A CN201810031464 A CN 201810031464A CN 108325399 A CN108325399 A CN 108325399A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 70
- 239000012528 membrane Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000004952 Polyamide Substances 0.000 title claims abstract description 22
- 229920002647 polyamide Polymers 0.000 title claims abstract description 22
- 239000008346 aqueous phase Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012071 phase Substances 0.000 claims abstract description 39
- 238000005266 casting Methods 0.000 claims abstract description 23
- 210000004379 membrane Anatomy 0.000 claims description 35
- 229920002492 poly(sulfone) Polymers 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 26
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 210000002469 basement membrane Anatomy 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 13
- 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 13
- 238000002604 ultrasonography Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005576 amination reaction Methods 0.000 claims description 12
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 12
- 238000012695 Interfacial polymerization Methods 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229940082004 sodium laurate Drugs 0.000 claims description 3
- 230000002000 scavenging effect Effects 0.000 claims description 2
- 238000001223 reverse osmosis Methods 0.000 abstract description 23
- 230000004907 flux Effects 0.000 abstract description 11
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract 1
- 150000001805 chlorine compounds Chemical class 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
Abstract
The present invention relates to reverse osmosis membrane technical field of modification, especially a kind of preparation method of graphene polyamide reverse osmose membrane, by selecting suitable modified graphene, addition is in casting solution, aqueous phase solution, oil-phase solution, the water delivery environment inside film is not only improved, increases the water flux of reverse osmosis membrane entirety, while the functional group of modified graphene is crosslinked with reverse osmosis compound is formed by amido bond, the structural stability for improving reverse osmosis inside extends the service life of reverse osmosis membrane.
Description
Technical field
The present invention relates to divide permeable membrane technical field of modification, especially a kind of preparation side of graphene polyamide reverse osmose membrane
Method.
Background technology
It is light to be widely used in seawater because having many advantages, such as high efficiency, low energy consumption, easy to operate for reverse osmosis membrane filtration technology
The fields such as change, wastewater treatment are always the hot spot in domestic and international UF membrane field.Reverse osmosis membrane is to push with film both sides static pressure difference
Power overcomes the osmotic pressure of solvent, selectively retains ionic species and only penetrates solvent, to realize the separation of liquid mixture.
Compared with other membrane separation techniques, reverse osmosis process is the most complicated, and separating behavior is also very big in addition to related with the size in hole
Dissolving, absorption and diffusion of the infiltration component in film are depended on to degree, this has closely with the chemistry of reverse osmosis membrane, physical property
Relationship.
Graphene be one kind by carbon atom with sp2The cellular flat film that hybrid form is formed, single layer of carbon atom are constituted
Graphene thickness be only 0.34nm, be most thin and most hard nano material at present.Graphene oxide spreads out as graphene
One of biology, structure is roughly the same with graphene, the basal plane that the two-dimensional space only constituted in single layer of carbon atom infinitely extends
On be connected with a large amount of oxygen-containing group, although oxygen-containing group intervention so that graphene carbon level in pi bond fracture, lose biography
The ability of conductive son, but assign graphene oxide some new properties, such as dispersibility, hydrophily, the compatibility with polymer
Deng.Meanwhile the oxygen-containing group in graphene oxide can obtain diverse functionalization graphene by modification.
With the fast development of graphene oxide composite material and universal, polymer and graphene oxide, especially polymer with
Modified graphene oxide has become the Main way of reverse osmosis membrane exploitation.A kind of polymeric membrane/stone as disclosed in CN102989331B
Black alkene hydridization NF membrane and preparation method thereof, by the way that graphene to be introduced into the functional layer of NF membrane, the water for improving NF membrane is logical
Amount and rejection.But the deficiency of this NF membrane is that service life is shorter, and after being cleaned multiple times, the performance of film declines.
Invention content
In order to solve the technical problems existing in the prior art, the present invention provides a kind of graphene polyamide reverse osmose membrane
Preparation method.
A kind of preparation method of graphene polyamide reverse osmose membrane, includes the following steps：
(1) carboxylated graphene, polysulfones are added in n,N-Dimethylformamide, heating ultrasound, vacuum defoamation is cast
Film liquid；
(2) casting solution is poured on progress knifing processing on glass plate, immerses in deionized water and cure, obtains polysulfones basement membrane；
(3) it takes amination graphene, 4-dimethylaminopyridine and m-phenylene diamine (MPD) to be added in deionized water, it is molten that water phase is made
Liquid；
(4) it takes chloride graphene and pyromellitic trimethylsilyl chloride to be added in hexamethylene, oil-phase solution is made；
(5) polysulfones basement membrane is immersed in aqueous phase solution, is taken out, the aqueous phase solution of excess surface is blown down with air knife, then immersed
In oil-phase solution, interface polymerization reaction is carried out, is taken out, the oil-phase solution of excess surface is blown down with air knife, deionized water is used in drying
Cleaning to get.
In the step (1), carboxylated graphene is 0.05~0.3g, and the mass percent of polysulfones is 15~25g, N, N-
Dimethylformamide is 250ml.
In the step (1), 2~4h of ultrasound is heated, heating temperature is 95~100 DEG C, 14~20h of vacuum defoamation time.
In the step (2), it is 10~15 μm to scrape film thickness, and the temperature of deionized water is 10~20 DEG C, and hardening time is
15~20min.
In the step (3), amination graphene is 0.5~2g, 0.1~0.2g of 4-dimethylaminopyridine, sodium laurate 3
~5g, m-phenylene diamine (MPD) are 150~350g, deionized water 5L.
In the step (4), chloride graphene be 0.1~1g, 5~10ml of ether, pyromellitic trimethylsilyl chloride be 20~
100g, hexamethylene 2L.
In the step (5), the temperature of aqueous phase solution is 10~15 DEG C, and the time for immersing aqueous phase solution is 40~60min,
The temperature of oil-phase solution be 30~40 DEG C, the interfacial polymerization time be 1~3min, 70 DEG C of drying temperature, drying time be 10~
20min, scavenging period 10min.
Compared with prior art, it has the following advantages：
1. the suitable modified graphene of selection, is entrained in the casting solution, aqueous phase solution, oil-phase solution for preparing reverse osmosis membrane
In, the preparation through reverse osmosis membrane passes through chemistry between modified graphene and the compound and modified graphene of reverse osmosis membrane
Amide is keyed, and is increased the structural stability of reverse osmosis inside, is extended the service life of reverse osmosis membrane.
2. the aramid layer and base membrane layer of reverse osmosis membrane, doped with modified graphene, the not only parent of surface aramid layer
It is aqueous to be enhanced, while the water flux of water transport channel is also improved in basement membrane, reverse osmosis whole water flux is increased.
Specific implementation mode
With reference to specific embodiment and test example, the following further describes the technical solution of the present invention, but wants
Ask the range of protection be not only limited to made by describe.
Embodiment 1
A kind of preparation method of graphene polyamide reverse osmose membrane, includes the following steps：
(1) 250mlN is added in 0.05g carboxylated graphene, 15g polysulfones, in dinethylformamide, heats ultrasound 2h,
Heating temperature is 95 DEG C, and vacuum defoamation 14h obtains casting solution；
(2) casting solution is poured on progress knifing processing on glass plate, it is 10 μm to scrape film thickness, immerses 10 DEG C of deionized water
In, cure 15min, obtains polysulfones basement membrane；
(3) 0.5g amination graphenes, 0.1g4- dimethylamino naphthyridines, 3g sodium laurates and 150g m-phenylene diamine (MPD)s is taken to add
Enter in 5L deionized waters, aqueous phase solution is made；
(4) it takes 0.1g chlorides graphene, 5ml ether and 20g pyromellitic trimethylsilyl chlorides to be added in 2L hexamethylenes, oil phase is made
Solution；
(5) polysulfones basement membrane is immersed in 10 DEG C of aqueous phase solution, 40min is kept in aqueous phase solution, taken out, blown with air knife
It except the aqueous phase solution of excess surface, then immerses in 30 DEG C of oil-phase solution, carries out interface polymerization reaction, the interfacial polymerization time is
1min takes out, and the oil-phase solution of excess surface is blown down with air knife, through 70 DEG C of drying 10min, cleans 10min with deionized water, i.e.,
.
Embodiment 2
A kind of preparation method of graphene polyamide reverse osmose membrane, includes the following steps：
(1) 250mlN is added in 0.15g carboxylated graphene, 20g polysulfones, in dinethylformamide, heats ultrasound 3h,
Heating temperature is 97 DEG C, and vacuum defoamation 17h obtains casting solution；
(2) casting solution is poured on progress knifing processing on glass plate, it is 13 μm to scrape film thickness, immerses 15 DEG C of deionized water
In, cure 18min, obtains polysulfones basement membrane；
(3) 1g amination graphenes, 0.15g4- dimethylamino naphthyridines, 4g sodium laurates and 250g m-phenylene diamine (MPD)s is taken to be added
In 5L deionized waters, aqueous phase solution is made；
(4) it takes 0.5g chlorides graphene, 7.5ml ether and 60g pyromellitic trimethylsilyl chlorides to be added in 2L hexamethylenes, oil is made
Phase solution；
(5) polysulfones basement membrane is immersed in 13 DEG C of aqueous phase solution, 50min is kept in aqueous phase solution, taken out, blown with air knife
It except the aqueous phase solution of excess surface, then immerses in 35 DEG C of oil-phase solution, carries out interface polymerization reaction, the interfacial polymerization time is
2min takes out, and the oil-phase solution of excess surface is blown down with air knife, through 70 DEG C of drying 15min, cleans 10min with deionized water, i.e.,
.
Embodiment 3
A kind of preparation method of graphene polyamide reverse osmose membrane, includes the following steps：
(1) 250mlN is added in 0.3g carboxylated graphene, 25g polysulfones, in dinethylformamide, heats ultrasound 4h,
Heating temperature is 100 DEG C, and vacuum defoamation 20h obtains casting solution；
(2) casting solution is poured on progress knifing processing on glass plate, it is 15 μm to scrape film thickness, immerses 20 DEG C of deionized water
In, cure 20min, obtains polysulfones basement membrane；
(3) take 2g amination graphenes, 0.2g4- dimethylamino naphthyridines, 5g sodium laurates and 350g m-phenylene diamine (MPD)s that 5L is added
In deionized water, aqueous phase solution is made；
(4) it takes 1g chlorides graphene, 10ml ether and 100g pyromellitic trimethylsilyl chlorides to be added in 2L hexamethylenes, oil phase is made
Solution；
(5) polysulfones basement membrane is immersed in 15 DEG C of aqueous phase solution, 60min is kept in aqueous phase solution, taken out, blown with air knife
It except the aqueous phase solution of excess surface, then immerses in 40 DEG C of oil-phase solution, carries out interface polymerization reaction, the interfacial polymerization time is
3min takes out, and the oil-phase solution of excess surface is blown down with air knife, through 70 DEG C of drying 20min, cleans 10min with deionized water, i.e.,
.
Embodiment 4
A kind of preparation method of graphene polyamide reverse osmose membrane, includes the following steps：
(1) 250mlN is added in 21g polysulfones, in dinethylformamide, heats ultrasound 2h, heating temperature is 98 DEG C, very
Empty deaeration 16h, obtains casting solution；
(2) casting solution is poured on progress knifing processing on glass plate, it is 12 μm to scrape film thickness, immerses 10 DEG C of deionized water
In, cure 18min, obtains polysulfones basement membrane；
(3) 1.2g amination graphenes, 0.12g4- dimethylamino naphthyridines, 3.5g sodium laurates and 180g m-phenylene diamine (MPD)s are taken
It is added in 5L deionized waters, aqueous phase solution is made；
(4) it takes 0.4g chlorides graphene, 6ml ether and 35g pyromellitic trimethylsilyl chlorides to be added in 2L hexamethylenes, oil phase is made
Solution；
(5) polysulfones basement membrane is immersed in 11 DEG C of aqueous phase solution, 55min is kept in aqueous phase solution, taken out, blown with air knife
It except the aqueous phase solution of excess surface, then immerses in 32 DEG C of oil-phase solution, carries out interface polymerization reaction, the interfacial polymerization time is
2min takes out, and the oil-phase solution of excess surface is blown down with air knife, through 70 DEG C of drying 18min, cleans 10min with deionized water, i.e.,
.
Embodiment 5
A kind of preparation method of graphene polyamide reverse osmose membrane, includes the following steps：
(1) 250mlN is added in 0.24g carboxylated graphene, 22g polysulfones, in dinethylformamide, heats ultrasound 4h,
Heating temperature is 97 DEG C, and vacuum defoamation 18h obtains casting solution；
(2) casting solution is poured on progress knifing processing on glass plate, it is 14 μm to scrape film thickness, immerses 13 DEG C of deionized water
In, cure 16min, obtains polysulfones basement membrane；
(3) 0.18g4- dimethylamino naphthyridines, 4.2g sodium laurates and 320g m-phenylene diamine (MPD)s is taken to be added in 5L deionized waters,
Aqueous phase solution is made；
(4) it takes 0.7g chlorides graphene, 8ml ether and 90g pyromellitic trimethylsilyl chlorides to be added in 2L hexamethylenes, oil phase is made
Solution；
(5) polysulfones basement membrane is immersed in 13 DEG C of aqueous phase solution, 45min is kept in aqueous phase solution, taken out, blown with air knife
It except the aqueous phase solution of excess surface, then immerses in 32 DEG C of oil-phase solution, carries out interface polymerization reaction, the interfacial polymerization time is
1min takes out, and the oil-phase solution of excess surface is blown down with air knife, through 70 DEG C of drying 14min, cleans 10min with deionized water, i.e.,
.
Embodiment 6
A kind of preparation method of graphene polyamide reverse osmose membrane, includes the following steps：
(1) 250mlN is added in 0.21g carboxylated graphene, 18g polysulfones, in dinethylformamide, heats ultrasound 3h,
Heating temperature is 95 DEG C, and vacuum defoamation 15h obtains casting solution；
(2) casting solution is poured on progress knifing processing on glass plate, it is 12 μm to scrape film thickness, immerses 11 DEG C of deionized water
In, cure 19min, obtains polysulfones basement membrane；
(3) 1.8g amination graphenes, 0.16g4- dimethylamino naphthyridines, 4.5g sodium laurates and 290g m-phenylene diamine (MPD)s are taken
It is added in 5L deionized waters, aqueous phase solution is made；
(4) it takes 9ml ether and 75g pyromellitic trimethylsilyl chlorides to be added in 2L hexamethylenes, oil-phase solution is made；
(5) polysulfones basement membrane is immersed in 15 DEG C of aqueous phase solution, 53min is kept in aqueous phase solution, taken out, blown with air knife
It except the aqueous phase solution of excess surface, then immerses in 38 DEG C of oil-phase solution, carries out interface polymerization reaction, the interfacial polymerization time is
2min takes out, and the oil-phase solution of excess surface is blown down with air knife, through 70 DEG C of drying 17min, cleans 10min with deionized water, i.e.,
.
Embodiment 7
A kind of preparation method of graphene polyamide reverse osmose membrane, includes the following steps：
(1) 250mlN is added in 0.19g carboxylated graphene, 16g polysulfones, in dinethylformamide, heating ultrasound
2.5h, heating temperature are 95 DEG C, and vacuum defoamation 18h obtains casting solution；
(2) casting solution is poured on progress knifing processing on glass plate, it is 12 μm to scrape film thickness, immerses 13 DEG C of deionized water
In, cure 19min, obtains polysulfones basement membrane；
(3) 2.5g chlorides graphene, 0.13g4- dimethylamino naphthyridines, 4.4g sodium laurates and 245g m-phenylene diamine (MPD)s are taken
It is added in 5L deionized waters, aqueous phase solution is made；
(4) it takes 1.2g amination graphenes, 8.5ml ether and 50g pyromellitic trimethylsilyl chlorides to be added in 2L hexamethylenes, oil is made
Phase solution；
(5) polysulfones basement membrane is immersed in 12 DEG C of aqueous phase solution, 53min is kept in aqueous phase solution, taken out, blown with air knife
It except the aqueous phase solution of excess surface, then immerses in 35 DEG C of oil-phase solution, carries out interface polymerization reaction, the interfacial polymerization time is
3min takes out, and the oil-phase solution of excess surface is blown down with air knife, through 70 DEG C of drying 17min, cleans 10min with deionized water, i.e.,
.
Embodiment 8
A kind of preparation method of graphene polyamide reverse osmose membrane, includes the following steps：
(1) 250mlN is added in 0.25g amination graphenes, 25g polysulfones, in dinethylformamide, heats ultrasound 4h,
Heating temperature is 96 DEG C, and vacuum defoamation 14h obtains casting solution；
(2) casting solution is poured on progress knifing processing on glass plate, it is 11 μm to scrape film thickness, immerses 16 DEG C of deionized water
In, cure 16min, obtains polysulfones basement membrane；
(3) 1.5g carboxylated graphene, 0.14g4- dimethylamino naphthyridines, 3.8g sodium laurates and 280g m-phenylene diamine (MPD)s are taken
It is added in 5L deionized waters, aqueous phase solution is made；
(4) it takes 0.35g chlorides graphene, 6.5ml ether and 70g pyromellitic trimethylsilyl chlorides to be added in 2L hexamethylenes, is made
Oil-phase solution；
(5) polysulfones basement membrane is immersed in 13 DEG C of aqueous phase solution, 47min is kept in aqueous phase solution, taken out, blown with air knife
It except the aqueous phase solution of excess surface, then immerses in 34 DEG C of oil-phase solution, carries out interface polymerization reaction, the interfacial polymerization time is
1min takes out, and the oil-phase solution of excess surface is blown down with air knife, through 70 DEG C of drying 16min, cleans 10min with deionized water, i.e.,
.
Embodiment 9
A kind of preparation method of graphene polyamide reverse osmose membrane, includes the following steps：
(1) 250mlN is added in 0.75g chlorides graphene, 19g polysulfones, in dinethylformamide, heats ultrasound 2h,
Heating temperature is 98 DEG C, and vacuum defoamation 15h obtains casting solution；
(2) casting solution is poured on progress knifing processing on glass plate, it is 15 μm to scrape film thickness, immerses 13 DEG C of deionized water
In, cure 15min, obtains polysulfones basement membrane；
(3) 1.7g amination graphenes, 0.13g4- dimethylamino naphthyridines, 5g sodium laurates and 300g m-phenylene diamine (MPD)s is taken to add
Enter in 5L deionized waters, aqueous phase solution is made；
(4) it takes 1.5g carboxylated graphene, 8ml ether and 85g pyromellitic trimethylsilyl chlorides to be added in 2L hexamethylenes, oil phase is made
Solution；
(5) polysulfones basement membrane is immersed in 10 DEG C of aqueous phase solution, 40min is kept in aqueous phase solution, taken out, blown with air knife
It except the aqueous phase solution of excess surface, then immerses in 40 DEG C of oil-phase solution, carries out interface polymerization reaction, the interfacial polymerization time is
2min takes out, and the oil-phase solution of excess surface is blown down with air knife, through 70 DEG C of drying 17min, cleans 10min with deionized water, i.e.,
.
Test example
Sample sets 1-9 is reverse osmosis membrane prepared by embodiment 1-9, is comparison with NF membrane disclosed in CN102989331B
Group.
The filter effect of sample sets 1-9 and contrast groups are tested.Test fluid is the NaCl solution of 2000ppm, operation
Pressure is 150psi, and pH value 7.3 tests the water flux and rejection of first time 48h caudacoria.Then, to the film of experimental group into
Row regeneration washing 30min tests the water flux and rejection of second of 48h caudacoria.Later, it is handed over " cleaning and regeneration " and " test "
For 8 experiments are carried out, membrane flux and rejection after the 48h of third to the tenth time are tested, recording it, the results are shown in Table 1：
Table 1
Table 1 (continued)
Table 1 (continued)
As can be seen from the above table, the reverse osmosis membrane that prepared by sample sets 1-3 has higher water flux and preferable retention
Rate, for water flux after 10 cleanings, pollution level is about 5% or so.The reverse osmosis membrane of sample sets 4 is tested at the 8th time
When, there is exception in the trend of water flux and rejection, and there are the phenomenons of membrane structure breakage.The reverse osmosis membrane of sample sets 5,6, because of portion
Point preparation process lacks the addition of modified graphene, and filter effect is decreased obviously, and especially sample sets 6 is reverse osmosis
Film, fouling membrane degree are in increase tendency.The reverse osmosis membrane of sample sets 7-9, in first test, performance is good, but by again
Occurs film disrepair phenomenon after raw cleaning, water flux increases, and rejection declines, and stability is poor.And the NF membrane of contrast groups, the 7th
When secondary test, water flux starts to increase, and rejection reduces, and damage phenomenon occurs in membrane structure.
Claims (7)
1. a kind of preparation method of graphene polyamide reverse osmose membrane, which is characterized in that include the following steps：
(1) carboxylated graphene, polysulfones are added in n,N-Dimethylformamide, heating ultrasound, vacuum defoamation obtains casting film
Liquid；
(2) casting solution is poured on progress knifing processing on glass plate, immerses in deionized water and cure, obtains polysulfones basement membrane；
(3) it takes amination graphene, 4-dimethylaminopyridine, sodium laurate and m-phenylene diamine (MPD) to be added in deionized water, water is made
Phase solution；
(4) it takes chloride graphene, ether and pyromellitic trimethylsilyl chloride to be added in hexamethylene, oil-phase solution is made；
(5) polysulfones basement membrane is immersed in aqueous phase solution, is taken out, the aqueous phase solution of excess surface is blown down with air knife, then immerse oil phase
In solution, interface polymerization reaction is carried out, is taken out, the oil-phase solution of excess surface is blown down with air knife, drying is clear with deionized water
Wash to get.
2. the preparation method of graphene polyamide reverse osmose membrane as described in claim 1, which is characterized in that the step (1)
In, carboxylated graphene is 0.05~0.3g, and the mass percent of polysulfones is 15~25g, and n,N-Dimethylformamide is
250ml。
3. the preparation method of graphene polyamide reverse osmose membrane as described in claim 1, which is characterized in that the step (1)
In, 2~4h of ultrasound is heated, heating temperature is 95~100 DEG C, 14~20h of vacuum defoamation time.
4. the preparation method of graphene polyamide reverse osmose membrane as described in claim 1, which is characterized in that the step (2)
In, it is 10~15 μm to scrape film thickness, and the temperature of deionized water is 10~20 DEG C, and hardening time is 15~20min.
5. the preparation method of graphene polyamide reverse osmose membrane as described in claim 1, which is characterized in that the step (3)
In, amination graphene is 0.5~2g, and 4-dimethylaminopyridine is 0.1~0.2g, 3~5g of sodium laurate, and m-phenylene diamine (MPD) is
150~350g, deionized water 5L.
6. the preparation method of graphene polyamide reverse osmose membrane as described in claim 1, which is characterized in that the step (4)
In, chloride graphene is 0.1~1g, and 5~10ml of ether, pyromellitic trimethylsilyl chloride is 20~100g, hexamethylene 2L.
7. the preparation method of graphene polyamide reverse osmose membrane as described in claim 1, which is characterized in that the step (5)
In, the temperature of aqueous phase solution is 10~15 DEG C, and the time for immersing aqueous phase solution is 40~60min, and the temperature of oil-phase solution is 30
~40 DEG C, the interfacial polymerization time is 1~3min, and 70 DEG C of drying temperature, drying time is 10~20min, and scavenging period is
10min。
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