CN109126486A - A kind of polyamide reverse osmose membrane and its preparation method and application that bulk doped CNO is modified - Google Patents
A kind of polyamide reverse osmose membrane and its preparation method and application that bulk doped CNO is modified Download PDFInfo
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- CN109126486A CN109126486A CN201811122133.0A CN201811122133A CN109126486A CN 109126486 A CN109126486 A CN 109126486A CN 201811122133 A CN201811122133 A CN 201811122133A CN 109126486 A CN109126486 A CN 109126486A
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- 239000012528 membrane Substances 0.000 title claims abstract description 95
- 229920002647 polyamide Polymers 0.000 title claims abstract description 47
- 239000004952 Polyamide Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000460 chlorine Substances 0.000 claims abstract description 31
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 31
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 28
- 239000008346 aqueous phase Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 59
- 229920002492 poly(sulfone) Polymers 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 18
- 238000010612 desalination reaction Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- MCPANHZWUBLTMU-UHFFFAOYSA-N chloro(trimethyl)silane hexane Chemical compound C[Si](Cl)(C)C.CCCCCC MCPANHZWUBLTMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000013535 sea water Substances 0.000 description 25
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 17
- 229940018564 m-phenylenediamine Drugs 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 235000002639 sodium chloride Nutrition 0.000 description 14
- 239000013505 freshwater Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000002131 composite material Substances 0.000 description 10
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- 239000004760 aramid Substances 0.000 description 8
- 229920003235 aromatic polyamide Polymers 0.000 description 8
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000012466 permeate Substances 0.000 description 8
- 229960002668 sodium chloride Drugs 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000000149 penetrating effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 230000010148 water-pollination Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- -1 CNO Amide Chemical class 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock 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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to technical field of function materials, are related to a kind of polyamide reverse osmose membrane and its preparation method and application that bulk doped CNO is modified.By the way that CNO is added in the aqueous phase solution of polyamide reverse osmose membrane interface polymerization reaction, the modified polyamide reverse osmosis membrane of CNO hydridization is prepared.CNO is added in PA membrane separating layer by the method for bulk doped, CNO has oxygen-containing group abundant, with good water dispersible and potential inoxidizability, makes the chlorine resistance for the hybridized film being prepared obtain significantly improving, prolong the service life.The modified polyamide film prepared by the method for the invention, flux improve, and rejection is basically unchanged, the anti-chlorine performance that Modified Membrane has had, and being capable of stable operation.
Description
Technical field
The invention belongs to technical field of function materials, be related to a kind of polyamide reverse osmose membrane that bulk doped CNO is modified and
Preparation method and application.
Background technique
Polyamide-based reverse osmosis membrane is widely used in ultrapure water preparation, sea water desalination and brackish water desalination etc..But at present
The chlorine resistance of polyamide-based reverse osmosis membrane is poor, crosslinking aromatic polyamides under the action of free chlorine, on polyamide reverse osmose membrane
Chlorizating depolymerization causes polyamide reverse osmose membrane rejection to be gradually reduced, and reduces the service life of film.So polyamide reverse osmose membrane
Chlorine resistance modification be one of hot spot of study on the modification.
Summary of the invention
The purpose of the present invention is to provide a kind of bulk doped CNO modified polyamide reverse osmose membrane and preparation method thereof and
Using.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A kind of preparation method for the polyamide reverse osmose membrane that the bulk doped CNO with chlorine resistance is modified, including following step
It is rapid:
It takes out PS membrane and is fixed on plate, dry up moisture with air knife, CNO aqueous phase solution is poured over PS membrane table
Face is outwelled extra aqueous phase solution, and is dried up with air knife after a period of time, then oil-phase solution is poured on film surface, a period of time
Afterwards, extra oil-phase solution is outwelled；
Film obtained above is placed in an oven, after being heat-treated a period of time, taking-up is cleaned to be changed up to bulk doped CNO
The polyamide reverse osmose membrane of property.
The configuration method of the CNO aqueous phase solution are as follows: the MPD aqueous solution that configuration quality score is 1.0~3.0%, by one
The CNO for determining quality is added in above-mentioned solution, and ultrasound a period of time is to get CNO aqueous phase solution.
The oil-phase solution is the pyromellitic trimethylsilyl chloride hexane solution that mass fraction is 0.1~0.5%.
The temperature of the heat treatment is 60~80 DEG C, and the time of heat treatment is 1~10min.
The preparation method of the CNO includes the following steps:
(1) a certain amount of urea is added in crucible, is heated to 500~550 DEG C in Muffle furnace with 5~10 DEG C/min, protected
1~4h of temperature, takes out after being cooled to room temperature, and grinding obtains g-C3N4Powder；
(2) a certain amount of g-C is weighed3N4, (concentrated nitric acid and the concentrated sulfuric acid are added in the mixed solution of concentrated nitric acid and the concentrated sulfuric acid
Mixed proportion be 2:1), evenly dispersed submergence g-C3N4, stirring 12~for 24 hours；
(3) step (2) resulting solution is poured into deionized water, is precipitated after filtering；Precipitating is washed with deionized water
It washs to neutrality, dries at room temperature, obtained product is CNO.
A kind of polyamide reverse osmose membrane that the bulk doped CNO of method preparation as described above is modified.
The bulk doped CNO modified polyamide reverse osmose membrane has chlorine resistance.
A kind of polyamide reverse osmose membrane that bulk doped CNO as described above is modified is in ultrapure water preparation, sea water desalination
With the application in brackish water desalination.
The present invention has the advantage that compared with the existing technology
The present invention utilizes the method for modifying of bulk doped, will have hydrophily and there is antioxidative CNO to be grafted to virtue
The modified polyamide reverse osmose membrane of CNO is prepared in the surface of fragrant polyamide composite reverse osmosis membrane.CNO has hydrophily and resists
Oxidisability can greatly improve the chlorine resistance of Modified Membrane, and membrane separating property reduction is unobvious.The advantage of the invention is that reaction
Mild condition, method be simple, lower production costs and film properties are stablized.
CNO is added in PA membrane separating layer by the method for bulk doped, CNO has oxygen-containing group abundant,
With good water dispersible and potential inoxidizability, obtain the chlorine resistance for the hybridized film being prepared significantly
It improves, prolongs the service life.The modified polyamide film prepared by the method for the invention, flux improve, and rejection is basically unchanged, changes
The anti-chlorine performance that property film has had, and being capable of stable operation.
Detailed description of the invention
Fig. 1 is the surface texture scanning electron microscope (SEM) photograph of PS membrane；
Fig. 2 is that the surface texture of the aromatic polyamide composite reverse osmosis membrane of CNO doping vario-property prepared by embodiment 1 scans electricity
Mirror figure；
Fig. 3 is that the surface texture of the aromatic polyamide composite reverse osmosis membrane of CNO doping vario-property prepared by embodiment 2 scans electricity
Mirror figure；
Fig. 4 is that the surface texture of the aromatic polyamide composite reverse osmosis membrane of CNO doping vario-property prepared by embodiment 3 scans electricity
Mirror figure；
Fig. 5 is that the surface texture undoped with modified aromatic polyamide composite reverse osmosis membrane prepared by comparative example 1 scans electricity
Mirror figure.
Fig. 6 is the structural schematic diagram of the reverse osmosis desalination device in embodiment 4；
Wherein, the above drawings include the following reference numerals: 1, seawater inlet port；2, high-pressure pump；3, the second air conduit；4,
Primary filter；5, bulk doped CNO modified polyamide reverse osmose membrane component；6, the first air conduit；7, gas chamber；8, light
Change water water outlet；9, medical stone filtering layer；10, fresh water water pipe；11, concentrated seawater water pipe；12, concentrated seawater outlet；13, it is concentrated
Seawater surge chamber；14, fresh-water tank.
Specific embodiment
The invention will be further described below.
Embodiment 1
(1) by polysulfones (PS) ultrafiltration membrane (molecular cut off 30000), pure water is used to clean up spare as supporting layer；
(2) m-phenylene diamine (MPD) (MPD) aqueous solution that configuration quality score is 2.0%；By CNO ultrasound one hour of 0.005g/L
It is dispersed in above-mentioned MPD solution, obtains CNO-MPD aqueous phase solution；
(3) configuration of oil-phase solution: pyromellitic trimethylsilyl chloride (TMC) hexane solution that configuration quality score is 0.1%；
(4) it prepares CNO modified polyamide reverse osmosis membrane: taking out PS film and be fixed on glass plate, dry up water with air knife
Point, CNO-MPD aqueous phase solution is poured over PS film surface, outwells extra aqueous phase solution after five minutes, and dried up with air knife, then
Oil-phase solution is poured on film surface, reacts 1 minute, outwells extra oil-phase solution.
(5) film obtained above is placed in 80 DEG C of baking oven, is heat-treated 5 minutes；Film is taken out, pure water cleaning is spare.
Fig. 1 is the surface texture scanning electron microscope (SEM) photograph of PS membrane；Fig. 2 is that the fragrance of CNO doping vario-property prepared by embodiment 1 is poly-
The surface texture scanning electron microscope (SEM) photograph of amide complex reverse osmosis membrane.
The test of membrane flux and rejection: by modified reverse osmosis membrane obtained, filted chroma is at 1.55MPa, 25 DEG C
Its initial permeate flux and rejection are tested after the sodium-chloride water solution 30min that 2000ppm volume is 6.0L.Membrane flux and chlorination
Sodium rejection is calculated respectively with following formula.
Flux=penetrating fluid volume/(time × membrane area)
Rejection=(feeding liquid conductivity-penetrating fluid conductivity)/feeding liquid conductivity
Filtered at 1.55MPa, 25 DEG C 2000ppm sodium-chloride water solution test to obtain Modified Membrane initial permeate flux and
Salt rejection rate is shown in Table 1.
Chlorine resistance experiment: configuration sodium hypochlorite concentration is 500ppm, adjusts pH=7 with HCL, will test initial performance
Film is immersed in liquor natrii hypochloritis, carries out chlorine resistance experiment, and (condition is same for the membrane flux and rejection after test immersion 30h
On).
The chlorine resistance experimental result of Modified Membrane prepared by embodiment 1 is shown in Table 2.
Embodiment 2
(1) by polysulfones (PS) ultrafiltration membrane (molecular cut off 30000), pure water is used to clean up spare as supporting layer；
(2) m-phenylene diamine (MPD) (MPD) aqueous solution that configuration quality score is 2.0%；By CNO ultrasound one hour of 0.01g/L
It is dispersed in above-mentioned MPD solution, obtains CNO-MPD aqueous phase solution；
(3) configuration of oil-phase solution: pyromellitic trimethylsilyl chloride (TMC) hexane solution that configuration quality score is 0.1%；
(4) it prepares CNO modified polyamide reverse osmosis membrane: taking out PS film and be fixed on glass plate, dry up water with air knife
Point, CNO-MPD aqueous phase solution is poured over PS film surface, outwells extra aqueous phase solution after five minutes, and dried up with air knife, then
Oil-phase solution is poured on film surface, reacts 1 minute, outwells extra oil-phase solution.
(5) film obtained above is placed in 80 DEG C of baking oven, is heat-treated 5 minutes；Film is taken out, pure water cleaning is spare.
Fig. 3 is that the surface texture of the aromatic polyamide composite reverse osmosis membrane of CNO doping vario-property prepared by embodiment 2 scans electricity
Mirror figure.
The test of membrane flux and rejection: by modified reverse osmosis membrane obtained, filted chroma is at 1.55MPa, 25 DEG C
Its initial permeate flux and rejection are tested after the sodium-chloride water solution 30min that 2000ppm volume is 6.0L.Membrane flux and chlorination
Sodium rejection is calculated respectively with following formula.
Flux=penetrating fluid volume/(time × membrane area)
Rejection=(feeding liquid conductivity-penetrating fluid conductivity)/feeding liquid conductivity
Filtered at 1.55MPa, 25 DEG C 2000ppm sodium-chloride water solution test to obtain Modified Membrane initial permeate flux and
Salt rejection rate is shown in Table 1.
Chlorine resistance experiment: configuration sodium hypochlorite concentration is 500ppm, adjusts pH=7 with HCL, will test initial performance
Film is immersed in liquor natrii hypochloritis, carries out chlorine resistance experiment, and (condition is same for the membrane flux and rejection after test immersion 30h
On).
The chlorine resistance experimental result of Modified Membrane prepared by embodiment 2 is shown in Table 2.
Embodiment 3
(1) by polysulfones (PS) ultrafiltration membrane (molecular cut off 30000), pure water is used to clean up spare as supporting layer；
(2) m-phenylene diamine (MPD) (MPD) aqueous solution that configuration quality score is 2.0%；By CNO ultrasound one hour of 0.02g/L
It is dispersed in above-mentioned MPD solution, obtains CNO-MPD aqueous phase solution；
(3) configuration of oil-phase solution: pyromellitic trimethylsilyl chloride (TMC) hexane solution that configuration quality score is 0.1%；
(4) it prepares CNO modified polyamide reverse osmosis membrane: taking out PS film and be fixed on glass plate, dry up water with air knife
Point, CNO-MPD aqueous phase solution is poured over PS film surface, outwells extra aqueous phase solution after five minutes, and dried up with air knife, then
Oil-phase solution is poured on film surface, reacts 1 minute, outwells extra oil-phase solution.
(5) film obtained above is placed in 80 DEG C of baking oven, is heat-treated 5 minutes；Film is taken out, pure water cleaning is spare.
Fig. 4 is that the surface texture of the aromatic polyamide composite reverse osmosis membrane of CNO doping vario-property prepared by embodiment 3 scans electricity
Mirror figure.
The test of membrane flux and rejection: by modified reverse osmosis membrane obtained, filted chroma is at 1.55MPa, 25 DEG C
Its initial permeate flux and rejection are tested after the sodium-chloride water solution 30min that 2000ppm volume is 6.0L.Membrane flux and chlorination
Sodium rejection is calculated respectively with following formula.
Flux=penetrating fluid volume/(time × membrane area)
Rejection=(feeding liquid conductivity-penetrating fluid conductivity)/feeding liquid conductivity
Filtered at 1.55MPa, 25 DEG C 2000ppm sodium-chloride water solution test to obtain Modified Membrane initial permeate flux and
Salt rejection rate is shown in Table 1.
Chlorine resistance experiment: configuration sodium hypochlorite concentration is 500ppm, adjusts pH=7 with HCL, will test initial performance
Film is immersed in liquor natrii hypochloritis, carries out chlorine resistance experiment, and (condition is same for the membrane flux and rejection after test immersion 30h
On).
The chlorine resistance experimental result of Modified Membrane prepared by embodiment 3 is shown in Table 2.
Comparative example 1
(1) by polysulfones (PS) ultrafiltration membrane (molecular cut off 30000), pure water is used to clean up spare as supporting layer；
(2) m-phenylene diamine (MPD) (MPD) aqueous solution that configuration quality score is 2.0%；
(3) configuration of oil-phase solution: pyromellitic trimethylsilyl chloride (TMC) hexane solution that configuration quality score is 0.1%；It will
MPD aqueous phase solution is poured over PS film surface, outwells extra aqueous phase solution after five minutes, and dried up with air knife, then by oil-phase solution
It is poured on film surface, reacts 1 minute, outwells extra oil-phase solution.
(5) film obtained above is placed in 80 DEG C of baking oven, is heat-treated 5 minutes；Film is taken out, pure water cleaning is spare.
Fig. 5 is that the surface texture undoped with modified aromatic polyamide composite reverse osmosis membrane prepared by comparative example 1 scans electricity
Mirror figure.
The test of membrane flux and rejection: by modified reverse osmosis membrane obtained, filted chroma is at 1.55MPa, 25 DEG C
Its initial permeate flux and rejection are tested after the sodium-chloride water solution 30min that 2000ppm volume is 6.0L.Membrane flux and chlorination
Sodium rejection is calculated respectively with following formula.
Flux=penetrating fluid volume/(time × membrane area)
Rejection=(feeding liquid conductivity-penetrating fluid conductivity)/feeding liquid conductivity
Filtered at 1.55MPa, 25 DEG C 2000ppm sodium-chloride water solution test to obtain Modified Membrane initial permeate flux and
Salt rejection rate is shown in Table 1.
The chlorine resistance experimental result of former film 30h prepared by comparative example 1 is shown in Table 2.
1 membrane flux of table and rejection test:
The experiment of 2 chlorine resistance of table
Test result shows: compared to unmodified reverse osmosis membrane, the modification prepared using the method for the present invention is reverse osmosis multiple
Film is closed after sodium hypochlorite impregnates, rejection decaying is obviously reduced, and shows good chlorine resistance.
Embodiment 4
A kind of reverse osmosis desalination device is modified poly- including high-pressure pump 2, primary filter 4, bulk doped CNO
Amide reverse osmosis membrane assembly 5, fresh-water tank 14, concentrated seawater surge chamber 13, described 2 one end of high-pressure pump are connected with seawater inlet port 1,
The other end is connected with primary filter 4, the primary filter 4 and bulk doped CNO modified polyamide reverse osmose membrane
Component 5 is connected, and bulk doped CNO modified polyamide reverse osmose membrane component 5 is connected by conduit with fresh-water tank 14, the fresh water
The top of case 14 is equipped with gas chamber 7, and the fresh-water tank 14 is connected with fresh water water pipe 10, and the end of fresh water water pipe 10 is desalination water water outlet
Mouth 8, desalination water water outlet 8 are connected with mesolow pump；The bulk doped CNO modified polyamide reverse osmose membrane component 5 passes through
Concentrated seawater water pipe 11 is connected with concentrated seawater surge chamber 13, and concentrated seawater water pipe end is concentrated seawater outlet 12.
The first air conduit 6 is connected with above gas chamber 7 in the fresh-water tank 14, first air conduit 6 leads to sea
Above plane.
The second air conduit 3 is connected with above the concentrated seawater surge chamber 13, second air conduit 3 leads to Hai Ping
Above face.
The fresh-water tank 14, primary filter 4, the polyamide reverse osmose membrane component 5 of bulk doped CNO modification, concentration
Seawater surge chamber 13 has the surface being in contact with seawater, is coated with the different nanometer of partial size on the surface being in contact from seawater
Inorganic ceramic powder, can anti-seawater corrosion, abrasionproof, shock resistance.
Medical stone filtering layer 9 is serially connected among the fresh water water pipe 10.
Original seawater enters primary filter 4 under the action of high-pressure pump 2, through seawater inlet port 1, and it is dense to reduce seawater
Degree, by the barrier of the microorganisms such as algae outside device, subsequently into the modified polyamide reverse osmose membrane component 5 of bulk doped CNO,
Reverse osmosis treatment is carried out to seawater, the type of reverse osmosis membrane is polyamide composite film, is up to 98%- to the salt rejection rate of seawater
99%, enter desalination water tank 14 by the desalination water of bulk doped CNO modified polyamide reverse osmose membrane component 5, desalinates water tank
The gas chamber 7 at 14 tops passes through fresh water water pipe 10, warp by the first air conduit 6 and the air communication above sea level, desalination water
It crosses after the further fine filtering of medical stone filtering layer 9 and is connected by desalination water water outlet 8 with external mesolow pump, desalination water
It is extracted utilization；The concentrated seawater generated after the modified polyamide reverse osmose membrane component 5 of bulk doped CNO initially enters dense
Contracting seawater surge chamber 13 is discharged directly into sea through concentrated seawater outlet 12 after buffering and a degree of dilution, or
It is connected with the pump on sea level, is extracted rear secondary use, such as extract sea salt.
The present invention using the method for simple direct bulk doped will there is the CNO of abundant oxygen-containing group to be doped to polyamides
In the functional layer of amine film, the polyamide reverse osmosis composite film of CNO hybrid modification is prepared, CNO is g-C3N4A kind of derivative
Object, with g-C3N4It compares, the surface CNO is dispersed with the oxygen-containing functional group of a large amount of polarity, and hydrophily is more preferable, and CNO is remained again simultaneously
g-C3N4Class graphene-structured, lamella is thin, good dispersion, oxygen-containing group abundant have potential inoxidizability can be improved
The chlorine resistance of PA membrane, and Modified Membrane is with good stability.
Claims (10)
1. a kind of preparation method for the polyamide reverse osmose membrane that the bulk doped CNO with chlorine resistance is modified, which is characterized in that packet
Include following steps:
It takes out PS membrane to be simultaneously fixed on plate, dries up moisture with air knife, CNO aqueous phase solution is poured over polysulfones film surface, one
Extra aqueous phase solution is outwelled after the section time, and is dried up with air knife, then oil-phase solution is poured on film surface, after a period of time,
Fall extra oil-phase solution；
Film obtained above is placed in an oven, after being heat-treated a period of time, takes out and cleans what bulk doped CNO to obtain the final product was modified
Polyamide reverse osmose membrane.
2. the preparation side of the bulk doped CNO according to claim 1 with chlorine resistance modified polyamide reverse osmose membrane
Method, which is characterized in that the configuration method of the CNO aqueous phase solution are as follows: the MPD that configuration quality score is 1.0~3.0% is water-soluble
The CNO of certain mass is added in above-mentioned solution by liquid, and ultrasound a period of time is to get CNO aqueous phase solution.
3. the preparation side of the bulk doped CNO according to claim 1 with chlorine resistance modified polyamide reverse osmose membrane
Method, which is characterized in that the oil-phase solution is the pyromellitic trimethylsilyl chloride hexane solution that mass fraction is 0.1~0.5%.
4. the preparation side of the bulk doped CNO according to claim 1 with chlorine resistance modified polyamide reverse osmose membrane
Method, which is characterized in that the temperature of the heat treatment is 60~80 DEG C, and the time of heat treatment is 1~10min.
5. the bulk doped CNO according to any one of claims 1-4 with chlorine resistance modified polyamide reverse osmosis
The preparation method of film, which is characterized in that the preparation method of the CNO includes the following steps:
(1) a certain amount of urea is added in crucible, is warming up to certain temperature with certain heating rate in Muffle furnace, kept the temperature
For a period of time, it is taken out after being cooled to room temperature, obtains g-C3N4；
(2) a certain amount of g-C is weighed3N4, it is added in the mixed solution of concentrated nitric acid and the concentrated sulfuric acid, stirs；
(3) step (2) resulting solution is poured into deionized water, is precipitated after filtering；Precipitating be washed with deionized to
Neutrality is dried at room temperature, and obtained product is CNO.
6. the preparation side of the bulk doped CNO according to claim 5 with chlorine resistance modified polyamide reverse osmose membrane
Method, which is characterized in that in the step (1), a certain amount of urea is added in crucible, is added in Muffle furnace with 5~10 DEG C/min
Heat keeps the temperature 1~4h to 500~550 DEG C.
7. the preparation side of the bulk doped CNO according to claim 5 with chlorine resistance modified polyamide reverse osmose membrane
Method, which is characterized in that the mixed proportion of the concentrated nitric acid and the concentrated sulfuric acid is 2:1.
8. a kind of as modified polyamide reverse osmose membrane such as the bulk doped CNO of claim 1-7 any one the method preparation.
9. bulk doped CNO according to claim 8 modified polyamide reverse osmose membrane, which is characterized in that the ontology
Adulterating the modified polyamide reverse osmose membrane of CNO has chlorine resistance.
10. a kind of polyamide reverse osmose membrane that bulk doped CNO as claimed in claim 8 or 9 is modified is in ultrapure water preparation, sea
Application in water desalination and brackish water desalination.
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| CN109985536A (en) * | 2019-04-04 | 2019-07-09 | 河海大学 | A kind of g-C3N4- PVDF composite membrane, preparation method and application |
| CN110756061A (en) * | 2019-10-12 | 2020-02-07 | 万华化学集团股份有限公司 | Oxidation-resistant high-flux reverse osmosis membrane and preparation method and application thereof |
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| CN114699919A (en) * | 2022-03-28 | 2022-07-05 | 河海大学 | Mixed matrix reverse osmosis membrane and preparation method and application thereof |
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| CN115400612A (en) * | 2022-08-31 | 2022-11-29 | 西北工业大学 | Modified polyamide separation membrane for resisting scaling and oxidation and preparation method thereof |
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| CN110756061A (en) * | 2019-10-12 | 2020-02-07 | 万华化学集团股份有限公司 | Oxidation-resistant high-flux reverse osmosis membrane and preparation method and application thereof |
| CN110756061B (en) * | 2019-10-12 | 2022-01-07 | 万华化学集团股份有限公司 | Oxidation-resistant high-flux reverse osmosis membrane and preparation method and application thereof |
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| CN115400612A (en) * | 2022-08-31 | 2022-11-29 | 西北工业大学 | Modified polyamide separation membrane for resisting scaling and oxidation and preparation method thereof |
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| CN115337800B (en) * | 2022-09-21 | 2024-05-03 | 万华化学集团股份有限公司 | High-desalination antioxidant polyamide reverse osmosis membrane, preparation method and application thereof |
| CN116440711A (en) * | 2023-06-20 | 2023-07-18 | 中国农业大学 | Seawater desalination reverse osmosis membrane with water flux and boron removal rate and preparation method thereof |
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