CN108479395A - A kind of forward osmosis membrane and preparation method thereof - Google Patents
A kind of forward osmosis membrane and preparation method thereof Download PDFInfo
- Publication number
- CN108479395A CN108479395A CN201810160910.4A CN201810160910A CN108479395A CN 108479395 A CN108479395 A CN 108479395A CN 201810160910 A CN201810160910 A CN 201810160910A CN 108479395 A CN108479395 A CN 108479395A
- Authority
- CN
- China
- Prior art keywords
- osmosis membrane
- forward osmosis
- supporting layer
- solution
- polysulfone supporting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 72
- 238000009292 forward osmosis Methods 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 41
- 101001115830 Homo sapiens Prostate-associated microseminoprotein Proteins 0.000 claims abstract description 24
- 102100025013 Prostate-associated microseminoprotein Human genes 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 230000000694 effects Effects 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 61
- 239000004697 Polyetherimide Substances 0.000 claims description 38
- 229920001601 polyetherimide Polymers 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 17
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 14
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 7
- 239000012965 benzophenone Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229940113088 dimethylacetamide Drugs 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- -1 acyl Imide Chemical class 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims 1
- MCPANHZWUBLTMU-UHFFFAOYSA-N chloro(trimethyl)silane hexane Chemical compound C[Si](Cl)(C)C.CCCCCC MCPANHZWUBLTMU-UHFFFAOYSA-N 0.000 claims 1
- FTZPKSZFFYCLOH-UHFFFAOYSA-N formyl chloride hexane Chemical compound CCCCCC.C(=O)Cl FTZPKSZFFYCLOH-UHFFFAOYSA-N 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 30
- 230000035699 permeability Effects 0.000 abstract description 11
- 238000005266 casting Methods 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 9
- 230000010148 water-pollination Effects 0.000 abstract description 9
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 5
- 238000011017 operating method Methods 0.000 abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- 230000004907 flux Effects 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 230000008595 infiltration Effects 0.000 description 6
- 238000001764 infiltration Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/002—Forward osmosis or direct osmosis
-
- 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
- B01D61/002—Forward osmosis or direct osmosis
- B01D61/0022—Apparatus 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
- B01D67/0016—Coagulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
-
- 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
- B01D69/12—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
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
- B01D2323/345—UV-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/38—Graft polymerization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/40—Details relating to membrane preparation in-situ membrane formation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/64—Use of a temporary support
-
- 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
- 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
Abstract
The present invention discloses a kind of forward osmosis membrane and preparation method thereof, the present invention uses the polysulfone supporting layer of sacrificial layer joint casting method preparation bottom macropore first, then use the method for uv photo initiated grafting that hydrophilic PSMP polymer is grafted to bottom and the hole inner wall of PSf supporting layers, it finally uses the method for interfacial polymerization to prepare active cortex at the top of polysulfone supporting layer, obtains forward osmosis membrane.The method that the present invention is grafted hydrophily PSMP polymer using ultraviolet irradiation is only hydrophilically modified to the inner wall progress of the bottom of porous support layer and hole, has not only maintained the stability of active cortex in this way, but also further improve the water permeability of forward osmosis membrane.Operating procedure of the present invention is simple and practicable, and effect stability is apparent, good water permeability, and the separation selectivity just permeated improves a lot.
Description
Technical field
The present invention relates to positive infiltration technology field more particularly to a kind of forward osmosis membranes and preparation method thereof.
Background technology
Currently, people take the various water process sides such as sea water desalination, Sewage treatment to obtain enough fresh water supplies
Method, but to consume mass energy as cost, therefore reduce between actual consumption and the thermodynamics minimum separation energy of solution
Gap has been a hot spot of research.Wherein, positive infiltration is a kind of emerging desalination and isolation technics, it is to utilize semi-permeable membrane both ends
The difference of osmotic pressure realizes the spontaneous separation of solution.Positive infiltration is applied to many fields in recent years, such as：Seawater is de-
Salt, sewage disposal, concentrated waste percolate etc..In water treatment field, compared to traditional technology such as micro-filtration, ultrafiltration, nanofiltration, anti-
The membrane process such as infiltration, positive process of osmosis have the advantages such as low energy consumption, low stain trend, easy cleaning.However, positive infiltration still suffers from
Many problems, wherein concentration polarization is to influence one of the main problem of positive permeance property, and concentration polarization phenomenon is UF membrane mistake
Generally existing in journey fails to accumulate in film surface through the part of semi-permeable membrane in material liquid since semi-permeable membrane has crown_interception
Tire out the accumulation either due to solute caused by the non-homogeneous structural of film inside film and significantly reduce osmotic pressure, to drop
The low performance of positive infiltration.
Forward osmosis membrane is made of active cortex and porous support layer, and in recent years, a large amount of research is dedicated to improving film
The structure and performance of supporting layer reduce concentration polarization phenomenon to improve forward osmosis membrane performance.Such as：By changing casting solution
Solvent, the composition of polymer and concentration obtain the supporting layer with finger, or being added, there is hydrophilic substance to obtain
Hydrophilic supporting layer.Since hydrophilic supporting layer hole wall surface can be by solution effective wetting, to promote mass transfer to reduce
Concentration polarization.But the problem of there is also the following aspects during supporting layer is hydrophilically modified：（1）Hydrophilic supporter machine
Tool stability is reduced, is easily swollen in water；（2）It influences interface polymerization reaction or changes the property of active cortex.
Therefore, the existing technology needs to be improved and developed.
Invention content
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of forward osmosis membrane and preparation method thereof,
Aim to solve the problem that existing supporting layer it is hydrophilically modified there are hydrophilic supporter mechanical stability reduce, be easily swollen in water, shadow
The problem of ringing interface polymerization reaction or changing the property of active cortex.
Technical scheme is as follows：
A kind of preparation method of forward osmosis membrane, wherein including：
Step A, polysulfones solution and polyetherimide solution is respectively configured, and respectively that the polysulfones solution and polyetherimide is molten
Liquid stirs 6-7 hours at 60-80 DEG C；
Step B, by polyetherimide solution, striking is at polyetherimide film on a glass, then by polysulfones solution in polyethers
Striking is at polysulphone film on imide membrane；
Step C, it tears the polyetherimide film off and obtains polysulfone supporting layer, will be close to the one side conduct of polyetherimide film
The bottom of the polysulfone supporting layer；
Step D, polysulfone supporting layer is put into the methanol solution of benzophenone and is impregnated 1.5-2.5 hours, take out the polysulfones branch
Support layer is put into SMP solution, and the bottom of the polysulfone supporting layer supports under ultra violet lamp in the polysulfones towards ultraviolet lamp
The bottom of layer and hole inner wall are grafted PSMP polymer；
Step E, m-phenylene diamine (MPD) aqueous solution and pyromellitic trimethylsilyl chloride hexane solution is respectively configured, the polysulfones branch that step D is obtained
It is soaked in m-phenylene diamine (MPD) aqueous solution 3-10 minutes at the top of support layer；Then equal benzene three will be soaked at the top of obtained polysulfone supporting layer again
Formyl chloride hexane solution 1-3 minutes.Active cortex is prepared at the top of polysulfone supporting layer.
The preparation method of the forward osmosis membrane, wherein in the step A, the polysulfones solution is by N, N- dimethyl second
Amide, polyethylene glycol 400 and polysulfones configure to obtain.
The preparation method of the forward osmosis membrane, wherein in the step A, the polyetherimide solution is by N- methyl
Pyrrolidones and polyetherimide configure to obtain.
The preparation method of the forward osmosis membrane, wherein include step before the step D：Polysulphone film is put into first
Alcohol solution for soaking 1.5-2.5 hours.
The preparation method of the forward osmosis membrane, wherein in the step D, in the methanol solution of the benzophenone, institute
State a concentration of 0.1-0.2mol/L of benzophenone.
The preparation method of the forward osmosis membrane, wherein in the step D, the time of the ultra violet lamp is 20-40
Minute.
The preparation method of the forward osmosis membrane, wherein in the step D, the time of the ultra violet lamp is 30 points
Clock.A kind of forward osmosis membrane, wherein described including polysulfone supporting layer and the active cortex being compound at the top of the polysulfone supporting layer
The bottom of polysulfone supporting layer and hole inner wall are grafted with PSMP polymer；The forward osmosis membrane is prepared using method of the present invention
It obtains.
The forward osmosis membrane, wherein the aperture of the polysulfone supporting layer is 25-35 nanometers.
The forward osmosis membrane, wherein the thickness of the polysulfone supporting layer is 80-120 microns, the thickness of the activity cortex
Degree is 5-15 nanometers.
Advantageous effect：Sacrificial layer is combined the method and ultraviolet irradiation that casting prepares bottom macropore supporting layer by the present invention for the first time
The method of grafting hydrophily PSMP polymer modifications combines the comprehensive positive permeance property for promoting film.The present invention utilizes ultraviolet spoke
It is only hydrophilically modified to the inner wall progress of the bottom of porous support layer and hole according to the method for grafting hydrophily PSMP polymer, in this way
Not only the stability of active cortex had been maintained, but also has further improved the water permeability of forward osmosis membrane.Operating procedure of the present invention is simple
Easy, effect stability is apparent, good water permeability, and the separation selectivity just permeated improves a lot.
Description of the drawings
Fig. 1 is that the forward osmosis membrane of non-grafted PSMP and the SEM for the forward osmosis membrane for being grafted PSMP scheme in embodiment.
Specific implementation mode
A kind of forward osmosis membrane of present invention offer and preparation method thereof, to make the purpose of the present invention, technical solution and effect more
Add clear, clear, the present invention is described in more detail below.It should be appreciated that specific embodiment described herein is only used
To explain the present invention, it is not intended to limit the present invention.
The present invention discloses a kind of preparation method of forward osmosis membrane, wherein including：
Step A, polysulfones solution and polyetherimide solution is respectively configured, and respectively that the polysulfones solution and polyetherimide is molten
Liquid stirs 6-7 hours at 60-80 DEG C；
Step B, by polyetherimide solution, striking is at polyetherimide film on a glass, then by polysulfones solution in polyethers
Striking is at polysulphone film on imide membrane；
Step C, it tears the polyetherimide film off and obtains polysulfone supporting layer, will be close to the one side conduct of polyetherimide film
The bottom of the polysulfone supporting layer；
Step D, polysulfone supporting layer is put into the methanol solution of benzophenone and is impregnated 1.5-2.5 hours, take out the polysulfones branch
Support layer is put into SMP monomer solutions, and the bottom of the polysulfone supporting layer is towards ultraviolet lamp, in the polysulfones under ultra violet lamp
The bottom of supporting layer and hole inner wall are grafted PSMP polymer；
Step E, m-phenylene diamine (MPD) aqueous solution and pyromellitic trimethylsilyl chloride hexane solution is respectively configured, the polysulfones branch that step D is obtained
It is soaked in m-phenylene diamine (MPD) aqueous solution 3-10 minutes at the top of support layer；Then equal benzene three will be soaked at the top of obtained polysulfone supporting layer again
Formyl chloride hexane solution 1-3 minutes.Active cortex is prepared at the top of polysulfone supporting layer.
Traditional forward osmosis membrane it is hydrophilically modified be all by increase polymer in hydrophilic radical content or with parent
The method that waterborne polymeric is blended, these methods make the top and bottom of supporting layer all have hydrophily, to activity
Cortex performance has a certain impact, and the cutoff performance of salt reduces.However, top hydrophobic can be prepared by the method for the invention
The hydrophilic macropore supporting layer in bottom so that prepare the active cortex of performance stabilization at the top of supporting layer, do not influencing pair in this way
Salt improves the water flux of forward osmosis membrane in the case of retaining.Hydrophilic polymer is grafted by the present invention by the method for uv photo initiated grafting
To porous support layer bottom and hole inner wall, relative to the method for traditional surface grafting polymerization object, the method and step of uv photo initiated grafting
Simply, grafting time is short, easy to operate, and grafting result is stably and controllable.
The polysulfone supporting layer of bottom macropore, the sacrificial layer connection are prepared using sacrificial layer joint casting method by the present invention
It closes casting method and specifically includes step A-C：
The step A is specifically included：Two kinds of polymer solution is configured first.Wherein polysulfones solution is by DMAC N,N' dimethyl acetamide
（DMAc）, polyethylene glycol 400（PEG400）And polysulfones（PSf）Configuration obtains；Polyetherimide solution is by N-Methyl pyrrolidone
（NMP）And polyetherimide（PEI）Configuration obtains.Respectively by two solution in 60 DEG C of -80 DEG C of stirring in water bath 6-7 hours until polymerization
Object is completely dissolved.
The step B is specifically included：First PEI solution is poured on the glass plate of dried flat, is scraped with 100 μm of scrapers
PEI films are made in PEI solution；PSf solution is poured on PEI films again and is scraped with 300 μm of scraper, PSf films are made.
The step C is specifically included：Glass plate is placed in pure water 1-2 minutes, it is therefore an objective to utilize inversion of phases so that high score
Sub- polymer is quickly precipitated at interface, forms very thin compacted zone, and porous layer is formd below compacted zone, is formed outer close
Interior thin membrane structure.It tears the PEI films off and obtains PSf supporting layers, will be close to the one side of PEI films as PSf supporting layers
Bottom.
The present invention use uv photo initiated grafting method, by hydrophilic PSMP polymer be grafted to PSf supporting layers bottom and
Hole inner wall.Relative to the method for traditional surface grafting polymerization object, the method and step of uv photo initiated grafting of the present invention is simple, grafting time
Short, easy to operate, grafting result is stably and controllable.And top hydrophobic bottom can be prepared in the method for uv photo initiated grafting through the invention
The hydrophilic macropore PSf supporting layers in portion so that the active cortex that performance stabilization is prepared at the top of PSf supporting layers, in this way in not shadow
Ring the water flux that forward osmosis membrane is improved in the case of being retained to salt.The method of the uv photo initiated grafting is step D：
Step D is specifically included：Polysulfone supporting layer is put into methanol solution and is impregnated 1.5-2.5 hours（Such as two hours）, make described
Polysulfone supporting layer surface impurity is cleaned.Then polysulfone supporting layer is taken out from methanol solution be put into 0.1-0.2mol/L's
Benzophenone（BP）Methanol solution（As photoinitiator, make polysulfone supporting layer surface active）Middle immersion 1.5-2.5 hours（Such as
Two hours）.The certain density SMP that polysulfone supporting layer is put into 100-200mL is finally taken out from the methanol solution of benzophenone
(wherein solvent is volume ratio V methanol in monomer solution：Water=4 V：A concentration of 0.025-0.15g/mL of 1, SMP monomer, such as
0.05g/mL, 0.1g/mL or 0.15g/mL), it is placed in ultraviolet lamp box illumination 20-40 minutes（Such as 30 minutes）It is poly- to be grafted PSMP
Object is closed, by the bottom-up of polysulfone supporting layer, a piece of quartz glass plate is placed on top, reducing solvent monomer volatilization keeps monomer dense
Degree variation, reduces test error.
Polyamide activity cortex, the interface is prepared by the method for interfacial polymerization in the present invention in polysulfone supporting layer
The method of polymerization is step E：
Step E is specifically included：Configure the m-phenylene diamine (MPD) that 25mL mass percents are 3wt%（MPD）Aqueous solution and 25mL mass percentages
Than the pyromellitic trimethylsilyl chloride for 0.15wt%（TMC）Hexane solution.The obtained polysulfone supporting layers of step D are placed on fixture,
The water-soluble drops of MPD are placed in the top of polysulfone supporting layer using dropper, until being completely covered, are kept for 3-10 minutes, it will be extra
MPD aqueous solutions remove；Then recycle dropper that TMC hexane solutions drop is placed in the top of polysulfone supporting layer, until covering completely
Lid is kept for 1-3 minutes, and extra TMC hexane solutions are removed.It is prepared at the top of polysulfone supporting layer by interfacial polymerization
Active cortex.
The present invention uses sacrificial layer joint casting method to prepare the polysulfone supporting layer of bottom macropore first, then uses ultraviolet
Hydrophilic PSMP polymer is grafted to bottom and the hole inner wall of PSf supporting layers by the method for grafting, finally uses interfacial polymerization
Method active cortex is prepared at the top of polysulfone supporting layer, obtain forward osmosis membrane.After the forward osmosis membrane is prepared in the present invention,
Positive osmosis deaslination test is carried out to the forward osmosis membrane.
Positive osmosis deaslination test：The water permeability of forward osmosis membrane is measured with positive permeability apparatus and the separation of NaCl is selected
Property.Material liquid is pure water, draws the NaCl solution that liquid is 0.5-4M.The conductance of material liquid certain period of time is measured with conductivity meter
Rate changes, when calculating the transit dose of certain period of time salt according to the function curve of conductivity and NaCl concentration, and measuring this section
It is interior to draw the volume change of liquid to determine the water flux of forward osmosis membrane.
The hydrophilic modifying of traditional forward osmosis membrane be all by increase polymer in hydrophilic radical content or with it is hydrophilic
Property polymer be blended method, and the present invention be using ultraviolet irradiation grafting hydrophily PSMP polymer method only to porous branch
The inner wall progress for supportting the bottom and hole of layer is hydrophilically modified, has not only maintained the stability of active cortex in this way, but also further improve
The water permeability of forward osmosis membrane.The present invention for the first time by sacrificial layer combine casting prepare bottom macropore supporting layer method with it is ultraviolet
The method of irradiation grafting hydrophily PSMP polymer modifications combines the comprehensive positive permeance property for promoting film.The present invention operates step
Rapid simple and practicable, effect stability is apparent, good water permeability, and the separation selectivity just permeated improves a lot.
The present invention also provides a kind of forward osmosis membranes, wherein including polysulfone supporting layer and is compound in the polysulfone supporting layer top
The active cortex in portion, the bottom of the polysulfone supporting layer and hole inner wall are grafted with PSMP polymer；The forward osmosis membrane is using this
The invention method is prepared.The effective aperture of the polysulfone supporting layer is about 25-35 nanometers（Such as 30 nanometers）.It is described poly-
The thickness of sulfone supporting layer is about 80-120 microns（Such as 100 microns）, the thickness of the activity cortex is about 5-15 nanometers（Such as 10 receive
Rice）.
Below by embodiment, the present invention is described in detail.
The preparation method of the present embodiment forward osmosis membrane, includes the following steps：
1, the PSf supporting layers of bottom macropore are prepared using sacrificial layer joint casting：
Two kinds of polymer solution, polysulfones solution are configured first：By 18g polysulfones（PSf）Material is dissolved in 74g N, N- dimethylacetamides
Amine（DMAC）In solution, 15g polyethylene glycol is added（PEG400）；Polyetherimide solution：By 17g polyetherimide（PEI）It is molten
In N-Methyl pyrrolidone（NMP）In.Then two solution are respectively placed in 65 DEG C of stirring in water bath 7 hours, the rotating speed 380r/ of stirring
min。
First PEI solution is poured on the glass plate of dried flat, scrapes PEI solution with 100 μm of scrapers, then PSf is molten
Liquid is poured on PEI and is scraped with 300 μm of scraper, is finally placed in glass plate in pure water 1 minute, tears PEI layers off and obtains PSf supports
Layer, will be close to bottom of PEI layers of the one side as PSf supporting layers.Obtained PSf supporting layers are stored in deionized water.
2, PSMP polymer is grafted using ultraviolet lighting：
PSf supporting layers are put into methanol solution and are impregnated two hours, surface impurity is made to be cleaned.PSf supporting layers are put again
Enter 0.13mol/L benzophenone（BP）Methanol solution（Photoinitiator）It is middle to impregnate two hours.Finally take out the PSf branch handled well
In the SMP monomer solutions for the 0.05g/mL that support layer is put into 100mL, it is placed in illumination half an hour grafting PSMP polymerizations in ultraviolet lamp box
A piece of quartz glass plate is placed in the bottom of object, PSf supporting layers towards ultraviolet lamp on top, reduces solvent in monomer solution and volatilizees
So that monomer concentration is changed, reduces test error.
3, active cortex is prepared using the method for interfacial polymerization：
Configure the m-phenylene diamine (MPD) of 25mL 2wt%（MPD）The pyromellitic trimethylsilyl chloride of aqueous solution and 25mL 0.1wt%（TMC）N-hexane
Solution.PSf supporting layers are placed on fixture, the water-soluble drops of MPD are placed in the upper surface of polysulfone supporting layer using dropper, until
It is completely covered, is kept for 5 minutes, extra MPD aqueous solutions are removed；Then dropper is recycled to be placed in TMC hexane solutions drop
The upper surface of PSf supporting layers is kept for 2 minutes until being completely covered, and extra TMC hexane solutions are removed.Active cortex system
It is standby to complete, and forward osmosis membrane is stored in deionized water.
4, positive osmosis deaslination test：
The water permeability of forward osmosis membrane is measured with positive permeability apparatus and to the separation selectivity of NaCl.Material liquid is pure water, is drawn
Liquid is respectively the NaCl solution of 0.5M, 1M, 1.5M, 2M, 4M.Forward osmosis membrane is measured in AL-FS（Cortex is against material liquid）And AL-
DS（Cortex is opposite to draw liquid）Water flux under two patterns and reversed flux salt.Reversed flux salt is measured using conductivity meter
The conductivity variations of material liquid certain period of time calculate certain period of time salt according to the function curve of conductivity and NaCl concentration
Transit dose.Water flux is to draw the volume change of liquid in this time by measuring and determine the water flux of forward osmosis membrane.When
0.5M NaCl are that water flux may be up to 24L/m when drawing under liquid AL-DS patterns2H, and reversed flux salt only has the left sides 0.5g
The right side shows remarkable separation selectivity.
5, the structural characterization of forward osmosis membrane：
As shown in Figure 1, Fig. 1 a are the forward osmosis membrane cortex of non-grafted PSMP, it is close in the forward osmosis membrane that Fig. 1 d are non-grafted PSMP
The section structure of cortex；Fig. 1 b are the forward osmosis membrane cortex for being grafted PSMP, and Fig. 1 e are to be grafted in the forward osmosis membrane of PSMP to lean on
The section structure of nearly cortex.As can be seen from Fig., non-grafted forward osmosis membrane cortex is relatively coarse, and the PSMP being grafted is just
The cortex of permeable membrane is relatively more smooth, and more stable cortex contributes to the retention to NaCl.
In conclusion a kind of forward osmosis membrane provided by the invention and preparation method thereof, the hydrophilic modifying of traditional forward osmosis membrane
All it is the content or the method that is blended with hydrophilic polymer by increasing hydrophilic radical in polymer, and the present invention is sharp
Hydrophily only is carried out to the bottom of porous support layer and the inner wall in hole with the method that ultraviolet irradiation is grafted hydrophily PSMP polymer
It is modified, the stability of active cortex had not only been maintained in this way, but also further improved the water permeability of forward osmosis membrane.The present invention is for the first time
Sacrificial layer is combined into the method and ultraviolet irradiation grafting hydrophily PSMP polymer modifications that casting prepares bottom macropore supporting layer
Method combines the comprehensive positive permeance property for promoting film.Operating procedure of the present invention is simple and practicable, and effect stability is apparent, water penetration
It is good, and the separation selectivity just permeated improves a lot.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of preparation method of forward osmosis membrane, which is characterized in that including：
Step A, polysulfones solution and polyetherimide solution is respectively configured, and respectively that the polysulfones solution and polyetherimide is molten
Liquid stirs 6-7 hours at 60-80 DEG C；
Step B, by polyetherimide solution, striking is at polyetherimide film on a glass, then by polysulfones solution in polyethers
Striking is at polysulphone film on imide membrane；
Step C, it tears the polyetherimide film off and obtains polysulfone supporting layer, will be close to the one side conduct of polyetherimide film
The bottom of the polysulfone supporting layer；
Step D, polysulfone supporting layer is put into the methanol solution of benzophenone and is impregnated 1.5-2.5 hours, take out the polysulfones branch
Support layer is put into SMP solution, and the bottom of the polysulfone supporting layer supports under ultra violet lamp in the polysulfones towards ultraviolet lamp
The bottom of layer and hole inner wall are grafted PSMP polymer；
Step E, m-phenylene diamine (MPD) aqueous solution and pyromellitic trimethylsilyl chloride hexane solution is respectively configured, the polysulfones branch that step D is obtained
It is soaked in m-phenylene diamine (MPD) aqueous solution 3-10 minutes at the top of support layer；Then equal benzene three will be soaked at the top of obtained polysulfone supporting layer again
Formyl chloride hexane solution 1-3 minutes, is prepared active cortex at the top of polysulfone supporting layer.
2. the preparation method of forward osmosis membrane according to claim 1, which is characterized in that in the step A, the polysulfones is molten
Liquid is configured to obtain by DMAC N,N' dimethyl acetamide, polyethylene glycol 400 and polysulfones.
3. the preparation method of forward osmosis membrane according to claim 1, which is characterized in that in the step A, the polyethers acyl
Imide liquor is configured to obtain by N-Methyl pyrrolidone and polyetherimide.
4. the preparation method of forward osmosis membrane according to claim 1, which is characterized in that include step before the step D：
Polysulphone film is put into methanol solution and is impregnated 1.5-2.5 hours.
5. the preparation method of forward osmosis membrane according to claim 1, which is characterized in that in the step D, the hexichol first
In the methanol solution of ketone, a concentration of 0.1-0.2mol/L of the benzophenone.
6. the preparation method of forward osmosis membrane according to claim 1, which is characterized in that in the step D, the ultraviolet lamp
The time of irradiation is 20-40 minutes.
7. the preparation method of forward osmosis membrane according to claim 6, which is characterized in that in the step D, the ultraviolet lamp
The time of irradiation is 30 minutes.
8. a kind of forward osmosis membrane, which is characterized in that including polysulfone supporting layer and the activity being compound at the top of the polysulfone supporting layer
Cortex, the bottom of the polysulfone supporting layer and hole inner wall are grafted with PSMP polymer；The forward osmosis membrane uses claim 1-7
Any one of them method is prepared.
9. forward osmosis membrane according to claim 8, which is characterized in that the aperture of the polysulfone supporting layer is 25-35 nanometers.
10. forward osmosis membrane according to claim 8, which is characterized in that the thickness of the polysulfone supporting layer is that 80-120 is micro-
The thickness of rice, the activity cortex is 5-15 nanometers.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810160910.4A CN108479395B (en) | 2018-02-27 | 2018-02-27 | Forward osmosis membrane and preparation method thereof |
| PCT/CN2018/124702 WO2019165840A1 (en) | 2018-02-27 | 2018-12-28 | Forward osmosis membrane, and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810160910.4A CN108479395B (en) | 2018-02-27 | 2018-02-27 | Forward osmosis membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108479395A true CN108479395A (en) | 2018-09-04 |
| CN108479395B CN108479395B (en) | 2020-12-15 |
Family
ID=63340616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810160910.4A Active CN108479395B (en) | 2018-02-27 | 2018-02-27 | Forward osmosis membrane and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN108479395B (en) |
| WO (1) | WO2019165840A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718667A (en) * | 2019-01-31 | 2019-05-07 | 深圳大学 | A kind of multi-functional forward osmosis membrane and preparation method thereof |
| WO2019165840A1 (en) * | 2018-02-27 | 2019-09-06 | 深圳大学 | Forward osmosis membrane, and preparation method therefor |
| CN113996182A (en) * | 2021-10-21 | 2022-02-01 | 浙江工业大学 | Method for preparing polyvinyl composite nanofiltration membrane by reverse phase interfacial polymerization |
| CN114797493A (en) * | 2022-04-26 | 2022-07-29 | 西南石油大学 | Temperature-resistant composite separation membrane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010086852A1 (en) * | 2009-01-29 | 2010-08-05 | Ben-Gurion University Of The Negev Research And Development Authority | A method for modifying composite membranes for liquid separations |
| US20110147308A1 (en) * | 2009-12-21 | 2011-06-23 | Siemens Water Technologies Corp. | Charged Porous Polymeric Membranes and Their Preparation |
| CN105457509A (en) * | 2015-11-27 | 2016-04-06 | 浙江大学 | Polyamide reverse osmosis composite membrane having renewable chlorine resistance and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8181794B2 (en) * | 2009-08-24 | 2012-05-22 | Oasys Water, Inc. | Forward osmosis membranes |
| CN108495700A (en) * | 2015-11-24 | 2018-09-04 | Oasys水有限公司 | Supporting layer for forward osmosis membrane |
| CN105617885A (en) * | 2016-03-25 | 2016-06-01 | 北京碧水源膜科技有限公司 | Device and method for continuously preparing forward osmosis composite membrane |
| CN105854630B (en) * | 2016-05-11 | 2019-03-29 | 黑龙江八一农垦大学 | A kind of forward osmosis membrane and preparation method thereof |
| CN108479395B (en) * | 2018-02-27 | 2020-12-15 | 深圳大学 | Forward osmosis membrane and preparation method thereof |
-
2018
- 2018-02-27 CN CN201810160910.4A patent/CN108479395B/en active Active
- 2018-12-28 WO PCT/CN2018/124702 patent/WO2019165840A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010086852A1 (en) * | 2009-01-29 | 2010-08-05 | Ben-Gurion University Of The Negev Research And Development Authority | A method for modifying composite membranes for liquid separations |
| US20110147308A1 (en) * | 2009-12-21 | 2011-06-23 | Siemens Water Technologies Corp. | Charged Porous Polymeric Membranes and Their Preparation |
| CN105457509A (en) * | 2015-11-27 | 2016-04-06 | 浙江大学 | Polyamide reverse osmosis composite membrane having renewable chlorine resistance and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| GANG CHEN等: "Open porous hydrophilic supported thin-film composite forward osmosis membrane via co-casting for treatment of high-salinity wastewater", 《DESALINATION》 * |
| MASAHIDE TANIGUCHI等: "Low fouling synthetic membranes by UV-assisted graft polymerization: monomer selection to mitigate fouling by natural organic matter", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| YUN LI等: "Hydrophilicporouspoly(sulfone)membranesmodified byUV-initiated polymerizationforvanadium flow battery application", 《JOURNAL OF MEMBRANE SCIENCE》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019165840A1 (en) * | 2018-02-27 | 2019-09-06 | 深圳大学 | Forward osmosis membrane, and preparation method therefor |
| CN109718667A (en) * | 2019-01-31 | 2019-05-07 | 深圳大学 | A kind of multi-functional forward osmosis membrane and preparation method thereof |
| CN113996182A (en) * | 2021-10-21 | 2022-02-01 | 浙江工业大学 | Method for preparing polyvinyl composite nanofiltration membrane by reverse phase interfacial polymerization |
| CN114797493A (en) * | 2022-04-26 | 2022-07-29 | 西南石油大学 | Temperature-resistant composite separation membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019165840A1 (en) | 2019-09-06 |
| CN108479395B (en) | 2020-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108479395A (en) | A kind of forward osmosis membrane and preparation method thereof | |
| Mansourizadeh et al. | Preparation of blend polyethersulfone/cellulose acetate/polyethylene glycol asymmetric membranes for oil–water separation | |
| Qi et al. | Double-skinned forward osmosis membranes based on layer-by-layer assembly—FO performance and fouling behavior | |
| Liu et al. | Construction of a composite microporous polyethylene membrane with enhanced fouling resistance for water treatment | |
| Maurya et al. | Preparation of polysulfone–polyamide thin film composite hollow fiber nanofiltration membranes and their performance in the treatment of aqueous dye solutions | |
| CN105498559B (en) | Composite membrane based on functional protein | |
| WO2018120476A1 (en) | Supramolecular composite nano-filtration membrane and preparation method therefor and use thereof | |
| Gol et al. | Facile in situ PEGylation of polyamide thin film composite membranes for improving fouling resistance | |
| CN113262644B (en) | High-flux positively-charged nanofiltration membrane and preparation method thereof | |
| Shen et al. | Green and feasible fabrication of loose nanofiltration membrane with high efficiency for fractionation of dye/NaCl mixture by taking advantage of membrane fouling | |
| CN104474925A (en) | Preparation method of composite high-water-flux polyamide reverse-osmosis membrane | |
| JP2016518982A (en) | Polyamide-based water treatment separation membrane excellent in salt removal rate and permeation flow rate characteristics and method for producing the same | |
| Ji et al. | Thin-film composite nanofiltration membrane with unprecedented stability in strong acid for highly selective dye/NaCl separation | |
| WO2009104705A1 (en) | Hollow-fiber ultrafiltration membrane with excellent fouling resistance | |
| CN111408281A (en) | Composite forward osmosis membrane and preparation method thereof | |
| CN107469650A (en) | A kind of preparation method of hydrophobic macropore polyimide nano-fiber forward osmosis membrane | |
| CN115121128A (en) | Preparation method of composite membrane and composite membrane | |
| CN107715708A (en) | Preparation method and its renovation process for the renewable polyelectrolyte film of positive infiltration technology | |
| CN109012214A (en) | A method of high-permeability ultrafiltration membrane is prepared based on chemical pore-forming | |
| Lee et al. | Interfacial polymerization on hydrophobic PVDF UF membranes surface: Membrane wetting through pressurization | |
| CN109718667A (en) | A kind of multi-functional forward osmosis membrane and preparation method thereof | |
| Lin et al. | Preparation and characterization of low-pressure and high MgSO 4 rejection thin-film composite NF membranes via interfacial polymerization process | |
| CN112221363B (en) | Forward osmosis composite membrane and preparation method and application thereof | |
| Alipoor et al. | Toward fabrication of fouling resistant pervaporation membrane for desalination: Surface modification of TFC membrane via grafting of mPEG-NH2 | |
| JP7120523B2 (en) | Method for producing water treatment separation membrane and water treatment separation membrane produced thereby |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |