CN109304107A - A kind of large flux forward osmosis hollow fiber membrane and preparation method thereof - Google Patents
A kind of large flux forward osmosis hollow fiber membrane and preparation method thereof Download PDFInfo
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- CN109304107A CN109304107A CN201710628674.XA CN201710628674A CN109304107A CN 109304107 A CN109304107 A CN 109304107A CN 201710628674 A CN201710628674 A CN 201710628674A CN 109304107 A CN109304107 A CN 109304107A
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- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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- 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
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- 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
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- 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
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- 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
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
- B01D69/088—Co-extrusion; Co-spinning
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- 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
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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Abstract
The invention discloses a kind of big positive permeable hollow fibers films of flux and preparation method thereof.The preparation method includes: to provide the hybrid reaction system comprising polymer, function monomer, initiator, additive and solvent, and heating the hybrid reaction system makes function monomer that polymerization-cross-linking reaction occur and form half interpenetrating network structure, obtains spinning solution；And, the spinning solution and the core liquid comprising acyl chlorides monomer are coextruded through spinning nozzle in a manner of spinning, it immerses in the coagulating bath comprising amine monomers later and is formed by curing hollow-fibre membrane, and make acyl chlorides monomer and amine monomers that interfacial polymerization occur in the inner and outer wall moment of hollow-fibre membrane while film-forming, loose ultra-thin polyamide functional layer is generated, the positive permeable hollow fibers film of big flux is obtained.The positive osmotic water flux of hollow-fibre membrane of the invention is big, mechanical strength is excellent, while preparation method is simple and easy to do, is easy to be mass produced and apply.
Description
Technical field
The invention belongs to technical field of membrane separation more particularly to a kind of positive permeable hollow fibers film of big flux and its preparation sides
Method.
Background technique
Positive process of osmosis is a kind of membrane separation technique emerging in recent years, is the important means for realizing sea water desalination.It by
The solute concentration difference of film two sides drives, and is not necessarily to additional driving force, energy-saving.Also, the material liquid after being concentrated can be made into one
Step processing, the liquid that draws after dilution can be by the extraction of concentration technique again pure water therein, and what acquisition was concentrated again draws liquid, real
Recycling for liquid is now drawn, operating cost is low, and added value is high.
Interfacial polymerization is to prepare one of most common method of forward osmosis membrane, and classical interfacial polymerization process is first by support membrane
It immerses in the aqueous solution containing activity monomer or prepolymer, takes the film out after a certain period of time and remove the extra water phase of film surface
Solution, then the sample is immersed in the organic solution containing another active monomer, two kinds of activity monomers are only sent out at interface
Raw reaction, forms epidermis, and by heat treatment appropriate, fine and close polymeric skin is formed in membrane surface, so that positive infiltration
Water flux it is smaller.And common forward osmosis membrane is plate membrane, space utilization rate is lower.Therefore, existing in the prior art
The above problem is urgently to be resolved.
Summary of the invention
It is existing to overcome the purpose of the present invention is to provide a kind of big positive permeable hollow fibers film of flux and preparation method thereof
Deficiency in technology.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of preparation methods of big positive permeable hollow fibers film of flux comprising:
The hybrid reaction system for including at least polymer, function monomer, initiator, additive and solvent is provided, is being protected
Property atmosphere in heat the hybrid reaction system make function monomer occur polymerization-cross-linking reaction and form half interpenetrating network structure,
Obtain spinning solution；
And be coextruded the spinning solution and the core liquid comprising acyl chlorides monomer through spinning nozzle, immersing later includes amine
It is formed by curing hollow-fibre membrane in the coagulating bath of monomer, and makes acyl chlorides monomer and amine monomers hollow while film-forming
Interfacial polymerization occurs for the inner and outer wall moment of tunica fibrosa, generates loose ultra-thin polyamide functional layer, obtains the big flux
Positive permeable hollow fibers film.
In some embodiments of the present invention, the preparation method includes:
(1) in protective atmosphere, polymer, function monomer, additive is uniformly mixed in solvent at least, are heated to
20~130 DEG C, initiator is added, and react 0.5~60 hour in 60~150 DEG C, make the function monomer that polymerization-friendship occur
Connection reacts and forms half interpenetrating network structure, obtains spinning solution；
(2) using acyl chlorides monomer solution as core liquid, using amine monomers solution as coagulating bath, by step (1) obtained spinning
Liquid is coextruded with core liquid through spinning nozzle, is stopped 0.5~60 second in air, is then immersed film-forming in coagulating bath, and in 60
~120 DEG C are heat-treated 0.5~10 minute, obtain the big positive permeable hollow fibers film of flux.
The embodiment of the invention also provides the positive permeable hollow fibers films of the big flux prepared by the method.
Preferably, the positive permeable hollow fibers film of the big flux includes:
Doughnut membrane body comprising the half interpenetrating network structure for mainly being polymerize-being cross-linked to form by function monomer；
And at least it is distributed in the hollow-fibre membrane inner body wall and outer wall, loose ultra-thin polyamide functional layer.
Compared with prior art, the invention has the advantages that
(1) preparation method of the positive permeable hollow fibers film of big flux provided by the invention, by acyl chlorides monomer solution and amine
Monomer solution completes interfacial polymerization respectively as core liquid and coagulating bath during spinning, and moment reaction generates loose surpass
Thin polyamide functional layer obtains the positive permeable hollow fibers film of big flux；
(2) function monomer polymerization-crosslinking in a polymer solution in the hollow-fibre membrane of the method for the present invention preparation, forms
Stable half interpenetrating network structure, eluting rate is low, can for a long time, persistently assign the hollow-fibre membrane excellent mechanical strength；
(3) preparation method median surface polymerization provided by the invention and the preparation of hollow-fibre membrane synchronously complete, high-efficient, system
It is standby simple and easy to do, it is easy to be mass produced and apply.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
As the one aspect of technical solution of the present invention, involved in be a kind of positive permeable hollow fibers film of big flux
Preparation method comprising:
The hybrid reaction system for including at least polymer, function monomer, initiator, additive and solvent is provided, is being protected
Property atmosphere in heat the hybrid reaction system make function monomer occur polymerization-cross-linking reaction and form half interpenetrating network structure,
Obtain spinning solution；
And be coextruded the spinning solution and the core liquid comprising acyl chlorides monomer through spinning nozzle, immersing later includes amine
It is formed by curing hollow-fibre membrane in the coagulating bath of monomer, and makes acyl chlorides monomer and amine monomers hollow while film-forming
Interfacial polymerization occurs for the inner and outer wall moment of tunica fibrosa, generates loose ultra-thin polyamide functional layer, obtains the big flux
Positive permeable hollow fibers film.
In some embodiments of the present invention, the preparation method includes:
(1) in protective atmosphere, polymer, function monomer, additive is uniformly mixed in solvent at least, are heated to
20~130 DEG C, initiator is added, and react 0.5~60 hour in 60~150 DEG C, make the function monomer that polymerization-friendship occur
Connection reacts and forms half interpenetrating network structure, obtains spinning solution；
(2) using acyl chlorides monomer solution as core liquid, using amine monomers solution as coagulating bath, by step (1) obtained spinning
Liquid is coextruded with core liquid through spinning nozzle, is stopped 0.5~60 second in air, is then immersed film-forming in coagulating bath, and in 60
~120 DEG C are heat-treated 0.5~10 minute, obtain the big positive permeable hollow fibers film of flux.
In some embodiments, the hybrid reaction system includes 5~35wt% polymer, 0.5~15wt% function list
Body, 0.1~5wt% initiator, 0.01~20wt% additive, rest part include solvent.
Preferably, the polymer includes polysulfones, sulfonated polysulfone, polyether sulfone, polyacrylonitrile, polyimides, polyvinylidene fluoride
Any one in alkene and cellulose acetate etc. or two or more combinations, but not limited to this.
Preferably, the function monomer includes acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, methyl
Acrylic acid diethylamino ethyl ester, acrylamide, hydroxyethyl methacrylate, methoxypolyethylene glycol methacrylate, N- second
Any one in vinyl pyrrolidone and n-isopropyl acrylamide etc. or two or more combinations, but not limited to this.
Preferably, the additive includes polyethylene glycol, polyoxyethylene, polyethyleneimine, graphene, carbon nanotube, two
Silicon oxide nanoparticle, titanium dioxide nano-particle, gold nanoparticle and N, it is any one in N '-methylene-bisacrylamide etc.
Kind or two or more combinations, but not limited to this.
Preferably, the initiator includes azodiisobutyronitrile, but not limited to this.
Preferably, the solvent includes dimethyl sulfoxide, N-Methyl pyrrolidone, N, N '-dimethyl formamide, N, N '-
Any one in dimethyl acetamide, acetone and trimethyl phosphate etc. or two or more combinations, but not limited to this.
In some embodiments of the present invention, the core liquid includes the acyl chlorides monomer hexane solution of 0.01~10wt%
(i.e. organic phase solution).
Preferably, the acyl chlorides monomer includes m-phthaloyl chloride, paraphthaloyl chloride, o-phthaloyl chloride, equal benzene three
Any one in the chloro- isophthaloyl chlorine of formyl chloride, 5- oxygen formyl and 5- isocyanates-isophthaloyl chlorine etc. or two or more groups
It closes, but not limited to this.
In some embodiments, the coagulating bath includes 0.01~10wt% amine monomers aqueous solution (i.e. aqueous phase solution).
Preferably, the amine monomers include m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, piperazine, ethylenediamine, 1,2- second
Any one in diamines, Isosorbide-5-Nitrae-cyclohexanediamine, 1,3- hexamethylene dimethylamine and diethyl triamine etc. or two or more combinations, but
It is without being limited thereto.
Preferably, the preparation method includes:
The spinning solution and the core liquid (i.e. organic phase solution) comprising acyl chlorides monomer are coextruded through spinning nozzle, immersed later
It is formed by curing hollow-fibre membrane in coagulating bath (i.e. aqueous phase solution) comprising amine monomers, and is made while film-forming organic
Phase solution liquid compatible with water flows separately through hollow-fibre membrane inner and outer wall, and interfacial polymerization occurs for moment, generates loose ultra-thin
Polyamide functional layer obtains the positive permeable hollow fibers film of big flux.
Wherein, as one more specifically one of embodiment, the preparation method may comprise steps of:
Step (1): polymer, function monomer, additive and solvent are added in reaction kettle, lead to nitrogen, 20~130 DEG C are held
Continuous stirring adds azodiisobutyronitrile and causes function monomer polymerization to being completely dissolved, and 60~150 DEG C are reacted 0.5~60 hour,
Obtain spinning solution；Wherein the mass percent concentration of polymer is 5~35%, and the mass percent concentration of function monomer is 0.5
~15%, the mass percent concentration of additive is 0.01~20%, the mass percent concentration of azodiisobutyronitrile is 0.1~
5%, remaining as solvent；
Step (2): spinning solution prepared by step (1) is coextruded by metering pump through spinning nozzle with core liquid, in air
It stops 0.5~60 second, then immerses film-forming in coagulating bath, cleaning is heat-treated 0.5~10 minute then at 60~120 DEG C, is done
Dry, winding obtains the positive permeable hollow fibers film of big flux；Wherein, core liquid is the oil that mass percent concentration is 0.01~10%
Phase acyl chlorides monomer hexane solution, coagulating bath are that mass percent concentration is 0.01~10% amine monomers aqueous solution.
As the other side of technical solution of the present invention, further relate to just permeated by big flux prepared by preceding method
Empty fiber membrane.
Preferably, the positive permeable hollow fibers film of the big flux includes:
Doughnut membrane body comprising the half interpenetrating network structure for mainly being polymerize-being cross-linked to form by function monomer；
And at least it is distributed in the hollow-fibre membrane inner body wall and outer wall, loose ultra-thin polyamide functional layer.
Preferably, the ultra-thin polyamide functional layer with a thickness of 5~30nm；
Preferably, the tensile strength of the positive permeable hollow fibers film of the big flux is 3.2~6.8MPa, and pure water flux is
42.7~93.8Lm-2h-1, the rejection to sodium chloride is 82.5~98.9%.
By aforementioned preparation process, using acyl chlorides monomer solution and amine monomers solution as core liquid and coagulating bath,
Interfacial polymerization is completed during spinning, moment reaction generates loose ultra-thin polyamide functional layer, obtains the positive infiltration of big flux
Saturating hollow-fibre membrane.Function monomer polymerization-crosslinking in a polymer solution in the hollow-fibre membrane of the method for the present invention preparation, shape
At stable half interpenetrating network structure, eluting rate is low, and it is strong can for a long time, persistently to assign the excellent mechanics of the hollow-fibre membrane
Degree.The polymerization of preparation method median surface and the preparation of hollow-fibre membrane provided by the invention synchronously complete, high-efficient, prepare easy to be easy
Row is easy to be mass produced and apply.
More detailed illustrate is made to technical solution of the present invention below in conjunction with several preferred embodiments.
Embodiment 1
(1) 5 grams of polysulfones, 0.5 gram of acrylic acid, 20 grams of polyethylene glycol and 74.5 grams of dimethyl sulfoxides are added in reaction kettle,
Logical nitrogen, 130 DEG C continue stirring until and are completely dissolved, and add 0.1 gram of azodiisobutyronitrile and cause acroleic acid polymerization, 60 DEG C of reactions
60 hours, obtain spinning solution；
(2) hexane solution for the m-phthaloyl chloride for being 0.01% with mass percent concentration by the spinning solution passes through
Metering pump is coextruded through spinning nozzle, is stopped 0.5 second in air, is then immersed the isophthalic two that mass percent concentration is 0.01%
Film-forming in amine aqueous solution, cleaning are heat-treated 0.5 minute then at 60 DEG C, dry, and winding obtains the positive permeable hollow of big flux
Tunica fibrosa.
After tested, the aramid layer of hollow-fibre membrane manufactured in the present embodiment with a thickness of 12nm, tensile strength is
It is pure water flux 42.7Lm when drawing liquid that 5.1MPa, which is 2mol/L sodium chloride solution with concentration,-2·h-1, to sodium chloride
Rejection is 91.5%.
Embodiment 2
(1) by 35 grams of sulfonated polysulfone, 15 grams of methacrylic acids, 0.01 gram of graphene and 49.99 grams of N-Methyl pyrrolidones
It is added in reaction kettle, leads to nitrogen, 20 DEG C continue stirring until and are completely dissolved, and add 5 grams of azodiisobutyronitriles and cause metering systems
Acid polymerization, 150 DEG C are reacted 0.5 hour, obtain spinning solution；
(2) hexane solution for the paraphthaloyl chloride for being 10% by the spinning solution and mass percent concentration passes through meter
Amount pump is coextruded through spinning nozzle, is stopped in air 60 seconds, then immersing mass percent concentration is that 10% o-phenylenediamine is water-soluble
Film-forming in liquid, cleaning are heat-treated 10 minutes then at 120 DEG C, dry, and winding obtains the positive permeable hollow fibers film of big flux.
After tested, the aramid layer of hollow-fibre membrane manufactured in the present embodiment with a thickness of 5nm, tensile strength is
It is pure water flux 67.8Lm when drawing liquid that 4.4MPa, which is 2mol/L sodium chloride solution with concentration,-2·h-1, to sodium chloride
Rejection is 98.9%.
Embodiment 3
(1) by 10 grams of polyether sulfones, 2 grams of dimethylaminoethyl methacrylates, 1 gram of polyoxyethylene and 87 grams of N, N '-diformazan
Base formamide is added in reaction kettle, leads to nitrogen, and 40 DEG C continue stirring until and are completely dissolved, and adds 0.2 gram of azodiisobutyronitrile and draws
Dimethylaminoethyl methacrylate polymerization is sent out, 70 DEG C are reacted 5 hours, and spinning solution is obtained；
(2) hexane solution for the o-phthaloyl chloride for being 0.1% with mass percent concentration by the spinning solution passes through
Metering pump is coextruded through spinning nozzle, is stopped in air 5 seconds, then immersing mass percent concentration is 0.1% p-phenylenediamine water
Film-forming in solution, cleaning are heat-treated 1 minute then at 70 DEG C, dry, and winding obtains the positive permeable hollow fibers film of big flux.
After tested, the aramid layer of hollow-fibre membrane manufactured in the present embodiment with a thickness of 22nm, tensile strength is
It is pure water flux 57.1Lm when drawing liquid that 3.2MPa, which is 2mol/L sodium chloride solution with concentration,-2·h-1, to sodium chloride
Rejection is 86.2%.
Embodiment 4
(1) by 15 grams of polyacrylonitrile, 4 grams of diethyl aminoethyl methacrylates, 5 grams of polyethyleneimines and 76 grams of N,
N '-dimethyl acetamide is added in reaction kettle, leads to nitrogen, and 50 DEG C continue stirring until and are completely dissolved, and it is different to add 0.5 gram of azo two
Butyronitrile causes diethyl aminoethyl methacrylate polymerization, and 80 DEG C are reacted 10 hours, obtains spinning solution；
(2) hexane solution for the pyromellitic trimethylsilyl chloride for being 0.3% with mass percent concentration by the spinning solution passes through
Metering pump is coextruded through spinning nozzle, is stopped in air 10 seconds, then immersing mass percent concentration is 0.2% piperazine aqueous solution
Middle film-forming, cleaning are heat-treated 3 minutes then at 80 DEG C, dry, and winding obtains the positive permeable hollow fibers film of big flux.
After tested, the aramid layer of hollow-fibre membrane manufactured in the present embodiment with a thickness of 27nm, tensile strength is
It is pure water flux 88.3Lm when drawing liquid that 6.8MPa, which is 2mol/L sodium chloride solution with concentration,-2·h-1, to sodium chloride
Rejection is 99.1%.
Embodiment 5
(1) by 20 grams of polyimides, 5 grams of acrylamides, 8 grams of carbon nanotubes and 67 grams of N, N '-dimethyl formamide is added
In reaction kettle, lead to nitrogen, 70 DEG C continue stirring until and are completely dissolved, and it adds 1 gram of azodiisobutyronitrile and causes acrylamide polymerization,
90 DEG C are reacted 15 hours, and spinning solution is obtained；
(2) hexane solution for the chloro- isophthaloyl chlorine of 5- oxygen formyl for being 1% by the spinning solution and mass percent concentration
It is coextruded, is stopped in air 20 seconds, then immersing mass percent concentration is 0.5% ethylenediamine through spinning nozzle by metering pump
Film-forming in aqueous solution, cleaning are heat-treated 5 minutes then at 90 DEG C, dry, and winding obtains the positive permeable hollow fibers of big flux
Film.
After tested, the aramid layer of hollow-fibre membrane manufactured in the present embodiment with a thickness of 30nm, tensile strength is
It is pure water flux 93.8Lm when drawing liquid that 5.9MPa, which is 2mol/L sodium chloride solution with concentration,-2·h-1, to sodium chloride
Rejection is 82.5%.
Embodiment 6
(1) by 25 grams of Kynoar, 10 grams of hydroxyethyl methacrylates, 1.5 grams of Nano particles of silicon dioxide and 63.5
Gram trimethyl phosphate is added in reaction kettle, leads to nitrogen, and 80 DEG C continue stirring until and are completely dissolved, and adds 5 grams of azodiisobutyronitriles
Cause hydroxyethyl methacrylate polymerization, 100 DEG C are reacted 20 hours, and spinning solution is obtained；
(2) the 5- isocyanates-isophthaloyl chlorine hexane solution for being 4% by the spinning solution and mass percent concentration
It is coextruded, is stopped in air 30 seconds, then immersing mass percent concentration is 6%1,2- second two through spinning nozzle by metering pump
Film-forming in amine aqueous solution, cleaning are heat-treated 6 minutes then at 100 DEG C, dry, winding, and it is fine to obtain the positive permeable hollow of big flux
Tie up film.
After tested, the aramid layer of hollow-fibre membrane manufactured in the present embodiment with a thickness of 17nm, tensile strength is
It is pure water flux 61.2Lm when drawing liquid that 4.7MPa, which is 2mol/L sodium chloride solution with concentration,-2·h-1, to sodium chloride
Rejection is 93.6%.
Embodiment 7
(1) by 30 grams of cellulose acetates, 15 grams of methoxypolyethylene glycol methacrylates, 2.5 grams of titanium dioxide nano granules
Son and 52.5 grams of acetone are added in reaction kettles, lead to nitrogen, and 60 DEG C continue stirring until and are completely dissolved, and it is different to add 2.5 grams of azos two
Butyronitrile causes methoxypolyethylene glycol methacrylate, and 60 DEG C are reacted 25 hours, obtains spinning solution；
(2) the 5- isocyanates-isophthaloyl chlorine hexane solution for being 5% by the spinning solution and mass percent concentration
It is coextruded by metering pump through spinning nozzle, stops in air 30 seconds, then immerse Isosorbide-5-Nitrae-ring that mass percent concentration is 5%
Film-forming in hexamethylene diamine, cleaning are heat-treated 8 minutes then at 105 DEG C, dry, and winding obtains the positive permeable hollow fibers of big flux
Film.
After tested, the aramid layer of hollow-fibre membrane manufactured in the present embodiment with a thickness of 21nm, tensile strength is
It is pure water flux 87.6Lm when drawing liquid that 6.3MPa, which is 2mol/L sodium chloride solution with concentration,-2·h-1, to sodium chloride
Rejection is 90.4%.
Embodiment 8
(1) by 12.5 grams of polysulfones, 12.5 grams of n-vinyl pyrrolidone, 2 grams of gold nanoparticles and 73 grams of N, N '-dimethyl
Formamide is added in reaction kettle, leads to nitrogen, and 100 DEG C continue stirring until and are completely dissolved, and adds 3 grams of azodiisobutyronitriles and causes N-
Vinyl pyrrolidone polymerization, 120 DEG C are reacted 36 hours, obtain spinning solution；
(2) hexane solution for the o-phthaloyl chloride for being 8% by the spinning solution and mass percent concentration passes through meter
Amount pump is coextruded through spinning nozzle, is stopped 40 seconds in air, is then immersed 1, the 3- hexamethylene diformazan that mass percent concentration is 6%
Film-forming in amine aqueous solution, cleaning are heat-treated 2 minutes then at 100 DEG C, dry, winding, and it is fine to obtain the positive permeable hollow of big flux
Tie up film.
After tested, the aramid layer of hollow-fibre membrane manufactured in the present embodiment with a thickness of 28nm, tensile strength is
It is pure water flux 71.3Lm when drawing liquid that 5.9MPa, which is 2mol/L sodium chloride solution with concentration,-2·h-1, to sodium chloride
Rejection is 93.6%.
Embodiment 9
(1) by 16 grams of polyether sulfones, 9 grams of n-isopropyl acrylamide, 1 gram of N, N '-methylene-bisacrylamide and 67 grams of N,
N '-dimethyl acetamide is added in reaction kettle, leads to nitrogen, and 120 DEG C continue stirring until and are completely dissolved, and adds 0.8 gram of azo two
Isobutyronitrile causes n-isopropyl acrylamide polymerization, and 130 DEG C are reacted 50 hours, obtains spinning solution；
(2) hexane solution for the o-phthaloyl chloride for being 2.5% with mass percent concentration by the spinning solution passes through
Metering pump is coextruded through spinning nozzle, is stopped 50 seconds in air, is then immersed the diethyl three that mass percent concentration is 2.5%
Film-forming in amine aqueous solution, cleaning are heat-treated 6 minutes then at 120 DEG C, dry, winding, and it is fine to obtain the positive permeable hollow of big flux
Tie up film.
After tested, the aramid layer of hollow-fibre membrane manufactured in the present embodiment with a thickness of 17nm, tensile strength is
It is pure water flux 79.1Lm when drawing liquid that 6.4MPa, which is 2mol/L sodium chloride solution with concentration,-2·h-1, to sodium chloride
Rejection is 86.7%.
Reference examples 1:
The preparation method of this reference examples includes: that support membrane is first immersed the aqueous solution containing activity monomer or prepolymer
In, it takes the film out the sample is immersed in the organic solution containing another active monomer again after a certain period of time, carry out interface
Reaction obtains hollow-fibre membrane.
It is when drawing liquid that the hollow-fibre membrane of this reference examples preparation, which is 2mol/L sodium chloride solution with concentration, and tensile strength is
It is pure water flux 20.1Lm when drawing liquid that 1.8MPa, which is 2mol/L sodium chloride solution with concentration,-2·h-1, to sodium chloride
Rejection is 50.6%.
Reference examples 2: this reference examples is substantially the same manner as Example 1, and difference place is: step (1) is not added with function monomer
It carries out polymerizeing-cross-linking reaction.
It is when drawing liquid that the hollow-fibre membrane of this reference examples preparation, which is 2mol/L sodium chloride solution with concentration, and tensile strength is
It is pure water flux 24.6Lm when drawing liquid that 1.2MPa, which is 2mol/L sodium chloride solution with concentration,-2·h-1, to sodium chloride
Rejection is 58.1%.
It has been found by contrast that the obtained hollow-fibre membrane of reference examples 1 and 2 in tensile strength, pure water flux and cuts sodium chloride
Stay the performances such as rate are convenient to be nothing like the obtained hollow-fibre membrane of 1-9 of the embodiment of the present invention.
In addition, inventor also refers to the mode of embodiment 1- embodiment 9, with the other raw materials listed in this specification
It is tested with condition etc., and the positive permeable hollow of big flux that positive osmotic water flux is big, mechanical strength is excellent has equally been made
Tunica fibrosa.
It should be appreciated that the above is only specific application examples of the invention, any limit is not constituted to protection scope of the present invention
System.Any technical scheme formed by adopting equivalent transformation or equivalent replacement, all falls within rights protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the positive permeable hollow fibers film of big flux, characterized by comprising:
The hybrid reaction system for including at least polymer, function monomer, initiator, additive and solvent is provided, in protectiveness gas
The hybrid reaction system is heated in atmosphere makes function monomer that polymerization-cross-linking reaction occur and form half interpenetrating network structure, obtains
Spinning solution；
And be coextruded the spinning solution and the core liquid comprising acyl chlorides monomer through spinning nozzle, immersing later includes amine monomers
Coagulating bath in film-forming, obtain the big positive permeable hollow fibers film of flux.
2. preparation method according to claim 1, which is characterized in that the preparation method specifically includes:
(1) in protective atmosphere, at least polymer, function monomer, additive are uniformly mixed in solvent, it is heated to 20~
130 DEG C, initiator is added, and react 0.5~60 hour in 60~150 DEG C, make the function monomer that polymerization-crosslinking occur anti-
It answers and forms half interpenetrating network structure, obtain spinning solution；
(2) using acyl chlorides monomer solution as core liquid, using amine monomers solution as coagulating bath, by step (1) obtained spinning solution with
Core liquid is coextruded through spinning nozzle, is stopped 0.5~60 second in air, is then immersed film-forming in coagulating bath, and in 60~120
DEG C heat treatment 0.5~10 minute, obtain the big positive permeable hollow fibers film of flux.
3. preparation method according to claim 1, it is characterised in that: the hybrid reaction system is poly- comprising 5~35wt%
Object, 0.5~15wt% function monomer, 0.1~5wt% initiator, 0.01~20wt% additive are closed, rest part includes molten
Agent.
4. preparation method according to any one of claim 1-3, it is characterised in that: the polymer includes polysulfones, sulphur
Change polysulfones, polyether sulfone, polyacrylonitrile, polyimides, in Kynoar and cellulose acetate any one or it is two or more
Combination.
5. preparation method according to any one of claim 1-3, it is characterised in that: the function monomer includes propylene
Acid, methacrylic acid, dimethylaminoethyl methacrylate, diethyl aminoethyl methacrylate, acrylamide, methyl-prop
Appointing in olefin(e) acid hydroxyl ethyl ester, methoxypolyethylene glycol methacrylate, n-vinyl pyrrolidone and n-isopropyl acrylamide
Meaning a combination of one or more.
6. preparation method according to any one of claim 1-3, it is characterised in that: the additive includes poly- second two
Alcohol, polyoxyethylene, polyethyleneimine, graphene, carbon nanotube, Nano particles of silicon dioxide, titanium dioxide nano-particle, Jenner
Rice corpuscles and N, any one in N '-methylene-bisacrylamide or two or more combinations；
And/or the initiator includes azodiisobutyronitrile；
And/or the solvent includes dimethyl sulfoxide, N-Methyl pyrrolidone, N, N '-dimethyl formamide, N, N '-dimethyl
Any one in acetamide, acetone and trimethyl phosphate or two or more combinations.
7. preparation method according to claim 2, it is characterised in that: the core liquid includes the acyl chlorides list of 0.01~10wt%
Body hexane solution；Preferably, the acyl chlorides monomer include m-phthaloyl chloride, paraphthaloyl chloride, o-phthaloyl chloride,
Any one in the chloro- isophthaloyl chlorine of three formyl chloride of benzene, 5- oxygen formyl and 5- isocyanates-isophthaloyl chlorine or two or more groups
It closes.
8. according to claim 1, preparation method described in any one of 2,3,7, it is characterised in that: the coagulating bath includes 0.01
~10wt% amine monomers aqueous solution；Preferably, the amine monomers include m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, piperazine
Any one in piperazine, ethylenediamine, 1,2- ethylenediamine, 1,4- cyclohexanediamine, 1,3- hexamethylene dimethylamine and diethyl triamine or two
Kind or more combination.
9. the positive permeable hollow fibers film of big flux prepared by any one of claim 1-8 the method.
10. the positive permeable hollow fibers film of big flux according to claim 9, characterized by comprising:
Doughnut membrane body comprising the half interpenetrating network structure for mainly being polymerize-being cross-linked to form by function monomer；
And at least it is distributed in the hollow-fibre membrane inner body wall and outer wall, loose ultra-thin polyamide functional layer；
Preferably, the ultra-thin polyamide functional layer with a thickness of 5~30nm；
Preferably, the tensile strength of the positive permeable hollow fibers film of the big flux be 3.2~6.8MPa, pure water flux be 42.7~
93.8Lm-2h-1, the rejection to sodium chloride is 82.5~98.9%.
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