CN106731901A - Polyester fiber weaves the preparation method of tube enhancement type composite hollow fibre forward osmosis membrane - Google Patents

Polyester fiber weaves the preparation method of tube enhancement type composite hollow fibre forward osmosis membrane Download PDF

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CN106731901A
CN106731901A CN201710039263.7A CN201710039263A CN106731901A CN 106731901 A CN106731901 A CN 106731901A CN 201710039263 A CN201710039263 A CN 201710039263A CN 106731901 A CN106731901 A CN 106731901A
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film
solution
osmosis membrane
forward osmosis
woven tube
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CN106731901B (en
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王磊
李陈
张慧慧
陈立成
***
吕永涛
苗瑞
朱振亚
王雷磊
王佳璇
刘婷婷
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Xian University of Architecture and Technology
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Xian University of Architecture and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/48Polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/002Forward osmosis or direct osmosis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08Hollow fibre membranes
    • B01D69/087Details relating to the spinning process
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12Composite membranes; Ultra-thin membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/24Mechanical properties, e.g. strength
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/30Chemical resistance
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/36Hydrophilic membranes

Abstract

The invention discloses the preparation method that a kind of polyester fiber weaves tube enhancement type composite hollow fibre forward osmosis membrane, including:Polymer, organic additive, inorganic additive and organic solvent are proportionally configured to homogeneous casting solution;Casting solution is evenly applied in polyester fiber braiding pipe outer wall and its internal gutter, producing inner external wall film coated woven tube is obtained;Overlay film woven tube is by entering inversion of phases film forming in coagulating bath behind certain air residence time;First the remaining organic solvent of immersion removal soaks first film forming in hot bath in deionized water, is taken out after finally being soaked in glycerin solution and dried, and polyester fiber braiding tube enhancement type composite hollow fibre forward osmosis membrane is obtained.The step of polymeric casting film liquid one is coated on woven tube inside and outside wall and obtains high-strength composite doughnut forward osmosis membrane by the present invention using immersion precipitation phase inversion process, and filming technology is simple;Organic and inorganic blending film-forming method improves water flux, selectivity, hydrophily, stability and the service life of film.

Description

Polyester fiber weaves the preparation method of tube enhancement type composite hollow fibre forward osmosis membrane
Technical field
The invention belongs to field of membrane preparation, and in particular to a kind of polyester fiber braiding tube enhancement type composite hollow fibre just oozes Permeable membrane and preparation method thereof.
Background technology
Membrane separation technique quickly grows in recent years, in clean water treatment, wastewater treatment and reuse and Treatment of Industrial Water field It is widely used.Positive infiltration technology (FO) has very big as a kind of membrane separation technique of green in sewage disposal and resource Application potential.Positive infiltration refers to water from the mistake flowed to by permoselective membrane compared with Hyposmolality side compared with hyperosmosis side Journey.Positive infiltration technology has the advantages that energy consumption is low, fouling membrane is small, the Water Sproading rate extensive pass by domestic and foreign scholars high because of it Note.
Exploitation to high-performance forward osmosis membrane material is always the positive study hotspot for permeating field, and preferable forward osmosis membrane should Possess that rejection is high, water flux big, good hydrophilic property, thickness of thin, porosity are high, high mechanical strength, while also needing possess corrosion-resistant The feature such as ability is relatively strong and range of application is wider.Organic matter and the masking technique of inorganic matter blending can increase compound film strength And the life-span, improve hydrophilicity, the water flux of film is improved, while making film that there is good resistance tocrocking.At present, developed The forward osmosis membrane component for going out includes plate and hollow fiber type.However, plate film component has, film bulk density is small, be difficult Cleaning, flow regime it is bad easily cause concentration polarization it is more serious the shortcomings of.Hollow fiber type is generally without the hollow of supporting layer Tunica fibrosa, has the shortcomings that mechanical strength is low, contamination resistance is poor.Beijing Ege Technology Co., Ltd. (CN205109419U, CN105126654A) is prepared for inner support type doughnut forward osmosis membrane, and the method is in support tube Surface is prepared for active layer by interfacial polymerization, and the cohesive force deficiency between active layer and supporting layer cause film easily layering and Deformation, and composite membrane is easily oxidized, causes film properties to reduce, service life shortens, pollution aggravation.This seminar is by a leaching one Polymeric casting film liquid is coated to roll process the surfaces externally and internally of PET woven tubes using coating twice, is prepared for high intensity, anti-soil high Metachromia and cutoff performance composite hollow fibre milipore filter high.The method is needed to coat twice, and woven tube process is soaked in casting solution Middle coat thickness is difficult to control to and influences the secondary coating effect of casting solution, causes film thickness to increase, and the technique is not suitable for just The preparation of permeable membrane, in addition preparation technology complexity, equipment requirement high, high cost, not easy to operate.
Based on this, it is desirable to provide it is short that one kind solves low existing positive permeable hollow fibers film-strength, easy pollution, service life, Inner support type hollow-fibre membrane is easily layered, unstable properties, new way the problems such as filming technology is complicated whard to control.Also, The invention of polyester fiber woven tube/polymer composite hollow fibre forward osmosis membrane is prepared there is not yet report using phase inversion.
The content of the invention
It is short that the purpose of the present invention is directed to low existing positive permeable hollow fibers film-strength, easy pollution, service life, inner support Separating layer is yielding, the caused film properties that come off are unstable for the activation of type hollow-fibre membrane, the problems such as filming technology is complicated, it is proposed that A kind of polyester fiber braiding tube enhancement type composite hollow fibre forward osmosis membrane and preparation method thereof.
The invention provides the preparation method that a kind of polyester fiber weaves tube enhancement type composite hollow fibre forward osmosis membrane, bag Include following steps:
1) preparation of casting solution:Mass ratio is first added to the organic solvent of 69-83% for the inorganic additive of 1-3% In obtain organic solution, when one section of ultrasonic disperse after, the organic additive of the polymer of 14-20%, 2-8% is added to State in organic solution, stirring, vacuum defoamation obtains homogeneous casting solution;
2) woven tube is producing inner external wall film coated:Homogeneous casting solution is clamp-oned under 0.05-0.2Mpa nitrogen pressures by gear pump In circular spinning appts, control casting solution enters woven tube internal pressure, and casting solution is evenly applied to weave pipe outer wall, while Into in internal gutter, producing inner external wall film coated woven tube hollow fiber film thread is obtained;
3) just film forming is formed:Under wire winding device driving, producing inner external wall film coated woven tube is by behind 5-30s air residence times The inversion of phases film forming into outer coagulating bath;
4) film silk post processing:By step 3) hollow-fibre membrane that obtains soak in deionized water 24h go it is remaining in membrane removal Organic solvent, after film silk is put into 60-90 DEG C of hot bath and soaks 0.5-4h, be finally putting into volumetric concentration for 10-40% 6-12h is soaked in glycerin solution, preservation is dried after taking-up, that is, prepare FDY and DTY polyester PETs fiber or PET/ PBT fiber blends weave tube enhancement type doughnut forward osmosis membrane.
Further, step 1) in, after inorganic additive adds organic solvent, the ultrasonic disperse time is 30min-2h.
Further, vacuum defoamation 10-36h at 12-24h, 25-60 DEG C is stirred under the conditions of 25-60 DEG C.
Further, the inorganic additive include but is not limited to CNT, sulfonation titanium dioxide, nano silicon or The mixture of one or more in zinc chloride.
Further, sulfonation titanium dioxide is obtained by the following method:1 part of titanium dioxide powder is added to 15 parts of 1mol/L In sulfuric acid solution and 20 parts of mixed solutions of methyl alcohol, resulting solution is vacuum dried 48h by ultrasonic disperse 2h under the conditions of 120 DEG C Obtain sulfonation titanium dioxide.
Further, the organic solvent includes but is not limited to dimethylacetylamide DMAc, dimethylformamide DMF, diformazan The mixing of one kind or above-mentioned several solvents in base sulfoxide DMSO, N-methyl pyrrolidones NMP, 1,4- dioxane or acetone Thing.
Further, the polymer is cellulose acetate CA, Triafol T CTA, polyacrylonitrile (PAN) or polyphenyl and miaow The mixture of one or more in azoles PBI.
Further, the organic additive includes but is not limited to polyvinylpyrrolidone PVP, PVAC polyvinylalcohol, poly- second two The mixture of one or more in alcohol PEG, triethylene glycol TEG or glycerine.
Further, the woven tube is FDY and DTY polyester PETs fiber or PET/PBT fiber blend woven tubes, outside it In 1.0-2.0mm, internal diameter is in 0.5-1.2mm in footpath.
Further, step 3) the outer coagulating bath is that deionized water or mass percent are the organic solution of 5-40%;Its Middle organic solution is dimethylacetylamide DMAc, dimethylformamide DMF, dimethyl sulfoxide (DMSO) DMSO, N-methyl pyrrolidones The aqueous solution of the mixture of one kind or above-mentioned several solvents in NMP, 1,4- dioxane or acetone.
Compared with, advantages of the present invention and have the beneficial effect that compared with prior art:
The woven tube that the present invention is obtained from FDY with DTY polyester PETs fiber or the braiding of PET/PBT fiber blends, with reference to The woven tube outer fiber beam that blending is obtained is loose, fluffy, and internal face smooths closely knit architectural feature, is turned by immersion precipitation phase Be evenly applied to the step of casting solution one in the outer wall of woven tube and internal gutter by change method, and casting solution is tightly combined with woven tube, solution Positive permeable hollow fibers film-strength of having determined is low, composite membrane separating layer is easy to fall off, the complicated problem of multiprogram filming technology;While by Forward osmosis membrane mechanical strength is combined in the presence of support tube to significantly improve;Use a step masking of organic and inorganic blending inversion of phases Method can be easily controlled film coat thickness, it is adaptable to the preparation of forward osmosis membrane, improve the hydrophilic of compound forward osmosis membrane Property, water flux, stability and antifouling property, be prepared for the excellent doughnut forward osmosis membrane of selectivity.
And the filming technology is simple, equipment requirement is low.The invention equipment therefor simple and fast, it is easily operated, practical, Low cost, it is easy to carry out large-scale industrial production.
Specific embodiment
The present invention is further detailed below in conjunction with instantiation, but the example is not constituted to the present invention Limitation.
Polyester fiber of the present invention weaves the preparation method of tube enhancement type composite hollow fibre forward osmosis membrane, including:
1) preparation of casting solution:First by mass ratio for the inorganic additive of 1-3% (CNT, sulfonation titanium dioxide, is received The mixture of one or more in rice silica or zinc chloride) it is added to the organic solvent (dimethylacetamide of 69-83% In amine DMAc, dimethylformamide DMF, dimethyl sulfoxide (DMSO) DMSO, N-methyl pyrrolidones NMP, 1,4- dioxane or acetone One kind or above-mentioned several solvents mixture) in obtain organic solution, after ultrasonic disperse 30min-2h, by the poly- of 14-20% Compound (in cellulose acetate CA, Triafol T CTA, polyacrylonitrile (PAN) or polybenzimidazoles PBI one or more Mixture), organic additive (polyvinylpyrrolidone PVP, PVAC polyvinylalcohol, polyethylene glycol PEG, the triethylene glycol of 2-8% The mixture of one or more in TEG or glycerine) it is added in above-mentioned organic solution, 12- is stirred under the conditions of 25-60 DEG C Vacuum defoamation 10-36h at 24h, 25-60 DEG C, obtains homogeneous casting solution.
Wherein inorganic additive sulfonation titanium dioxide is obtained by the following method:
1 part of titanium dioxide powder is added in 15 parts of 1mol/L sulfuric acid solutions and 20 parts of mixed solutions of methyl alcohol, ultrasound Dispersion 2h, is vacuum dried resulting solution 48h and obtains sulfonation titanium dioxide under the conditions of 120 DEG C.
2) woven tube is producing inner external wall film coated:
Woven tube is FDY and DTY polyester PETs fiber or PET/PBT fiber blend woven tubes, external diameter in 1.0-2.0mm, Internal diameter is in 0.5-1.2mm.The characteristics of woven tube that FDY is obtained with DTY polyester PET fiber blends is combined two kinds of materials has outside Fibre bundle is loose, fluffy, and internal face smooths closely knit architectural feature.And the woven tube that PET/PBT fiber blends are obtained can be protected Stay PET material rigidly indeformable advantage, simultaneously as PBT it is filametntary exist make woven tube have certain telescopic resilience, compared with Big porosity and water imbibition.Control pressure makes a part of casting solution enter woven tube internal gutter in casting solution coating procedure Middle that the solidification that is separated first occurs, casting solution combines closely with woven tube, while casting solution penetrates further into hindered avoiding Casting solution block woven tube inside, uniformly coated so as to obtain inside and outside wall, coat and woven tube it is compact enhanced multiple Close film.
During homogeneous casting solution is clamp-oned into circular spinning appts by gear pump under 0.05-0.2Mpa nitrogen pressures, control Casting solution enters woven tube internal pressure, casting solution is evenly applied to weave pipe outer wall, while into internal gutter, obtaining Producing inner external wall film coated woven tube hollow fiber film thread.
3) just film forming is formed:Under wire winding device driving, producing inner external wall film coated woven tube is by behind 5-30s air residence times The inversion of phases film forming into outer coagulating bath;Outer coagulating bath is that deionized water or mass percent are the organic solution of 5-40%;Its Middle organic solution is dimethylacetylamide DMAc, dimethylformamide DMF, dimethyl sulfoxide (DMSO) DMSO, N-methyl pyrrolidones The aqueous solution of the mixture of one kind or above-mentioned several solvents in NMP, 1,4- dioxane or acetone.
4) film silk post processing:By step 3) hollow-fibre membrane that obtains soak in deionized water 24h go it is remaining in membrane removal Organic solvent, after film silk is put into 60-90 DEG C of hot bath and soaks 0.5-4h, be finally putting into volumetric concentration for 10-40% 6-12h is soaked in glycerin solution, preservation is dried after taking-up, that is, prepare FDY and DTY polyester PETs fiber or PET/ PBT fiber blends weave tube enhancement type doughnut forward osmosis membrane.
The present invention is further illustrated with reference to specific embodiment.
Embodiment 1:
14% cellulose acetate CA, 6% polyvinylpyrrolidone are added to 1% CNT of ultrasonic disperse 30min 45% acetone+34%1 is mixed in, in the mixed solvent of 4- dioxane, the stirring and dissolving 12h at 60 DEG C, vacuum takes off at 40 DEG C Bubble 12h, obtains homogeneous casting solution.
Casting solution is clamp-oned into circular spinning appts under 0.1Mpa nitrogen pressures by gear pump, woven tube is evenly applied to In outer wall and internal gutter, just into overlay film hollow fiber film thread by immersing to enter in 0 DEG C of deionized water behind 10s air residence times Row inversion of phases film forming.Selected woven tube is the woven tube that FDY is obtained with DTY polyester PET fiber blends, external diameter 1.8mm, internal diameter 1.2mm。
To obtain film silk in deionized water immersion 24h remove remaining organic solvent in membrane removal, after by film silk be put into 60 DEG C hot bath in soak 0.5h, be finally putting into volumetric concentration to soak 6h in 25% glycerin solution, guarantor is dried after taking-up Deposit, that is, prepare braiding tube enhancement type doughnut forward osmosis membrane.
When using 1mol/L NaCl solutions as liquid is drawn, forward osmosis membrane water flux prepared in the present embodiment is 10.97L/m2H, salt back-mixing flux is 5.37g/m2·h.Modified composite membrane tensile strength is high, in being tested beyond laboratory The test scope (5000CN ± 0.5%) of hollow fiber film stretching strength tester HD021NS.
Embodiment 2:
7% cellulose acetate CA+7% Triafol Ts CTA, 2% PVAC polyvinylalcohol are added to ultrasonic disperse The 1% sulfonation titanium dioxide of 60min is mixed in 83%1,4- dioxane, the stirring and dissolving 16h at 40 DEG C, vacuum at 60 DEG C Deaeration 10h, obtains homogeneous casting solution.
Casting solution is clamp-oned into circular spinning appts under 0.2Mpa nitrogen pressures by gear pump, woven tube is evenly applied to In outer wall and internal gutter, just into overlay film hollow fiber film thread by immersing 0 DEG C of 25% dimethyl second behind 5s air residence times Inversion of phases film forming is carried out in the acid amides DMAc aqueous solution.Selected woven tube is the woven tube that PET/PBT fiber blends are obtained, external diameter 1.0mm, internal diameter 0.5mm.
To obtain film silk in deionized water immersion 24h remove remaining organic solvent in membrane removal, after by film silk be put into 80 DEG C hot bath in soak 1h, be finally putting into volumetric concentration to soak 10h in 10% glycerin solution, guarantor is dried after taking-up Deposit, that is, prepare braiding tube enhancement type doughnut forward osmosis membrane.
When using 1mol/L NaCl solutions as liquid is drawn, forward osmosis membrane water flux prepared in the present embodiment is 12.05L/m2H, salt back-mixing flux is 5.86g/m2·h.Modified composite membrane tensile strength is high, in being tested beyond laboratory The test scope (5000CN ± 0.5%) of hollow fiber film stretching strength tester HD021NS.
Embodiment 3:
20% poly- benzopyrazoles PBI, the polyethylene glycol of 2% polyvinylpyrrolidone+6% are added to ultrasonic disperse 2h's 3% nano silicon is mixed in 69% dimethylacetylamide, the stirring and dissolving 24h at 25 DEG C, vacuum defoamation at 25 DEG C 36h, obtains homogeneous casting solution.
Casting solution is clamp-oned into circular spinning appts under 0.05Mpa nitrogen pressures by gear pump, braiding is evenly applied to In pipe outer wall and internal gutter, just into overlay film hollow fiber film thread by immersing 0 DEG C of 40% dimethyl behind 30s air residence times Inversion of phases film forming is carried out in formyl amine aqueous solution.Selected woven tube is the woven tube that PET/PBT fiber blends are obtained, external diameter 2.0mm, internal diameter 0.6mm.
To obtain film silk in deionized water immersion 24h remove remaining organic solvent in membrane removal, after by film silk be put into 90 DEG C hot bath in soak 4h, be finally putting into volumetric concentration to soak 12h in 40% glycerin solution, guarantor is dried after taking-up Deposit, that is, prepare braiding tube enhancement type doughnut forward osmosis membrane.
When using 1mol/L NaCl solutions as liquid is drawn, forward osmosis membrane water flux prepared in the present embodiment is 12.88L/m2H, salt back-mixing flux is 5.98g/m2·h.Modified composite membrane tensile strength is high, in being tested beyond laboratory The test scope (5000CN ± 0.5%) of the tester HD021NS of hollow fiber film stretching intensity.
From above-described embodiment as can be seen that the composite hollow fibre forward osmosis membrane prepared by the present invention shows water higher Flux and relatively low salt back-mixing flux, its water flux are not less than 10.97L/m2H, salt back-mixing flux is not higher than 5.98g/m2H, Therefore the composite membrane has excellent selectivity;One step film preparation is simple for process, is easy to control, composite membrane mechanical strength Greatly, it is a kind of good polyester fiber braiding tube enhancement type composite hollow fibre forward osmosis membrane of processing characteristics.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto, Any one skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in, Should all be included within the scope of the present invention.

Claims (10)

1. a kind of polyester fiber weaves the preparation method of tube enhancement type composite hollow fibre forward osmosis membrane, it is characterised in that the party Method is comprised the following steps:
1) preparation of casting solution:First mass ratio is obtained for the inorganic additive of 1-3% is added in the organic solvent of 69-83% To organic solution, when one section of ultrasonic disperse after, the organic additive of the polymer of 14-20%, 2-8% is added to above-mentioned to be had In machine solution, stirring, vacuum defoamation obtains homogeneous casting solution;
2) woven tube is producing inner external wall film coated:Homogeneous casting solution is clamp-oned into circle under 0.05-0.2Mpa nitrogen pressures by gear pump In spinning appts, control casting solution enters woven tube internal pressure, and casting solution is evenly applied to weave pipe outer wall, while into In internal gutter, producing inner external wall film coated woven tube hollow fiber film thread is obtained;
3) just film forming is formed:Under wire winding device driving, producing inner external wall film coated woven tube enters by behind 5-30s air residence times Inversion of phases film forming in outer coagulating bath;
4) film silk post processing:By step 3) hollow-fibre membrane that obtains soaks 24h and goes remaining in membrane removal to have in deionized water Machine solvent, after film silk is put into 60-90 DEG C of hot bath and soaks 0.5-4h, it is 10-40% the third three to be finally putting into volumetric concentration 6-12h is soaked in alcohol solution, preservation is dried after taking-up, that is, prepare FDY fine with DTY polyester PETs fiber or PET/PBT Dimension blending woven tube enhancement type doughnut forward osmosis membrane.
2. method according to claim 1, it is characterised in that step 1) in, after inorganic additive adds organic solvent, surpass Sound jitter time is 30min-2h.
3. method according to claim 1, it is characterised in that stirred under the conditions of 25-60 DEG C at 12-24h, 25-60 DEG C Vacuum defoamation 10-36h.
4. method according to claim 1, it is characterised in that the inorganic additive include but is not limited to CNT, The mixture of one or more in sulfonation titanium dioxide, nano silicon or zinc chloride.
5. method according to claim 4, it is characterised in that sulfonation titanium dioxide is obtained by the following method:By 1 part two Titanium oxide powder is added in 15 parts of 1mol/L sulfuric acid solutions and 20 parts of mixed solutions of methyl alcohol, ultrasonic disperse 2h, and gained is molten Liquid is vacuum dried 48h under the conditions of 120 DEG C and obtains sulfonation titanium dioxide.
6. method according to claim 1, it is characterised in that the organic solvent includes but is not limited to dimethylacetylamide In DMAc, dimethylformamide DMF, dimethyl sulfoxide (DMSO) DMSO, N-methyl pyrrolidones NMP, 1,4- dioxane or acetone A kind of mixture of or above-mentioned several solvents.
7. method according to claim 1, it is characterised in that the polymer is cellulose acetate CA, triacetate fiber The mixture of one or more in plain CTA, polyacrylonitrile (PAN) or polybenzimidazoles PBI.
8. method according to claim 1, it is characterised in that the organic additive includes but is not limited to polyvinyl pyrrole The mixture of one or more in alkanone PVP, PVAC polyvinylalcohol, polyethylene glycol PEG, triethylene glycol TEG or glycerine.
9. method according to claim 1, it is characterised in that the woven tube be FDY with DTY polyester PETs fiber or PET/PBT fiber blend woven tubes, in 1.0-2.0mm, internal diameter is in 0.5-1.2mm for its external diameter.
10. method according to claim 1, it is characterised in that step 3) the outer coagulating bath is deionized water or quality Percentage is the organic solution of 5-40%;Wherein organic solution is dimethylacetylamide DMAc, dimethylformamide DMF, diformazan The mixture of one kind or above-mentioned several solvents in base sulfoxide DMSO, N-methyl pyrrolidones NMP, 1,4- dioxane or acetone The aqueous solution.
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CN107855007A (en) * 2017-07-13 2018-03-30 枫科(北京)膜技术有限公司 A kind of asymmetric forward osmosis membrane and preparation method thereof
CN108325400A (en) * 2018-02-09 2018-07-27 陕西省膜分离技术研究院有限公司 A kind of preparation method of LBL self-assembly doughnut forward osmosis membrane
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CN109395591A (en) * 2018-10-12 2019-03-01 南京龙源环保有限公司 A kind of preparation method of reinforced graphite alkene polyvinylidene fluoride microporous film
CN112316736A (en) * 2020-10-26 2021-02-05 武汉工程大学 Method for preparing tubular composite membrane by limited space phase inversion, external coating device, internal coating device and composite membrane

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CN107376668A (en) * 2017-09-06 2017-11-24 天津工业大学 A kind of pressure resistant type doughnut reverse osmosis membrane and preparation method thereof
CN108325400A (en) * 2018-02-09 2018-07-27 陕西省膜分离技术研究院有限公司 A kind of preparation method of LBL self-assembly doughnut forward osmosis membrane
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CN109395591A (en) * 2018-10-12 2019-03-01 南京龙源环保有限公司 A kind of preparation method of reinforced graphite alkene polyvinylidene fluoride microporous film
CN109260971A (en) * 2018-11-19 2019-01-25 天津工业大学 A kind of preparation method and applications of hybridized hydrogel filter membrane
CN112316736A (en) * 2020-10-26 2021-02-05 武汉工程大学 Method for preparing tubular composite membrane by limited space phase inversion, external coating device, internal coating device and composite membrane

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