CN107376668A - A kind of pressure resistant type doughnut reverse osmosis membrane and preparation method thereof - Google Patents
A kind of pressure resistant type doughnut reverse osmosis membrane and preparation method thereof Download PDFInfo
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- CN107376668A CN107376668A CN201710796182.1A CN201710796182A CN107376668A CN 107376668 A CN107376668 A CN 107376668A CN 201710796182 A CN201710796182 A CN 201710796182A CN 107376668 A CN107376668 A CN 107376668A
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- reverse osmosis
- osmosis membrane
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- pressure resistant
- resistant type
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Classifications
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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
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
- B01D71/16—Cellulose acetate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/20—Plasticizers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of pressure resistant type doughnut reverse osmosis membrane and preparation method thereof.The doughnut reverse osmosis membrane includes the Triafol T separating layer of outer layer and the hollow woven tube enhancement layer of internal layer；The thickness of the Triafol T separating layer is 50 400 μm, and the thickness of hollow woven tube enhancement layer is 500 1100 μm；The permeation flux of doughnut reverse osmosis membrane is 5 50 Lm‑2·h‑1MPa, salt rejection rate are 90 99%.This method is using hollow woven tube as reinforcement, so that the doughnut reverse osmosis membrane has had the advantages of wall is thin and pressure-resistant concurrently simultaneously, solve the problems, such as Triafol T doughnut reverse osmosis membrane permeation flux it is low, it is easy compacting and operating cost it is high, improve its pressure-resistant performance, ensure the stable permeation flux of film, operating pressure is reduced, operating cost is saved, is easy to industrial implementation.
Description
Technical field
The present invention relates to doughnut technical field of membrane, specifically a kind of pressure resistant type doughnut reverse osmosis membrane and its preparation
Method.
Background technology
Reverse osmosis technology is using film pressure at both sides difference as motive force, makes solvent (being typically water) permselective membrane and realizes molten
Agent, solute separation process, have be not related to phase transformation, energy consumption is low, floor space is small, simple to operate, strong adaptability, environmental pollution
The advantages that few, played an important role in sea-water brackish water desalination, ultra-pure water preparation etc..With application of membrane separation technology field
Continuous expansion, the requirement more and more higher to membrane material.Hollow fiber separating film has self supporting structure, component preparation technology letter
Single, enlarge-effect is small, and bigger membrane area can be provided in unit volume, and bulk density is bigger than tubular membrane, pretreatment and maintenance
It is more simpler than rolled film.
Existing doughnut membrane reverse osmosis material is mainly based on cellulose acetate, particularly Triafol T.Three vinegar
Acid cellulose (CTA) has the advantages that chlorine-resistant property is good, mechanical performance is high, desalting performance is good as reverse osmosis membrane materials, together
When its is cheap, wide material sources, be widely used in nanofiltration/positive infiltration/reverse osmosis membrane.The Triafol T reported
Hollow-fibre membrane mainly has Screw Extrusion gel spinning method and melt spinning method.Though both the above spinning process prepare film-strength compared with
Height, but Cellulose Triacetate Membranes For Reverse Osmosis is easily compacted under high operating pressure, causes the decay of film permeation flux.If pass through increasing
Blooming wall thickness improves resistance to pressure, then can have a strong impact on film permeation flux, and needs bigger operating pressure, add operation into
This.
At present, enhancement type hollow fiber film research focuses mostly in using enhancing matrix, filament fiber or woven tube enhancing method
Prepare enhanced doughnut and surpass/microfiltration membranes, the preparation method on enhanced doughnut reverse osmosis membrane is not reported so far.
The content of the invention
In view of the shortcomings of the prior art, it is anti-that the technical problem that the present invention intends to solve is to provide a kind of pressure resistant type doughnut
Permeable membrane and preparation method thereof.Using hollow woven tube as reinforcement simultaneously so that the doughnut reverse osmosis membrane has concurrently
The advantages of wall is thin and pressure-resistant, solves low Triafol T doughnut reverse osmosis membrane permeation flux, easy compacting and operating cost
The problem of high, its pressure-resistant performance is improved, ensure the stable permeation flux of film, reduce operating pressure, save operating cost, be easy to work
Industry is implemented.
It is hollow that the present invention solves the problems, such as that the technical scheme of the doughnut reverse osmosis membrane technology is to provide a kind of pressure resistant type
Fibre reverse osmosis film, it is characterised in that Triafol T separating layer and internal layer of the doughnut reverse osmosis membrane including outer layer
Hollow woven tube enhancement layer；The thickness of the Triafol T separating layer is 50-400 μm, the thickness of hollow woven tube enhancement layer
Spend for 500-1100 μm；The permeation flux of doughnut reverse osmosis membrane is 5-50Lm-2·h-1MPa, salt rejection rate 90-
99%.
The technical scheme that the present invention solves the preparation method technical problem is to provide a kind of pressure resistant type doughnut reverse osmosis
The preparation method of permeable membrane, it is characterised in that comprise the following steps：
A, the preparation of hollow woven tube：Fiber filament is woven into by hollow woven tube using control of two-dimensional braided technology；
B, the preparation of film forming system：Triafol T, plasticizer and additive are blended to obtain film forming system；Described three
Cellulose acetate：Plasticizer：The mass ratio of additive is 3-6:2-5:1-3；
C, the preparation of doughnut reverse osmosis membrane：Film forming system through screw extruder melting extrusion and is passed through into annular spinneret
Melt is evenly applied to hollow braiding tube outer surface by head, then drawing-off is cooled and shaped into coagulating bath, obtains the hollow fibre of pressure resistant type
Tie up reverse osmosis membrane.
Compared with prior art, beneficial effect of the present invention is：
(1) using hollow woven tube as reinforcement so that the doughnut reverse osmosis membrane had concurrently simultaneously wall it is thin with it is resistance to
The advantages of pressure, solve the problems, such as Triafol T doughnut reverse osmosis membrane permeation flux it is low, it is easy compacting and operating cost it is high,
Its pressure-resistant performance is improved, ensures the stable permeation flux of film, reduces operating pressure, save operating cost, be easy to industrial implementation.
(2) casting solution of molten condition is directly combined with hollow woven tube reinforcement using melt spinning method, avoided
The defects of enhanced material thermodynamic compatibility difference, while compared to common wet method enhancement method, simplify step.
Embodiment
The specific embodiment of the present invention is given below.Specific embodiment is only used for that the present invention is further described, unlimited
The application scope of the claims processed.
The invention provides a kind of pressure resistant type doughnut reverse osmosis membrane, it is characterised in that the doughnut reverse osmosis membrane bag
Include the Triafol T separating layer of outer layer and the hollow woven tube enhancement layer of internal layer；The thickness of the Triafol T separating layer
Spend for 50-400 μm, the thickness of hollow woven tube enhancement layer is 500-1100 μm；The permeation flux of doughnut reverse osmosis membrane is
5-50L·m-2·h-1MPa, salt rejection rate 90-99%.
Invention also provides a kind of preparation method of pressure resistant type doughnut reverse osmosis membrane (abbreviation method), its feature
It is to comprise the following steps：
A, the preparation of hollow woven tube：Fiber filament is woven into by hollow woven tube using control of two-dimensional braided technology, in formation
Layer network structure, and the enhancement layer of doughnut reverse osmosis membrane is used as using the hollow woven tube；
Using high-temperature fibre, (180 DEG C of temperatures above are subjected in the long period can keep its original to the fiber filament
The fiber of physical and mechanical properties), specifically Fanglun 1313, pet fiber or
At least one of polypropylene fibre；
B, the preparation of film forming system：Triafol T, plasticizer and additive are blended in closed high speed mixer
Obtain film forming system；The Triafol T：Plasticizer：The mass ratio of additive is 3-6:2-5:1-3；
The plasticizer is sulfolane；The additive is in ethylene glycol, polyethylene glycol -200, benzoic acid or maleic acid
It is at least one；
C, the preparation of doughnut reverse osmosis membrane：Film forming system through screw extruder melting extrusion and is passed through into annular spinneret
Melt is evenly applied to hollow braiding tube outer surface by head, then drawing-off is cooled and shaped into coagulating bath, obtains the hollow fibre of pressure resistant type
Tie up reverse osmosis membrane.
The coagulating bath is made up of sulfolane, ethylene glycol and water；Sulfolane：Ethylene glycol：The mass ratio of water is 20:10:70；
The screw extruder is single screw extrusion machine and double screw extruder；
Embodiment 1
A, the preparation of hollow woven tube：Fanglun 1313 long filament is woven using control of two-dimensional braided technology
Into the hollow woven tube that thickness is 700 μm；
B, the preparation of film forming system：The increasing blending of Triafol T, sulfolane, polyethylene glycol -200 and maleic acid is obtained
Film forming system；Triafol T accounts for the 33wt.% of film forming system quality, and plasticizer accounts for the 47wt.% of film forming system quality, added
Agent is added to account for the 20wt.% of film forming system quality；The mass ratio of polyethylene glycol -200 and maleic acid is 9:6；
C, the preparation of doughnut reverse osmosis membrane：Film forming system through screw extruder melting extrusion and is passed through into annular spinneret
Melt is evenly applied to hollow braiding tube outer surface by head, then drawing-off to by 20wt.% sulfolane/10wt.% ethylene glycol/
It is cooled and shaped in the coagulating bath that 70wt.% water is formed, obtains the pressure resistant type doughnut counter-infiltration that separating layer thickness is 100 μm
Film.
By prepared pressure resistant type doughnut reverse osmosis membrane in concentration 2000mg/L sodium chloride solution, 4MPa operations
Follow-on test 1 hour under pressure, the removal efficiency 96.8% of monovalent ion, permeation flux 26Lm-2·h-1·MPa。
Triafol T doughnut reverse osmosis membrane compared to same film forming system, with technique but without enhancement layer, identical survey
The attenuation rate (calculation formula=(flux after initial flux -1h)/initial flux) of examination time test reduces 20%.
Embodiment 2
A, the preparation of hollow woven tube：Pet fiber long filament is woven using control of two-dimensional braided technology
Into the hollow woven tube that thickness is 800 μm；
B, the preparation of film forming system：The increasing blending of Triafol T, sulfolane, polyethylene glycol -200 and maleic acid is obtained
Film forming system；Triafol T accounts for the 40wt.% of film forming system quality, and plasticizer accounts for the 45wt.% of film forming system quality, added
Agent is added to account for the 15wt.% of film forming system quality；The mass ratio of polyethylene glycol -200 and maleic acid is 9:6；
C, the preparation of doughnut reverse osmosis membrane：Film forming system through screw extruder melting extrusion and is passed through into annular spinneret
Melt is evenly applied to hollow braiding tube outer surface by head, then drawing-off to by 20wt.% sulfolane/10wt.% ethylene glycol/
It is cooled and shaped in the coagulating bath that 70wt.% water is formed, obtains the pressure resistant type doughnut counter-infiltration that separating layer thickness is 150 μm
Film.
By prepared pressure resistant type doughnut reverse osmosis membrane in concentration 2000mg/L sodium chloride solution, 4MPa operations
Follow-on test 1 hour under pressure, the removal efficiency 97.6% of monovalent ion, permeation flux 15Lm-2·h-1·MPa。
Triafol T doughnut reverse osmosis membrane compared to same film forming system, with technique but without enhancement layer, identical survey
Trying the attenuation rate of time test reduces by 17%.
Embodiment 3
A, the preparation of hollow woven tube：Use control of two-dimensional braided technology that polypropylene fibre long filament is woven into thickness for 900 μm
Hollow woven tube；
B, the preparation of film forming system：The increasing blending of Triafol T, sulfolane, polyethylene glycol -200 and maleic acid is obtained
Film forming system；Triafol T accounts for the 45wt.% of film forming system quality, and plasticizer accounts for the 40wt.% of film forming system quality, added
Agent is added to account for the 15wt.% of film forming system quality；The mass ratio of polyethylene glycol -200 and maleic acid is 9:6；
C, the preparation of doughnut reverse osmosis membrane：Film forming system through screw extruder melting extrusion and is passed through into annular spinneret
Melt is evenly applied to hollow braiding tube outer surface by head, then drawing-off to by 20wt.% sulfolane/10wt.% ethylene glycol/
It is cooled and shaped in the coagulating bath that 70wt.% water is formed, obtains the pressure resistant type doughnut counter-infiltration that separating layer thickness is 180 μm
Film.
By prepared pressure resistant type doughnut reverse osmosis membrane in concentration 2000mg/L sodium chloride solution, 4MPa operations
Follow-on test 1 hour under pressure, the removal efficiency 98.1% of monovalent ion, permeation flux 12Lm-2·h-1·MPa。
Triafol T doughnut reverse osmosis membrane compared to same film forming system, with technique but without enhancement layer, identical survey
Trying the attenuation rate of time test reduces by 14%.
Embodiment 4
A, the preparation of hollow woven tube：Pet fiber long filament is woven using control of two-dimensional braided technology
Into the hollow woven tube that thickness is 1000 μm；
B, the preparation of film forming system：The increasing blending of Triafol T, sulfolane, polyethylene glycol -200 and maleic acid is obtained
Film forming system；Triafol T accounts for the 46wt.% of film forming system quality, and plasticizer accounts for the 44wt.% of film forming system quality, added
Agent is added to account for the 10wt.% of film forming system quality；The mass ratio of polyethylene glycol -200 and maleic acid is 9:6；
C, the preparation of doughnut reverse osmosis membrane：Film forming system through screw extruder melting extrusion and is passed through into annular spinneret
Melt is evenly applied to hollow braiding tube outer surface by head, then drawing-off to by 20wt.% sulfolane/10wt.% ethylene glycol/
It is cooled and shaped in the coagulating bath that 70wt.% water is formed, obtains the pressure resistant type doughnut counter-infiltration that separating layer thickness is 200 μm
Film.
By prepared pressure resistant type doughnut reverse osmosis membrane in concentration 2000mg/L sodium chloride solution, 4MPa operations
Follow-on test 1 hour under pressure, the removal efficiency 98.6% of monovalent ion, permeation flux 9Lm-2·h-1·MPa。
Triafol T doughnut reverse osmosis membrane compared to same film forming system, with technique but without enhancement layer, identical survey
Trying the attenuation rate of time test reduces by 10%.
The present invention does not address part and is applied to prior art.
Claims (7)
1. a kind of pressure resistant type doughnut reverse osmosis membrane, it is characterised in that the doughnut reverse osmosis membrane includes three acetic acid of outer layer
The hollow woven tube enhancement layer of cellulose separating layer and internal layer；The thickness of the Triafol T separating layer is 50-400 μm,
The thickness of hollow woven tube enhancement layer is 500-1100 μm；The permeation flux of doughnut reverse osmosis membrane is 5-50 Lm-2·h-1MPa, salt rejection rate 90-99%.
2. a kind of preparation method of pressure resistant type doughnut reverse osmosis membrane, it is characterised in that comprise the following steps：
A, the preparation of hollow woven tube：Fiber filament is woven into by hollow woven tube using control of two-dimensional braided technology；
B, the preparation of film forming system：Triafol T, plasticizer and additive are blended to obtain film forming system；Three acetic acid
Cellulose：Plasticizer：The mass ratio of additive is 3-6: 2-5: 1-3；
C, the preparation of doughnut reverse osmosis membrane：Be tod by film forming system through screw extruder melting extrusion and by annular spinning head
Melt is evenly applied to hollow braiding tube outer surface, then drawing-off is cooled and shaped into coagulating bath, and it is anti-to obtain pressure resistant type doughnut
Permeable membrane.
3. pressure resistant type doughnut reverse osmosis membrane preparation method according to claim 1, it is characterised in that the fiber length
Silk is at least one in Fanglun 1313, pet fiber or polypropylene fibre
Kind.
4. pressure resistant type doughnut reverse osmosis membrane preparation method according to claim 1, it is characterised in that the plasticizer
For sulfolane.
5. pressure resistant type doughnut reverse osmosis membrane preparation method according to claim 1, it is characterised in that the additive
It is at least one of ethylene glycol, polyethylene glycol -200, benzoic acid or maleic acid.
It is 6. according to claim 1, it is characterised in that the coagulating bath is made up of sulfolane, ethylene glycol and water；Sulfolane：
Ethylene glycol：The mass ratio of water is 20:10:70.
7. pressure resistant type doughnut reverse osmosis membrane preparation method according to claim 1, it is characterised in that the screw rod squeezes
It is single screw extrusion machine and double screw extruder to go out machine.
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| Application Number | Priority Date | Filing Date | Title |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108479399A (en) * | 2018-04-09 | 2018-09-04 | 天津工业大学 | A kind of fiber reinforcement type Cellulose Triacetate Membranes For Reverse Osmosis and preparation method thereof |
| CN108816047A (en) * | 2018-06-25 | 2018-11-16 | 长春三真实业有限公司 | A kind of traditional Chinese medicine extraction reverse osmosis unit |
| CN111672332A (en) * | 2020-06-23 | 2020-09-18 | 天津工业大学 | Enhanced hollow fiber nanofiltration membrane and preparation method thereof |
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| CN108816047A (en) * | 2018-06-25 | 2018-11-16 | 长春三真实业有限公司 | A kind of traditional Chinese medicine extraction reverse osmosis unit |
| CN111672332A (en) * | 2020-06-23 | 2020-09-18 | 天津工业大学 | Enhanced hollow fiber nanofiltration membrane and preparation method thereof |
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Application publication date: 20171124 |