CN1188207C - Large flux polyvinyl chlorid doughnut film, and its mfg. method - Google Patents
Large flux polyvinyl chlorid doughnut film, and its mfg. method Download PDFInfo
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- CN1188207C CN1188207C CNB021361096A CN02136109A CN1188207C CN 1188207 C CN1188207 C CN 1188207C CN B021361096 A CNB021361096 A CN B021361096A CN 02136109 A CN02136109 A CN 02136109A CN 1188207 C CN1188207 C CN 1188207C
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Abstract
The present invention discloses a large-flux polyvinyl chloride hollow-fibre film and a manufacturing method thereof. Polyvinyl chloride is a raw material, 1-methyl-2-pyrrolidone is a solvent, polyethyleneglycol is an additive, the polyvinyl chloride is 16 wt% to 19 wt%, and the weight ratio of the solvent to the additive is controlled as 50 to 58:43 to 50. A dry-wet spinning method technology, the polyvinyl chloride, the solvent and the additive are dissolved at the temperature of 60 DEG C to 95 DEG C, the dry spinning route is from 30cm to 80cm, the extruded volume flow rate is from 3 to 20 ml/min, and the temperature of spinning liquid is from 25 DEG C to 85 DEG C. The obtained large-flux polyvinyl chloride hollow-fibre film forms a five-layer bidirectional asymmetric structure orderly comprising an outer dense layer, a finger-shaped hole supporting layer, a spongy layer, a finger-shaped hole layer and an inner dense layer, wherein abundant holes are distributed in the spongy layer. Because the water permeating rate of the hollow-fibre film prepared by the method of the present invention is from 500 to 900 L/m and the catch molecular weight is from 80 to 150 thousand, the hollow-fibre film has the advantages of large strength, self support and low cost. Therefore, the hollow-fibre film is especially suitable for deeply treating and recovering waste water.
Description
Affiliated technical field
The present invention relates to the method for a kind of PVC hollow fiber membrane and preparation thereof, particularly relate to the method for a kind of big flux PVC hollow fiber membrane and preparation thereof.
Background technology
Along with industrialized development, a large amount of life and industrial wastewaters enter water body, and the water source that the mankind are depended on for existence is polluted day by day.And on the other hand, available water source of fresh water is but more and more rare on the earth, and the city of listing the lack of water zone in is more and more, and national governments all wish and can improve the utilization rate of existing water resource by advanced treating and the reuse to industrial wastewater.These all cause traditional coagulation, precipitation, filter and disinfect the water quality requirement that technology has been difficult to satisfy increasingly stringent.And membrane separation technique is subjected to relevant researcher's attention, and demonstrates its great application potential in the environmental protection field because of it has separative efficiency height, simple, easy to operate, the no phase transformation of equipment and advantage such as energy-conservation.At present, various membrane separation techniques are widely used in the concentrating of molecular solution, purifying in industrial and separate at chemistry, food and medicine.And in bioengineering, also show its wide application prospect., in Japan Patent JP62087204, the JP01111404 of application, just disclosed respectively and be applicable to that enzyme is handled, the PVC hollow fiber membrane of plasma separation as Japanese Toyo Soda Mfg.Co. company.Yet, the cost of manufacture costliness of these films, particularly it is subjected to restrictions such as permeability rate, molecular cut off, can't be used in the high-turbidity water process field at all.This is because in feedwater and sewage disposal, biggest obstacle is that concentration polarization and film pollute in the application of membrane separation technology.Pollutant in the water descends water flux, and especially film pollutes institute and causes the irreversible of water flux decline, makes processing cost sharply rise.In addition, existing many disadvantages on the membrane structure as membrane aperture wider distribution, unstable properties etc., has limited the application of membrane technology in field of waste water treatment more.For this reason, " polyvinyl chloride (PVC) milipore filter and industrialization " (" Beijing University of Technology's journal " 1992,2,80～87) discloses a kind of industrialized polyvinyl chloride milipore filter that is applicable to.It adopts polyvinyl chloride is raw material, and solvent adopts N-N-methyl-2-2-pyrrolidone N-or dimethyl formamide, and additive can adopt polyethylene glycol, makes preparation liquid by the certain mass proportioning, with phase inversion method casting film-forming on base material.Although it has tried hard to improve the permeability rate and the molecular cut off of film on the basis that reduces cost, because it is optimizing material prescription, suitable aspects such as spinning technique, to fail perfectly, the film that is obtained finally is difficult to realize the advanced treating and the reuse of waste water.
Summary of the invention
The present invention is exactly for advanced treating that solves industrial wastewater and reuse problem, improve membrane structure, improve the self property of film, and provide a kind of on this basis and reduce processing cost, have good self property, and the big flux PVC hollow fiber membrane that can support and the method for preparation thereof.
Technical scheme of the present invention is achieved in that with the polyvinyl chloride to be raw material, and 1-Methyl-2-Pyrrolidone is a solvent, and polyethylene glycol is an additive, and polyvinyl chloride quality percentage composition is that the mass ratio of 16-19% solvent and additive is controlled to be 50～58: 50～42.Adopt dry-wet spinning method technology, dissolve under 60～95 ℃ of temperature, dry-spinning path is 30～80cm, and extruding volume flow rate is 3～20ml/min, and the spinning solution temperature is 25-85 ℃.The big flux PVC hollow fiber membrane that is obtained is five layers of two-way dissymmetrical structure, is followed successively by outer compacted zone, finger-like pore supporting layer, spongy layer, finger-like pore layer and internal dense lamella, the abundant hole that distributing in the spongy layer, and permeability rate is 500～900L/m
2H.
Beneficial effect of the present invention is: adopted the mass ratio of rational solvent and additive, made the membrane structure that is obtained have inside and outside two cortex constructions, and be five layers two-way asymmetric; When improving film permeability rate and mechanical strength, can make spinning solution remain on suitable viscosity, good spinnability.Adopted the versatile material polyvinyl chloride, cost reduces greatly.
The present invention is further described below in conjunction with drawings and Examples.
Accompanying drawing is a cross section structure schematic diagram of the present invention.
In the accompanying drawing, 1. outer compacted zone, 2. finger-like pore supporting layer, 3. spongy layer, 4. finger-like pore layer, 5. internal dense lamella
The specific embodiment
One embodiment of the present of invention are a kind of big flux PVC hollow fiber membrane that are applicable to waste water advanced processing.Adopting polyvinyl chloride general, with low cost is raw material, and 1-Methyl-2-Pyrrolidone is a solvent, and the polyethylene glycol that adopts the pore better performances is as additive, and the mass ratio with solvent and additive is controlled to be 50～58 simultaneously: 50～42.Earlier various raw materials are dissolved under 60～95 ℃ of temperature, adopt dry-wet spinning method to prepare big flux PVC hollow fiber membrane then: dry-spinning path is 30～80cm, and extruding volume flow rate is 3-20ml/min, and the spinning solution temperature is 25～85 ℃.The hollow-fibre membrane of gained is five layers of two-way dissymmetrical structure, is followed successively by outer compacted zone 1, finger-like pore supporting layer 2, spongy layer 3, finger-like pore layer 4 and internal dense lamella 5.The abundant hole that distributing in the spongy layer, permeability rate is 500～900L/m
2More than the h, molecular cut off 8～150,000.Because this doughnut film-strength is big, therefore the energy self-supporting when carrying out the advanced treating of waste water, need not set up any support object again.
An alternative embodiment of the invention is a kind of big flux PVC hollow fiber membrane that is applicable to waste water from dyestuff advanced treating and reuse.The composition of membrane material and preparation method are suitable with a last embodiment, but the quality percentage composition of material pvc is controlled within 16～19% scopes.Resulting hollow-fibre membrane is similarly five layers of two-way dissymmetrical structure, but the self property of hollow-fibre membrane has had further raising, and its permeability rate can reach 900L/m
2H, molecular cut off can reach 10～150,000.
Claims (4)
1. one kind big flux PVC hollow fiber membrane, it is characterized in that described big flux PVC hollow fiber membrane is raw material with the polyvinyl chloride, 1-Methyl-2-Pyrrolidone is a solvent, polyethylene glycol is an additive, the mass ratio of solvent and additive is 50～58: 50～42, film is five layers of two-way dissymmetrical structure, be followed successively by outer compacted zone (1), finger-like pore supporting layer (2), spongy layer (3), finger-like pore layer (4) and internal dense lamella (5), the abundant hole that distributing in the spongy layer, permeability rate is 500～900L/m
2H.
2. material that is used to make the described big flux PVC hollow fiber membrane of claim 1, it is characterized in that: be raw material with the polyvinyl chloride, 1-Methyl-2-Pyrrolidone is a solvent, and polyethylene glycol is an additive, and the mass ratio of solvent and additive is 50～58: 50～42.
3. according to the material of the big flux PVC hollow fiber membrane of the described manufacturing of claim 2, the quality percentage composition that it is characterized in that described material pvc is 16～19%.
4. method for preparing the described big flux PVC hollow fiber membrane of claim 1, it is characterized in that: be raw material with the polyvinyl chloride, 1-Methyl-2-Pyrrolidone is a solvent, polyethylene glycol is an additive, the mass ratio of solvent and additive is 50～58: 50～42, dissolves under 60～95 ℃ of temperature, and dry-spinning path is 30～80cm, extruding volume flow rate is 3-20ml/min, and the spinning solution temperature is 25-85 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021361096A CN1188207C (en) | 2002-07-19 | 2002-07-19 | Large flux polyvinyl chlorid doughnut film, and its mfg. method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021361096A CN1188207C (en) | 2002-07-19 | 2002-07-19 | Large flux polyvinyl chlorid doughnut film, and its mfg. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1418723A CN1418723A (en) | 2003-05-21 |
| CN1188207C true CN1188207C (en) | 2005-02-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB021361096A Expired - Fee Related CN1188207C (en) | 2002-07-19 | 2002-07-19 | Large flux polyvinyl chlorid doughnut film, and its mfg. method |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254422B (en) * | 2007-12-12 | 2011-06-29 | 深圳市诚德来实业有限公司 | High intensity PVC hollow fiber hyperfiltration membrane and method of preparing the same |
| KR101596994B1 (en) * | 2009-08-21 | 2016-02-23 | 도레이 카부시키가이샤 | Water-vapor-permeable membrane, hollow-fiber membrane, and hollow-fiber membrane module |
| WO2012091028A1 (en) * | 2010-12-28 | 2012-07-05 | 東レ株式会社 | Medical material and hollow fiber membrane module |
| CN102151491B (en) * | 2011-05-23 | 2014-04-09 | 刘镇江 | Modified polyvinyl chloride alloy ultra-filtration membrane and preparation method of hollow fiber ultra-filtration membrane |
| CN103007785A (en) * | 2013-01-06 | 2013-04-03 | 东华大学 | Method of preparing polrvinyl chloride/polyether sulfone/cellulose derivative blend membrane |
| CN103111189B (en) * | 2013-02-05 | 2015-03-25 | 江苏苏净集团有限公司 | High-flux polyvinylidene fluoride hollow fiber membrane |
| CN105396464A (en) * | 2015-11-20 | 2016-03-16 | 吕畅宇 | Extracurricular high-strength stain-resistant hollow fiber membrane for middle school physics and preparation method thereof |
| CN107551833B (en) * | 2017-10-10 | 2019-10-29 | 重庆云天化瀚恩新材料开发有限公司 | A kind of pair of modified hollow fiber ultrafiltration membrane and preparation method thereof |
| CN114669203A (en) * | 2020-12-01 | 2022-06-28 | 赖枝帅 | Anti-pollution modified polyvinyl chloride composite membrane |
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2002
- 2002-07-19 CN CNB021361096A patent/CN1188207C/en not_active Expired - Fee Related
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| CN1418723A (en) | 2003-05-21 |
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