CN107261866A - A kind of preparation method of through hole membrane for water treatment - Google Patents
A kind of preparation method of through hole membrane for water treatment Download PDFInfo
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- CN107261866A CN107261866A CN201710681726.XA CN201710681726A CN107261866A CN 107261866 A CN107261866 A CN 107261866A CN 201710681726 A CN201710681726 A CN 201710681726A CN 107261866 A CN107261866 A CN 107261866A
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- polyacrylonitrile
- water treatment
- organic solvent
- preparation
- casting solution
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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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- 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
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention relates to a kind of preparation method of through hole membrane for water treatment, belong to macromolecule member material technical field, polyacrylonitrile is added in organic solvent by the present invention obtains casting solution, casting solution is infused in female mold tool, and mold bottom is placed in liquid nitrogen, in the presence of liquid nitrogen cryogenics, the organic solvent crystal for being grown from the bottom to top along mould vertical direction and being mutually total to wall is formed in casting solution, after after casting solution completely solidification, take out and be freeze-dried, organic solvent crystal distils and obtains through hole membrane for water treatment.The polyacrylonitrile membrane for water treatment that the present invention is prepared has higher water flux, compensate for the shortcoming of polyacrylonitrile hydrophily difference, and with technique is simple, safety and environmental protection the features such as, available for professional domains such as water process.
Description
Technical field
The present invention relates to a kind of preparation method of through hole membrane for water treatment, belong to macromolecule member material construction applications.
Background technology
The fast development of modern industry also brings a series of environmental problems, wherein topmost is exactly water pollution.In work
In industry waste water, substantial amounts of harmful substance is there is, these pollutants such as will cause huge injury without processing to environment, more
Can seriously great threat be brought to health.Macromolecule via membrane due to its without phase transformation, Non-energy-consumption, separative efficiency it is high,
The features such as energy-conserving and environment-protective, it is widely used in water treatment field, and achieves quite excellent effect.
At present, via membrane is mainly by high scores such as polyacrylonitrile (PAN), polyvinyl chloride (PVC), Kynoar (PVDF)
Sub- polymer is prepared from, wherein PVC and PVDF due to not environmentally, preparation technology higher to human health and cost
Complicated reason, is not suitable for realizing the big production membrane for water treatment of industry, and PAN has excellent chemical stability and antibiotic property, because
This is praised highly by people.
However, the hydrophily of polyacrylonitrile is not strong, therefore in order to lift the water flux of via membrane, it is necessary to at it
Reason, before this, has had Patents to report such as hydrophilic treated.Patent No. CN201010148305.9, invention
A kind of preparation method of entitled hydrophilic ultrafiltration membrane, the patent describe poly glycol monomethyl ether being grafted to polyacrylonitrile etc.
The surface of milipore filter, to reach the enhancing hydrophilic purpose of milipore filter；Such as Patent No. CN201210014069.0, denomination of invention
For a kind of wet-type polyacrylonitrile flat-plate ultrafiltration membrane and preparation method thereof, the patent proposes nothing is added in polyacrylonitrile solution
Machine nano particle, for lifting the hydrophily of milipore filter；And for example Patent No. CN201410491434.6, entitled one kind
Preparation method with chelating function hollow fiber ultrafiltration membrane, the patent proposes synthesized by way of copolymerization polyacrylonitrile-
Polyvinyl tetrazole milipore filter.Above several ways are by way of graft copolymerization and blending by hydrophilic radical or hydrophile
Matter is incorporated into basal lamina material, but the membrane for water treatment complex process that these modes are obtained, and the reaction of copolymerized grafting is uncontrollable,
Homogeneity is poor, and waste liquid is more, easily causes secondary pollution, and other additive has potential threat to health.
In summary, a kind of method for preparing through hole membrane for water treatment is developed, not only needs the water for strengthening membrane for water treatment to lead to
Amount, it is necessary to the technology mode with environmental protection, while it is easy to meet step, it is easy to the characteristics of producing.And meet at present
The through hole membrane for water treatment preparation method of requirements above is no, and therefore, we set about having probed into this through hole membrane for water treatment
Preparation method.
The content of the invention
For above-mentioned problem, it is an object of the invention to provide one kind by material of polyacrylonitrile, pass through physics side
Formula obtains the preparation method of through hole membrane for water treatment, and preparation method technique proposed by the present invention is simple, and environmental protection is set without costliness
Standby, the through hole membrane for water treatment hydrophily prepared is strong, with higher industrial application value.
To achieve these goals, technical solution of the invention is that a kind of preparation method of through hole membrane for water treatment is made
Preparation Method is carried out according to the following steps：
A. polyacrylonitrile is added in organic solvent, is stirred to polyacrylonitrile and fully dissolves at normal temperatures, obtain
Mass concentration is 1%~10% polyacrylonitrile solution.
B. polyacrylonitrile solution made from step a is statically placed in vacuum in 0.05~0.1MPa environment to enter within 2~5 hours
Row vacuum defoamation, obtains casting solution.
C. it is the female mold tool that 0.5~2mm, thickness of groove bottom are 2~10mm by casting solution injection groove depth made from step b
In, the bottom of mould is placed in liquid nitrogen, in the presence of liquid nitrogen cryogenics, the casting solution in mould is along mould vertical direction under
It is supreme slowly to solidify to form using organic solvent crystal as core, the pillar cell body by skin of polyacrylonitrile, and adjacent cells body it
Between altogether wall complex, completely solidification after, be removed from the molds.
D. it is -65~-55 DEG C the obtained complexs of step c to be placed in into temperature, and vacuum is progress in 2~5Pa environment
The organic solvent crystal in removal unit body is freeze-dried, is taken out after drying 12~72 hours, it is 30 to obtain each unit body aperture
~100 μm of through hole membrane for water treatment.
Described organic solvent is dimethyl sulfoxide (DMSO) or 1,4- dioxane.
The material of the mould is one kind in glass or ceramics or metal.
As a result of above technical scheme, advantageous effects of the present invention are：
1 present invention utilizes directional solidification seasoning, in the glass plate immersion liquid nitrogen that will be equipped with polyacrylonitrile solution, in liquid nitrogen
In the presence of low temperature, larger thermograde can be formed between solution bottom and top, organic solvent crystal is first formed in bottom,
Then along thermograde direction oriented growth, until polyacrylonitrile molecule is separated out from solution surface, treat that organic solvent crystal is given birth to
Solution, which is placed in low-temp low-pressure environment, after the completion of length makes organic solvent crystal distil, and obtains orienting stephanoporate polyacrylonitrile film, from
And strengthen the hydrophily of polyacrylonitrile.Wherein, the unit body aperture of polyacrylonitrile film can be adjusted by the concentration of polyacrylonitrile
Section, with the rise of polyacrylonitrile concentration, the polyacrylonitrile cortex of pillar cell body is thicker, and organic solvent crystal column is thinner, therefore,
Unit body aperture reduces in the film ultimately formed, wall thickness increase.
What the through hole membrane for water treatment obtained by 2 present invention was realized by control structure form, it is not added with process of production
Other hydrophilic substances, meet the theory of environmental protection, meanwhile, the hydrophilicity of process film is made by way of changing physical arrangement
It is more durable.
The preparation method of 3 present invention, organic solvent price is more cheap, and raw material environmental pollution is small, and technological process is few, behaviour
Facilitate easily-controllable as process, it is easy to accomplish industrialized production.
Embodiment
The present invention is described in further detail with reference to specific embodiment.
A kind of preparation method of through hole membrane for water treatment, described preparation method is carried out according to the following steps：
A. polyacrylonitrile is added in organic solvent, is stirred to polyacrylonitrile and fully dissolves at normal temperatures, obtain
Mass concentration is 1%~10% polyacrylonitrile solution.
B. polyacrylonitrile solution made from step a is statically placed in vacuum in 0.05~0.1MPa environment to enter within 2~5 hours
Row vacuum defoamation, obtains casting solution.
C. it is 0.5~2mm by casting solution injection groove depth made from step b, thickness of groove bottom is 2~10mm female mold tool
In, wherein, the material of mould is one kind in glass or ceramics or metal.The bottom of mould is placed in liquid nitrogen, it is low in liquid nitrogen
In the presence of temperature, the casting solution in mould slowly solidify to form from the bottom to top along mould vertical direction using organic solvent crystal as
After core, the pillar cell body by skin of polyacrylonitrile, and the complex of wall altogether between adjacent cells body, completely solidification, from mould
Taken out in tool.
D. it is -65~-55 DEG C the obtained complexs of step c to be placed in into temperature, and vacuum is progress in 2~5Pa environment
Freeze-drying removes the organic solvent crystal in each unit body, is taken out after drying 12~72 hours, obtaining each unit body aperture is
30~100 μm of through hole membrane for water treatment.
Described organic solvent is dimethyl sulfoxide (DMSO) or 1,4- dioxane.
Specific embodiment
Embodiment 1
A. 10g polyacrylonitrile is added in 90g dimethyl sulfoxide (DMSO)s, be stirred at normal temperatures fully molten to polyacrylonitrile
Solution, obtains the polyacrylonitrile solution that mass concentration is 10%.
B. polyacrylonitrile solution made from step a is statically placed in into vacuum to take off for 5 hours progress vacuum in 0.1MPa environment
Bubble, obtains casting solution.
C. casting solution injection groove depth step b deaerations obtained is 0.5mm, and thickness of groove bottom is 2mm glass female mold tool
In, the thickness of casting solution is 0.2mm, and the bottom of mould is placed in liquid nitrogen, in the presence of liquid nitrogen cryogenics, the casting film in mould
Liquid is slowly solidify to form using organic solvent crystal as core from the bottom to top along mould vertical direction, the column list by skin of polyacrylonitrile
The complex of common wall between first body, and adjacent cells body, completely after solidification, is removed from the molds.
D. the obtained complexs of step c are placed in temperature for -65 DEG C, vacuum is is freeze-dried in 2Pa environment
The organic solvent crystal in each unit body is removed, is taken out after drying 12 hours, obtains each unit body aperture between 30~50 μm
Through hole membrane for water treatment.
Embodiment 2
A. 1g polyacrylonitrile is added in 99g Isosorbide-5-Nitrae-dioxane, is stirred to polyacrylonitrile fills at normal temperatures
Divide dissolving, obtain the polyacrylonitrile solution that mass concentration is 1%.
B. polyacrylonitrile solution made from step a is statically placed in into vacuum to take off for 2 hours progress vacuum in 0.05MPa environment
Bubble, obtains casting solution.
C. casting solution injection groove depth step b deaerations obtained is 2mm, and thickness of groove bottom is 10mm ceramic female mold tool
In, the thickness of casting solution is 1mm, and the bottom of mould is placed in liquid nitrogen, in the presence of liquid nitrogen cryogenics, the casting solution in mould
Slowly it is solidify to form from the bottom to top using organic solvent crystal as core along mould vertical direction, using polyacrylonitrile as the pillar cell of skin
The complex of common wall between body, and adjacent cells body, completely after solidification, is removed from the molds.
D. the obtained complexs of step c are placed in temperature for -55 DEG C, vacuum is is freeze-dried in 5Pa environment
The organic solvent crystal in each unit body is removed, is taken out after drying 72 hours, obtains each unit body aperture between 80~100 μm
Through hole membrane for water treatment.
Embodiment 3
A. 5g polyacrylonitrile is added in 45g dimethyl sulfoxide (DMSO)s, be stirred at normal temperatures fully molten to polyacrylonitrile
Solution, obtains the polyacrylonitrile solution that mass concentration is 5%.
B. polyacrylonitrile solution made from step a is statically placed in into vacuum to take off for 3 hours progress vacuum in 0.07MPa environment
Bubble, obtains casting solution.
C. casting solution injection groove depth step b deaerations obtained is 1mm, and thickness of groove bottom is in 5mm copper female mold tool.Casting
The thickness of film liquid is 0.5mm, and the bottom of mould is placed in liquid nitrogen, in the presence of liquid nitrogen cryogenics, the casting solution edge in mould
Mould vertical direction is slowly solidify to form using organic solvent crystal as core from the bottom to top, using polyacrylonitrile as the pillar cell of skin
The complex of common wall between body, and adjacent cells body, completely after solidification, is removed from the molds.
D. the obtained complexs of step c are placed in temperature for -60 DEG C, vacuum is is freeze-dried in 3Pa environment
The organic solvent crystal in each unit body is removed, is taken out after drying 48 hours, obtains each unit body aperture between 50~70 μm
Through hole membrane for water treatment.
Claims (3)
1. a kind of preparation method of through hole membrane for water treatment, it is characterised in that：Described preparation method is carried out according to the following steps：
A. polyacrylonitrile is added in organic solvent, is stirred to polyacrylonitrile and fully dissolves at normal temperatures, obtain quality
Concentration is 1%~10% polyacrylonitrile solution；
B. polyacrylonitrile solution made from step a is statically placed in into vacuum to carry out very for 2~5 hours in 0.05~0.1MPa environment
Empty deaeration, obtains casting solution；
C., will in being the female mold tool that 0.5~2mm, thickness of groove bottom are 2~10mm by casting solution injection groove depth made from step b
The bottom of mould is placed in liquid nitrogen, in the presence of liquid nitrogen cryogenics, the casting solution in mould along mould vertical direction from the bottom to top
Slowly it solidify to form using organic solvent crystal as core, the pillar cell body by skin of polyacrylonitrile, and between adjacent cells body altogether
After the complex of wall, completely solidification, it is removed from the molds；
D. the obtained complexs of step c are placed in temperature for -65~-55 DEG C, vacuum is is freezed in 2~5Pa environment
Dry the organic solvent crystal removed in each unit body, taken out after drying 12~72 hours, obtain each unit body aperture for 30~
100 μm of through hole membrane for water treatment.
2. a kind of preparation method of through hole membrane for water treatment as claimed in claim 1, it is characterised in that：Described organic solvent is
Dimethyl sulfoxide (DMSO) or 1,4- dioxane.
3. a kind of preparation method of through hole membrane for water treatment as claimed in claim 1, it is characterised in that：The material of the mould is
One kind in glass or ceramics or metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710681726.XA CN107261866A (en) | 2017-08-10 | 2017-08-10 | A kind of preparation method of through hole membrane for water treatment |
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| CN201710681726.XA CN107261866A (en) | 2017-08-10 | 2017-08-10 | A kind of preparation method of through hole membrane for water treatment |
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| CN107261866A true CN107261866A (en) | 2017-10-20 |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380131A (en) * | 2002-01-25 | 2002-11-20 | 中国科学院化学研究所 | Preparation method of dry type polyacrylointrile ultrafiltration membrane |
| CN101785877A (en) * | 2010-04-07 | 2010-07-28 | 华中科技大学 | Method for preparing bionic composite material with lamellar multilevel structure |
| CN101824160A (en) * | 2010-03-30 | 2010-09-08 | 东华大学 | Preparation method of chitosan/polyvinyl alcohol/polylactic acid blended porous membrane |
| CN101908645A (en) * | 2010-07-30 | 2010-12-08 | 哈尔滨工业大学 | Ceramic/solid polymer electrolyte composite material with continuously and directionally-distributed wild phases and preparation method thereof |
| CN102418161A (en) * | 2011-09-19 | 2012-04-18 | 北京化工大学常州先进材料研究院 | Method for preparing synthetic polymer nano-fiber membrane by freeze-drying |
| CN104119554A (en) * | 2014-07-15 | 2014-10-29 | 天津工业大学 | Method for preparing organic porous film by adopting freezing method |
| CN104693475A (en) * | 2013-12-06 | 2015-06-10 | 天津工业大学 | Preparation method of polymer porous material |
| CN106362492A (en) * | 2016-09-28 | 2017-02-01 | 陕西科技大学 | Preparation method of cellulose-based biodegradable type air filtering material |
-
2017
- 2017-08-10 CN CN201710681726.XA patent/CN107261866A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380131A (en) * | 2002-01-25 | 2002-11-20 | 中国科学院化学研究所 | Preparation method of dry type polyacrylointrile ultrafiltration membrane |
| CN101824160A (en) * | 2010-03-30 | 2010-09-08 | 东华大学 | Preparation method of chitosan/polyvinyl alcohol/polylactic acid blended porous membrane |
| CN101785877A (en) * | 2010-04-07 | 2010-07-28 | 华中科技大学 | Method for preparing bionic composite material with lamellar multilevel structure |
| CN101908645A (en) * | 2010-07-30 | 2010-12-08 | 哈尔滨工业大学 | Ceramic/solid polymer electrolyte composite material with continuously and directionally-distributed wild phases and preparation method thereof |
| CN102418161A (en) * | 2011-09-19 | 2012-04-18 | 北京化工大学常州先进材料研究院 | Method for preparing synthetic polymer nano-fiber membrane by freeze-drying |
| CN104693475A (en) * | 2013-12-06 | 2015-06-10 | 天津工业大学 | Preparation method of polymer porous material |
| CN104119554A (en) * | 2014-07-15 | 2014-10-29 | 天津工业大学 | Method for preparing organic porous film by adopting freezing method |
| CN106362492A (en) * | 2016-09-28 | 2017-02-01 | 陕西科技大学 | Preparation method of cellulose-based biodegradable type air filtering material |
Non-Patent Citations (1)
| Title |
|---|
| 连经社等: "《油田化学应用技术》", 30 April 2007, 中国石油大学出版社 * |
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