CN109224877A - A kind of asymmetric polyether sulfone micro-filtration membrane preparation method - Google Patents
A kind of asymmetric polyether sulfone micro-filtration membrane preparation method Download PDFInfo
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- CN109224877A CN109224877A CN201811420480.1A CN201811420480A CN109224877A CN 109224877 A CN109224877 A CN 109224877A CN 201811420480 A CN201811420480 A CN 201811420480A CN 109224877 A CN109224877 A CN 109224877A
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- polyether sulfone
- solvent
- filtration membrane
- membrane preparation
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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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
Abstract
The invention discloses a kind of asymmetric polyether sulfone micro-filtration membrane preparation methods, include the following steps: to produce prepared slurry, preparation slurry includes 20-30 parts of solvent, 50-70 parts of non-solvent and 10-20 parts of polyether sulfone plastic particle in parts by weight, non-solvent and solvent are uniformly mixed to prepare mixed liquor, polyether sulfone plastic particle is added slowly in mixed liquor, is stirred；Preparation slurry is coated in conductive base plate；Conductive base plate is immediately placed on heat source, the upper space region of heat source adjusts relative humidity and temperature；Conductive base plate is taken out after control heating, is immersed in water-bath at once and completes microfiltration membranes forming；Via cleaning, can be wound after drying.Filming technology of the present invention is simple, and all parameter controllabilities are strong, is conducive to production control.
Description
Technical field
The present invention relates to polyethersulfone membranes preparation technical field more particularly to a kind of asymmetric polyether sulfone micro-filtration film preparation sides
Method.
Background technique
In filtering industry, membrane filtration, which occupies important one seat, especially microfiltration membranes used in precision, is industrially
It is indispensable.The production of film is the process of a various parameters strict control, including formula, temperature, humidity, gas velocity
Degree and time etc., many complex parameters are added together last manufacture into the filter being distributed with desired flow, hole size, hole
Film.Traditionally, the production of film is the slurry that coating is entered based on non-solvent steam (usually steam), is carried out in pulp surface
Phase decomposition (or inversion of phases or mutually separate), then enters inside gradually, from top to bottom finally, by table to interior formation film, this
Method is known as steam guidance phase inversion or vapour draws phase point-score.The sky of a certain amount of relative humidity is mentioned in patent US4900449
The Polymer Solution after coating is crossed in air-blowing, is again imported in water the film of blank after Polymer Solution completes inversion of phases and is completed finally
Film.Another method is that slurry is directly entered liquid (being largely water or aqueous solution) and forms a film afterwards, this method is known as liquid and draws
It leads phase inversion or liquid draws phase point-score, also there is referred to as non-solvent guidance phase inversion or non-solvent to draw phase point-score.This method exists
It is common in the technique of ultrafiltration membrane to arrive.Since water or aqueous solution have quite high mass transfer in Polymer Solution, it is formed by film
Hole is all very small.If microfiltration membranes to be formed, the speed of this mass transfer will be slow.In patent US4203847
It mentions using a large amount of organic non-solvents as lead-in groove, mass transfer velocity of these non-solvents in Polymer Solution
With regard to the opposite hole for slowing down and forming microfiltration membranes.Only because on the one hand being caused potential using a large amount of organic non-solvents
On the one hand danger of combustion causes the harm of operator, it is often more important that post-processing and abandon problem.So raw in microfiltration membranes
It produces industrial impure liquid and draws phase point-score.Another industrial less method is that temperature guidance phase inversion or temperature are drawn
Phase point-score.This is to generate mutually to separate in temperature-rise period with the combination of special solution using certain macromolecules, i.e., by clearly single
Two-phase or multiphase is mutually formed by cloud point.It is mentioned in the patent of US5444097 and utilizes some specific solvents by polyether sulfone
When dissolution, generates when temperature reaches some critical point and mutually separate.These programs are by least semicentennial research and change
Into can accomplish symmetric membrane, anisotropic membrane and high anisotropic membrane now (two-sided fenestra gap is at 10 times or more).
In Fuji's patent (US4933081), macropore medial small hole up and down can achieve via control program parameter
Film；Also there is the patent of more anisotropic membranes in Solution, for example US5886059.The anisotropic membrane of Fuji and quite you non-right
Claim film to have a difference: the close layer of Fuji's anisotropic membrane is in hourglass shape in the internal layer of film；And quite your close layer is under film
Side (or top) is in V-shape (or inverted v-shaped).Each method has respective advantage and disadvantage.For example, draw in phase point-score in gas,
Mutually opposite slow of speed of separation, can not produce the film of big quantity in the short term；Draw in phase point-score in liquid, time and liquid are dense
The control of degree will be accurate, is otherwise not easy to obtain desired product；In Wen Yinxiang point-score, suitable macromolecule-solution is found
Matching is not simple procedure, while time and being precisely controlled for temperature are also not nothing the matter.
Summary of the invention
The purpose of the present invention is to provide a kind of asymmetric polyether sulfone micro-filtration membrane preparation methods, to solve above-mentioned each preparation side
Difficult point and deficiency in method.
In order to achieve the above objectives, the technical solution adopted by the present invention is that: a kind of asymmetric polyether sulfone micro-filtration membrane preparation method,
Include the following steps:
S1 prepared slurry) is produced, the prepared slurry includes following component in parts by weight: 50-70 parts of non-solvent, solvent
20-30 parts and plastic pellet 10-20 parts, non-solvent and solvent are uniformly mixed to prepare mixed liquor, plastic pellet is slowly added
Enter into mixed liquor, stirs；
S2) preparation slurry is coated in conductive base plate；
S3) conductive base plate is immediately placed on heat source, the upper space region of heat source has moving air, and can adjust
Save relative humidity and temperature, relative humidity RH=50-95%；
S4 conductive base plate is taken out after) heating, is immersed in water-bath at once and completes microfiltration membranes forming, can contained in water-bath non-molten
Agent component and solvent composition；
S5 it) cleans, drying.
Further, the prepared slurry has lower critical solution temperature.
Further, the non-solvent has the following structure general formula:
X-[O-(CH2)a-(CH(CH3))b]c-OX
Wherein, X is hydrogen or alkyl, and the range of a is 1-4, and b is 0 or 1, and the range of c is 1-8.
Further, the non-solvent is diethylene glycol diethylene glycol (DEG), triethylene glycol, three propyleneglycoles ethers, tetraethylene glycol or four
One or more of glyme, when select it is one such or it is several do non-solvent when, pulp solution just presents lower
Critical solution temperature, when temperature is increased beyond this temperature, pulp solution just generates phase decomposition phenomenon, utilizes this of pulp solution
A physical characteristic can carry out phase decomposition to generate film.
Further, the solvent is n-methyl-2-pyrrolidone, dimethylformamide, dimethyl acetamide, dimethyl
One or more of sulfoxide, tetrahydrofuran, gamma-butyrolacton or epsilon-caprolactams.
Further, the plastic pellet is polyethersulfone granules or polysulfones particle.
Further, coating thickness is 50-500 μm.
Further, the conductive base plate is stainless steel plate, aluminium sheet or copper sheet, with a thickness of 0.5-5mm.
Further, the heat source temperature is 40-100 DEG C, is higher than the critical solution temperature of prepared slurry.
The present invention is to be utilized that gas draws phase point-score, liquid draws phase point-score and three kinds of methods of Wen Yinxiang point-score are in the same production journey
In sequence, vapour is generated in the top of very thin coating sizing-agent and draws phase point-score, lower section generates Wen Yinxiang point-score, and generates liquid in centre and draw
Phase point-score；Using the control of multiple parameter to reach desired membrane structure, drawing in traditional temperature be added in membrane formation process to top sky
The humidity of gas makes the appropriate adjustments, so that the fault structure of film can be controlled freely, and it is different to draw membrane formation process with traditional temperature.
When starting to carry out phase decomposition below slurry, the air of certain relative humidity is also touched above slurry, it is right
Slurry starts to carry out phase decomposition.The phase decomposition to be come up by lower section and the phase decomposition got off by top can be in the intermediate somewheres of primary membrane
It merges and completes the setting value and contact heat of the formation of primary membrane, top relative air humidity and temperature degree and lower section heat source temperature
Source time length fully relies on the requirement specification of most telolemma to set.
Upper film surface carries out steam immersion, and lower film surface carries out hot guidance, thereby results in asymmetric membrane, generates via hot guidance method
Film temperature it is higher, contact the heat source time it is more long when, the hole of generation is bigger, and bubbling point is lower；In steam immersion method
In, humidity is higher, and hole is smaller, and anisotropic membrane is caused when both methods is met in the middle part of film.
Specific embodiment
The following is specific embodiments of the present invention, and technical scheme of the present invention will be further described, but the present invention is simultaneously
It is not limited to these embodiments.
Since in production line operation, production line has certain speed, so the time heated in embodiment is fixed as 4 seconds
Kind, sample leaves heating zone after 4 seconds kinds, immerses dipping bath slot using 2-3 seconds or so samples, following embodiment shows the present invention
(embodiment 1) and tradition Wen Yinxiang point-score (embodiment 2) obtain different product performances under the conditions of same temperature is drawn.
Embodiment 1
A kind of asymmetric polyether sulfone micro-filtration membrane preparation method, includes the following steps:
S1 prepared slurry) is produced, preparation slurry includes following component in parts by weight: 60 parts of triethylene glycol, N- methyl -2- pyrrole
28 parts and 12 parts of polyether sulfone particle of pyrrolidone, triethylene glycol and n-methyl-2-pyrrolidone are uniformly mixed to prepare mixed liquor, will be gathered
Ether sulfone particle (E6020P, BASF) is added slowly in mixed liquor, is stirred, and the cloud point that rises for testing preparation slurry is
40 DEG C, i.e., the critical solution temperature of prepared slurry is 40 DEG C；
S2) preparation slurry is coated on 1mm thickness stainless steel plate, coating thickness is 10mil (254 μm)；
S3) stainless steel plate is placed at once on 85 DEG C of heat source, the upper space region of heat source have adjust relative humidity be
80% air did not arrheaed；
S4 stainless steel plate is taken out after) heating 4 seconds, and immerses in water-bath and completes microfiltration membranes forming；
S5 it) cleans, drying.
Embodiment 2
A kind of asymmetric polyether sulfone micro-filtration membrane preparation method, includes the following steps:
S1 prepared slurry) is produced, preparation slurry includes following component in parts by weight: 60 parts of triethylene glycol, N- methyl -2- pyrrole
28 parts and 12 parts of polyether sulfone particle of pyrrolidone, triethylene glycol and n-methyl-2-pyrrolidone are uniformly mixed to prepare mixed liquor, will be gathered
Ether sulfone particle (E6020P, BASF) is added slowly in mixed liquor, is stirred；
S2) preparation slurry is coated on 1mm thickness stainless steel plate, coating thickness is 10mil (254 μm)；
S3) stainless steel plate is placed at once on 85 DEG C of heat source, the upper space region of heat source does not have any humidity regulation；
Prevailing circumstances humidity about 45-50%, about 23 DEG C of air themperature；
S4 stainless steel plate is taken out after) heating 4 seconds, and immerses in water-bath and completes microfiltration membranes forming；
S5 it) cleans, drying.
Flow detection is carried out to asymmetric polyether sulfone micro-filtration membrane made from embodiment 1 and embodiment 2, specific detection data is such as
Shown in table 1.
The asymmetric polyether sulfone micro-filtration membrane flow measuring data of table 1
The water flow of the film that heat source upper layer is formed in the air of relatively dry in embodiment 2 seen from table 1, film is only omited
1/4 or so of film is prepared greater than embodiment 1.
In conclusion the preparation method of asymmetric microfiltration membranes of the invention, filming technology is simple, and controllability is strong, is conducive to
Production control, compared with general invention, the clear water flow of asymmetric microfiltration membranes prepared by the present invention is about traditional 3 to 4 times
Left and right.
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (9)
1. a kind of asymmetric polyether sulfone micro-filtration membrane preparation method, which comprises the steps of:
S1 prepared slurry) is produced, the prepared slurry includes following component in parts by weight: 50-70 parts of non-solvent, solvent 20-
30 parts and plastic pellet 10-20 parts, non-solvent and solvent are uniformly mixed to prepare mixed liquor, plastic pellet is added slowly to
In mixed liquor, stir；
S2) preparation slurry is coated in conductive base plate；
S3) conductive base plate is immediately placed on heat source, the upper space region of heat source has moving air, and adjustable phase
To humidity and temperature, relative humidity numberical range is RH=50-95%；
S4 conductive base plate is taken out after) heating, is immersed in water-bath at once and completes microfiltration membranes forming；
S5 it) cleans, drying.
2. asymmetric polyether sulfone micro-filtration membrane preparation method according to claim 1, which is characterized in that the prepared slurry tool
There is lower critical solution temperature.
3. asymmetric polyether sulfone micro-filtration membrane preparation method according to claim 1, which is characterized in that S1) described in it is non-molten
Agent has the following structure general formula:
X-[O-(CH2)a-(CH(CH3))b]c-OX
Wherein, X is hydrogen or alkyl, and the range of a is 1-4, and b is 0 or 1, and the range of c is 1-8.
4. asymmetric polyether sulfone micro-filtration membrane preparation method according to claim 3, which is characterized in that the non-solvent is two
One or more of ethylene glycol diethylene glycol (DEG), triethylene glycol, three propyleneglycoles ethers, tetraethylene glycol or tetraethylene glycol dimethyl ether.
5. asymmetric polyether sulfone micro-filtration membrane preparation method according to claim 1, which is characterized in that S1) described in solvent
For n-methyl-2-pyrrolidone, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, tetrahydrofuran, gamma-butyrolacton or
One or more of epsilon-caprolactams.
6. asymmetric polyether sulfone micro-filtration membrane preparation method according to claim 1, which is characterized in that S1) described in plastics
Particle is polyethersulfone granules or polysulfones particle.
7. asymmetric polyether sulfone micro-filtration membrane preparation method according to claim 1, which is characterized in that S2) in coating thickness
It is 50-500 μm.
8. asymmetric polyether sulfone micro-filtration membrane preparation method according to claim 1, which is characterized in that S2) described in it is thermally conductive
Bottom plate is stainless steel plate, aluminium sheet or copper sheet, with a thickness of 0.5-5mm.
9. asymmetric polyether sulfone micro-filtration membrane preparation method according to claim 1, which is characterized in that S3) described in heat source
Temperature is 40-100 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912825A (en) * | 2019-02-26 | 2019-06-21 | 华东理工大学 | A kind of preparation method of polylactic acid durable hydrophobic surfaces |
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|---|---|---|---|---|
| KR20010106681A (en) * | 2000-05-22 | 2001-12-07 | 이영무 | Method for manufacturing asymmetric polyacrylonitrile membrane having the sponge-type structure and asymmetric polyacrylonitrile membrane manufactured thereby |
| CN101264425A (en) * | 2007-03-16 | 2008-09-17 | 私立中原大学 | Unsymmetrical film material forming method and device thereby |
| CN103272484A (en) * | 2013-05-27 | 2013-09-04 | 河北工业大学 | Method for preparing high-hydrophobicity microporous membrane |
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| CN109912825A (en) * | 2019-02-26 | 2019-06-21 | 华东理工大学 | A kind of preparation method of polylactic acid durable hydrophobic surfaces |
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