CN108745008A - A kind of preparation method of polysulfone composite membrane - Google Patents
A kind of preparation method of polysulfone composite membrane Download PDFInfo
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- CN108745008A CN108745008A CN201810755687.8A CN201810755687A CN108745008A CN 108745008 A CN108745008 A CN 108745008A CN 201810755687 A CN201810755687 A CN 201810755687A CN 108745008 A CN108745008 A CN 108745008A
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
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Abstract
The present invention relates to a kind of preparation methods of polysulfone composite membrane, belong to Nanofiltration-membrane technique field.The present invention is by adding nano-titanium dioxide to polysulfones membrane modifying, utilize the high-specific surface area of nano-titanium dioxide, it is set easily to adsorb the hydroxyl in water, micropore increases in film section structure, finger-like hole length increases, effectively improve the hydrophily and resistance tocrocking of film, in combination with carbon nanotube, by scraper, striking is molded on melt-blow nonwoven, due to the hole on the active force and melt-blow nonwoven of scraper, carbon nanotube and nano-titanium dioxide is promoted orderly to infiltrate into the hole of melt-blow nonwoven, so that the bottom surface cortex construction that is generated between film layer and fusion spray cloth and imperfect, and the finger-like pore structure of supporting layer is acted on due to carbon nanotube, so that finger-like pore structure further increases, so that in filter process, increase some resistance, it can also improve rejection simultaneously, improve separating capacity.
Description
Technical field
The present invention relates to a kind of preparation methods of polysulfone composite membrane, belong to Nanofiltration-membrane technique field.
Background technology
With the development of modern industry with the raising of living standards of the people, a large amount of oil-containing and organic contamination will be given off
The waste water of object.Oil of the grain size less than 30 μm and organic pollution cannot effectively be removed using usual way.Therefore necessary
The standard of discharge and reuse can be reached by carrying out advanced treating to these waste water.Membrane separation technique is dirty to oil-containing and organic matter
Water carries out the feasible and effective method of advanced treating.When membrane separation process handles oil-containing and organic pollution sewage, film is easily by oil
The pollutions such as matter, film surface forms gel layer, or even can also cause the blocking of fenestra.The film for handling such sewage at present has organic film
And inoranic membrane.Organic film preparation process is simple, and membrane material is wide in variety, is easy to be modified, and flexibility is good, cheap, can be made into each
The membrane module of kind form.But organic film has non-refractory, pH value narrow application range, pore-size distribution is wide, and mechanical strength is low, oozes
Saturating rate is low, the shortcomings of being easy to hydrolyze.With the development of material science, inoranic membrane is sent out as a new and high technology in recent decades
Exhibition is got up.Inoranic membrane has high temperature resistant, resistance to strong acid, highly basic and organic solvent, resistance to microbial attack, high mechanical strength, aperture point
The advantages that cloth is narrow, the poor reproducibility of film complicated (calcining) but there is also filming technologies prepare small-bore film difficulty, and matter is crisp
Flexibility is poor, it is of high cost the shortcomings of.Therefore, it develops and has the composite membrane of organic film and inoranic membrane two-fold advantage concurrently as current film point
One of exploitation hot spot from field.
In preparative separation film high polymer material used at present, polysulfones has many good mechanical performances, chemistry steady
Qualitative, easy film forming, but there is the defect for much limiting its application in this polymer：Hydrophily is poor, leads to the polysulfones prepared
Film pure water flux is very low.Separation of small molecuies ability is low, generally all applies in ultrafiltration membrane, and there are no be used alone in nanofiltration so far
Among film.Contamination resistance is poor.Based on above defect, physical and chemical modified appropriate is carried out to polysulfones, to improve point of film
From property and pure water flux.Common method of modifying is by polysulfones sulfonation, and preferable hydrophilic sulphur can be provided by being prepared to have
The sulfonated polysulfone of acid groups.Although sulfonated polysulfone has preferable hydrophily, the performance that sulfonated polysulfone individually forms a film is simultaneously bad.
More seriously, when the sulfonation degree of sulfonated polysulfone is more than certain value, Swelling can occur in water for sulfonated polysulfone, lead
It is caused to may not apply in water treatment field, therefore there is an urgent need for develop a kind of polysulfone composite membrane improvement present situation.
Invention content
The technical problems to be solved by the invention：It is poor for current PS membrane hydrophily, cause pure water flux very low, small point
Sub- separating capacity is low, and the problem of contamination resistance difference provides a kind of preparation method of polysulfone composite membrane.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
（1）It takes nano-titanium dioxide, carbon nanotube, polyethylene glycol-400, is added in n,N-dimethylacetamide, with 200~
300r/min is stirred, and is added glacial acetic acid 2~3h of insulated and stirred, is obtained dispersion liquid；
（2）Be added in n,N-dimethylacetamide after taking polysulfones, polyvinylpyrrolidone drying, at 60~80 DEG C with 150~
200r/min is stirred to transparent and homogeneous, adds dispersion liquid, and 2~4h of insulated and stirred obtains casting solution；
（3）Melt-blow nonwoven is entirely fixed on a glass, casting solution is poured on melt-blow nonwoven, waits for scraper
At the uniform velocity pass through, obtains liquid primary membrane；
（4）After liquid primary membrane is evaporated 10~15s in air, it is transferred to 1~2h in 90~100 DEG C of pure water coagulating bath, is waited for
3~5h of immersion in pure water is taken out and be transferred to polysulfone composite membrane by liquid primary membrane after being fully cured, takes out to obtain polysulfone composite membrane.
Step（1）The parts by weight of the material of the dispersion liquid be 0.3~0.5 part of nano-titanium dioxide, 0.01~0.02 part
Carbon nanotube, 2~3 parts of polyethylene glycol-400,80~100 parts of n,N-dimethylacetamide, 0.1~0.2 part of glacial acetic acid.
Step（1）The insulated and stirred temperature is 60~70 DEG C.
Step（2）The polysulfones, polyvinylpyrrolidone, the parts by weight of n,N-dimethylacetamide are poly- for 10~15 parts
Sulfone, 5.0~7.5 parts of polyvinylpyrrolidones, 80~100 parts of n,N-dimethylacetamide.
Step（2）The mass ratio of the polysulfones and nano-titanium dioxide is 20：1~50：1.
Step（3）The nascent film thickness of the liquid is 50~100 μm.
Step（3）The scraper speed is 40~50cm/s.
Compared with other methods, advantageous effects are the present invention：
The present invention makes it to polysulfones membrane modifying by adding nano-titanium dioxide using the high-specific surface area of nano-titanium dioxide
Easily adsorb the hydroxyl in water, micropore increases in film section structure, and finger-like hole length increases, effectively improve film hydrophily and
Resistance tocrocking, in combination with carbon nanotube, by scraper, striking is molded on melt-blow nonwoven, due to scraper active force with
And the hole on melt-blow nonwoven, promote carbon nanotube and nano-titanium dioxide orderly to infiltrate into the hole of melt-blow nonwoven
It is interior so that the bottom surface cortex construction that is generated between film layer and fusion spray cloth is simultaneously imperfect, and the finger-like pore structure of supporting layer due to
Carbon nanotube acts on so that finger-like pore structure further increases so that in filter process, some resistance is increased, while
Rejection can be improved, separating capacity is improved.
Specific implementation mode
0.3~0.5g nano-titanium dioxides, 0.01~0.02g carbon nanotubes, 2~3g polyethylene glycol-400 is taken to be added 80
In~100gN, N- dimethylacetylamide, 10~20min is stirred with 200~300r/min, adds 0.1~0.2g glacial acetic acid,
2~3h of insulated and stirred, obtains dispersion liquid at 60~70 DEG C, and 10~15g polysulfones, 5.0~7.5g polyvinylpyrrolidones is taken to be packed into
In drying box, dry 2~3h at 120~130 DEG C is added 80~100gN after dry, in N- dimethylacetylamides,
It is stirred to transparent and homogeneous with 150~200r/min at 60~80 DEG C, adds dispersion liquid, heat preservation persistently stirs 2~4h, obtains casting film
Melt-blow nonwoven is entirely fixed on a glass, adjusts the position of scraper by liquid, and thickness control is adjusted at 50~100 μm
The speed of film applicator scraper is 40~50cm/s, and casting solution is poured on melt-blow nonwoven, waits for that scraper at the uniform velocity passes through, obtains liquid
State primary membrane after liquid primary membrane is evaporated 10~15s in air, is transferred to 1~2h in 90~100 DEG C of pure water coagulating bath,
Polysulfone composite membrane is taken out to after liquid primary membrane is fully cured and is transferred in pure water 3~5h of immersion, take out polysulfones is compound
Film.
Example 1
Take 0.3g nano-titanium dioxides, 0.01g carbon nanotubes, 2g polyethylene glycol-400 that 80gN, N- dimethylacetylamides is added
In, 10min is stirred with 200r/min, adds 0.1g glacial acetic acid, insulated and stirred 2h, obtains dispersion liquid at 60 DEG C, takes 10g poly-
Sulfone, 5.0g polyvinylpyrrolidones, is fitted into drying box, and dry 2h, 80gN, N- diformazans are added after dry at 120 DEG C
It in yl acetamide, is stirred to transparent and homogeneous with 150r/min at 60 DEG C, adds dispersion liquid, heat preservation is persistently stirred 2h, must be cast
Melt-blow nonwoven is entirely fixed on a glass, adjusts the position of scraper by film liquid, and thickness control is adjusted and applied at 50 μm
The speed of film machine scraper is 40cm/s, and casting solution is poured on melt-blow nonwoven, waits for that scraper at the uniform velocity passes through, and it is nascent to obtain liquid
Film after liquid primary membrane is evaporated 10s in air, is transferred to 1h in 90 DEG C of pure water coagulating bath, waits for that liquid primary membrane is completely solid
Polysulfone composite membrane is taken out after change and is transferred in pure water and impregnates 3h, takes out to obtain polysulfone composite membrane.
Example 2
Take 0.4g nano-titanium dioxides, 0.01g carbon nanotubes, 2g polyethylene glycol-400 that 90gN, N- dimethylacetylamides is added
In, 15min is stirred with 250r/min, adds 0.1g glacial acetic acid, insulated and stirred 2h, obtains dispersion liquid at 65 DEG C, takes 12g poly-
Sulfone, 6g polyvinylpyrrolidones, is fitted into drying box, and dry 2h, 90gN, N- dimethyl are added after dry at 125 DEG C
It in acetamide, is stirred to transparent and homogeneous with 180r/min at 70 DEG C, adds dispersion liquid, heat preservation persistently stirs 3h, obtains casting film
Melt-blow nonwoven is entirely fixed on a glass, adjusts the position of scraper by liquid, and thickness control adjusts film at 80 μm
The speed of machine scraper is 45cm/s, and casting solution is poured on melt-blow nonwoven, waits for that scraper at the uniform velocity passes through, and it is nascent to obtain liquid
Film after liquid primary membrane is evaporated 12s in air, is transferred to 1h in 90 DEG C of pure water coagulating bath, waits for that liquid primary membrane is completely solid
Polysulfone composite membrane is taken out after change and is transferred in pure water and impregnates 4h, takes out to obtain polysulfone composite membrane.
Example 3
Take 0.5g nano-titanium dioxides, 0.02g carbon nanotubes, 3g polyethylene glycol-400 that 100gN, N- dimethylacetylamides is added
In, 20min is stirred with 300r/min, adds 0.2g glacial acetic acid, insulated and stirred 3h, obtains dispersion liquid at 70 DEG C, takes 15g poly-
Sulfone, 7.5g polyvinylpyrrolidones, is fitted into drying box, and dry 3h, 100gN, N- bis- are added after dry at 130 DEG C
It in methylacetamide, is stirred to transparent and homogeneous with 200r/min at 80 DEG C, adds dispersion liquid, heat preservation is persistently stirred 4h, obtained
Melt-blow nonwoven is entirely fixed on a glass, adjusts the position of scraper by casting solution, and thickness control is adjusted at 100 μm
The speed of film applicator scraper is 50cm/s, and casting solution is poured on melt-blow nonwoven, waits for that scraper at the uniform velocity passes through, at the beginning of obtaining liquid
Filming after liquid primary membrane is evaporated 15s in air, is transferred to 2h in 100 DEG C of pure water coagulating bath, waits for that liquid primary membrane is complete
Polysulfone composite membrane is taken out after solidification and is transferred in pure water and impregnates 5h, takes out to obtain polysulfone composite membrane.
The polysulfone composite membrane of polysulfone composite membrane and the production of Zhejiang company prepared by the present invention is detected, it is specific to detect
As a result such as following table table 1：
1 polysulfone composite membrane performance characterization of table
The polysulfone composite membrane for preparing of the present invention as shown in Table 1, hydrophilicity is good, and pure water flux is high, may be implemented to monovalent salt from
The efficient retention of son and divalent salt ion has extremely vast market prospect and application value.
Claims (7)
1. a kind of preparation method of polysulfone composite membrane, which is characterized in that the specific steps are：
（1）It takes nano-titanium dioxide, carbon nanotube, polyethylene glycol-400, is added in n,N-dimethylacetamide, with 200~
300r/min is stirred, and is added glacial acetic acid 2~3h of insulated and stirred, is obtained dispersion liquid；
（2）Be added in n,N-dimethylacetamide after taking polysulfones, polyvinylpyrrolidone drying, at 60~80 DEG C with 150~
200r/min is stirred to transparent and homogeneous, adds dispersion liquid, and 2~4h of insulated and stirred obtains casting solution；
（3）Melt-blow nonwoven is entirely fixed on a glass, casting solution is poured on melt-blow nonwoven, waits for scraper
At the uniform velocity pass through, obtains liquid primary membrane；
（4）After liquid primary membrane is evaporated 10~15s in air, it is transferred to 1~2h in 90~100 DEG C of pure water coagulating bath, is waited for
3~5h of immersion in pure water is taken out and be transferred to polysulfone composite membrane by liquid primary membrane after being fully cured, takes out to obtain polysulfone composite membrane.
2. a kind of preparation method of polysulfone composite membrane as described in claim 1, which is characterized in that step（1）The dispersion liquid
Material parts by weight be 0.3~0.5 part of nano-titanium dioxide, 0.01~0.02 part of carbon nanotube, 2~3 parts of polyethylene glycol-
400,80~100 parts of n,N-dimethylacetamide, 0.1~0.2 part of glacial acetic acid.
3. a kind of preparation method of polysulfone composite membrane as described in claim 1, which is characterized in that step（1）The heat preservation is stirred
It is 60~70 DEG C to mix temperature.
4. a kind of preparation method of polysulfone composite membrane as described in claim 1, which is characterized in that step（2）The polysulfones gathers
Vinylpyrrolidone, n,N-dimethylacetamide parts by weight be 10~15 parts of polysulfones, 5.0~7.5 parts of polyvinylpyrrolidines
Ketone, 80~100 parts of n,N-dimethylacetamide.
5. a kind of preparation method of polysulfone composite membrane as described in claim 1, which is characterized in that step（2）The polysulfones with
The mass ratio of nano-titanium dioxide is 20：1~50：1.
6. a kind of preparation method of polysulfone composite membrane as described in claim 1, which is characterized in that step（3）At the beginning of the liquid
Filming thickness is 50~100 μm.
7. a kind of preparation method of polysulfone composite membrane as described in claim 1, which is characterized in that step（3）The scraper speed
Degree is 40~50cm/s.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114653230A (en) * | 2020-12-22 | 2022-06-24 | 浙江迪萧环保科技有限公司 | Preparation method of high-selectivity separating composite membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104147943A (en) * | 2014-08-15 | 2014-11-19 | 武汉大学 | Preparation method and application of high-molecular forward osmosis membrane |
| CN105879710A (en) * | 2016-05-10 | 2016-08-24 | 东华大学 | Polyvinylidene fluoride based micro-pore film and preparation method thereof |
-
2018
- 2018-07-11 CN CN201810755687.8A patent/CN108745008A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104147943A (en) * | 2014-08-15 | 2014-11-19 | 武汉大学 | Preparation method and application of high-molecular forward osmosis membrane |
| CN105879710A (en) * | 2016-05-10 | 2016-08-24 | 东华大学 | Polyvinylidene fluoride based micro-pore film and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114653230A (en) * | 2020-12-22 | 2022-06-24 | 浙江迪萧环保科技有限公司 | Preparation method of high-selectivity separating composite membrane |
| CN114653230B (en) * | 2020-12-22 | 2023-08-18 | 浙江迪萧科技有限公司 | Preparation method of high-selectivity separation composite membrane |
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Application publication date: 20181106 |