CN108421425A - A kind of preparation method of heavy metal-organic matter double filtration effect polyacrylonitrile-radical ultrafiltration membrane - Google Patents
A kind of preparation method of heavy metal-organic matter double filtration effect polyacrylonitrile-radical ultrafiltration membrane Download PDFInfo
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- CN108421425A CN108421425A CN201810189779.4A CN201810189779A CN108421425A CN 108421425 A CN108421425 A CN 108421425A CN 201810189779 A CN201810189779 A CN 201810189779A CN 108421425 A CN108421425 A CN 108421425A
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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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
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
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Abstract
The invention discloses the methods of the preparation of heavy metal species organic matter double filtration effect ultrafiltration membrane, it is matrix that this method, which is based on polyacrylonitrile, polyacrylonitrile ultrafiltration film is prepared by using phase inversion, and it is grafted amidoxime group using its chemical property, the ultrafiltration membrane preparation process mild condition, method is simple, can either retain organic matter again and can adsorb the heavy metal ion in water, has a good application prospect in wastewater treatment and household tap water purification.
Description
Technical field
The present invention relates to technology field of membrane materials, and in particular to a kind of heavy metal-organic matter double filtration effect polypropylene
The preparation method of itrile group ultrafiltration membrane.
Background technology
With the fast development of industry globalization, heavy metal pollution of water body getting worse simultaneously unprecedented restricts full people
The survival and development of class.China's heavy metal pollution form is quite severe, how to effectively remove heavy metal ion and organic matter in water
Equal pollutants, have important environment and economic value.Therefore, it no matter from environmental protection or the angle for health of drinking water, removes
The pollutants such as heavy metal ion and organic matter are all extremely important in water.
The method of heavy-metal ion removal has very much, there is chemical precipitation method, ion-exchange and absorption method.Chemical precipitation method
Heavy metal ion can be adsorbed, but treatment cost is high, need to carry out processing recycling to sludge, it is no it will cause secondary pollution and
The wasting of resources；The defect of ion-exchange is resin vulnerable to pollution used, can make oxidation deactivation, and regeneration is frequent, and the period is long, operation
Costly, it is to improve resin durability and intensity to solve the technology in the key of waste water treatment applications, extends the continuous use time,
This method is difficult to operate；Of the present invention is the method for membrane technology, membrane technology have without phase-change, it is easy to operate, efficient,
The features such as energy saving and equipment is simple.Membrane technology is suitable for processing waste water, and treated water can be with reuse, can be with by concentrating experiment
Recycle simple metal.Amidoxime group all has adsorptivity since it has amino and carboxyl simultaneously to most of heavy metal, can incite somebody to action
Heavy metal ion in waste water is adsorbed from waste water, is had a good application prospect in the absorption of heavy metal and recycle.
The material existing forms of currently used amidoxim are mainly resin shape and fiber shape.Since resin material has
Hydrophily is poor, and the rate of adsorption is slow, and fibrous material intensity is low, easy swelling, service life is short, operating process is complicated, production efficiency
Low disadvantage limits its use.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of retention absorption heavy metal ion ultrafiltration membrane.This method is not
Merely with the characteristic of ultrafiltration membrane itself, larger molecular organics are retained, and trap water can be adsorbed by modified ultrafiltration membrane
Middle heavy metal ion has good application value in terms of sewage disposal and domestic running water purification.
The purpose of the present invention is to provide a kind of preparation methods of heavy metal-organic matter double filtration effect ultrafiltration membrane, should
Method adopts the following technical scheme that realization：
Step 1, the preparation of polyacrylonitrile-radical ultrafiltration membrane
Polyacrylonitrile is weighed, organic solvent is dissolved in, compound concentration is the polyacrylonitrile casting solution of 15-19%, is stirred,
Until be completely dissolved, vacuum stands 24-48h, deaeration, and casting solution is scraped to be put into deionized water after wet film and is exchanged, directly
To film forming.
Step 2, polyacrylonitrile ultrafiltration film are grafted the preparation of amidoxime group
Configuration concentration is the hydroxylamine hydrochloride solution of 0.1-0.3mol/L, adjusts pH value with natrium carbonicum calcinatum or calcium carbonate, gathers
Acrylonitrile ultrafiltration membrane pours into hydroxylamine hydrochloride solution, until polyacrylonitrile ultrafiltration film is flooded completely, is reacted under the conditions of 50-70 DEG C
2-3 hours, taking-up polyacrylonitrile ultrafiltration film is put to be preserved in deionized water, so far obtains heavy metal-organic matter double filtration work(
Imitate ultrafiltration membrane.
According to technical solution above, in the case of preferred, organic solvent is selected from N-N- dimethyl formyls in the step 1
Amine, N-N- dimethylacetylamides, dimethyl sulfoxide (DMSO), nitrobenzene, ethylene carbonate or lactic acid nitrile.
According to technical solution above, in the case of preferred, the weight average molecular weight of polyacrylonitrile is in the step 1
60000-100000g/mol。
According to technical solution above, in the case of preferred, the thickness of wet film is 150 μm in the step 1.
According to technical solution above, in the case of preferred, a concentration of the 17% of polyacrylonitrile casting solution in the step 1.
According to technical solution above, in the case of preferred, a concentration of 0.1mol/ of hydroxylamine hydrochloride solution in the step 2
L。
According to technical solution above, in the case of preferred, reaction temperature is 60 DEG C in the step 2.
According to technical solution above, in the case of preferred, the reaction time is 2 hours in the step 2.In addition of the invention
Further relate to heavy metal-organic matter double filtration effect polyacrylonitrile-radical ultrafiltration membrane of Sustainable use above method preparation.
The preparation method of the polyacrylonitrile ultrafiltration film of heavy metal-organic matter double filtration effect ultrafiltration membrane in the step 1
It is phase inversion, and the ultrafiltration membrane prepared is functional.
The use of graft is amidoxime group in the step 2, makes reaction process mild condition.
The cyano of polyacrylonitrile (PAN) and hydroxylamine hydrochloride (HONH are utilized in the step 23Cl it is anti-) to be easy to happen grafting
Amidoxime group should be formed, reaction mechanism is：
Amidoxim contains nitrogen and oxygen electron rich group, can adsorb most of heavy metal ion, have very to heavy metal ion
Strong suction-operated.Hydroxylamine hydrochloride is a kind of colourless crystallization, and deliquescent chemical substance is used to prepare oxime in organic synthesis.
The hydrazine hydrate that also has of graft reaction, ethanol amine occurs with the cyano of polyacrylonitrile simultaneously, but since their toxicity is very big, pollutes
Seriously, so using hydroxylamine hydrochloride graft reaction occurs for the present invention.
Beneficial effects of the present invention：
The present invention is amidoxime group to be grafted to the advantage for making it not only with membrane material in membrane material, but also have absorption work(
Can, larger molecular organics that can not only be in effectively catching water, and floor space is small, it is at low cost, it is easy to operate, on its basis
The novel separation film of upper exploitation retention absorption heavy metal ion has a good application prospect.
It is matrix the present invention is based on polyacrylonitrile, prepares polyacrylonitrile ultrafiltration film by using phase inversion, and utilize it
Chemical property is grafted amidoxime group, and amidoxim contains nitrogen and oxygen electron rich group, the polyacrylonitrile ultrafiltration film modified condition temperature
With adsorption effect is good, effectively removes heavy metal ion and larger molecular organics in water.By modified polyacrylonitrile ultrafiltration film point
Not Yong 10mg/L Cu2+, Pb2+, Cd2+Solion is tested, it is found that it is preferable modified ultrafiltration membrane has heavy metal ion
Suction-operated, after 8 hours, to Cu2+, Pb2+, Cd2+The removal rate of three heavy metal species ions is all 95% or more；Modified
The Cu of polyacrylonitrile ultrafiltration film 3.33mg/L2+, Pb2+, Cd2+Three heavy metal species ions make total concentration be 10mg/L mixed solutions
It is tested, modified polyacrylonitrile ultrafiltration membrane Preferential adsorption Cu2+, and removal rate has reached 100%, followed by Pb after 6 hours2 +, adsorption equilibrium is basically reached after 3 hours, removal rate has reached 19%, but to Cd2+The removal of ion is essentially 0, thus illustrates
Sewage containing heavy metal ion is not only filtered off by modified ultrafiltration membrane in addition to larger molecular organics, and heavy metal has also been adsorbed
Ion has a good application prospect in wastewater treatment and household tap water purification.
Description of the drawings
Fig. 1 is the plane and profile scanning Electronic Speculum after the polyacrylonitrile ultrafiltration film prepared is modified with polyacrylonitrile ultrafiltration film
Figure, wherein a are unmodified, and b is modified；
Fig. 2 is the unmodified and modified infrared spectrogram of polyacrylonitrile ultrafiltration film；
Fig. 3 is modified polyacrylonitrile ultrafiltration film to Cu2+, Pb2+, Cd2+The removal rate of three heavy metal species ions；
Fig. 4 is modified polyacrylonitrile ultrafiltration film to Cu2+, Pb2+, Cd2+The removal of three heavy metal species Ar ion mixing liquid
Rate.
Specific implementation mode
Following nonlimiting examples can make those skilled in the art be more fully understood the present invention, but not with
Any mode limits the present invention.In addition, in following embodiments, unless otherwise specified, used experimental method is conventional side
Method, material therefor, reagent etc. can be bought from biological or chemical Reagent Company.
The weight average molecular weight of polyacrylonitrile in following embodiment is 60000g/mol.
The weight average molecular weight of polyacrylonitrile is 60000
The preparation of 1 polyacrylonitrile-radical ultrafiltration membrane of embodiment
It takes 50g N-N- dimethyl formamide solutions in reagent bottle, weighs 10.24g polyacrylonitrile, be configured to concentration
It for 17% polyacrylonitrile casting solution, is stirred on magnetic stirring apparatus, until being completely dissolved, standing is vacuumized with vacuum drying oven
For 24 hours, deaeration scrapes the film that thickness is 150 μm with the casting solution steeped is taken off on knifing machine, the wet film scraped is put into rapidly
It is exchanged in ionized water, until film forming.
2 polyacrylonitrile ultrafiltration film of embodiment is grafted the preparation of amidoxime group
Polyacrylonitrile ultrafiltration film is prepared according to method described in embodiment 1.
6.949g hydroxylamine hydrochlorides are weighed, the hydroxylamine hydrochloride solution of a concentration of 0.1mol/L is configured in 1L volumetric flasks, are used
Natrium carbonicum calcinatum adjusts pH to 7, is put into large beaker and cuts polyacrylonitrile ultrafiltration film, pours into the hydrochloric acid hydroxyl of 0.1mol/L
Beaker is placed on until polyacrylonitrile ultrafiltration film is flooded completely in 60 DEG C of water bath with thermostatic control by amine aqueous solution, is reacted 2 hours, is taken out
Polyacrylonitrile ultrafiltration film is put to be preserved in deionized water, so far completes the system of heavy metal-organic matter double filtration effect ultrafiltration membrane
It is standby.
It is seen in fig. 1, that modification has no too big influence to the internal structure of film, the supporting layer of finger-like pore can be clearly visible
With thin skin layer, in both structures, rise main separation and it is chemosmotic be cortex, the supporting layer of finger-like pore mainly plays support
Effect, it is modified film surface is influenced it is bigger, although film surface all can't see the presence in hole after before modified, film surface before modified
Smoother, modified change it is coarse, this is because caused by polyacrylonitrile ultrafiltration film surface grafting amidoxime group, original cyanogen
Base is replaced by the amidoxime group of volume bigger, and backbone structure deformation causes surface slight projection, with the progress of modified-reaction,
The amidoxime group of grafting is more and more, and protrusion is gradually amplified, thus formed it can be seen that rough surface.
As seen from Figure 2, the characteristic absorption peak of polyacrylonitrile is mainly C-C, C-H ,-C ≡ N, and modified polypropylene
After nitrile is due to grafting amidoxime group, there is the absorption of the keys such as O-H, N-H, N-O and C=N in addition to original characteristic absorption peak,
3500~3000cm-1There is wide and scattered absorption peak in place, this is O-H, the characteristic absorption peak of N-H stretching vibrations, and
1652.78cm-1There are corresponding N-H bending shock absorptions peaks at place.Therefore, it is feasible first to prepare the method that ultrafiltration membrane is modified again,
And reaction is easy to carry out, mild condition.
Embodiment 3 adsorbs Heavy metal
The polyacrylonitrile film that embodiment 1 is not modified is weighed into the 0.5g fragments, is respectively 10mg/L's with mass concentration
Cu2+, Pb2+, Cd2+Solion, volume are that 500mL is tested, and calculate removal rate Q (Q=(C0-Ct) V/m, wherein C0Be from
The initial concentration of sub- solution, CtIt is the ion concentrations of time t in the solution after adsorbing, v is overall solution volume, and m is the weight of film
Amount), find polyacrylonitrile film surface substantially without adsorbing metal ions, thus illustrate polyacrylonitrile film do not have adsorbing metal from
The property of son.
The modified polyacrylonitrile ultrafiltration film of embodiment 2 is weighed into the 0.5g fragments, uses the Cu of 10mg/L respectively2+, Pb2+,
Cd2+Solion is tested, and removal rate Q is calculated according to above-mentioned formula, investigates removal rate with the variation of adsorption time, such as Fig. 3
It is shown, it is found that modified ultrafiltration membrane has preferable suction-operated to heavy metal ion, heavy metal ion is gone in 1 hour
Except rate highest, extension at any time, removal rate increases slowly, and gradually tends to balance, and after 6 hours, removal rate Q is no longer at any time
Between significant change occurs, after 8 hours, to Cu2+, Pb2+, Cd2+The removal rate of three heavy metal species ions is all 95% or more.It will be real
It applies the modified polyacrylonitrile ultrafiltration film of example 2 and weighs the 0.5g fragments again, configure the Cu of 3.33mg/L2+, Pb2+, Cd2+Three kinds
Heavy metal ion makes total concentration be the mixed solution of 10mg/L, and volume is that 500mL is tested, and calculates and removes according to above-mentioned formula
Rate Q investigates variation of the removal rate with adsorption time, as shown in figure 4, modified polyacrylonitrile ultrafiltration membrane Preferential adsorption Cu2+, and 6
Removal rate has reached 100%, followed by Pb after hour2+, basically reaching adsorption equilibrium after 3 hours, removal rate has reached 19%, but
To Cd2+The removal of ion is essentially 0, thus illustrates that the sewage containing heavy metal ion is not only filtered off by modified ultrafiltration membrane
In addition to larger molecular organics, heavy metal ion has also been adsorbed.
The preparation of 4 polyacrylonitrile-radical ultrafiltration membrane of embodiment
It takes 50g N-N- dimethyl formamide solutions in reagent bottle, weighs 11.445g polyacrylonitrile, be configured to concentration
For 19% polyacrylonitrile casting solution, stirred on magnetic stirring apparatus, until be completely dissolved, with vacuum drying oven vacuumize it is quiet for 24 hours,
Deaeration scrapes the film that thickness is 150 μm with the casting solution steeped is taken off on knifing machine, the wet film scraped is put into rapidly deionization
It is exchanged in water, until film forming.
5 polyacrylonitrile ultrafiltration film of embodiment is grafted the preparation of amidoxime group
Polyacrylonitrile ultrafiltration film is prepared according to the method described in embodiment 4.
13.898g hydroxylamine hydrochlorides are weighed, the hydroxylamine hydrochloride solution of a concentration of 0.2mol/L is configured in 1L volumetric flasks, are used
Natrium carbonicum calcinatum adjusts pH to 7, is put into large beaker and cuts polyacrylonitrile ultrafiltration film, pours into the hydrochloric acid hydroxyl of 0.2mol/L
Beaker is placed on until polyacrylonitrile ultrafiltration film is flooded completely in 60 DEG C of water bath with thermostatic control by amine aqueous solution, is reacted 2 hours, is taken out
Polyacrylonitrile ultrafiltration film is put to be preserved in deionized water, so far completes the system of heavy metal-organic matter double filtration effect ultrafiltration membrane
It is standby.
The preparation of 6 polyacrylonitrile-radical ultrafiltration membrane of embodiment
It takes 50g N-N- dimethylacetamide solutions in reagent bottle, weighs 9.035g polyacrylonitrile, be configured to concentration
It for 15% polyacrylonitrile casting solution, is stirred on magnetic stirring apparatus, until being completely dissolved, standing is vacuumized with vacuum drying oven
For 24 hours, deaeration scrapes the film that thickness is 150 μm with the casting solution steeped is taken off on knifing machine, the wet film scraped is put into rapidly
It is exchanged in ionized water, until film forming.
7 polyacrylonitrile ultrafiltration film of embodiment is grafted the preparation of amidoxime group
Polyacrylonitrile ultrafiltration film is prepared according to the method described in embodiment 6.
20.847g hydroxylamine hydrochlorides are weighed, the hydroxylamine hydrochloride solution of a concentration of 0.3mol/L is configured in 1L volumetric flasks, are used
Natrium carbonicum calcinatum adjusts pH to 7, is put into large beaker and cuts polyacrylonitrile ultrafiltration film, pours into the hydrochloric acid hydroxyl of 0.3mol/L
Beaker is placed on until polyacrylonitrile ultrafiltration film is flooded completely in 60 DEG C of water bath with thermostatic control by amine aqueous solution, is reacted 2 hours, is taken out
Polyacrylonitrile ultrafiltration film is put to be preserved in deionized water, so far completes the system of heavy metal-organic matter double filtration effect ultrafiltration membrane
It is standby.
Claims (9)
1. a kind of preparation method of heavy metal-organic matter double filtration effect polyacrylonitrile-radical ultrafiltration membrane, which is characterized in that including
Following steps：
Step 1, the preparation of polyacrylonitrile-radical ultrafiltration membrane
Weigh polyacrylonitrile, be dissolved in organic solvent, compound concentration is the polyacrylonitrile casting solution of 15-19%, stirring until
It is completely dissolved, vacuum stands 24-48h, deaeration, casting solution is scraped to be put into deionized water after wet film is exchanged, directly
To film forming；
Step 2, polyacrylonitrile ultrafiltration film are grafted the preparation of amidoxime group
Configuration concentration is the hydroxylamine hydrochloride solution of 0.1-0.3mol/L, and pH value is adjusted to 6.8- with natrium carbonicum calcinatum or calcium carbonate
7.2, hydroxylamine hydrochloride solution is poured into polyacrylonitrile ultrafiltration film, until polyacrylonitrile ultrafiltration film is flooded completely, in 50-70 DEG C of item
It is reacted 2-3 hours under part, so far obtains heavy metal-organic matter double filtration effect ultrafiltration membrane.
2. the preparation method of heavy metal-organic matter double filtration effect polyacrylonitrile-radical ultrafiltration membrane according to claim 1,
It is characterized in that, organic solvent is selected from N-N- dimethylformamides, N-N- dimethylacetylamides, dimethyl Asia in the step 1
Sulfone, nitrobenzene, ethylene carbonate or lactic acid nitrile.
3. the preparation method of heavy metal-organic matter double filtration effect polyacrylonitrile-radical ultrafiltration membrane according to claim 1,
The weight average molecular weight of polyacrylonitrile is 60000-100000g/mol in the step 1.
4. the preparation method of heavy metal-organic matter double filtration effect polyacrylonitrile-radical ultrafiltration membrane according to claim 1,
It is characterized in that, the thickness of wet film is 150 μm in the step 1.
5. the preparation method of heavy metal-organic matter double filtration effect polyacrylonitrile-radical ultrafiltration membrane according to claim 1,
It is characterized in that, in the step 1 polyacrylonitrile casting solution a concentration of 17%.
6. the preparation method of heavy metal-organic matter double filtration effect polyacrylonitrile-radical ultrafiltration membrane according to claim 1,
It is characterized in that, in the step 2 hydroxylamine hydrochloride solution a concentration of 0.1mol/L.
7. the preparation method of heavy metal-organic matter double filtration effect polyacrylonitrile-radical ultrafiltration membrane according to claim 1,
It is characterized in that, reaction temperature is 60 DEG C in the step 2.
8. the preparation method of heavy metal-organic matter double filtration effect polyacrylonitrile-radical ultrafiltration membrane according to claim 1,
It is characterized in that, the reaction time is 2 hours in the step 2.
9. heavy metal-organic matter double filtration effect polyacrylonitrile-radical ultrafiltration membrane prepared by the method as described in 1-8 any one.
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| CN201810036202 | 2018-01-15 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112108002A (en) * | 2020-09-11 | 2020-12-22 | 广德华东电子电路发展有限公司 | Ultrafiltration membrane for wastewater treatment and preparation method thereof |
| CN113663660A (en) * | 2021-08-24 | 2021-11-19 | 南京海关工业产品检测中心 | Preparation method of heavy metal element adsorption film |
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| KR950004917B1 (en) * | 1991-12-30 | 1995-05-16 | 주식회사코오롱 | Manufacturing method for ultra filteration membrane |
| WO1996004070A1 (en) * | 1994-08-05 | 1996-02-15 | Gkss-Forschungszentrum Geesthacht Gmbh | Modified polyacrylonitrile membranes |
| CN104437129A (en) * | 2013-09-25 | 2015-03-25 | 江阴玉杉医药科技有限公司 | Modification of hydroxylamine hydrochloride and nitrate in polyacrylonitrile solution and preparation of amidoxime polyacrylonitrile affinity hollow fiber ultrafiltration membrane |
| CN106861435A (en) * | 2017-01-16 | 2017-06-20 | 湖北大学 | A kind of preparation method of the polyacrylonitrile bionic thin film for for oil hydrosol separate |
-
2018
- 2018-03-08 CN CN201810189779.4A patent/CN108421425A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR950004917B1 (en) * | 1991-12-30 | 1995-05-16 | 주식회사코오롱 | Manufacturing method for ultra filteration membrane |
| WO1996004070A1 (en) * | 1994-08-05 | 1996-02-15 | Gkss-Forschungszentrum Geesthacht Gmbh | Modified polyacrylonitrile membranes |
| CN104437129A (en) * | 2013-09-25 | 2015-03-25 | 江阴玉杉医药科技有限公司 | Modification of hydroxylamine hydrochloride and nitrate in polyacrylonitrile solution and preparation of amidoxime polyacrylonitrile affinity hollow fiber ultrafiltration membrane |
| CN106861435A (en) * | 2017-01-16 | 2017-06-20 | 湖北大学 | A kind of preparation method of the polyacrylonitrile bionic thin film for for oil hydrosol separate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112108002A (en) * | 2020-09-11 | 2020-12-22 | 广德华东电子电路发展有限公司 | Ultrafiltration membrane for wastewater treatment and preparation method thereof |
| CN113663660A (en) * | 2021-08-24 | 2021-11-19 | 南京海关工业产品检测中心 | Preparation method of heavy metal element adsorption film |
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Application publication date: 20180821 |