CN107519847A - A kind of preparation method of heavy metal ion adsorbed film - Google Patents
A kind of preparation method of heavy metal ion adsorbed film Download PDFInfo
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- CN107519847A CN107519847A CN201710682614.6A CN201710682614A CN107519847A CN 107519847 A CN107519847 A CN 107519847A CN 201710682614 A CN201710682614 A CN 201710682614A CN 107519847 A CN107519847 A CN 107519847A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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Abstract
The present invention relates to a kind of preparation method of heavy metal ion adsorbed film, belong to field of environment engineering.The preparation method of the present invention adds a certain proportion of wool powder in the macromolecule material solution for being dissolved in organic solvent, using orientation freezing technology control ice-crystal growth direction, forms regular structure.Aqueous phase macromolecule material solution after freezing is freeze-dried under vacuum low-temperature environment forms doughnut array structure, improves filter efficiency.Organic solvent selects the organic solvent of high freezing point in the present invention, greatly shortens freeze-off time, avoids the loss of the energy, and the preparation method technique of the present invention is simple, and cost is cheap；Super water-purifying filter film prepared by the absorption property of the inventive method combination wool powder has uniform aperture, can be widely applied to the fields such as chemical industry, oil, light industry, daily use chemicals.
Description
Technical field
The present invention relates to a kind of preparation method of heavy metal ion adsorbed film, belong to field of environment engineering.
Background technology
With the rapid growth of economy, the development of city and agro-industry is also extremely rapid, and substantial amounts of heavy metal passes through various
Approach is discharged into environment, causes serious heavy metal pollution.Heavy metal contaminants have high toxicity, difficult degradation, biology rich
The features such as collection, it can enter human body by approach such as food chain, drinking-water, breathing or skin contacts, endanger human health, wherein,
Arsenic, chromium, cadmium and the heavy metal species of nickel four can increase the risk that the mankind suffer from the cancers such as lung cancer, cutaneum carcinoma, alimentary tract cancer, breast cancer；
Lead, cadmium, mercury and the heavy metal species of arsenic four can interfere with the metabolism of human hormone, cause various cental systems, reproductive system and the heart
The disease of blood vessel；In addition, although copper, manganese, zinc etc. are the necessary trace elements of human body, Excess free enthalpy can also be made to health
Into injury.Therefore, a kind of effective, environmental protection heavy metal ion adsorbing material is developed, for protection water body health and environment, people
The health of class all has great importance.
At present, the processing method of heavy metal ion mainly has：Chemical method, bioanalysis and physical chemistry.In application number
200710056397.6 patent of invention in, describe a kind of heavy metal ion adsorbed film and preparation method, the heavy metal ion
Adsorbed film is made up of polyvinyl alcohol and amino polymer, and Space network of polymer is formed by cross-linking agents.The introducing of amino
The water-swellable of the film of polyvinyl alcohol is not only increased, while causes the adsorption capacity of film heavy metal ion to have very big carry
It is high.But substantial amounts of amino is consumed in cross-linking process, reduce the ability of processing heavy metal ion.
Chinese invention patent：A kind of environmentally friendly heavy metal ion adsorbing material and preparation method thereof, the inventive method
Used raw material is maize straw, Paulownia elongata leaf and chlorella, belongs to environmentally friendly composition, not only to each heavy metal species
Ion has the good removal effect of meeting, while cost is relatively low and will not cause secondary injury to environment.But preparation process is added
Substantial amounts of chemical reagent, and technological process is numerous and diverse time-consuming longer, is unfavorable for industrial production.In Application No. 201610273898.9
In patent of invention, a kind of heavy metal ion adsorbed film and preparation method thereof is introduced, the adsorbed film is by metal-organic framework material, 2-
The organic solvents such as base benzimidazole, modifying agent, stabilizer composition is dredged, the absorption that can strengthen adsorbed film heavy metal ion is held
Amount.But this method has used a large amount of reagents and organic solvent in preparation process, adsorbed film has organic solvent and reagent
Residual causes secondary injury to water body, and preparation technology technological process complexity is cumbersome.Therefore, prepare a kind of efficient, environmentally friendly, cheap
Sorbing material be particularly important.The inside that made as described above method obtains is rambling loose structure, processing
The speed of heavy metal ion is relatively slow and treating capacity is smaller.
The content of the invention
Problem be present for above-mentioned, it is an object of the invention to provide a kind of preparation method of heavy metal ion adsorbed film,
To achieve the above object, technical scheme：
A kind of preparation method of heavy metal ion adsorbed film, described preparation method are carried out according to the following steps：
A. the preparation of high polymer material/wool powder solution
High polymer material is added in dimethyl sulfoxide or Isosorbide-5-Nitrae-dioxane, by stirring until being completely dissolved, Xiang Gao
Molecular material solution adds wool powder and is placed in after stirring 1~4 hour 2~5 in the environment that vacuum is 0.05~0.1MPa
Hour, the bubble in solution is removed, that is, obtains high polymer material/wool powder solution.
Wherein, described high polymer material is one kind in polyurethane or polyacrylonitrile.
The specification of described wool powder is 300~800 mesh.
Described wool powder and the mass ratio of high polymer material are 1：1~2：1.
The mass fraction of described high polymer material/wool powder solution is 4~6%.
B. the preparation of high polymer material/wool powder base substrate
By stent putting above metallic conductor, metallic conductor is immersed in liquid nitrogen, then the macromolecule that will be prepared through a steps
Material/wool powder solution is poured into mould, the solution layer that height is 5~10mm is formed in a mold, in the work of liquid nitrogen cryogenics
Under, high polymer material/wool powder solution in mould is slowly formed by curing with organic from the bottom to top along mould vertical direction
Solvent crystal is core, and high polymer material/wool powder is the column body unit of skin, and between adjacent cells body co-walled face high score
The base substrate of sub- material/wool powder base substrate, base substrate is taken out from mould, it is standby.
Wherein, mould is the insertion column that wall thickness made of polytetrafluoroethylmaterial material is 3~10mm.
C. the preparation of heavy metal ion adsorbed film
By base substrate prepared by above-mentioned b step be placed in temperature be -55~-65 DEG C and vacuum be 2~5Pa in the environment of freeze
To dry, remove the core in base substrate cylindrical body unit, formed using aperture as 30~100 μm, wall thickness is 1~5 μm of hollow tube, and
The array structure in co-walled face between adjacent hollow pipe, heavy metal ion adsorbed film is obtained after 24~36h.
The metallic conductor is one kind in copper conductor or aluminium conductor or silver conductor.
As a result of above technical scheme, the present invention preparation process add can effectively adsorbing heavy metal in water from
The wool powder of son, wool powder is a kind of protein, has good adsorption effect for heavy metal ion；In addition, wool
The adsorption effect of powder has close ties with its particle diameter, and as particle diameter is smaller, filter area is also big, and its adsorption effect is better, because
This, the specification of wool powder is 800~900 mesh.Polyurethane, polyacrylonitrile and PLA these three high polymer material materials tool
There is good chemical stability, the service life of filtering material can be extended.
The preparation method of the present invention is placed on metallic conductor block using orientation freezing technology induction ice-crystal growth, mould,
Metallic conductor is immersed in liquid nitrogen, the open upper end of mould, and the low temperature of liquid nitrogen is transmitted by lower end metallic conductor, the height in mould
Molecular material/wool powder solution slowly solidifies from the bottom to top along mould vertical direction, high polymer material/wool powder in solution
Aggregation rearrangement is carried out in the case where the pushing of oriented growth solidification ice crystal is repelled, is ultimately formed using organic solvent crystal as core, aqueous phase is high
Molecular material be skin column body unit, and between adjacent cells body the doughnut array structure in co-walled face base substrate, solidification
Base substrate removal so that the sandwich layer in each unit body directly distils under low-pressure low-temperature environment after shaping, that is, obtain using aperture as 30
~100 μm, wall thickness is 1~5 μm of doughnut, and between adjacent hollow fiber the array structure in co-walled face ultra-clean water filtration
Film.
In order to avoid ambient temperature has an impact to freezing solution, so as to ensure the final integrality of material, mould
Material selection be heat conductivility difference polytetrafluoroethylmaterial material and there is certain wall thickness.In addition, in order that obtain solution
Freeze within a short period of time, reduce the undue waste of the energy, the column of mould selection insertion, so contribute to metallic conductor
Directly contacted with solution；Metallic conductor selects thermal conductivity factor preferable copper, aluminium or silver；Organic solvent selection has high chill point
Dimethyl sulfoxide (DMSO) or Isosorbide-5-Nitrae-dioxane in one of which.The solution layer height that solution is formed in a mold is 5~10mm,
Ultimately form the thick super water-purifying filter films of 5~10mm, the ultra-clean water filtration formed when solution layer height is relatively low in freezing process
Film dynamic performance is poor, when solution layer height is higher, is unfavorable for solution quick freezing, wastes the substantial amounts of energy, and work as solution
When thickness is spent, final water purification film thickness is thicker, substantially reduces its filter effect, therefore the height of solution is finally 5 in a mold
Between~10mm.
For solution in course of dissolution because stirring can produce substantial amounts of bubble, bubble destroys array structure in freezing process,
Therefore solution needs bubble removing before orientation is freezed, and is mainly realized by the method for vacuum defoamation.The solution being stirred is put
Deaeration processing is carried out in the environment of vacuum is 0.05~0.1MPa, in order to fully remove the bubble in solution, according to solution
The difference of the mass fraction of middle high polymer material/wool powder base substrate, under environment under low pressure, the time of standing is 2~5 hours.
In the forming process of base substrate, with the increase of the mass fraction of high polymer material/wool powder base substrate in solution,
Hollow array structure is become apparent from, but its aperture is gradually reduced, and wall thickness increase, therefore the controllable aperture of method simple whereby is big
It is small, meet different places requirement.Increase however as the mass fraction of high polymer material in solution/wool powder base substrate,
The viscosity of solution is gradually increasing, and viscosity is excessive, and the organic solvent crystal that oriented growth solidifies in freezing process is not sufficiently large
Push squeeze repel solution in high polymer material, it is carried out aggregation rearrangement, the hole ultimately formed gradually tends to closure state,
Filter effect can be influenceed in use by tending to the hole of closure.Therefore, the matter of the mass fraction of high polymer material/wool powder base substrate
Fractional domination is measured 4~6%.Wherein, the mass ratio of wool powder and high polymer material is 1：1~2：1, when wool powder content
When less, adsorption effect is not obvious enough, but when wool powder content it is higher when, substantial amounts of wool powder blocks space and caused
Liquid can not be by reducing filter effect.
The preparation method of the present invention is using orientation freezing technology induction ice-crystal growth and Freeze Drying Technique, the letter of its technique
Single, cost is low, will not cause the waste of resource and the pollution of environment.
Embodiment
The present invention is described in further detail with reference to specific embodiment：
With the rapid growth of economy, the development of city and agro-industry is also extremely rapid, and substantial amounts of heavy metal passes through various
Approach is discharged into environment, causes serious heavy metal pollution, and wool has good as native protein, its heavy metal ion
Good absorption property.Freezing technology induction ice-crystal growth is oriented, removing solvent components are formed highly oriented under low-temp low-pressure environment
Doughnut array structure so that high polymer material material has a larger specific surface area, therefore with preferable adsorptivity and
Water imbibition.
A kind of preparation method of heavy metal ion adsorbed film, described preparation method are carried out according to the following steps：
A. the preparation of high polymer material/wool powder solution
One kind in polyurethane or polyacrylonitrile these three high polymer materials is added to dimethyl sulfoxide or Isosorbide-5-Nitrae-dioxy six
In ring, by stirring until being completely dissolved, using the mass ratio of wool split and high polymer material as 1：1~2：1 adds into solution
Enter the wool powder that specification is 300~800 mesh and be placed in after stirring 1~4 hour 2 in the environment that vacuum is 0.05~0.1MPa
~5 hours, the bubble in solution is removed, that is, obtains high polymer material/wool powder solution that mass fraction is 4~6%.
B. the preparation of high polymer material/wool powder base substrate
By wall thickness is 3~10mm made of polytetrafluoroethylmaterial material insertion column stent putting by copper or aluminium or
The top of metallic conductor made of silver, metallic conductor are immersed in liquid nitrogen, then the high polymer material/wool that will be prepared through a steps
Powder solution is poured into mould, forms the solution layer that height is 5~10mm, in the presence of liquid nitrogen cryogenics, mould in a mold
Interior high polymer material/wool powder solution be slowly formed by curing from the bottom to top along mould vertical direction using organic solvent crystal as
Core, high polymer material/wool powder be skin column body unit, and between adjacent cells body co-walled face high polymer material/sheep
The base substrate of hair powder base substrate, base substrate is taken out from mould, it is standby.
C. the preparation of heavy metal ion adsorbed film
By base substrate prepared by above-mentioned b step be placed in temperature be -55~-65 DEG C and vacuum be 2~5Pa in the environment of freeze
To dry, remove the core in base substrate cylindrical body unit, formed using aperture as 30~100 μm, wall thickness is 1~5 μm of hollow tube, and
The array structure in co-walled face between adjacent hollow pipe, heavy metal ion adsorbed film is obtained after 24~36h.
Specific embodiment
Embodiment one
A. the preparation of polyurethane/wool powder solution
2g polyurethane is added in 96g dimethyl sulfoxide, by stirring until being completely dissolved, 2g is added into solution
Specification is the wool powder of 300 mesh and is placed in 2h in the environment that vacuum is 0.05MPa after stirring 1h, removes the gas in solution
Bubble, that is, obtain polyurethane/wool powder solution that mass fraction is 4%.
B. the preparation of polyurethane/wool powder base substrate
By made of polytetrafluoroethylmaterial material wall thickness be 3mm insertion column stent putting by copper or aluminium or silvery
Into metallic conductor top, metallic conductor is immersed in liquid nitrogen, then the high polymer material/wool powder that will be prepared through a steps
Solution is poured into mould, forms the solution layer that height is 5mm, in the presence of liquid nitrogen cryogenics, the poly- ammonia in mould in a mold
Ester/wool powder solution is slowly formed by curing using dimethyl sulfoxide crystal as core from the bottom to top along mould vertical direction, polyurethane and
Wool powder be skin column body unit, and between adjacent cells body the polyurethane/wool powder base substrate in co-walled face base substrate, will
Base substrate takes out from mould, standby.
C. the preparation of super water-purifying filter film
By base substrate prepared by above-mentioned b step be placed in temperature be -55 DEG C and vacuum be 5Pa in the environment of be freeze-dried, go
Except the core in base substrate cylindrical body unit, formed using aperture as 70~100 μm, wall thickness is 1~2 μm of hollow tube, and it is adjacent in
The array structure in co-walled face between blank pipe, super water-purifying filter film is obtained after 36h.
Embodiment two
A. the preparation of polyurethane/wool powder solution
2g polyurethane is added in 95g Isosorbide-5-Nitrae-dioxane, by stirring until being completely dissolved, added into solution
Enter the wool powder that 3g specifications are 500 mesh and be placed in 3h in the environment that vacuum is 0.07MPa after stirring 2.5h, remove in solution
Bubble, that is, obtain mass fraction be 5% polyurethane/wool powder solution.
B. the preparation of polyurethane/wool powder base substrate
By made of polytetrafluoroethylmaterial material wall thickness be 7mm insertion column stent putting by copper or aluminium or silvery
Into metallic conductor top, metallic conductor is immersed in liquid nitrogen, then the high polymer material/wool powder that will be prepared through a steps
Solution is poured into mould, forms the solution layer that height is 7mm, in the presence of liquid nitrogen cryogenics, the poly- ammonia in mould in a mold
Ester/wool powder solution is slowly formed by curing using Isosorbide-5-Nitrae-dioxane crystal as core from the bottom to top along mould vertical direction, poly- ammonia
Ester and wool powder are the column body unit of skin, and between adjacent cells body the polyurethane/wool powder base substrate in co-walled face base
Body, base substrate is taken out from mould, it is standby.
C. the preparation of super water-purifying filter film
By base substrate prepared by above-mentioned b step be placed in temperature be -60 DEG C and vacuum be 3Pa in the environment of be freeze-dried, go
Except the core in base substrate cylindrical body unit, formed using aperture as 50~70 μm, wall thickness is 2~3 μm of hollow tube, and adjacent hollow
The array structure in co-walled face between pipe, super water-purifying filter film is obtained after 30h.
Embodiment three
A. the preparation of polyurethane/wool powder solution
2g polyurethane is added in 94g dimethyl sulfoxide, by stirring until being completely dissolved, 4g is added into solution
Specification is the wool powder of 800 mesh and is placed in 5h in the environment that vacuum is 0.1MPa after stirring 4h, removes the bubble in solution,
Obtain polyurethane/wool powder solution that mass fraction is 6%.
B. the preparation of polyurethane/wool powder base substrate
By made of polytetrafluoroethylmaterial material wall thickness be 10mm insertion column stent putting by copper or aluminium or silver
The top of manufactured metallic conductor, metallic conductor are immersed in liquid nitrogen, then the high polymer material/wool powder that will be prepared through a steps
Liquid solution is poured into mould, forms the solution layer that height is 10mm in a mold, poly- in mould in the presence of liquid nitrogen cryogenics
Urethane/wool powder solution is slowly formed by curing using dimethyl sulfoxide crystal as core from the bottom to top along mould vertical direction, polyurethane
With wool powder be skin column body unit, and between adjacent cells body the polyurethane/wool powder base substrate in co-walled face base substrate,
Base substrate is taken out from mould, it is standby.
C. the preparation of super water-purifying filter film
By base substrate prepared by above-mentioned b step be placed in temperature be -65 DEG C and vacuum be 2Pa in the environment of be freeze-dried, go
Except the core in base substrate cylindrical body unit, formed using aperture as 30~50 μm, wall thickness is 3~5 μm of hollow tube, and adjacent hollow
The array structure in co-walled face between pipe, super water-purifying filter film is obtained after 24h.
Example IV
A. the preparation of polyacrylonitrile/wool powder solution
2g polyacrylonitrile is added in 96g Isosorbide-5-Nitrae-dioxane, by stirring until being completely dissolved, into solution
Add 2g specifications to be the wool powder of 300 mesh and be placed in 2h in the environment that vacuum is 0.05MPa after stirring 1h, remove in solution
Bubble, that is, obtain mass fraction be 4% polyacrylonitrile/wool powder solution.
B. the preparation of polyacrylonitrile/wool powder base substrate
By made of polytetrafluoroethylmaterial material wall thickness be 3mm insertion column stent putting by copper or aluminium or silvery
Into metallic conductor top, metallic conductor is immersed in liquid nitrogen, then the high polymer material/wool powder that will be prepared through a steps
Solution is poured into mould, forms the solution layer that height is 5mm, in the presence of liquid nitrogen cryogenics, poly- third in mould in a mold
Alkene nitrile/wool powder solution is slowly formed by curing using Isosorbide-5-Nitrae-dioxane crystal as core from the bottom to top along mould vertical direction, is gathered
Acrylonitrile and wool powder are the column body unit of skin, and between adjacent cells body co-walled face polyacrylonitrile/wool powder base
The base substrate of body, base substrate is taken out from mould, it is standby.
C. the preparation of super water-purifying filter film
By base substrate prepared by above-mentioned b step be placed in temperature be -55 DEG C and vacuum be 5Pa in the environment of be freeze-dried, go
Except the core in base substrate cylindrical body unit, formed using aperture as 70~100 μm, wall thickness is 1~2 μm of hollow tube, and it is adjacent in
The array structure in co-walled face between blank pipe, super water-purifying filter film is obtained after 36h.
Embodiment five
A. the preparation of polyacrylonitrile/wool powder solution
2g polyacrylonitrile is added in 95g dimethyl sulfoxide, by stirring until being completely dissolved, added into solution
3g specifications are the wool powder of 500 mesh and are placed in 3h in the environment that vacuum is 0.07MPa after stirring 2.5h, remove in solution
Bubble, that is, obtain polyacrylonitrile/wool powder solution that mass fraction is 5%.
B. the preparation of polyacrylonitrile/wool powder base substrate
By made of polytetrafluoroethylmaterial material wall thickness be 7mm insertion column stent putting by copper or aluminium or silvery
Into metallic conductor top, metallic conductor is immersed in liquid nitrogen, then the high polymer material/wool powder that will be prepared through a steps
Solution is poured into mould, forms the solution layer that height is 7mm, in the presence of liquid nitrogen cryogenics, poly- third in mould in a mold
Alkene nitrile/wool powder solution is slowly formed by curing using dimethyl sulfoxide crystal as core from the bottom to top along mould vertical direction, polypropylene
Nitrile and the column body unit that wool powder is skin, and the polyacrylonitrile/wool powder base substrate in co-walled face between adjacent cells body
Base substrate, base substrate is taken out from mould, it is standby.
C. the preparation of super water-purifying filter film
By base substrate prepared by above-mentioned b step be placed in temperature be -60 DEG C and vacuum be 3Pa in the environment of be freeze-dried, go
Except the core in base substrate cylindrical body unit, formed using aperture as 50~70 μm, wall thickness is 2~3 μm of hollow tube, and adjacent hollow
The array structure in co-walled face between pipe, super water-purifying filter film is obtained after 30h.
Embodiment six
A. the preparation of polyacrylonitrile/wool powder solution
2g polyacrylonitrile is added in 94g Isosorbide-5-Nitrae-dioxane, by stirring until being completely dissolved, into solution
Add 4g specifications to be the wool powder of 800 mesh and be placed in 5h in the environment that vacuum is 0.1MPa after stirring 4h, remove in solution
Bubble, that is, obtain mass fraction be 6% polyacrylonitrile/wool powder solution.
B. the preparation of polyacrylonitrile/wool powder base substrate
By made of polytetrafluoroethylmaterial material wall thickness be 10mm insertion column stent putting by copper or aluminium or silver
The top of manufactured metallic conductor, metallic conductor are immersed in liquid nitrogen, then the high polymer material/wool powder that will be prepared through a steps
Liquid solution is poured into mould, forms the solution layer that height is 10mm in a mold, poly- in mould in the presence of liquid nitrogen cryogenics
Acrylonitrile/wool powder solution is slowly formed by curing using Isosorbide-5-Nitrae-dioxane crystal as core from the bottom to top along mould vertical direction,
Polyacrylonitrile and wool powder are the column body unit of skin, and between adjacent cells body co-walled face polyacrylonitrile/wool powder
The base substrate of base substrate, base substrate is taken out from mould, it is standby.
C. the preparation of super water-purifying filter film
By base substrate prepared by above-mentioned b step be placed in temperature be -65 DEG C and vacuum be 2Pa in the environment of be freeze-dried, go
Except the core in base substrate cylindrical body unit, formed using aperture as 30~50 μm, wall thickness is 3~5 μm of hollow tube, and adjacent hollow
The array structure in co-walled face between pipe, super water-purifying filter film is obtained after 24h.
Embodiment seven
A. the preparation of PLA/wool powder solution
2g PLA is added in 96g dimethyl sulfoxide, by stirring until being completely dissolved, 2g is added into solution
Specification is the wool powder of 300 mesh and is placed in 2h in the environment that vacuum is 0.05MPa after stirring 1h, removes the gas in solution
Bubble, that is, obtain PLA/wool powder solution that mass fraction is 4%.
B. the preparation of PLA/wool powder base substrate
By made of polytetrafluoroethylmaterial material wall thickness be 3mm insertion column stent putting by copper or aluminium or silvery
Into metallic conductor top, metallic conductor is immersed in liquid nitrogen, then the high polymer material/wool powder that will be prepared through a steps
Solution is poured into mould, forms the solution layer that height is 5mm, in the presence of liquid nitrogen cryogenics, the poly- breast in mould in a mold
Acid/wool powder solution is slowly formed by curing using dimethyl sulfoxide crystal as core from the bottom to top along mould vertical direction, PLA and
Wool powder be skin column body unit, and between adjacent cells body the PLA/wool powder base substrate in co-walled face base substrate, will
Base substrate takes out from mould, standby.
C. the preparation of super water-purifying filter film
By base substrate prepared by above-mentioned b step be placed in temperature be -55 DEG C and vacuum be 5Pa in the environment of be freeze-dried, go
Except the core in base substrate cylindrical body unit, formed using aperture as 70~100 μm, wall thickness is 1~2 μm of hollow tube, and it is adjacent in
The array structure in co-walled face between blank pipe, super water-purifying filter film is obtained after 36h.
Embodiment eight
A. the preparation of PLA/wool powder solution
2g PLA is added in 95g Isosorbide-5-Nitrae-dioxane, by stirring until being completely dissolved, added into solution
Enter the wool powder that 3g specifications are 500 mesh and be placed in 3h in the environment that vacuum is 0.07MPa after stirring 2.5h, remove in solution
Bubble, that is, obtain mass fraction be 5% PLA/wool powder solution.
B. the preparation of PLA/wool powder base substrate
By made of polytetrafluoroethylmaterial material wall thickness be 7mm insertion column stent putting by copper or aluminium or silvery
Into metallic conductor top, metallic conductor is immersed in liquid nitrogen, then the high polymer material/wool powder that will be prepared through a steps
Solution is poured into mould, forms the solution layer that height is 7mm, in the presence of liquid nitrogen cryogenics, the poly- breast in mould in a mold
Acid/wool powder solution is slowly formed by curing using Isosorbide-5-Nitrae-dioxane crystal as core from the bottom to top along mould vertical direction, gathers breast
Acid and wool powder be skin column body unit, and between adjacent cells body the PLA/wool powder base substrate in co-walled face base
Body, base substrate is taken out from mould, it is standby.
C. the preparation of super water-purifying filter film
By base substrate prepared by above-mentioned b step be placed in temperature be -60 DEG C and vacuum be 3Pa in the environment of be freeze-dried, go
Except the core in base substrate cylindrical body unit, formed using aperture as 50~70 μm, wall thickness is 2~3 μm of hollow tube, and adjacent hollow
The array structure in co-walled face between pipe, super water-purifying filter film is obtained after 30h.
Embodiment nine
A. the preparation of PLA/wool powder solution
2g PLA is added in 94g dimethyl sulfoxide, by stirring until being completely dissolved, 4g is added into solution
Specification is the wool powder of 800 mesh and is placed in 5h in the environment that vacuum is 0.1MPa after stirring 4h, removes the bubble in solution,
Obtain PLA/wool powder solution that mass fraction is 6%.
B. the preparation of PLA/wool powder base substrate
By made of polytetrafluoroethylmaterial material wall thickness be 10mm insertion column stent putting by copper or aluminium or silver
The top of manufactured metallic conductor, metallic conductor are immersed in liquid nitrogen, then the high polymer material/wool powder that will be prepared through a steps
Liquid solution is poured into mould, forms the solution layer that height is 10mm in a mold, poly- in mould in the presence of liquid nitrogen cryogenics
Lactic acid/wool powder solution is slowly formed by curing using dimethyl sulfoxide crystal as core from the bottom to top along mould vertical direction, PLA
With wool powder be skin column body unit, and between adjacent cells body the PLA/wool powder base substrate in co-walled face base substrate,
Base substrate is taken out from mould, it is standby.
C. the preparation of super water-purifying filter film
By base substrate prepared by above-mentioned b step be placed in temperature be -65 DEG C and vacuum be 2Pa in the environment of be freeze-dried, go
Except the core in base substrate cylindrical body unit, formed using aperture as 30~50 μm, wall thickness is 3~5 μm of hollow tube, and adjacent hollow
The array structure in co-walled face between pipe, super water-purifying filter film is obtained after 24h.
Claims (2)
1. a kind of preparation method of heavy metal ion adsorbed film, it is characterised in that described preparation method is carried out according to the following steps：
A. the preparation of high polymer material/wool powder solution
High polymer material is added in dimethyl sulfoxide or Isosorbide-5-Nitrae-dioxane, by stirring until being completely dissolved, to macromolecule
Material solution adds wool powder and is placed in after stirring 1~4 hour in the environment that vacuum is 0.05~0.1MPa 2~5 hours,
The bubble in solution is removed, that is, obtains high polymer material/wool powder solution；
Wherein, described high polymer material is one kind in polyurethane or polyacrylonitrile；
The specification of described wool powder is 300~800 mesh；
Described wool powder and the mass ratio of high polymer material are 1：1~2：1；
The mass fraction of described high polymer material/wool powder solution is 4~6%；
B. the preparation of high polymer material/wool powder base substrate
By stent putting above metallic conductor, metallic conductor is immersed in liquid nitrogen, then the macromolecule material that will be prepared through a steps
Material/wool powder solution is poured into mould, the solution layer that height is 5~10mm is formed in a mold, in the effect of liquid nitrogen cryogenics
Under, high polymer material/wool powder solution in mould is slowly formed by curing with organic molten from the bottom to top along mould vertical direction
Agent crystal is core, and high polymer material/wool powder is the column body unit of skin, and between adjacent cells body co-walled face macromolecule
The base substrate of material/wool powder base substrate, base substrate is taken out from mould, it is standby；
Wherein, mould is the insertion column that wall thickness made of polytetrafluoroethylmaterial material is 3~10mm；
C. the preparation of heavy metal ion adsorbed film
By base substrate prepared by above-mentioned b step be placed in temperature be -55~-65 DEG C and vacuum be 2~5Pa in the environment of freeze it is dry
It is dry, the core in base substrate cylindrical body unit is removed, is formed using aperture as 30~100 μm, wall thickness is 1~5 μm of hollow tube, and phase
The array structure in co-walled face between adjacent hollow tube, heavy metal ion adsorbed film is obtained after 24~36h.
A kind of 2. preparation method of heavy metal ion adsorbed film as claimed in claim 1, it is characterised in that：The metallic conductor
For one kind in copper conductor or aluminium conductor or silver conductor.
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