CN105080509A - Nanofiber membrane and membrane adsorbing assembly for extracting uranium from seawater and brine water and application of nanofiber membrane and membrane adsorbing assembly - Google Patents
Nanofiber membrane and membrane adsorbing assembly for extracting uranium from seawater and brine water and application of nanofiber membrane and membrane adsorbing assembly Download PDFInfo
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Abstract
The invention discloses a nanofiber membrane and a membrane adsorbing assembly for extracting uranium from seawater and brine water and application of the nanofiber membrane and the membrane adsorbing assembly. The nanofiber membrane is prepared by the steps: preparing polyacrylonitrile into a spinning solution; depositing polyacrylonitrile nanowires on a macromolecular non-woven fabric through an electrostatic spinning process to obtain a polyacrylonitrile nanofiber membrane; and then carrying out amidoximation on the polyacrylonitrile nanofiber membrane to obtain the nanofiber membrane. The membrane adsorbing assembly is prepared by the steps: preparing the nanofiber membrane into a rolled membrane assembly; and then carrying out amidoximation on the rolled membrane assembly to obtain the nanofiber membrane adsorbing assembly. The membrane adsorbing assembly disclosed by the invention is high in adsorption capacity, great in adsorption rate, stable in recycling performance and high in mechanical strength. The membrane adsorbing assembly not only is suitable for extracting uranium element from water bodies such as seawater or brine water and the like, but also is suitable for separating and recovering other noble metal or heavy metal ions from industrial wastewater, underground water and drinking water separately as well as removing metal ions from an organic phase.
Description
Technical field
The present invention relates to nanofiber technical field of membrane, be specifically related to a kind of sea water bittern and propose uranium nano fibrous membrane and film absorbent module and application thereof.
Background technology
Uranium is a kind of important strategic energy goods and materials, all significant to industry, agricultural, national defence and science and technology.Along with the exhaustion of fossil energy, the Nuclear Power cause obtains to be paid much attention to and fast development, and the demand of uranium also grows with each passing day.But the gross reserves of land uranium only has 3.0 × 10
9kg, only enough the mankind use decades.Along with developing rapidly of Chinese national economy, the demand of the energy grows with each passing day, and gives more and more higher attention to nuclear energy, and the nuclear power developing policy of China is adjusted to " develop actively " by " optimum development ".Cut-off the year two thousand twenty, China's nuclear power runs installed capacity will reach 7,000 ten thousand kilowatts, account for more than 5% of total installed capacity of electricity ratio.But China's land uranium resource reserves are limited, and the equal small scale of explored uranium deposit, grade are low, and China will increase severely to the demand of uranium, and the situation that uranium resource is in short supply will be more outstanding.Therefore, find and develop new uranium resource source and seem very urgent.
The source of uranium mainly contains land ore, seawater and salt lake bittern 3 source.On land, ore resource is limited, and when increasingly poor, in seawater and salt lake bittern, the extraction of uranium is subject to people's attention increasingly.But the content of URANIUM IN SEAWATER is extremely low (only 3 μ g/L), although the concentration of uranium is even up to ten thousand times, tens in seawater in salt lake bittern, its composition is more complicated, and ion concentration is higher, is also unfavorable for the extraction of uranium.Therefore, develop be applicable to low concentration uranium, new technology that polyhalide water body carries uranium and new material become the key of opening up new uranium ore source.
According to the existence form of uranium in seawater/bittern and there is environment, suitable method must be selected extract or enriching seawater uranium wherein.The method extracting uranium at present from seawater/bittern mainly contains coprecipitation, bioanalysis, ion-exchange and absorption method etc.In said method, absorption method due to have selective good, extraction efficiency is high, easy realization, the feature such as simple to operate, be the method most with application prospect.Conventional sorbent material is a lot, and comprise inorganic adsorbing material as hydrated titanium dioxide etc., organic adsorbent is as amidoxime group compound etc., and hybrid adsorbent is as imvite/amidoxim hybrid material etc.Inorganic adsorbing material, owing to there will be heavy losses in use procedure, limits the prospect of its commercial application; Amidoxime type functional material because of the selective height of its uranium, the rate of adsorption is fast, structure is simple, synthesis material is cheap and easy to get, preparation cost is low, be current most study is also that the seawater/bittern being considered to most probable commercial application carries uranium functional material.
The amidoxime group material mainly polymeric sorbent such as resin and fiber of current preparation.Although wherein resinae adsorbent mechanical strength is high, hydrophily is poor, the rate of adsorption is slow; Although the fiber-like absorption rate of adsorption is fast, mechanical strength is low, recycle performance difference, thus makes this two classes material be difficult to scale application.Therefore, develop that a kind of ion selectivity is good, the rate of adsorption is fast, adsorption capacity is large, mechanical strength is high, recycle the good novel amidoxime group polymer adsorption membrane material of performance and film absorbent module, have great importance.
Summary of the invention
The object of the invention is to, provide a kind of sea water bittern to put forward uranium nano fibrous membrane and film absorbent module, and this film absorbent module is in the application of extracting uranium in sea water bittern.
The technical scheme that the present invention is adopted for achieving the above object is as follows:
A kind of sea water bittern carries uranium nano fibrous membrane, this nano fibrous membrane prepares by the following method: polyacrylonitrile (PAN) is mixed with spinning solution, by electrostatic spinning process polyacrylonitrile nano silk deposited on macromolecule non-woven fabrics and obtain polyacrylonitrile nanofiber film, then amidoxim is carried out to polyacrylonitrile nanofiber film and obtain described sea water bittern and carry uranium nano fibrous membrane.Described macromolecule non-woven fabrics is PETG (PET), and the porosity of this non-woven fabrics is 40% ~ 80%, and thickness is 30 ~ 200 μm.The mass content of described polyacrylonitrile in polyacrylonitrile nanofiber film is 5% ~ 30%.
Particularly, described PAN is dissolved in N, in the mixed solution of dinethylformamide (DMF) and 1-METHYLPYRROLIDONE (NMP), be made into spinning solution, by electrostatic spinning process, PAN nano wire is deposited on PET non-woven fabrics, the PAN nanofiber membrane that to obtain with PET non-woven fabrics be substrate; Then PAN nanofiber membrane be immersed in the alkaline solution containing hydroxylamine hydrochloride, controlling hydroxylamine hydrochloride solution pH is between 7 ~ 10, carries out the amidoxim of nano fibrous membrane; Oximate terminates rear clean water membrane module to neutral, then can obtain sea water bittern after activation process in immersion acid solution and carry uranium nano fibrous membrane.Wherein, in described hydroxylamine hydrochloride input amount and PAN nanofiber membrane, the mol ratio of itrile group (-CN) is 1:0.002 ~ 1:0.5; Described hydroxylamine hydrochloride solution pH is the alkaline solution of 7 ~ 10, can by adding sodium carbonate and/or sodium acid carbonate regulates, and described sodium carbonate or the mass ratio of sodium acid carbonate and hydroxylamine hydrochloride are 1:1 ~ 1:3.
The present invention also provides a kind of sea water bittern to put forward uranium nano fibrous membrane absorbent module, this nano fibrous membrane absorbent module prepares by the following method: step 1, polyacrylonitrile is dissolved in N, be mixed with spinning solution in the mixed solution of dinethylformamide and 1-METHYLPYRROLIDONE, by electrostatic spinning process, polyacrylonitrile nano silk deposited acquisition polyacrylonitrile nanofiber film on macromolecule non-woven fabrics; Step 2, makes rolled membrane module by the polyacrylonitrile nanofiber film that abovementioned steps obtains; Step 3, carries out amidoximization i.e. obtained described nano fibrous membrane absorbent module by aforementioned rolled membrane module.
Particularly, to put forward uranium nano fibrous membrane absorbent module preparation manipulation process as follows for described sea water bittern:
(1), the preparation of composite polypropylene nitrile nanofibre film on PET non-woven fabrics: PAN is dissolved in N, in the mixed solution of dinethylformamide (DMF) and 1-METHYLPYRROLIDONE (NMP), be made into spinning solution, by electrostatic spinning process, PAN nano wire is deposited on PET non-woven fabrics, the PAN nanofiber membrane that to obtain with PET non-woven fabrics be substrate.
(2), the preparation of rolled membrane module: the PAN nanofiber membrane obtained in step (1) rolled by manual or volume film machine, described rolled membrane module comprises central tube, putamina, diaphragm, water distribution graticule mesh, sealing ring and film end water distribution component.
(3), the amidoxim of rolled membrane module: the rolling nanofiber membrane module obtained in step (2) is immersed in the alkaline solution containing hydroxylamine hydrochloride or by pump, the circulation of hydroxylamine hydrochloride alkaline solution is driven into PAN nanofiber membrane component internal and carry out amidoxim, oximate terminates rear clean water membrane module to neutral, then immerses in acid solution and can obtain nano fibrous membrane absorbent module after activation process.Used by acid solution desorption Posterior circle equally after adsorption process completes.Wherein, described alkaline solution can use one or more in sodium carbonate, sodium acid carbonate; Described acid solution can use one or more in hydrochloric acid, nitric acid, phosphoric acid; The reaction temperature of described amidoxim is 50 ~ 90 DEG C.
In above-mentioned steps (1), described macromolecule non-woven fabrics is PETG (PET) material, and porosity is 40% ~ 80%, and the thickness of non-woven fabrics is 30 ~ 200 μm.
In above-mentioned steps (1), the polymer number-average molecular weight in described PAN spinning solution is 150000 ~ 200000, and polymer concentration is 5 ~ 20wt.%, and the volume ratio of mixed solvent DMF/NMP is 1:10 to 1:1; Spinning voltage is 16 ~ 25kV, relative humidity 30% ~ 50%; Spinning nozzle is 8 ~ 15cm to the distance of receiver, and the fltting speed of spinning solution is 0.002mm/s-0.025mm/s, and preparing with PET is the PAN nanofiber membrane of substrate.
Preferably, in the described PET-PAN composite nano-fiber membrane of step (1), the thickness of PAN nano wire is the mass content of 60-200 μm, PAN nano wire in composite membrane is 5% ~ 30%.
In above-mentioned steps (2), the preparation of rolled membrane module rolls by manual or volume film machine.
In above-mentioned steps (2), described rolled membrane module comprises central tube, putamina, diaphragm, water distribution graticule mesh, sealing ring and film end water distribution component.
In above-mentioned steps (2), the central tube of described rolled membrane module does not offer gully-hole, and two ends seal, and only provides diaphragm and water distribution graticule mesh volume film to support and uses.
In above-mentioned steps (2), the diaphragm of described rolled membrane module and water distribution graticule mesh can single laminate roll films, also can multilayer alternately place after roll up film.
In above-mentioned steps (2), the sealing ring of described rolled membrane module is arranged on putamina side, and film end water distribution component is arranged on membrane module two ends.
In above-mentioned steps (3), the amidoxim of described rolled membrane module, realized by following operating process: at a certain temperature, by step 2) in preparation rolled membrane module be immersed in the hydroxylamine hydrochloride solution configured, maybe by the hydroxylamine hydrochloride solution configured by elevator pump circulation be driven into step 2) in preparation rolled membrane module in, controlling hydroxylamine hydrochloride solution pH is between 7 ~ 10, realizes the amidoxim modification of rolled membrane module.Used by acid solution desorption Posterior circle equally after adsorption process completes.In wherein said hydroxylamine hydrochloride input amount and membrane module, the mol ratio of the itrile group (-CN) of PAN is 1:0.002 ~ 1:0.5; Described pH is the alkaline solution of 7 ~ 10, can by adding sodium carbonate and/or sodium acid carbonate etc. to regulate, and the mass ratio of described sodium carbonate or sodium acid carbonate and hydroxylamine hydrochloride is 1:1 ~ 1:3.
The concentration range of the hydroxylamine hydrochloride in step (3) in amidoximation process, at 5 ~ 20wt.%, is preferably 8 ~ 12wt.%.
Preferably, in step (3), amidoximation temperature is 55 ~ 85 DEG C.
Preferably, in step (3), the amidoxim time is 120 ~ 360min.
Preferably, described in step (3), the pH of acid solution is 0.5 ~ 3.5.
Preferably, in step (3), film is 30 ~ 360min in the time of acid solution process.
Present invention also offers described sea water bittern and put forward uranium nano fibrous membrane absorbent module in the application of extracting uranium in seawater or bittern.
Additionally provide described sea water bittern and put forward uranium nano fibrous membrane absorbent module in the application of removing metal ion in the aqueous solution or organic solution, described metal ion is Pb
2+, Ni
2+, Co
2+, Ce
3+, Cr
6+, Au
+, Cu
2+, K
+, Ca
2+, Mg
2+, Na
+, Fe
2+, Fe
3+.
Compared with prior art, beneficial effect of the present invention is as follows:
1, the sea water bittern that the present invention makes public for the first time based on amidoxim polyacrylonitrile puies forward uranium nano fibrous membrane and film absorbent module, and the application of film absorbent module uranium or other metal ion in adsorbed water.The polyacrylonitrile nanofiber film prepared by electrostatic spinning has the outstanding advantages such as high-specific surface area, high porosity and the inner open-celled structure be communicated with, thus makes it in the adsorbing separation of heavy metal ion, show good absorption property and recycle performance.Nano-fiber material is introduced amidoxime group functional group uranyl ion to high absorption capacity, high selectivity, greatly can improve the adsorption efficiency of uranium.In addition, nano-fiber material is sticked in the process of electrostatic spinning macromolecule non-woven fabrics as PETG (PET) material greatly can improve nano fibrous membrane mechanical strength in use, thus the sea water bittern that acquisition has actual application value puies forward uranium nano fibrous membrane and film absorbent module.
2, the present invention makes full use of polymer nanofiber high-ratio surface sum high porosity, nonwoven cloth material high mechanical properties, amidoxime group has high uranyl ion-selective and adsorption capacity, rolled membrane module recycle good stability and be easy to the features such as mass production, and the film absorbent module adsorption capacity prepared is high, the rate of adsorption is fast, recycle that performance is stable, mechanical strength is high.This film absorbent module is not only applicable to extract the elements such as uranium from the water body such as seawater or bittern, is also applicable to other noble metal of separation and recovery or heavy metal ion from industrial wastewater, underground water and drinking water, is also applicable to removing of metal ion in organic phase.
3, the amidoxim modification of nano fibrous membrane absorbent module prepared by the present invention carries out after the polyacrylonitrile nanofiber film prepared in electrospinning is rolled into assembly, and technological process is simple, industrializing implementation is easy.
4, nano fibrous membrane absorbent module of the present invention preparation using PET non-woven fabrics and polyacrylonitrile as base material, low raw-material cost.
5, polyacrylonitrile nanofiber film specific area of the present invention is large, porosity is high, and oximation reaction speed is fast, oximate degree is high.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram that in the embodiment of the present invention, rolled membrane module carries out amidoximation.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
(1) 0.1m is prepared by electrostatic spinning
2pET-PAN nano fibrous membrane, wherein PAN nanofiber content is 0.625g, PAN nanofiber layer thickness is 40 μm.Using polyethylene (PE) hollow tube of long 50mm, external diameter 5mm as central tube, polyvinyl chloride (PVC) pipe of long 50mm, internal diameter 20mm is as putamina, and the PE grid of thickness 2mm rolls into rolled membrane module as water distribution graticule mesh is manual.It is in the hydroxylamine hydrochloride solution of 10% that the manual membrane module rolled is immersed into mass fraction, 70 DEG C of water-bath concussion 240min, pH value of reaction system is maintained between 7-10 by adding sodium carbonate in course of reaction, reaction terminates rear taking-up membrane module, clear water cyclic washing is aobvious neutral to pH, then the film that amidoximization is good is placed in pH be 0.6 hydrochloric acid solution process after 2 hours taking-up clear water cyclic washing aobvious neutral to pH.Film is placed in 80 DEG C of baking ovens to dry, obtain the film absorbent module quality after amidoxim and add 0.389g, the oximate rate that can be calculated PAN nanofiber membrane is 100%.
(2) the film absorbent module obtained is placed in the 10L uranyl nitrate solution (pH ~ 4.25) that uranium initial concentration is 100mg/L, solution temperature controls at 20 DEG C, water-bath is shaken, adsorption time is 72 hours, it is 2.7mg/L that absorption terminates uranium concentration in rear solution, uranium clearance is 97.3%, and the uranium adsorption capacity of the nano fibrous membrane absorbent module after oximate is 959mg/g.
(3) pH value absorption described in (2) being terminated rear solution adjusts to about 0.6,20 DEG C of water-bath concussion 30min, the uranyl ion in desorption nano fibrous membrane absorbent module.Uranium concentration after 30min in sampling and measuring solution is 100mg/L, and the uranium all desorptions be adsorbed on membrane module are described.Membrane module takes out clear water cyclic washing to neutral, recycles.
(4) using (2) step and (3) step as an adsorption-desorption cycle, repeat the uranium adsorption capacity of 10 caudacoria absorbent module still up to 700mg/g, uranyl ion still can realize complete desorption.
Embodiment 2
(1) 4.0m is prepared by electrostatic spinning
2pET-PAN nano fibrous membrane, wherein PAN nanofiber content is 50g, PAN nanofiber layer thickness is 40 μm.Using polyethylene (PE) hollow tube of long 1000mm, external diameter 20mm as central tube, polyvinyl chloride (PVC) pipe of long 1000mm, internal diameter 200mm is as putamina, and the PE grid of thickness 2mm utilizes volume film machine to roll into rolled membrane module as water distribution graticule mesh.See Fig. 1, this figure is the device schematic diagram that rolled membrane module carries out amidoximation.As shown in the figure, by the mass fraction configured be 10% hydroxylamine hydrochloride solution by drug dissolving tank 1 after feed pump 2 promotes by feeding pipe 3 by water distribution component 4 circulate be driven in the membrane module 5 rolled, get back in drug dissolving tank 1 via discharging pipeline 7 again, realize circular response.About wherein drug dissolving tank 1 arranges internal heating coils or external heat cover maintenance hydroxylamine hydrochloride solution temperature 70 C, membrane module 5 inside arranges central tube 6.Solution ph is maintained between 8-10 by adding in sodium acid carbonate to drug dissolving tank 1 in course of reaction, membrane module is unloaded after circular response 4hr, the membrane module clear water that oximate is good rinses to pH aobvious neutral repeatedly, and after the hydrochloric acid solution then membrane module that oximate is good being placed in pH1.0 processes 2hr, taking-up clear water cyclic washing pH is aobvious neutral.Membrane module is placed in 80 DEG C of hothouses to dry, obtain the film absorbent module quality after amidoxim and add 31.1g, the oximate rate that can be calculated PAN nanofiber membrane assembly is 100%.
(2) the rolling nano fibrous membrane absorbent module obtained is intercepted 100mm and be placed in the 7L uranyl nitrate solution (pH ~ 4.5) that uranium initial concentration is 50mg/L, solution temperature controls at 20 DEG C, water-bath is shaken, adsorption time is 48hr, it is 0.2mg/L that absorption terminates uranium concentration in rear solution, and uranium clearance is 99.6%.
(3) pH value absorption described in (2) being terminated rear solution adjusts to about 1.0,20 DEG C of water-bath concussion 60min, the uranyl ion in desorption nano fibrous membrane absorbent module.Uranium concentration after 60min in sampling and measuring solution is 50mg/L, and the uranium all desorptions be adsorbed on membrane module are described.Film absorbent module takes out clear water cyclic washing to neutral, recycles.
(4) using (2) step and (3) step as an adsorption-desorption cycle, after repeating 50 times, the adsorption rate of the uranium of membrane module still maintains more than 99%, and uranyl ion still can realize 100% desorption.
Embodiment 3
(1) 4.0m is prepared by electrostatic spinning
2pET-PAN nano fibrous membrane, wherein PAN nanofiber content is 50g, PAN nanofiber layer thickness is 40 μm.Using polyethylene (PE) hollow tube of long 1000mm, external diameter 20mm as central tube, polyvinyl chloride (PVC) pipe of long 1000mm, internal diameter 200mm is as putamina, and the PE grid of thickness 2mm utilizes volume film machine to roll into rolled membrane module as water distribution graticule mesh.By the mass fraction configured be as shown in Figure 1 10% hydroxylamine hydrochloride solution by drug dissolving tank 1 after feed pump 2 promotes by feeding pipe 3 by water distribution component 4 circulate be driven in the membrane module 5 rolled, get back in drug dissolving tank 1 via discharging pipeline 7 again, realize circular response.About wherein drug dissolving tank 1 arranges internal heating coils or external heat cover maintenance hydroxylamine hydrochloride solution temperature 70 C, membrane module 5 inside arranges central tube 6.Solution ph is maintained between 8-10 by adding in sodium acid carbonate to drug dissolving tank in course of reaction, membrane module is unloaded after circular response 4hr, the membrane module clear water that oximate is good rinses to pH aobvious neutral repeatedly, and after the hydrochloric acid solution then membrane module that oximate is good being placed in pH1.0 processes 2hr, taking-up clear water cyclic washing pH is aobvious neutral.Membrane module is placed in 80 DEG C of hothouses to dry, obtain the film absorbent module quality after amidoxim and add 31.1g, the oximate rate that can be calculated PAN nanofiber membrane assembly is 100%.
(2) the rolling nano fibrous membrane absorbent module obtained is intercepted 20mm (PAN nanofiber content is 1.0g) and be placed in 10L salt lake bittern (pH ~ 4.53 that uranium initial concentration is 785 μ g/L, salt content 45%), solution temperature controls at 20 DEG C, water-bath is shaken, adsorption time is 10d, it is 206 μ g/L that absorption terminates uranium concentration in rear salt lake bittern, and the uranium adsorption capacity that can be calculated the tunica fibrosa absorbent module after oximate is 3.57mg/g.
Embodiment 4
(1) 4.0m is prepared by electrostatic spinning
2pET-PAN nano fibrous membrane, wherein PAN nanofiber content is 50g, PAN nanofiber layer thickness is 40 μm.Using polyethylene (PE) hollow tube of long 1000mm, external diameter 20mm as central tube, polyvinyl chloride (PVC) pipe of long 1000mm, internal diameter 200mm is as putamina, and the PE grid of thickness 2mm utilizes volume film machine to roll into rolled membrane module as water distribution graticule mesh.By the mass fraction configured be as shown in Figure 1 10% hydroxylamine hydrochloride solution by drug dissolving tank 1 after feed pump 2 promotes by feeding pipe 3 by water distribution component 4 circulate be driven in the membrane module 5 rolled, get back in drug dissolving tank 1 via discharging pipeline 7 again, realize circular response.About wherein drug dissolving tank 1 arranges internal heating coils or external heat cover maintenance hydroxylamine hydrochloride solution temperature 70 C, membrane module 5 inside arranges central tube 6.Solution ph is maintained between 8-10 by adding in sodium acid carbonate to drug dissolving tank in course of reaction, membrane module is unloaded after circular response 4hr, the film absorbent module clear water that oximate is good rinses to pH aobvious neutral repeatedly, and after the hydrochloric acid solution then membrane module that oximate is good being placed in pH1.0 processes 2hr, taking-up clear water cyclic washing pH is aobvious neutral.Membrane module is placed in 80 DEG C of hothouses to dry, obtain the film absorbent module quality after amidoxim and add 31.1g, the oximate rate that can be calculated PAN nanofiber membrane assembly is 100%.
(2) the rolling nano fibrous membrane absorbent module obtained is intercepted 20mm (PAN nanofiber content is 1.0g), in order to remove the trace metal ion in technical grade trifluoro propyl cyclotrisiloxane, comprise Pb
2+, Ni
2+, Co
2+, Ce
3+, Cr
6+, Au
+, Cu
2+, K
+, Ca
2+, Mg
2+, Na
+, Fe
2+, Fe
3+deng.Concrete steps are as follows: by the ultrapure water multipass of the 20mm membrane module of above-mentioned intercepting in the indoor 18.2M Ω of cleaning, then use N
2dry up, afterwards the membrane module handled well is placed in the technical grade trifluoro propyl cyclotrisiloxane (purity 98.5% of 2500g/L, main organic sila matter is higher boiling organosiloxane etc., metal ion total content is 6.2ppm), seal with aseptic sealed membrane, temperature controls at 20 DEG C, water-bath concussion 24hr, absorption terminates rear sample analysis, after being adsorbed by the known nanofiber membrane module of GC and ICP-MS test result, trifluoro propyl cyclotrisiloxane purity is 99.98%, and metal ion content is less than 1.0ppb.
Above are only part preferred embodiment of the present invention, the present invention is not limited in the content of embodiment.To those skilled in the art, can have various change and change in the concept of technical solution of the present invention, any change done and change, all within scope.
Claims (10)
1. a sea water bittern carries uranium nano fibrous membrane, this nano fibrous membrane prepares by the following method: polyacrylonitrile is mixed with spinning solution, by electrostatic spinning process, polyacrylonitrile nano silk is deposited acquisition polyacrylonitrile nanofiber film on macromolecule non-woven fabrics, then amidoxim is carried out to polyacrylonitrile nanofiber film and obtain described nano fibrous membrane.
2. a kind of sea water bittern as claimed in claim 1 carries uranium nano fibrous membrane, it is characterized in that: the porosity of described macromolecule non-woven fabrics is 40% ~ 80%, and thickness is 30 ~ 200 μm.
3. a kind of sea water bittern as claimed in claim 1 carries uranium nano fibrous membrane, it is characterized in that: the mass content of described polyacrylonitrile in polyacrylonitrile nanofiber film is 5% ~ 30%.
4. sea water bittern puies forward a uranium nano fibrous membrane absorbent module, and this nano fibrous membrane absorbent module prepares by the following method:
Step 1, polyacrylonitrile is dissolved in the mixed solution of DMF and 1-METHYLPYRROLIDONE and is mixed with spinning solution, by electrostatic spinning process, polyacrylonitrile nano silk is deposited acquisition polyacrylonitrile nanofiber film on macromolecule non-woven fabrics;
Step 2, makes rolled membrane module by the polyacrylonitrile nanofiber film that abovementioned steps obtains;
Step 3, carries out amidoximization i.e. obtained described nano fibrous membrane absorbent module by aforementioned rolled membrane module.
5. a kind of sea water bittern as claimed in claim 4 puies forward uranium nano fibrous membrane absorbent module, it is characterized in that: described macromolecule non-woven fabrics is pet material, and the porosity of non-woven fabrics is 40% ~ 80%, thickness is 30 ~ 200 μm.
6. a kind of sea water bittern as claimed in claim 4 puies forward uranium nano fibrous membrane absorbent module, it is characterized in that: in described polyacrylonitrile spinning solution, and polyacrylonitrile number-average molecular weight is 150000 ~ 200000, and polymer quality percent concentration is 5% ~ 20%.
7. a kind of sea water bittern as claimed in claim 4 puies forward uranium nano fibrous membrane absorbent module, it is characterized in that, in described step 3 to the process that rolled membrane module carries out amidoxim be: rolled membrane module is immersed in hydroxylamine hydrochloride solution, or hydroxylamine hydrochloride solution is driven in rolled membrane module by pump circulation, controlling hydroxylamine hydrochloride solution pH value is between 7 ~ 10, amidoxim is carried out to rolled membrane module, oximation reaction terminates rear clear water and is washed till neutrality, then immerses in acid solution and namely obtains nano fibrous membrane absorbent module after activation process.
8. a kind of sea water bittern as claimed in claim 7 puies forward uranium nano fibrous membrane absorbent module, it is characterized in that: carry out in the process of amidoxim at described rolled membrane module, in described hydroxylamine hydrochloride addition and membrane module polyacrylonitrile polymer itrile group between mol ratio be 1:0.002 ~ 1:0.5.
9. a kind of sea water bittern described in claim 4-8 puies forward uranium nano fibrous membrane absorbent module in the application of extracting uranium in seawater or bittern.
10. a kind of sea water bittern described in claim 4-8 puies forward uranium nano fibrous membrane absorbent module in the application of removing metal ion in the aqueous solution or organic solution, and described metal ion is Pb
2+, Ni
2+, Co
2+, Ce
3+, Cr
6+, Au
+, Cu
2+, K
+, Ca
2+, Mg
2+, Na
+, Fe
2+, Fe
3+.
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| CN113969465A (en) * | 2020-07-22 | 2022-01-25 | 中国科学院上海高等研究院 | Preparation method and application of biological pollution resistant material |
| CN114425309A (en) * | 2020-10-28 | 2022-05-03 | 海南大学 | Nano silicate mineral-polyamidoxime double-network hydrogel adsorption material, preparation thereof and application thereof in uranium enrichment in seawater |
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| CN115385461A (en) * | 2021-05-24 | 2022-11-25 | 中国科学院上海高等研究院 | Test evaluation device for extracting uranium from seawater and using method thereof |
| CN115805064A (en) * | 2022-11-22 | 2023-03-17 | 核工业北京化工冶金研究院 | Modified polyacrylonitrile hollow fiber membrane and preparation method and application thereof |
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| CN115385461A (en) * | 2021-05-24 | 2022-11-25 | 中国科学院上海高等研究院 | Test evaluation device for extracting uranium from seawater and using method thereof |
| CN113699620A (en) * | 2021-09-06 | 2021-11-26 | 核工业北京化工冶金研究院 | Amino and amidoxime group polyacrylonitrile nano-fiber and preparation method and application thereof |
| CN114588884A (en) * | 2022-03-02 | 2022-06-07 | 中国科学院合肥物质科学研究院 | Preparation method and application of polyimide dioxime/polyethyleneimine composite membrane |
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