CN108579709A - A kind of porous structure elastic composite and preparation method thereof for the extraction of uranium from seawater - Google Patents
A kind of porous structure elastic composite and preparation method thereof for the extraction of uranium from seawater Download PDFInfo
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- CN108579709A CN108579709A CN201810383228.1A CN201810383228A CN108579709A CN 108579709 A CN108579709 A CN 108579709A CN 201810383228 A CN201810383228 A CN 201810383228A CN 108579709 A CN108579709 A CN 108579709A
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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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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Abstract
The present invention provides a kind of porous structure elastic composite preparation method for the extraction of uranium from seawater, includes the following steps：Prepare amidoxim polyacrylonitrile solution；By amidoxim polyacrylonitrile solution and strong alkali aqueous solution it is miscible and keep heating stirring to dissolve；Solution addition after stirring is capable of in the high molecular material aqueous solution of cross-linked gel, is uniformly mixed；Porous structure elastic material is immersed into mixed solution, vacuum outgas bubble；It is dry；Porous structure elastic material after drying is immersed in progress cross-linked gel in cross-linking agent solution；With clear water rinse to get.The present invention is compound by the high molecular material aqueous solution progress cross-linked gelization for capableing of cross-linked gel, improves cladding intensity, improvement material flexibility, mechanical stability and hydrophily of the amidoxim polyacrylonitrile on porous structure elastic material skeleton；To obtain the high adsorption porous structure elastic composite for seawater extraction uranium ion.
Description
Technical field
The present invention relates to extraction of uranium from seawater sorbing material technical fields, more particularly to a kind of porous structure for the extraction of uranium from seawater
Elastic composite and preparation method thereof.
Background technology
Uranium is a kind of important energy goods and materials, it is all significant to industry, agricultural, national defence and science and technology, with it
Its marine chemical resource is compared, and uranium resource concentration is lower, and structure is more complicated, extracts difficulty higher.Therefore, the extraction for extracting uranium
Take agent or adsorbent that must have the extraction high to uranium or adsorption capacity and selectivity.Prepare to economy high efficiency, Gao Xuan
Selecting property is the key that realize the extensive extraction of uranium from seawater with durable extractant is stablized.There is the method for many research recycling uranium at present,
It mainly has：Absorption method, chemical precipitation method, biological treatment, membrane processing method, floatation, superconduction partition method and comprehensive use,
Wherein absorption method is one of optimum method.
When carrying out the extraction of uranium from seawater using adsorbent, adsorbent is placed into suitable marine site first and carries out long-time absorption,
Then adsorbent is collected to from seawater and is carried out a series of chemistry desorption programs, to obtain rich in uranium enrichment liquid and restore suction
Attached dose.Ideal adsorbent not only has the adsorbance and selectivity of good adsorption uranium, should also have preferable mechanical strength,
It can be subjected to adsorption and desorption processing procedure, and can be reused many times.Common high-molecule chelated adsorbent often has preferable
Adsorption and desorption performance, but mechanical strength is inadequate, and cannot for a long time, multiple Reusability.The adsorption material of the prior art
Expect that reuse rate is low, will can not be used since material is seriously damaged using later several times.
Invention content
For mirror with this, the present invention proposes a kind of porous structure elastic composite and preparation method thereof for the extraction of uranium from seawater,
Solve the problems, such as prior art sorbing material adsorption rate it is low and cannot for a long time, multiple Reusability.
The technical proposal of the invention is realized in this way：
A kind of porous structure elastic composite preparation method for the extraction of uranium from seawater includes the following steps：
(1) polyacrylonitrile is dissolved in progress amidoxim modification in organic solvent, obtains amidoxim polyacrylonitrile
Solution.
(2) by amidoxim polyacrylonitrile solution and strong alkali aqueous solution it is miscible and keep heating stirring to dissolve；Amidoxim
Change polyacrylonitrile solution and strong alkali aqueous solution is miscible can obtain water-soluble polymer solution.
(3) the solution addition after stirring is capable of in the high molecular material aqueous solution of cross-linked gel, is uniformly mixed；It will step
Suddenly (2) obtain water-soluble polymer solution addition and are capable of in the high molecular material aqueous solution of cross-linked gel, are conducive to the later stage
Mixing crosslinking, obtains the material of high-intensity and high-tenacity.
(4) porous structure elastic material is immersed into the mixed with polymers solution that step (3) obtains, is placed in vacuum ring
Bubble is de-gassed in border；
(5) the porous structure elastic material of adsorpting polymerization object mixed solution is dried；
(6) the porous structure elastic material after drying is immersed in cross-linking agent solution be crosslinked or illumination crosslinking；
(7) the porous structure elastic material in step (6) is taken out, after being rinsed with clear water to obtain the final product.
Further, it in the step (1), calculates by weight, 8~20 parts of hydroxylamine hydrochlorides is added to containing 500 parts
In the flask of DMF or DMSO or DMAC, stirs to being completely dissolved, 3~15 parts of alkali solid powder are then added, room temperature acutely stirs
It mixes, 5~25 parts of polyacrylonitrile raw material powders is then added, are reacted in 60~90 DEG C of isoperibols after sealing, centrifuged after cooling,
Solid insoluble is removed, DMF or DMSO or the DMAC solution of the amidoxim polyacrylonitrile in supernatant are collected.
Further, in the step (2), the highly basic used is sodium hydroxide, potassium hydroxide, sodium carbonate, tetramethyl hydrogen
One in amine-oxides, tetraethyl ammonium hydroxide, methyl triethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide
Kind is several.
Further, in the step (2), isometric amidoxim polyacrylonitrile solution and strong alkali aqueous solution are heated
To dissolving, the mass concentration of amidoxim polyacrylonitrile solution is 0.5%~10% for stirring；The molar concentration of strong alkali aqueous solution is
10~1000mM.
Further, in the step (2), heating temperature range is 50~100 DEG C, and mixing time is 0.5~30 minute.
Further, in the step (3), the mass concentration for capableing of the high molecular material aqueous solution of cross-linked gel is
0.5%~10%.
Further, in the step (3), be capable of cross-linked gel high molecular material be sodium alginate, chitosan or
Polyethyleneglycol diacrylate.
Further, in the step (4), porous structure elastic material is hydrophily sponge structure polymer foaming material
Material.
Further, in the step (5), the drying method of porous structure elastic material is in air dry oven
100 DEG C or less drying, or be freeze-drying, or be naturally dry.
Further, in the step (6), cross-linking agent solution is saturation calcium chloride solution or calcium chloride weak solution or penta 2
Aldehyde solution, or illumination crosslinking is carried out using ultraviolet light.
The present invention also proposes a kind of porous structure elastic composite for the extraction of uranium from seawater, according to above-mentioned preparation method
It is prepared.
Compared with prior art, the beneficial effects of the invention are as follows：
Porous structure elastic composite preparation method mild condition, process letter provided by the present invention for the extraction of uranium from seawater
Just, of low cost, it is easy to large-scale production manufacture.Industrialized porous structure elastic material can be directly used, such as
Hydrophily sponge structure polymeric foamable material not only has excellent mechanical property as structural support material, meets practical
The needs of application, and it is easy to the industrialization promotion of the extraction of uranium from seawater new material；It is dense by controlling amidoxim polyacrylonitrile solution
Degree and other technological parameters, significantly improve the amidoxime group active sites of porous structure elastic material sorbing material three-dimensional surface
Point；It is compound by the high molecular material aqueous solution progress cross-linked gelization for capableing of cross-linked gel, improve amidoximization poly- third
Cladding intensity, improvement material flexibility, mechanical stability and hydrophily of the alkene nitrile on porous structure elastic material skeleton；To obtain
It must be used for the high adsorption porous structure elastic composite of seawater extraction uranium ion.
Description of the drawings
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, the accompanying drawings in the following description is only the preferred embodiment of the present invention, for
For those of ordinary skill in the art, without having to pay creative labor, it can also be obtained according to these attached drawings
His attached drawing.
Fig. 1 is the product photo that the embodiment of the present invention 1 obtains.
Fig. 2 is scanning electron microscope (SEM) the photo figure for the product that the embodiment of the present invention 1 obtains.
Fig. 3 is the device photo that uranium absorption experiment is carried out in the embodiment of the present invention 1.
Fig. 4 is that the photo after uranium absorption experiment is carried out in the embodiment of the present invention 1.
Fig. 5 is that the photo after uranium elution is carried out in the embodiment of the present invention 1.
Specific implementation mode
In order to be best understood from the technology of the present invention content, be provided below specific embodiment, and in conjunction with attached drawing to the present invention do into
The explanation of one step.
The present invention proposes a kind of porous structure elastic composite preparation method for the extraction of uranium from seawater, including following step
Suddenly：
(1) it calculates by weight, 8~20 parts of hydroxylamine hydrochlorides is added to the flask containing 500 parts of DMF or DMSO or DMAC
In, it stirs to being completely dissolved, 3~15 parts of alkali solid powder is then added, preferably room temperature is vigorously stirred 0.5~2 hour, then
5~25 parts of polyacrylonitrile raw material powders are added, are preferably stirred to react in 60~90 DEG C of isoperibols 6~48 hours after sealing,
It is centrifuged after cooling, removes solid insoluble, collect DMF or DMSO or the DMAC solution of the amidoxim polyacrylonitrile in supernatant；
The step process neutral and alkali solid powder can be sodium hydroxide, sodium carbonate, potassium hydroxide or sodium bicarbonate etc., to adjust pH
Value.
(2) DMF of amidoxim polyacrylonitrile or DMSO or DMAC solution are extremely dissolved with strong alkali aqueous solution heating stirring,
Specifically, isometric amidoxim polyacrylonitrile solution and strong alkali aqueous solution progress is miscible, amidoxim polyacrylonitrile
The mass concentration of DMF or DMSO or DMAC solution is preferably 0.5%~10%, and the molar concentration of strong alkali aqueous solution is preferably 10~
1000mM, heating temperature range are preferably 50~100 DEG C, and mixing time is preferably 0.5~30 minute.
Herein it should be noted that mass concentration refers to that the quality of solute accounts for the percentage of complete soln quality.Mole
Concentration refers to the molal quantity of contained solute in 1 liter of solution.
The highly basic used is sodium hydroxide, potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, first
One or more of base triethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide.
(3) the solution addition after stirring is capable of in the high molecular material aqueous solution of cross-linked gel, is uniformly mixed；It is preferred that
, the mass concentration for capableing of the high molecular material aqueous solution of cross-linked gel is 0.5%~10%, is capable of the height of cross-linked gel
Molecular material is preferably sodium alginate, chitosan or polyethyleneglycol diacrylate (PEGDA) etc..
(4) porous structure elastic material is immersed into the mixed with polymers solution that step (3) obtains, is placed in vacuum ring
Bubble is de-gassed in border；Porous structure elastic material is hydrophily sponge structure polymeric foamable material, preferably melamine sponge
The various business sponges such as (nanosponges) or other polyurethane sponges, natural emulsion sponge, polyvinylalcohol sponge.
(5) the porous structure elastic material of adsorpting polymerization object mixed solution is dried, drying method is air blast
100 DEG C or less drying in drying box, or be freeze-drying, or be naturally dry；
(6) the porous structure elastic material after drying is immersed in progress cross-linked gel, crosslinking agent in cross-linking agent solution
Solution is saturation calcium chloride solution or calcium chloride weak solution or glutaraldehyde solution or ultraviolet light cross-linking (for can be by ultraviolet lighting
The hydrogel material of cross-linked polymeric such as PEGDA)；
(7) the porous structure elastic material in step (6) is taken out, after being rinsed with clear water to obtain the final product.Gained composite sponge work(
Energy material is used directly for uranium absorption application or is stored after drying spare.
Embodiment 1
A kind of porous structure elastic composite preparation method for the extraction of uranium from seawater includes the following steps：
(1) 8g hydroxylamine hydrochlorides are added in the flask of the DMF containing 500g, preferably magnetic agitation, until being completely dissolved, then
3g sodium hydroxide powders are added, room temperature is vigorously stirred 30 minutes, 5g polyacrylonitrile raw material powders is then added, at 60 DEG C after sealing
It is stirred to react in isoperibol 48 hours, is centrifuged with rotating speed 30000r/min after cooling, remove solid insoluble, collected in supernatant
Amidoxim polyacrylonitrile DMF solution.
(2) DMF solution of isometric amidoxim polyacrylonitrile is miscible with sodium hydrate aqueous solution and keep heating
Stirring is to being completely dissolved into limpid homogeneous phase solution, wherein and the mass concentration of the DMF solution of amidoxim polyacrylonitrile is 0.5%,
The molar concentration of sodium hydrate aqueous solution is 100mM.
(3) solution after stirring is added in the sodium alginate aqueous solution that mass concentration is 0.5%, is uniformly mixed.
(4) 200mg melamine sponges are immersed into the mixed with polymers solution that step (3) obtains, are placed in vacuum environment
In be de-gassed bubble.
(5) the melamine sponge for being filled mixed with polymers solution is subjected to forced air drying, is placed in 100 DEG C of temperature or less and thoroughly dries
It is dry.Weigh it is dry after composite sponge gross mass, and according to amidoxim polyacrylonitrile in polymer solution and sodium alginate
Mass concentration and mixed proportion calculate the content of amidoxim polyacrylonitrile in composite sponge.
(6) composite sponge after drying is immersed in crosslinking agent saturation calcium chloride solution and promotes sodium alginate cross-linking gel
Change.
(7) composite sponge is taken out, up to product after being rinsed with clear water, as shown in Figure 1.Can be directly used for seawater or other
The absorption of uranyl ion or drying for standby in water environment.Product is taken to be scanned electron microscope characterization, the results are shown in Figure 2.
(8) in order to examine or check the uranium absorption performance of resulting materials, following adsorption experiment is done：It is prepared with natural sea salt same with seawater
The simulated seawater of salinity；Suitable uranyl nitrate is added in simulated seawater, so as to get the simulated seawater solution of the uranium containing 10ppm
5L；Obtained compound sponges material is integrally fixed and is made by oneself in water circle device system, as shown in figure 3, passing through water pump tune
Water stream speed is 1L/min or so.Keep adsorption experiment for 24 hours after, as shown in figure 4, composite sponge material can be intuitive to see very much
Material becomes orange-yellow from white, and the uranyl ion in bright solution efficiently, is equably adsorbed onto on sponge.Pass through ICP-MS technologies
The variation of uranium concentration in the front and back solution of absorption is measured to measure the uranium absorption capacity of sponge material.In order to more intuitively illustrate gained
The uranium absorption performance of sponge material indicates uranium absorption capacity with two kinds of computational methods respectively：Whole adsorption capacity and function list
First adsorption capacity.Wherein, the quality of whole adsorption capacity=institute's adsorption uranium/composite sponge entirety gross mass (mg-U/g-Ads)；
And in quality/composite sponge of functional unit adsorption capacity=institute's adsorption uranium contained amidoxim polyacrylonitrile quality (mg-U/g-
PAO).After the completion of adsorption experiment, the composite sponge of adsorption uranium is placed in self-control water circulation system, 0.1M Na are used2CO3
+0.01M H2O2Mixed solution as eluent, carry out elution experiments.As shown in Figure 5, it is only necessary to 5 minutes elution processes, institute
The uranium of absorption can be very fast and be thoroughly eluted from composite sponge sorbing material.The solution after elution is taken, suitably
After dilution, uranium concentration in elution solution is measured by ICP-MS technologies.And do ratio with the uranium absorption amount on composite sponge before elution
Compared with to measure elution efficiency.
Embodiment 2
A kind of porous structure elastic composite preparation method for the extraction of uranium from seawater includes the following steps：
(1) 15g hydroxylamine hydrochlorides are added in the flask of the DMF containing 500g, magnetic agitation, until being completely dissolved, are then added
10g potassium hydroxide powders, room temperature are vigorously stirred 40 minutes, 18g polyacrylonitrile raw material powders are then added, in 75 DEG C of perseverances after sealing
It is stirred to react in warm environment 24 hours, is centrifuged with rotating speed 20000r/min after cooling, remove solid insoluble, collected in supernatant
The DMF solution of amidoxim polyacrylonitrile.
(2) DMF solution of isometric amidoxim polyacrylonitrile is miscible with potassium hydroxide aqueous solution and keep heating
Stirring is to limpid homogeneous phase solution is dissolved into, and the mass concentration of the DMF solution of amidoxim polyacrylonitrile is 5%, potassium hydroxide water
The molar concentration of solution is 500mM.
(3) solution after stirring is added in the sodium alginate aqueous solution that mass concentration is 7%, is uniformly mixed.
(4) 200mg melamine sponges are immersed into the mixed with polymers solution that step (3) obtains, are placed in vacuum environment
In be de-gassed bubble.
(5) the melamine sponge of the full mixed with polymers solution of absorption is freeze-dried.Composite sponge after weighing is dry
Gross mass, and calculated according to the mass concentration and mixed proportion of amidoxim polyacrylonitrile and sodium alginate in polymer solution
The content of amidoxim polyacrylonitrile in composite sponge.
(6) composite sponge after drying is immersed in promotion sodium alginate cross-linking gel in crosslinking agent calcium chloride weak solution
Change.
(7) composite sponge is taken out, up to product after being rinsed with clear water.It can be directly used for uranium in seawater or other water environments
The absorption of acyl ion or drying for standby.
(8) uranium absorption performance test is carried out according to the step (8) in embodiment 1.
Embodiment 3
A kind of porous structure elastic composite preparation method for the extraction of uranium from seawater includes the following steps：
(1) 20g hydroxylamine hydrochlorides are added in the flask of the DMSO containing 500g, magnetic agitation, until being completely dissolved, are then added
Enter 15g sodium hydroxide powders, room temperature is vigorously stirred 60 minutes, 25g polyacrylonitrile raw material powders is then added, at 90 DEG C after sealing
It is stirred to react in isoperibol 6 hours, is centrifuged with rotating speed 10000r/min after cooling, remove solid insoluble, collected in supernatant
Amidoxim polyacrylonitrile DMSO solution.
(2) DMSO solution of isometric amidoxim polyacrylonitrile is miscible with tetramethylammonium hydroxide aqueous solution and protect
Heating stirring is held to dissolving, the mass concentration of the DMSO solution of amidoxim polyacrylonitrile is 10%, tetramethylammonium hydroxide water
The molar concentration of solution is 1000mM.
(3) it is to be uniformly mixed in 10% sodium alginate aqueous solution mass concentration to be added in the solution after stirring.
(4) 200mg polyurethane sponges are immersed into the mixed with polymers solution that step (3) obtains, are placed in vacuum ring
Bubble is de-gassed in border.
(5) polyurethane sponge of adsorpting polymerization object mixed solution is subjected to naturally dry.Composite sponge after weighing is dry
Gross mass, and calculated according to the mass concentration and mixed proportion of amidoxim polyacrylonitrile and sodium alginate in polymer solution
The content of amidoxim polyacrylonitrile in composite sponge.
(6) the polyurethane composite sponge after drying is immersed in crosslinking agent saturation calcium chloride solution solution and promotes alginic acid
Sodium cross-linked gel.
(7) take out polyurethane composite sponge, after being rinsed with clear water to obtain the final product.It can be directly used in seawater or other water environments
The absorption of uranyl ion or drying for standby.
(8) uranium absorption performance test is carried out according to the step (8) in embodiment 1.
Comparative example 1
Difference lies in do not carry out the operation of step (2) highly basic processing, by step for comparative example 1 and embodiment 1 or embodiment 3
Suddenly (1) is directly entered the operation of step (3).
Experimental result finds that the DMF or DMSO solution of amidoxim polyacrylonitrile are substantially insoluble in sodium alginate aqueous solution
In, but be precipitated at milky floccule, later processing operation can not be carried out.Therefore, the highly basic of step (2) is handled to the present invention
Preparation method is most important, and after highly basic is handled, the DMF or DMSO solution of amidoxim polyacrylonitrile are changed into high water solubility
Molecular solution can carry out the miscible of arbitrary proportion and dilution with aqueous solution, and be conducive to later stage and the friendship of other high molecular materials
Join compound, the mechanical performance of reinforcing material and the high efficiency of additive capability to uranium ion.
Comparative example 2
Difference lies in exchange step (2) with the sequence of step (3), i.e., being first added can comparative example 2 with embodiment 1
In the high molecular material aqueous solution (sodium alginate aqueous solution) of cross-linked gel, it is mixed that strong base solution progress heating stirring is then added
It closes, remaining step is same as Example 1.
Experiment is found, after the DMF solution of amidoxim polyacrylonitrile is added directly into sodium alginate aqueous solution, solution becomes
Muddiness, and have the precipitation of milky floccule.Although the alkali process of next step can be such that part floccule dissolves, and mitigate muddy existing
As, but alkali process at this time is difficult that whole solid precipitates (amidoxim polyacrylonitrile) is completely dissolved.Thus again
Illustrate, the alkali process for first carrying out step (2) is very crucial to preparation method of the present invention, which can make amidoximization poly-
Acrylonitrile sufficiently thoroughly changes my water-soluble polymer solution, to facilitate following process to handle.
Comparative example 3
Difference lies in do not carry out the operation of step (5) drying process, deaerated by step (4) comparative example 3 with embodiment 1
It is directly entered step (6) after bubble and is immersed in crosslinking agent and promotes cross-linked gel, remaining step is same as Example 1.
Experiment discovery, amidoxim polyacrylonitrile and sodium alginate (calcium) gel can not be stably fixed to the hole of sponge
And on sponge skeleton, and it can dissolve out in aqueous solution.Therefore, drying steps are most important to preparation process of the present invention.Dry
In the process, amidoxim polyacrylonitrile and sodium alginate mixed polymer can concentrate, condense and uniformly, be stably adhered to sponge
On skeleton, as shown in scanning electron microscope (SEM) photo Fig. 2 of the product of the acquisition of the embodiment of the present invention 1.
In order to obtain the technological parameter of optimization, comparative example 4 has been carried out to comparative example 9, technological parameter is as shown in table 1.Its
Remaining process is with reference to described in embodiment 1.
Table 1
The product that embodiment 1 to 3 and comparative example 4 to 9 obtain is subjected to extraction of uranium from seawater experiment, experimental result such as 2 institute of table
Show：
Table 2
In addition, research also found, and in step (2), when the molar concentration of the strong alkali aqueous solution added is more than 1000mM,
The strand that amidoxim polyacrylonitrile can be interrupted, to destroy its molecular structure.
In conclusion the invention discloses a kind of porous structure elastic composite preparation method for the extraction of uranium from seawater,
Include the following steps：It is molten by amidoxim polyacrylonitrile is obtained after polyacrylonitrile in organic solvent amidoxim modification
Liquid；The amidoxim polyacrylonitrile solution and certain density strong base solution is miscible under heating；Add into the mixed solution
Enter the certain density high molecular material aqueous solution for capableing of cross-linked gel, is uniformly mixed；The mixed solution is poured into porous knot
In structure elastic composite, and by vacuumizing the remaining gas in removal porous structure elastic composite hole and solution
Body；The porous structure elastic composite drying for being filled mixed solution；Then it is dipped into cross-linking agent solution and allows to be crosslinked
The high molecular material of gelation is crosslinked, or is placed under ultraviolet light and is irradiated, and the high molecular material crosslinking of illumination polymerization crosslinking is allowed to；
The porous structure elastic composite of amidoxime group functionalization is obtained, which can be directly used in seawater or other aqueous solutions
The efficient absorption of uranium ion, and show efficient uranium absorption ability, elution efficiency and multiple adsorption-desorption and recycle the energy used
Power and good mechanical property.Method mild condition provided by the invention, process be easy, of low cost, easily large-scale production；
It is a kind of extraction of uranium from seawater material of novel concept and preparation method thereof.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (10)
1. a kind of porous structure elastic composite preparation method for the extraction of uranium from seawater, it is characterised in that：Include the following steps：
(1) polyacrylonitrile is dissolved in progress amidoxim modification in organic solvent, obtains amidoxim polyacrylonitrile solution；
(2) by amidoxim polyacrylonitrile solution and strong alkali aqueous solution it is miscible and keep heating stirring to dissolve；
(3) the solution addition after stirring is capable of in the high molecular material aqueous solution of cross-linked gel, is uniformly mixed；
(4) porous structure elastic material is immersed into the mixed with polymers solution that step (3) obtains, is placed in vacuum environment
It is de-gassed bubble；
(5) the porous structure elastic material of adsorpting polymerization object mixed solution is dried；
(6) the porous structure elastic material after drying is immersed in cross-linking agent solution be crosslinked or illumination crosslinking；
(7) the porous structure elastic material in step (6) is taken out, after being rinsed with clear water to obtain the final product.
2. the porous structure elastic composite preparation method according to claim 1 for the extraction of uranium from seawater, feature exists
In in the step (1), calculating by weight, 8~20 parts of hydroxylamine hydrochlorides be added to containing 500 parts of DMF or DMSO or DMAC
Flask in, stir to being completely dissolved, 3~15 parts of alkali solid powder be then added, room temperature is vigorously stirred, be then added 5~
25 parts of polyacrylonitrile raw material powders, react after sealing in 60~90 DEG C of isoperibols, are centrifuged after cooling, and removal solid is insoluble
Object collects DMF or DMSO or the DMAC solution of the amidoxim polyacrylonitrile in supernatant.
3. the porous structure elastic composite preparation method according to claim 1 for the extraction of uranium from seawater, feature exists
In in the step (2), the highly basic used is sodium hydroxide, potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide, tetraethyl hydrogen
One or more of amine-oxides, methyl triethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide.
4. the porous structure elastic composite preparation method according to claim 1 for the extraction of uranium from seawater, feature exists
In, in the step (2), isometric amidoxim polyacrylonitrile solution and strong alkali aqueous solution heating stirring are extremely dissolved, together with
The mass concentration of amidoxime polyacrylonitrile solution is 0.5%~10%；The molar concentration of strong alkali aqueous solution is 10~1000mM.
5. a kind of preparation method of water-soluble amidoxim polyacrylonitrile solution according to claim 1, it is characterised in that：
In the step (2), heating temperature range is 50~100 DEG C, and mixing time is 0.5~30 minute.
6. the porous structure elastic composite preparation method according to claim 1 for the extraction of uranium from seawater, feature exists
In in the step (3), the mass concentration for capableing of the high molecular material aqueous solution of cross-linked gel is 0.5%~10%.
7. the porous structure elastic composite preparation method according to claim 1 for the extraction of uranium from seawater, feature exists
In in the step (3), the high molecular material for capableing of cross-linked gel is two propylene of sodium alginate, chitosan or polyethylene glycol
Acid esters.
8. the porous structure elastic composite preparation method according to claim 1 for the extraction of uranium from seawater, feature exists
In in the step (4), porous structure elastic material is hydrophily sponge structure polymeric foamable material.
9. the porous structure elastic composite preparation method according to claim 1 for the extraction of uranium from seawater, feature exists
In in the step (6), cross-linking agent solution is saturation calcium chloride solution or calcium chloride weak solution or glutaraldehyde solution, or is used
Ultraviolet light carries out illumination crosslinking.
10. a kind of porous structure elastic composite for the extraction of uranium from seawater, according to claim 1 to 9 any one of them system
Preparation Method is prepared.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810383228.1A CN108579709B (en) | 2018-04-26 | 2018-04-26 | Porous structure elastic composite material for extracting uranium from seawater and preparation method thereof |
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| CN201810383228.1A CN108579709B (en) | 2018-04-26 | 2018-04-26 | Porous structure elastic composite material for extracting uranium from seawater and preparation method thereof |
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| CN108579709B CN108579709B (en) | 2020-08-14 |
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| CN109734832A (en) * | 2019-01-09 | 2019-05-10 | 海南大学 | A kind of water solubility amidoxime group polymer and its preparation method and application |
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| CN109908876A (en) * | 2019-04-22 | 2019-06-21 | 盐城工学院 | A kind of preparation method and application of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping |
| CN110684233A (en) * | 2019-10-11 | 2020-01-14 | 海南大学 | Porous hydrogel film for extracting uranium from seawater and preparation method thereof |
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| CN112354528A (en) * | 2020-11-09 | 2021-02-12 | 海南大学 | Phosphoric acid functionalized sponge composite material for extracting uranium from seawater and preparation method thereof |
| CN112354528B (en) * | 2020-11-09 | 2021-12-14 | 海南大学 | Phosphoric acid functionalized sponge composite material for extracting uranium from seawater and preparation method thereof |
| CN114870815A (en) * | 2022-04-26 | 2022-08-09 | 中国科学院合肥物质科学研究院 | Preparation method and application of polyimide dioxime film for gold recovery |
| CN115155544A (en) * | 2022-06-24 | 2022-10-11 | 山东大学 | Method for preparing polypropylene amidoxime-containing multilayer skeleton sphere uranium adsorbing material based on 3D printing |
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| CN116116396B (en) * | 2023-02-20 | 2023-11-14 | 哈尔滨工程大学 | Preparation method and application of amidoxime gel/graphite oxide/sponge composite material |
| CN116173922A (en) * | 2023-03-02 | 2023-05-30 | 北京理工大学 | High-strength uranium adsorbent with three-dimensional continuous multi-stage pore structure and preparation method thereof |
| CN116173922B (en) * | 2023-03-02 | 2024-09-24 | 北京理工大学 | High-strength uranium adsorbent with three-dimensional continuous multi-stage pore structure and preparation method thereof |
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