CN102614842A - Chelate fiber adsorbent for extracting uranium from seawater and preparation method for chelate fiber adsorbent - Google Patents
Chelate fiber adsorbent for extracting uranium from seawater and preparation method for chelate fiber adsorbent Download PDFInfo
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Abstract
The invention provides a preparation method for chelate fiber adsorbent for extracting uranium from seawater. The preparation method includes following steps that (1) ultra-high molecular weight polyethylene fibers are in irradiation treatment, and an irradiation source is a cobalt source or an electron beam; (2) the irradiated ultra-high molecular weight polyethylene fibers are mixed with solution containing graft monomers, graft polyacrylonitrile modified fibers are obtained via graft polymerization, the graft monomers are pure crylonitrile or mixed monomers including crylic acid and crylonitrile, and molar content ratio of the acrylic acid to the crylonitrile in the mixed monomers is smaller than or equal to 1:2; and (3) the graft polyacrylonitrile fibers are in amidoximation reaction, so that cyanogroup is converted into amidoxime group, and accordingly the chelate fiber adsorbent is prepared. The invention further provides the chelate fiber adsorbent obtained by the preparation method, and the adsorbent not only has excellent mechanical properties of the ultra-high molecular weight polyethylene fibers, but also has a fine effect of adsorbing the uranium, and can be reused for extracting the uranium from the seawater for a long time.
Description
Technical field
The present invention relates to a kind of extraction of uranium from seawater with adsorbent and preparation method thereof, relate in particular to a kind of extraction of uranium from seawater with chelate fibre adsorbent and preparation method thereof.
Background technology
Nuclear energy power generation is fast-developing in the world wide in recent years, and the demand of nuclear fuel uranium is increased fast, is fit to only enough decades of uranium ore of exploitation according to present depletion rate land.The URANIUM IN SEAWATER reserves are huge, have 4,000,000,000 tons approximately, are 4000 times of land reserves.But the concentration of URANIUM IN SEAWATER is very low, has only 3ppb, must carry out enrichment to uranium with sorbing material and could realize " extraction of uranium from seawater ".The extraction of uranium from seawater is a lot of with sorbing material; What application potential was arranged most is polymer-based sorbing material, and they contain chelating groups such as amidoxim usually, can select the uranyl ion in the adsorbing seawater; Large ratio surface such as macromolecular fibre, film macromolecular material is suitable as the function sorbing material most.
When carrying out the extraction of uranium from seawater with adsorbent; At first adsorbent is placed into suitable marine site and adsorbs (being generally some months) for a long time; Then adsorbent is collected from seawater and carried out a series of chemical desorption programs, to obtain to be rich in the uranium enrichment liquid and the adsorbent that reduces.Desirable adsorbent not only has the adsorbance and the selectivity of good adsorption uranium, also should have mechanical strength preferably, can stand absorption, desorption processing procedure, and can reuse repeatedly.High-molecule chelated adsorbent commonly used often has absorption, desorption performance preferably, but mechanical strength is not enough, and can not be for a long time, repeatedly use repeatedly.
Summary of the invention
The extraction of uranium from seawater provides a kind of extraction of uranium from seawater with chelate fibre adsorbent and preparation method thereof with the problem of adsorbent poor mechanical property, repeat performance difference in the prior art in order to solve in the present invention, specifically adopts following technical scheme:
The invention provides a kind of extraction of uranium from seawater with chelate fibre preparation of adsorbent method, comprise the steps: that (1) carry out radiation treatment with superhigh molecular weight polyethylene fibers, said irradiation bomb is cobalt source or electron beam; (2) superhigh molecular weight polyethylene fibers behind the irradiation is mixed with the solution that contains grafted monomers through graft polymerization reaction acquisition graft polypropylene nitrile modified fibre; Said grafted monomers is pure acrylonitrile; Or the mix monomer of acrylic acid and acrylonitrile, the molar content of acrylic acid and acrylonitrile is than smaller or equal to 1: 2 in the mix monomer of said acrylic acid and acrylonitrile; (3) graft polypropylene nitrile fiber is carried out the amidoxime reaction, make cyanic acid be converted into amidoxime group, make the chelate fibre adsorbent.
Because the difficult reaction of acrylonitrile, acrylic acid reacts easily, and acrylic acid ratio is too big, will be difficult to effectively introduce acrylonitrile.The molar content of acrylic acid and acrylonitrile is than preferably smaller or equal to 1: 4 in the mix monomer of said acrylic acid and acrylonitrile.
In the step (2), said graft polymerization reaction is so that fiber reaches certain percent grafting is purpose, and the percent grafting of polyacrylonitrile component is 5～200%, and to the adsorption conditions of chelate fibre, preferable scope is 20～100%.
Wherein, the reaction purpose described in the step (3) be make cyanic acid in the polyacrylonitrile that is grafted on the UHMWPE fiber (CN) as far as possible fully the change of team for amidoxime group (C (NH
2)=N-OH).Method commonly used is following: the fiber after the grafting places in the aqueous solution of hydroxylamine hydrochloride and natrium carbonicum calcinatum; The mol ratio of hydroxylamine hydrochloride and natrium carbonicum calcinatum is 1: 0.5, keeps the molar fraction of hydroxylamine hydrochloride excessive than the molar fraction of cyanic acid in the fiber, regulates pH value 6～7 with aqueous sodium carbonate; Be 60～80 ℃ in temperature and carried out the hydroxamamide reaction 3～5 hours; Take out after the reaction, with distilled water washing and oven dry, the condition of washing and oven dry and method are conventional condition and method of this area.
Irradiation described in the step (1) is undertaken by following any mode: 1. when described radiation source is the cobalt source, described superhigh molecular weight polyethylene fibers is placed carry out radiation treatment in the cobalt source; The close rate of said irradiation is 0.01～10kGy/h, and the dosage of said irradiation is 0.1～100kGy; 2. when described radiation source is electron beam, described superhigh molecular weight polyethylene fibers is carried out radiation treatment through electron beam; The close rate of said irradiation is 1～100kGy/s, and the dosage of said irradiation is 5～100kGy.
The temperature of said irradiation and atmosphere are the conventional irradiation temperature and the atmosphere of this area; Described irradiation temperature is a room temperature; The atmosphere of said irradiation is any in air atmosphere, inert atmosphere, oxygen and the vacuum.
At described predose described superhigh molecular weight polyethylene fibers is carried out clean, purpose is to remove the slurry of fiber surface, promotes graft polymerization reaction.The step of described cleaning is: place normal heptane to soak 1～8 hour described superhigh molecular weight polyethylene fibers, use acetone rinsing again, oven dry.
By this area general knowledge, the superhigh molecular weight polyethylene fibers behind the described irradiation can store certain hour as required, takes out when to be used and carries out described graft polymerization reaction.
For realizing the percent grafting requirement, the grafted monomers concentration described in the step (2) in the solution is 20～100wt%; The temperature of said graft polymerization reaction is 30～80 ℃, preferably is 40～70 ℃.
The time of said graft polymerization reaction is 2～24 hours, and the preferable graft polymerization reaction time is 3～6 hours.The solvent of said solution is methyl alcohol, water, N, one or more in dinethylformamide (DMF), the dimethyl sulfoxide (DMSO) (DMSO).
Also can contain polymerization inhibitor in the described solution, said polymerization inhibitor is preferably 1.0 * 10
-4～2.0 * 10
-3The Mohr's salt of mol/L.
The present invention also provides a kind of extraction of uranium from seawater that is obtained by above-mentioned preparation method to use the chelate fibre adsorbent.
Superhigh molecular weight polyethylene fibers is to be raw material through a kind of high strength, the high modulus fibre of special process preparation with ultra-high molecular weight polyethylene (english abbreviation UHMWPE), has that density is little, intensity is high, excellent properties such as corrosion-resistant, shock resistance, anti-cutting, biologically inert.
On the basis that meets this area general knowledge, above-mentioned each optimum condition, but combination in any promptly get each preferred embodiments of the present invention.
Agents useful for same of the present invention and raw material are all commercially available to be got.
Positive progressive effect of the present invention is:
Adopt the good mechanical property of both having inherited superhigh molecular weight polyethylene fibers together with the chelate fibre of hydroxamamide group preferably that contains of method preparation of the present invention, have the performance of higher adsorption uranium again, can prolonged and repeatedly be used for the extraction of uranium from seawater.
The specific embodiment
Mode through embodiment further specifies the present invention below, but does not therefore limit the present invention among the described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example according to conventional method and condition, or is selected according to catalogue.
Superhigh molecular weight polyethylene fibers is purchased the product in the Beijing TongYiZhong special fiber Technology Development Co., Ltd among the following embodiment, trade mark FT-103, molecular weight 3,000,000,3.6 dawn of monofilament linear density.
The percent grafting of pure acrylonitrile monemer calculates according to formula with weight method:
Fibre weight * 100% before percent grafting=(the preceding fibre weight of fibre weight-grafting after the grafting)/grafting
When containing acrylic acid in the graft polymers; Use the percent grafting sum of the percent grafting of above-mentioned weight method acquisition, need proofread and correct, infra-red sepectrometry test: shred fiber earlier with infra-red sepectrometry as graft acrylic acid and acrylonitrile; Use pressing potassium bromide troche again, survey infared spectrum.
The filament properties test: adopt LLY-06E type electronic mono-fiber strong force instrument, by GB GB9997-88 test ultimate fibre tensile property, each sample in measurement is averaged for 50 times, the value of thrust that the fracture of a fiber of the powerful expression of monofilament needs, and unit is a li ox (cN).
The experiment of adsorption/desorption uranium: the fiber of the accurate a certain amount of amidoximization of weighing, place certain density uranium solution, adsorb certain hour in 30 ℃ of constant temperature oscillators, leach, measure the concentration of uranium in the solution of absorption back.Adsorbance is calculated with following formula:
Q＝(C
0-C)V/W
In the formula, Q is adsorbance (mg/g); C
0Be the uranium concentration (mg/L) in the solution before adsorbing; C is the uranium concentration (mg/L) in the solution of absorption back; V is liquor capacity (L); W is dry adsorbent (g).Fiber after the absorption is used carbonate aqueous solution drip washing, and uranyl ion and carbonate generate stable complex compound, after the desorption, the adsorption/desorption experiment is proceeded in the fiber washing oven dry.
Uranium concentration is measured: the concentration of uranium adopts the arsenazo spectrophotometry.Get the uranium titer in the 25mL colorimetric cylinder, add 0.4mL arsenazo (III) solution,, make reference, measure absorption spectrum, select the 650nm wavelength to measure the concentration of uranium down with ultraviolet-uisible spectrophotometer with reagent blank with the salpeter solution constant volume of pH=2.Under selected experiment condition, draw the working curve of uranium content and absorbance, the concentration of uranium obtains from working curve according to absorbance in the unknown solution.
Embodiment 1
(1) pre-irradiation.Accurately take by weighing 10.0 gram UHMWPE fibers and place a glass irradiation tube, with sealing behind the nitrogen replacement inner air tube.Irradiation tube is put into the cobalt source, irradiation 15 hours, the irradiation accumulated dose is 50kGy, close rate is 3.3kGy/h.
(2) graft polymerization reaction.Fiber sample behind the taking-up irradiation is put into the preprepared graft copolymer solution rapidly, and under the nitrogen protection, 60 ℃ were reacted 3 hours.Graft copolymer solution is totally 150 grams, consists of: acrylonitrile 60wt%, and acrylic acid 20wt% (acrylic acid and acrylonitrile mol ratio are 1: 4), DMF 20wt%, other contains H
2SO
40.1mol/L, Mohr's salt 2 * 10
-4Mol/L.Graft polymerization reaction finishes the back and takes out fiber sample, cleans with DMF, distilled water successively, dries to constant weight for 60 ℃ then; Weight is 18.5 grams, and percent grafting is 85%, proofreaies and correct with infrared method; The polyacrylonitrile percent grafting is 48% in the graft, and polyacrylic acid grafted rate is 37%.
(3) amidoxime reaction.With the fiber after the grafting in (2), place the 250ml aqueous solution that contains 14 gram hydroxylamine hydrochlorides and 10.6 gram natrium carbonicum calcinatums, regulate pH value about 7 with dense sodium carbonate liquor; Be heated to 70 ℃ then, reaction 3h takes out fiber; Washing; Oven dry obtains the amidoxime group fiber, weighs to such an extent that chelate fibre 20.9 restrains.
(4) get chelate fibre 0.50 gram, placing the 5L uranium concentration is that the simulated seawater of 1.00mg/L carries out adsorption experiment, and adsorption temp is 30 ℃, and adsorption time was 1 week, and uranium concentration is reduced to 0.72mg/L in the solution, and the adsorbance of calculating chelate fibre is 2.8mg/g.
(5) with the chelate fibre of adsorption uranium in (4) step with the carbonate solution drip washing of 0.5mol/L, uranium-bearing 1.4mg in the mensuration leacheate, the uranium of adsorbing fiber is described, and desorption is complete.
(6) circulate as an adsorption desorption by (4), (5) step, repeat 4 times, measure powerful, the calculating adsorbance of monofilament of each fiber respectively, data are listed in table 1.
Experimental data according to embodiment 1 can be known; Prepared chelate fibre after repeating to use for 5 times to the adsorbance of uranium still up to 2.4mg/g; The adsorbance 2.8mg/g that its adsorption capacity is used has relatively for the first time reduced by 14%; Filament strength is reduced to 68cN from 74cN, but still within spendable scope.Therefore, the prepared chelate fibre of present embodiment can guarantee the good adsorption performance as the extraction of uranium from seawater with adsorbent, can satisfy the requirement that is repeatedly used again.
When described radiation source was the cobalt source, the close rate scope of said irradiation was preferably 0.01～10kGy/h, and dosage range is preferably 0.1～100kGy.Above-mentioned graft polymerization reaction all can carry out under 30～80 ℃, preferably is 40～70 ℃.The graft polymerization reaction time all can carry out at 2～24 hours, and the preferable graft polymerization reaction time is 3～6 hours, and the time is long more, and percent grafting is high more, and the time is short more, and percent grafting is low more.The temperature range of hydroxamamide reaction is 60～80 ℃ carries out, and reaction time range is 3～5 hours.The percent grafting of polyacrylonitrile component is preferably 5～200%, and preferable scope is 20～100%.
Embodiment 2
(1) pre-irradiation.The UHMWPE fiber is wrapped with aluminium foil, used electron beam irradiation 20kGy, close rate is 50kGy/s, and irradiation atmosphere is air.
(2) graft polymerization reaction.Accurately take by weighing the fiber sample of 10.0 grams behind the irradiation, put into the preprepared graft copolymer solution, under the nitrogen protection, 60 ℃ of reactions 3 hours.Graft copolymer solution is totally 150 grams, forms: acrylonitrile 60wt%, distilled water 20wt%, DMF 20wt%, Mohr's salt 2 * 10
-4Mol/L.Graft polymerization reaction finishes the back and takes out sample, cleans with DMF, distilled water successively, dries to constant weight for 60 ℃ then, and weight is 13.5 grams, and percent grafting is 35%.
(3) amidoxime reaction.With the fiber after the grafting in the step (2), place the 250ml aqueous solution that contains 14 gram hydroxylamine hydrochlorides and 10.6g gram natrium carbonicum calcinatum, regulate pH value about 7 with dense sodium carbonate liquor; Be heated to 70 ℃ then, reaction 3h takes out fiber; Washing; Oven dry obtains the amidoxime group fiber, weighs to such an extent that chelate fibre 14.9 restrains.
(4) get chelate fibre 0.50 gram, placing the 5L uranium concentration is that the simulated seawater of 1.00mg/L carries out adsorption experiment, and adsorption temp is 30 ℃, and adsorption time was 1 week, and uranium concentration is reduced to 0.81mg/L in the solution, and the adsorbance of calculating chelate fibre is 1.9mg/g.
(5) with the chelate fibre of adsorption uranium in (4) step with the carbonate solution drip washing of 0.5mol/L, uranium-bearing 0.94mg in the mensuration leacheate, the uranium of adsorbing fiber is described, and desorption is complete basically.
(6) by (4), (5) step is operating as an adsorption desorption circulation, repeats 4 times, measures powerful, the calculating adsorbance of monofilament of each fiber respectively, data are listed in table 1.
Table 1
Experimental data according to embodiment 2 can be known; Prepared chelate fibre adsorbance to uranium after repeating 5 uses still reaches 1.7mg/g; The adsorbance 1.9mg/g that its adsorption capacity is used has relatively for the first time reduced by 11%; Filament strength is reduced to 85cN from 95cN, but still within spendable scope.The prepared chelate fibre of present embodiment can guarantee the good adsorption performance as the extraction of uranium from seawater with adsorbent, can satisfy the requirement that is repeatedly used again.
When described radiation source was electron beam, the close rate scope of said irradiation was preferably 1～100kGy/s, and the dosage range of said irradiation is preferably 5～100kGy.
Comparison through to two embodiment can know that the graft modification effect difference to superhigh molecular weight polyethylene fibers also must influence it and finally make the adsorption capacity of chelate fibre to uranium.
Embodiment 3
(1) pre-irradiation.Accurately take by weighing 10.0 gram UHMWPE fibers and place a glass irradiation tube, irradiation tube is put into the cobalt source, irradiation 6 hours, the irradiation accumulated dose is 5kGy, close rate is 0.8kGy/h.
(2) graft polymerization reaction.Fiber sample behind the taking-up irradiation is put into the preprepared graft copolymer solution, and under the nitrogen protection, 40 ℃ were reacted 8 hours.Graft copolymer solution is totally 150 grams, consists of: acrylonitrile 60wt%, and acrylic acid 10wt% (acrylic acid and acrylonitrile mol ratio are 1: 8), DMF 30wt%, other contains H
2SO
40.1mol/L, Mohr's salt 2 * 10
-4Mol/L.Graft polymerization reaction finishes the back and takes out fiber sample, cleans with DMF, distilled water successively, dries to constant weight for 60 ℃ then; Weight is 13.5 grams, and percent grafting is 35%, proofreaies and correct with infrared method; The polyacrylonitrile percent grafting is 18% in the graft, and polyacrylic acid grafted rate is 17%.
(3) amidoxime reaction.With embodiment 1, get chelate fibre 14.4 grams.
(4) get chelate fibre 0.50 gram, placing the 5L uranium concentration is that the simulated seawater of 1.00mg/L carries out adsorption experiment, and adsorption temp is 30 ℃, and adsorption time was 1 week, and uranium concentration is reduced to 0.84mg/L in the solution, and the adsorbance of calculating chelate fibre is 1.6mg/g.Data are listed in table 2.
Embodiment 4
1) pre-irradiation.Accurately take by weighing 10.0 gram UHMWPE fibers and place a glass irradiation tube, seal behind the nitrogen replacement inner air tube, irradiation tube is put into the cobalt source, irradiation 24 hours, the irradiation accumulated dose is 100kGy, close rate is 4.2kGy/h.
(2) graft polymerization reaction.With sample behind the irradiation, put into the preprepared graft copolymer solution rapidly, under the nitrogen protection, 60 ℃ were reacted 3 hours.Graft copolymer solution is totally 150 grams, forms: acrylonitrile 60wt%, distilled water 20wt%, DMF 20wt%, Mohr's salt 2 * 10
-4Mol/L.Graft polymerization reaction finishes the back and takes out sample, cleans with DMF, distilled water successively, dries to constant weight for 60 ℃ then, and weight is 17.5 grams, and percent grafting is 75%.
(3) amidoxime reaction.With embodiment 1, get chelate fibre 21.4 grams.
(4) get chelate fibre 0.50 gram, placing the 5L uranium concentration is that the simulated seawater of 1.00mg/L carries out adsorption experiment, and adsorption temp is 30 ℃, and adsorption time was 1 week, and uranium concentration is reduced to 0.78mg/L in the solution, and the adsorbance of calculating chelate fibre is 2.2mg/g.Data are listed in table 2.
Embodiment 5
(1) pre-irradiation.The UHMWPE fiber is wrapped with aluminium foil, used electron beam irradiation 100kGy, close rate is 10kGy/s, and irradiation atmosphere is air.
(2) graft polymerization reaction.Behind the radiation treatment sample 2 days, accurately take by weighing the fiber sample of 10.0 grams behind the irradiation, put into the preprepared graft copolymer solution, under the nitrogen protection, 70 ℃ of reactions 3 hours.Graft copolymer solution is totally 150 grams, consists of: acrylonitrile 60wt%, and acrylic acid 20wt% (acrylic acid and acrylonitrile mol ratio are 1: 4), DMF 20wt%, other contains H
2SO
40.1mol/L, Mohr's salt 2 * 10
-4Mol/L.Graft polymerization reaction finishes the back and takes out fiber sample, cleans with DMF, distilled water successively, dries to constant weight for 60 ℃ then; Weight is 22.5 grams, and percent grafting is 125%, proofreaies and correct with infrared method; The polyacrylonitrile percent grafting is 78% in the graft, and polyacrylic acid grafted rate is 47%.
(3) amidoxime reaction.With the fiber after the grafting in (2), place the 250ml aqueous solution that contains 21 gram hydroxylamine hydrochlorides and 15.3 gram natrium carbonicum calcinatums, regulate pH value about 7 with dense sodium carbonate liquor; Be heated to 70 ℃ then, reaction 3h takes out fiber; Washing, oven dry obtains amidoxime group chelate fibre 26.5 grams.
(4) get chelate fibre 0.50 gram, placing the 5L uranium concentration is that the simulated seawater of 1.00mg/L carries out adsorption experiment, and adsorption temp is 30 ℃, and adsorption time was 1 week, and uranium concentration is reduced to 0.66mg/L in the solution, and the adsorbance of calculating chelate fibre is 3.4mg/g.Data are listed in table 2.
Table 2
(annotate: embodiment 1 is to adsorb numerical value for the first time with the data of embodiment 2.)
Can also see that through embodiment 1-5 the acrylonitrile grafting rate is high, the ability of the chelate fibre adsorption uranium of modification is strong; Acrylic acid and acrylonitrile cograft help improving the percent grafting of acrylonitrile; The chelate fibre that obtains simultaneously has stronger adsorption uranium ability; Explain acrylic acid content in the mol ratio of acrylic acid and acrylonitrile at 0-1: 2 scope, the increase that is preferably in 1: 4 the scope can promote the adsorption capacity of amidoxime group to uranium.
Claims (11)
1. an extraction of uranium from seawater is with chelate fibre preparation of adsorbent method, and it comprises the steps:
(1) superhigh molecular weight polyethylene fibers is carried out radiation treatment, the irradiation bomb of said irradiation is cobalt source or electron beam;
(2) superhigh molecular weight polyethylene fibers behind the irradiation is mixed with the solution that contains grafted monomers through graft polymerization reaction acquisition graft polypropylene nitrile fiber; Said grafted monomers is pure acrylonitrile; Or the mix monomer of acrylic acid and acrylonitrile, acrylic acid compares smaller or equal to 1: 2 with the molar content of acrylonitrile in the said mix monomer.
(3) graft polypropylene nitrile fiber is carried out the amidoxime reaction, make cyanic acid be converted into amidoxime group, make the chelate fibre adsorbent.
2. preparation method as claimed in claim 1 is characterized in that, the molar content of acrylic acid and acrylonitrile is than smaller or equal to 1: 4 in the mix monomer of said acrylic acid and acrylonitrile.
3. preparation method as claimed in claim 1 is characterized in that, in the said step (2), the percent grafting of said polyacrylonitrile component is 5～200%.
4. preparation method as claimed in claim 3 is characterized in that, in the said step (2), the percent grafting of said polyacrylonitrile component is 20～100%.
5. preparation method as claimed in claim 1; It is characterized in that, in the said step (3), said graft polypropylene nitrile fiber is placed in the aqueous solution of hydroxylamine hydrochloride and natrium carbonicum calcinatum; The mol ratio of hydroxylamine hydrochloride and natrium carbonicum calcinatum is 1: 0.5; Keep the molar fraction of hydroxylamine hydrochloride excessive, regulate pH value 6～7, be 60～80 ℃ in temperature and carried out the hydroxamamide reaction 2-5 hour with aqueous sodium carbonate than the molar fraction of cyanic acid in the fiber.
6. preparation method as claimed in claim 1 is characterized in that, said irradiation is undertaken by following any mode:
1. when described radiation source is the cobalt source, described superhigh molecular weight polyethylene fibers is placed carry out radiation treatment in the cobalt source; The close rate of said irradiation is 0.01～10kGy/h, and the dosage of said irradiation is 0.1～100kGy;
2. when described radiation source is electron beam, described superhigh molecular weight polyethylene fibers is carried out radiation treatment through electron beam; The close rate of said irradiation is 1～100kGy/s, and the dosage of said irradiation is 5～100kGy.
7. like claim 1 or 6 described preparation methods, it is characterized in that the temperature of said irradiation is a room temperature; The atmosphere of said irradiation is any in air atmosphere, inert atmosphere, oxygen and the vacuum.
8. preparation method as claimed in claim 1 is characterized in that, the grafted monomers concentration in the said solution is 20～100wt%; The temperature of said graft polymerization reaction is 30～80 ℃.
9. preparation method as claimed in claim 1 is characterized in that, the time of said graft polymerization reaction is 2～24 hours.
10. preparation method as claimed in claim 1 is characterized in that, the solvent of said solution is methyl alcohol, water, N, one or more in dinethylformamide, the dimethyl sulfoxide (DMSO).
11. chelate fibre adsorbent that makes by the described preparation method of claim 1～10.
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