CN107722159B - A kind of nuclear grade ion-exchange resins base composite material of core-shell structure and preparation method thereof - Google Patents

A kind of nuclear grade ion-exchange resins base composite material of core-shell structure and preparation method thereof Download PDF

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CN107722159B
CN107722159B CN201710998181.5A CN201710998181A CN107722159B CN 107722159 B CN107722159 B CN 107722159B CN 201710998181 A CN201710998181 A CN 201710998181A CN 107722159 B CN107722159 B CN 107722159B
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王章忠
张泽武
巴志新
杭祖圣
卜小海
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Nanjing Institute of Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
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    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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Abstract

The present invention discloses a kind of nuclear grade ion-exchange resins base composite material of core-shell structure and preparation method thereof, and the composite material of core-shell structure is using light rare earth oxide as core, using nuclear leve strong-base anion-exchange resin as shell.Wherein, light rare earth oxide is cerium oxide, lanthana or praseodymium oxide；Nuclear leve strong-base anion-exchange resin is made by raw material of styrene, divinylbenzene, pore-foaming agent and initiator.The composite material the preparation method comprises the following steps: preparing rare earth oxide, the oil for being added to styrene, divinylbenzene, pore-foaming agent and initiator mixes in liquid, successively aggregated reaction, chloromethylation, quaternary ammonium reaction and isomerization, nuclear leve strong-base anion-exchange resin is grown in rare earth oxide surface aggregate, final composite material of core-shell structure obtained has high surface purity, excellent radiation element exchange capacity, good chemically-resistant and irradiation stability, which can be directly used as the water treatment agent in nuclear industry primary Ioops water circulation system.

Description

A kind of nuclear grade ion-exchange resins base composite material of core-shell structure and preparation method thereof
Technical field
The present invention relates to a kind of nuclear grade ion-exchange resins base composite material of core-shell structure and preparation method thereof, belong to core work Nuclear grade ion-exchange resins technology of preparing in industry field.
Background technique
Ion exchange technique is the important technology for being now widely used in nuclear power plant's major loop and auxiliary systemization appearance control, Key is to prepare high surface purity, high-exchange-capacity, chemically-resistant and the good nuclear grade ion-exchange resins of irradiation stability.Mesh Before, most common ion exchange resin is highly acid or strong basic ion exchange resin in nuclear industry field.But these ions Exchanger resin is not thorough enough due to making the transition, to be unfavorable for nuclear industry there are the foreign ion of some remnants in material internal Safe handling.Therefore, the nuclear grade ion-exchange resins for developing high transition rate are the key of nuclear industry.
Application No. is 201110462012.2 Chinese patent application disclose it is a kind of water-treated for light-water reactor Cation exchange resin is functionalized using chloride intermediates to form sulphur by the synthesis of the sequestration resin in journey, the patent Acyl chlorides resin, reacts with sulfonyl chloride resin that form sequestration resin miscellaneous largely to reduce followed by the ligand of polyamines The residual quantity of matter ion.But the chemically-resistant and irradiation stability of this resin are poor.
In order to improve the stability of resin, nuclear grade ion-exchange resins and inorganic material hydridization can be formed into high stable The resin complexes of property.Application No. is 201510546058.0 Chinese patent application disclose a kind of zirconium load capacity be 13%~ 37% nanometer basic zirconium phosphate-storng-acid cation exchange resin organic Hybrid Materials, the material have it is big to the adsorption capacity of caesium, The short feature of equilibration time.It is nuclear grade ion-exchange resins and inorganic material are compound and prepare performance from this angle Excellent composite material has good research application prospect.
Summary of the invention
Goal of the invention: aiming at the problems existing in the prior art, a kind of nuclear grade ion-exchange resins base core-shell structure is provided Composite material and preparation method, the nuclear grade ion-exchange resins composite material have high surface purity, excellent radiation Plain exchange capacity, good chemically-resistant and irradiation stability.
Technical solution: a kind of nuclear grade ion-exchange resins base composite material of core-shell structure of the present invention, the nucleocapsid knot Structure composite material is using light rare earth oxide as core, using nuclear leve strong-base anion-exchange resin as shell.
Wherein, light rare earth oxide is selected from one of cerium oxide, lanthana and praseodymium oxide.Nuclear leve strong alkalinity anion is handed over Resin is changed by the successively aggregated reaction, chloromethylation, quaternary ammoniated anti-of styrene, divinylbenzene, pore-foaming agent and initiator It should be made with after isomerization.
A kind of preparation method of nuclear grade ion-exchange resins base composite material of core-shell structure of the present invention, including it is following Step:
(1) at room temperature, by mass ratio 0.005:1~0.05:1 of rare-earth salts and ethylene glycol, rare-earth salts alcohol suspension is configured, By mass ratio 5:1~20:1 of ATS (Ammonium thiosulphate) and rare-earth salts, ATS (Ammonium thiosulphate) is added, stirs 20~60min, is transferred to reaction In kettle, 36~60h is reacted at 160 DEG C, is cooled to room temperature, washs filter cake with the deionized water of 100~500 times of rare earth salt qualities, 60~100 DEG C of vacuum drying 8~10h, 600~1200 DEG C of 4~12h of roasting obtain rare earth oxide；
(2) at room temperature, by mass ratio 0.005:1~0.01:1 of rare earth oxide and isopropanol, rare earth oxide is configured Alcoholic solution, then mass ratio 0.2:1~1:1 of silane coupling agent and rare earth oxide is pressed, silane coupling agent is added, is transferred to reaction In kettle, 12~36h is reacted at 120 DEG C, is cooled to room temperature, washs filter with the deionized water of 200~500 times of rare-earth oxidation amount of substance Cake obtains hydrophobic rare earth oxide；
(3) at room temperature, styrene, divinylbenzene, pore-foaming agent and initiator are stirred evenly, are heated to 60~90 DEG C, Oily liquid must be mixed, mass ratio 0.01:1~0.05:1 of liquid is mixed by hydrophobic rare earth oxide and oil, hydrophobic rare earth is added Oxide, 0.5~2h of ultrasonic disperse, is cooled to room temperature, and obtains composite oil phase reaction solution；Under nitrogen protection, by composite oil phase It is molten to be added to saturated sodium-chloride by volume ratio 0.2:1~0.5:1 of reaction solution and saturated sodium chloride solution for composite oil phase mixture In liquid, 60~80 DEG C are stirred and heated to, 2~5h of sustained response is warming up to boiling reflux, the reaction was continued 3~5h, cooled Filter, obtain styrene resin fat complexes crude product, successively with the ethyl alcohol of 10~100 times of styrene resin fat complexes crude product quality with Water rinses filter cake, and 60~80 DEG C of 6~9h of vacuum drying obtain styrene resin fat complexes；
(4) at room temperature, by volume ratio 1:1~3:1 of dichloroethanes and chloromethyl ether, dichloroethanes-chloromethyl ether mixing is configured Object, then volume ratio 2:1~4:1 of methylene chloride and chloromethyl ether is pressed, methylene chloride is added, chloromethylation liquid is made, by benzene Styrene obtained in step (3) is added in mass ratio 0.1:1~0.25:1 of vinyl compound and chloromethylation liquid Resin complexes, stirring 6~8h of swelling, are added catalyst, 40~60 DEG C are stirred to react 1~2h, and chloromethylation tree is obtained by filtration Fat complexes；
(5) at room temperature, the trimethylamine aqueous solution that configuration quality score is 20%~80%, by chloromethyl resin compound With mass ratio 0.2:1~0.5:1 of trimethylamine aqueous solution, chloromethyl resin compound made from step (4) is added, utilizes The Na of 0.5~1mol/L2CO3Aqueous solution adjusts the pH to 8~10 of mixed solution, is stirred to react 6~8h, filters, is washed to Property, obtain macroporous anion exchange resin compound；
(6) sodium bicarbonate aqueous solution that configuration quality score is 5%~15% at room temperature, by macroporous anion exchange resin Large pore anion friendship obtained in step (5) is added in mass ratio 0.02:1~0.05:1 of compound and sodium bicarbonate aqueous solution Change resin complexes, be stirred to react 6~8h, filter, with 50~100 times of macroporous anion exchange resin compound quality go from Sub- water washing filter cake, by mass ratio 0.01:1~0.05 of macroporous anion exchange resin compound and sodium hydrate aqueous solution: 1, obtained filter cake is added in the sodium hydrate aqueous solution that mass fraction is 30%~50%, return stirring reacts 6~8h, Filtering washs filter cake with the deionized water of 50~100 times of macroporous anion exchange resin compound quality, and 60~80 DEG C of vacuum are dry Dry 6~9h obtains nuclear grade ion-exchange resins base composite material of core-shell structure.
In above-mentioned steps (1), rare earth metal salt is preferably one of cerous nitrate, lanthanum nitrate, praseodymium nitrate.
In above-mentioned steps (2), silane coupling agent can be one of KH551, KH171, KH172.
In step (3), the constituent content that oil mixes liquid is preferred are as follows: 40~50 parts of styrene, divinylbenzene 5~10 Part, 1.5~3 parts and 0.2~1 part of initiator of pore-foaming agent.Wherein, pore-foaming agent can be ethyl alcohol, butanol or isopropanol, and initiator can be One of cyclohexanone peroxide, dibenzoyl peroxide, dicetyl peroxydicarbonate diisobutyl ester.
In step (4), catalyst is preferably SbCl5Or ZnCl2, the additive amount of catalyst is preferably that styrene resin is compound The 1~1.5% of object additional amount.
Inventive principle: (1) being core using light rare earth oxide, grows ion exchange resin, Ke Yichong in its surface aggregate The size control effect of light rare earth oxide is waved in distribution, to be conducive to prepare the nuclear grade ion-exchange resins of uniform particle diameter； (2) light rare earth metal oxide has specific Surface L ewis alkali, the presence of these alkali on the one hand can stablize strong basicity yin from Amino group in sub-exchange resin accelerates the dissociation of Cl- plasma, so as to significantly improve nuclear grade ion-exchange resins Transition rate；On the other hand, Surface L ewis alkali can further increase exchange of the nuclear grade ion-exchange resins to radioactivity anion Suction-operated, to improve the exchange capacity of anion exchange resin；(3) light rare earth metal oxide has excellent resistance to spoke It penetrates and chemical stability, can largely improve stabilization of the nuclear grade ion-exchange resins when nuclear industry is used using it as core Property.
The utility model has the advantages that compared with the prior art, the advantages of the present invention are as follows: nuclear grade ion-exchange resins base core of the invention Core-shell structure composite material has high surface purity, excellent radiation element exchange capacity, good chemically-resistant and stable radiation Property, which can be directly used as the water treatment agent in nuclear industry primary Ioops water circulation system.
Specific embodiment
Technical solution of the present invention is described further combined with specific embodiments below.
A kind of nuclear grade ion-exchange resins base composite material of core-shell structure of the invention, be using light rare earth oxide as core, Using nuclear leve strong-base anion-exchange resin as the composite material of core-shell structure of shell.
Wherein, light rare earth oxide is selected from one of cerium oxide, lanthana and praseodymium oxide.
Nuclear leve strong-base anion-exchange resin is successively aggregated by styrene, divinylbenzene, pore-foaming agent and initiator It is made after reaction, chloromethylation, quaternary ammonium reaction and isomerization.
Embodiment 1
At 25 DEG C, 0.5g cerous nitrate is dissolved in 50mL ethylene glycol, 2.5g ATS (Ammonium thiosulphate) is added, stirs 30min, is turned It moves in the reaction kettle of polytetrafluoro liner, reacts 40h at 160 DEG C, be cooled to room temperature, wash filter cake with 100mL deionized water, 80 DEG C vacuum drying 8h, be transferred in Muffle furnace, in 900 DEG C of roasting 5h, obtain rare earth oxide；50mL isopropanol is weighed, is added 0.2g rare earth oxide, ultrasonic disperse is uniform, and 0.2g KH551 is added, is transferred in the reaction kettle of polytetrafluoro liner, at 120 DEG C 36h is reacted, after cooled to room temperature, filter cake is washed with the deionized water of 100mL, obtains hydrophobic rare earth oxide；
At 25 DEG C, 40mL styrene, 5mL divinylbenzene, 1.5mL ethyl alcohol and 0.2g cyclohexanone peroxide are weighed respectively, It is put into reactor and stirs evenly, be heated to 60 DEG C, the hydrophobic rare earth oxide of 0.5g is added, ultrasonic disperse 0.5h is cooled to room Temperature obtains composite oil phase reaction solution；The saturated sodium chloride solution that 90mL concentration is 26.5% is configured, under nitrogen protection, is added Above-mentioned composite oil phase reaction solution is stirred and heated to 80 DEG C, and sustained response 2h is warming up to boiling reflux, the reaction was continued 3h, cooling Filtering, rinses filter cake with the ethyl alcohol of 500mL and deionized water respectively, and 60 DEG C of vacuum drying 6h obtain styrene resin fat complexes；Match The mixed solution of dichloroethanes containing 20mL, 20mL chloromethyl ether and 40mL methylene chloride is set, the styrene of the above-mentioned preparation of 9.6g is added Resin complexes, stirring swelling 6h, are added 0.1g SbCl5, 40 DEG C are stirred to react 1h, and it is compound that chloromethyl resin is obtained by filtration Object；The trimethylamine aqueous solution that 50mL mass fraction is 20% is configured, 10g chloromethyl resin compound obtained above is added, The Na for being 0.5mol/L using concentration2CO3Aqueous solution adjusts the pH to 8.5 of mixed solution, is stirred to react 6h, filters, uses deionization Water washing filter cake obtains macroporous anion exchange resin compound to neutrality；
At 25 DEG C, 4g macropore yin obtained above is added in the sodium bicarbonate aqueous solution that configuration 200mL mass fraction is 5% Ion exchange resin complexes are stirred to react 6h, and filtering washs filter cake with 200mL deionized water, filter cake is added to 400mL In the sodium hydrate aqueous solution that mass fraction is 30%, stir evenly, flow back it is lower react 6h, filtering, then with 200mL deionized water Filter cake is washed, 60 DEG C of vacuum drying 6h obtain nuclear grade ion-exchange resins base composite material of core-shell structure.
By microscope test find the nuclear grade ion-exchange resins base composite material of core-shell structure average grain diameter be 0.42mm, partial size between 0.25~0.65mm composite material granular accounting be 96%, tested by ICP-OES, the nuclear leve from OH in sub-exchange resin base composite material of core-shell structure-Content is 98%, remaining Cl-Content is 0.5 ‰, remaining SO4 -Content It is 0.1 ‰, surface purity is high.The volume full exchange capacity of the nuclear grade ion-exchange resins base composite material of core-shell structure is simultaneously 5.8mmol/mL, can in nuclear waste water environment continuous work 700h.
Embodiment 2
At 25 DEG C, 1.2g lanthanum nitrate is dissolved in 60mL ethylene glycol, 6.0g ATS (Ammonium thiosulphate) is added, stirs 50min, is turned It moves in the reaction kettle of polytetrafluoro liner, reacts 50h at 160 DEG C, be cooled to room temperature, wash filter cake with 550mL deionized water, 100 DEG C of vacuum drying 8h, are transferred in Muffle furnace, in 1100 DEG C of roasting 4h, obtain rare earth oxide；100mL isopropanol is weighed, is added Enter 0.8g rare earth oxide, ultrasonic disperse is uniform, and 0.8g KH171 is added, is transferred in the reaction kettle of polytetrafluoro liner, 120 DEG C Lower reaction for 24 hours, after cooled to room temperature, washs filter cake with the deionized water of 400mL, obtains hydrophobic rare earth oxide；
At 25 DEG C, 80mL styrene, two carbon of 16mL divinylbenzene, 4.4mL isopropanol and 1.2g peroxidating are weighed respectively Sour diisobutyl ester, is put into reactor and stirs evenly, and is heated to 90 DEG C, and the hydrophobic rare earth oxide of 4.5g, ultrasonic disperse is added 1.0h is cooled to room temperature, and obtains composite oil phase reaction solution；The saturated sodium chloride solution that 260mL concentration is 26.5% is configured, in nitrogen Under gas shielded, above-mentioned composite oil phase reaction solution is added, is stirred and heated to 70 DEG C, sustained response 5h is warming up to boiling reflux, after Continuous reaction 4h, cold filtration rinse filter cake, 80 DEG C of vacuum drying with the deionized water of the ethyl alcohol of 1000mL and 2400mL respectively 8h obtains styrene resin fat complexes；The mixed solution of dichloroethanes containing 10mL, 15mL chloromethyl ether and 50mL methylene chloride is configured, The styrene resin fat complexes of the above-mentioned preparation of 17.0g are added, 0.25g ZnCl is added in stirring swelling 8h2, 60 DEG C are stirred to react Chloromethyl resin compound is obtained by filtration in 2h；The trimethylamine aqueous solution that 25mL mass fraction is 80% is configured, is added on 10g State chloromethyl resin compound obtained, the Na for being 1mol/L using concentration2CO3Aqueous solution adjusts the pH to 10 of mixed solution, It is stirred to react 8h, filters, filter cake is washed with deionized to neutrality, obtains macroporous anion exchange resin compound；
At 25 DEG C, it is obtained above big that 12.5g is added in the sodium bicarbonate aqueous solution that configuration 250mL mass fraction is 15% Hole anion exchange resin compound, is stirred to react 8h, and filtering washs filter cake with 1200mL deionized water, then filter cake is added It in the sodium hydrate aqueous solution for being 50% to 250mL mass fraction, stirs evenly, flow back lower reaction 8h, filtering, then uses 1200mL Deionized water washs filter cake, and 80 DEG C of vacuum drying 8h obtain nuclear grade ion-exchange resins base composite material of core-shell structure.
By microscope test find the nuclear grade ion-exchange resins base composite material of core-shell structure average grain diameter be 0.72mm, partial size between 0.45~0.95mm composite material granular accounting be 94%, tested by ICP-OES, the nuclear leve from OH in sub-exchange resin base composite material of core-shell structure-Content is 93%, remaining Cl-Content is 2.4 ‰, remaining SO4 -Content It is 1.9 ‰, surface purity is high.The volume full exchange capacity of the nuclear grade ion-exchange resins base composite material of core-shell structure is simultaneously 3.2mmol/mL, can in nuclear waste water environment continuous work 600h.
Embodiment 3
At 25 DEG C, 0.64g praseodymium nitrate is dissolved in 80mL ethylene glycol, 6.4g ATS (Ammonium thiosulphate) is added, stirs 40min, It is transferred in the reaction kettle of polytetrafluoro liner, reacts 48h at 160 DEG C, be cooled to room temperature, wash filter cake with 200mL deionized water, 80 DEG C of vacuum drying 9h, are transferred in Muffle furnace, in 700 DEG C of roasting 12h, obtain rare earth oxide；125mL isopropanol is weighed, is added Enter 1.0g rare earth oxide, ultrasonic disperse is uniform, and 0.6g KH172 is added, is transferred in the reaction kettle of polytetrafluoro liner, 120 DEG C Lower reaction 12h after cooled to room temperature, washs filter cake with the deionized water of 300mL, obtains hydrophobic rare earth oxide；
At 25 DEG C, 100mL styrene, 20mL divinylbenzene, 3.5mL butanol and 0.8g diphenyl peroxide first are weighed respectively Acyl is put into reactor and stirs evenly, and is heated to 75 DEG C, and the hydrophobic rare earth oxide of 2.8g is added, and ultrasonic disperse 1.5h is cooled to Room temperature obtains composite oil phase reaction solution；The saturated sodium chloride solution that configuration 300mL concentration is 26.5% adds under nitrogen protection Enter above-mentioned composite oil phase reaction solution, be stirred and heated to 75 DEG C, sustained response 3h is warming up to boiling reflux, the reaction was continued 3h, cold But it filters, rinses filter cake with the deionized water of the ethyl alcohol of 600mL and 1200mL respectively, 75 DEG C of vacuum drying 8h obtain styrene resin Fat complexes；The mixed solution of dichloroethanes containing 15mL, 30mL chloromethyl ether and 100mL methylene chloride is configured, it is above-mentioned that 25.0g is added The styrene resin fat complexes of preparation, stirring swelling 7h, are added 0.3g ZnCl2, 50 DEG C are stirred to react 1h, and chloromethane is obtained by filtration Base resin complexes；The trimethylamine aqueous solution that 40mL mass fraction is 60% is configured, 16g chloromethylation obtained above is added Resin complexes, the Na for being 0.8mol/L using concentration2CO3Aqueous solution adjusts the pH to 9 of mixed solution, is stirred to react 7h, mistake Filter, is washed with deionized filter cake to neutrality, obtains macroporous anion exchange resin compound；
At 25 DEG C, 6.0g macropore obtained above is added in the sodium bicarbonate aqueous solution that configuration 200mL mass fraction is 10% Anion exchange resin compound is stirred to react 7h, and filtering washs filter cake with 400mL deionized water, then filter cake is added to It in the sodium hydrate aqueous solution that 150mL mass fraction is 40%, stirs evenly, flow back lower reaction 6h, filtering, then is gone with 400mL Ion water washing filter cake, 70 DEG C of vacuum drying 8h, obtains nuclear grade ion-exchange resins base composite material of core-shell structure.
By microscope test find the nuclear grade ion-exchange resins base composite material of core-shell structure average grain diameter be 0.61mm, partial size between 0.40~0.85mm composite material granular accounting be 91%, tested by ICP-OES, the nuclear leve from OH in sub-exchange resin base composite material of core-shell structure-Content is 92%, remaining Cl-Content is 2.9 ‰, remaining SO4 -Content It is 0.7 ‰, surface purity is high.The volume full exchange capacity of the nuclear grade ion-exchange resins base composite material of core-shell structure is simultaneously 2.9mmol/mL, can in nuclear waste water environment continuous work 480h.
Embodiment 4
At 25 DEG C, 0.3g cerous nitrate is dissolved in 50mL ethylene glycol, 3.0g ATS (Ammonium thiosulphate) is added, stirs 30min, is turned It moves in the reaction kettle of polytetrafluoro liner, reacts 48h at 160 DEG C, be cooled to room temperature, wash filter cake with 120mL deionized water, 80 DEG C vacuum drying 8h, be transferred in Muffle furnace, in 1000 DEG C of roasting 5h, obtain rare earth oxide；80mL isopropanol is weighed, is added 0.7g rare earth oxide, ultrasonic disperse is uniform, and 0.3g KH172 is added, is transferred in the reaction kettle of polytetrafluoro liner, at 120 DEG C Reaction for 24 hours, after cooled to room temperature, washs filter cake with the deionized water of 200mL, obtains hydrophobic rare earth oxide；
At 25 DEG C, 48mL styrene, 8mL divinylbenzene, 2.5mL butanol and 0.5g dicetyl peroxydicarbonate two are weighed respectively Isobutyl ester is put into reactor and stirs evenly, and is heated to 80 DEG C, and the hydrophobic rare earth oxide of 2.4g is added, and ultrasonic disperse 1h is cooling To room temperature, composite oil phase reaction solution is obtained；The saturated sodium chloride solution that 150mL concentration is 26.5% is configured, under nitrogen protection, Above-mentioned composite oil phase reaction solution is added, is stirred and heated to 70 DEG C, sustained response 4h is warming up to boiling reflux, the reaction was continued 4h, Cold filtration, successively rinses filter cake with the ethyl alcohol of 280mL and 600mL water, and it is compound to obtain styrene resin by 75 DEG C of vacuum drying 8h Object；The mixed solution of dichloroethanes containing 25mL, 75mL chloromethyl ether and 150mL methylene chloride is configured, the above-mentioned preparation of 37.5g is added Styrene resin fat complexes, stirring swelling 6h, are added 0.4g ZnCl2, 60 DEG C are stirred to react 2h, and chloromethylation tree is obtained by filtration Fat complexes；The trimethylamine aqueous solution that 50mL mass fraction is 50% is configured, it is multiple that 15g chloromethyl resin obtained above is added Object is closed, the Na for being 0.65mol/L using concentration2CO3Aqueous solution adjusts the pH to 9.5 of mixed solution, is stirred to react 7h, filters, and uses Deionized water washs filter cake to neutrality, obtains macroporous anion exchange resin compound；
At 25 DEG C, it is obtained above big that 10.0g is added in the sodium bicarbonate aqueous solution that configuration 250mL mass fraction is 12% Hole anion exchange resin compound, is stirred to react 8h, and filtering washs filter cake with 600mL deionized water, then filter cake is added to It in the sodium hydrate aqueous solution that 500mL mass fraction is 45%, stirs evenly, flow back lower reaction 7h, filtering, then is gone with 700mL Ion water washing filter cake, 75 DEG C of vacuum drying 7h, obtains nuclear grade ion-exchange resins base composite material of core-shell structure.
By microscope test find the nuclear grade ion-exchange resins base composite material of core-shell structure average grain diameter be 0.39mm, partial size between 0.20~0.50mm composite material granular accounting be 97%, tested by ICP-OES, the nuclear leve from OH in sub-exchange resin base composite material of core-shell structure-Content is 98%, remaining Cl-Content is 0.6 ‰, remaining SO4 -Content It is 0.1 ‰, surface purity is high.The volume full exchange capacity of the nuclear grade ion-exchange resins base composite material of core-shell structure is simultaneously 6.9mmol/mL, can in nuclear waste water environment continuous work 820h.
Embodiment 5
At 25 DEG C, 1.0g lanthanum nitrate is dissolved in 25mL ethylene glycol, 8.0g ATS (Ammonium thiosulphate) is added, stirs 60min, is turned It moves in the reaction kettle of polytetrafluoro liner, reacts 36h at 160 DEG C, be cooled to room temperature, wash filter cake with 300mL deionized water, 65 DEG C vacuum drying 9h, be transferred in Muffle furnace, in 700 DEG C of roasting 12h, obtain rare earth oxide；100mL isopropanol is weighed, is added 0.8g rare earth oxide, ultrasonic disperse is uniform, and 0.4g KH551 is added, is transferred in the reaction kettle of polytetrafluoro liner, at 120 DEG C 12h is reacted, after cooled to room temperature, filter cake is washed with the deionized water of 320mL, obtains hydrophobic rare earth oxide；
At 25 DEG C, 40mL styrene, 5mL divinylbenzene, 1.5mL butanol and 0.2g diphenyl peroxide first are weighed respectively Acyl is put into reactor and stirs evenly, and is heated to 60 DEG C, and the hydrophobic rare earth oxide of 1.8g is added, and ultrasonic disperse 2h is cooled to room Temperature obtains composite oil phase reaction solution；The saturated sodium chloride solution that 170mL concentration is 26.5% is configured, under nitrogen protection, is added Above-mentioned composite oil phase reaction solution is stirred and heated to 60 DEG C, and sustained response 2h is warming up to boiling reflux, the reaction was continued 5h, cooling Filtering, successively rinses filter cake with the ethyl alcohol of 300mL and 1500mL water, and 85 DEG C of vacuum drying 6h obtain styrene resin fat complexes；Match The mixed solution of dichloroethanes containing 20mL, 40mL chloromethyl ether and 120mL methylene chloride is set, the styrene of the above-mentioned preparation of 20g is added Resin complexes, stirring swelling 8h, are added 0.3g SbCl5, 50 DEG C are stirred to react 1h, and it is compound that chloromethyl resin is obtained by filtration Object；The trimethylamine aqueous solution that 100mL mass fraction is 20% is configured, 20g chloromethyl resin compound obtained above is added, The Na for being 0.85mol/L using concentration2CO3Aqueous solution adjust mixed solution pH to 8.5, be stirred to react 8h, filter, spend from Sub- water washing filter cake obtains macroporous anion exchange resin compound to neutrality；
At 25 DEG C, 8.0g macropore obtained above is added in the sodium bicarbonate aqueous solution that configuration 200mL mass fraction is 8% Anion exchange resin compound is stirred to react 6h, and filtering washs filter cake with 400mL deionized water, then filter cake is added to It in the sodium hydrate aqueous solution that 400mL mass fraction is 35%, stirs evenly, flow back lower reaction 8h, filtering, then is gone with 500mL Ion water washing filter cake, 70 DEG C of vacuum drying 8h, obtains nuclear grade ion-exchange resins base composite material of core-shell structure.
By microscope test find the nuclear grade ion-exchange resins base composite material of core-shell structure average grain diameter be 0.53mm, partial size between 0.35~0.75mm composite material granular accounting be 98%, tested by ICP-OES, the nuclear leve from OH in sub-exchange resin base composite material of core-shell structure-Content is 96%, remaining Cl-Content is 1.2 ‰, remaining SO4 -Content It is 0.4 ‰, surface purity is high.The volume full exchange capacity of the nuclear grade ion-exchange resins base composite material of core-shell structure is simultaneously 4.1mmol/mL, can in nuclear waste water environment continuous work 550h.

Claims (7)

1. a kind of nuclear grade ion-exchange resins base composite material of core-shell structure, which is characterized in that the composite material of core-shell structure with Light rare earth oxide is core, using nuclear leve strong-base anion-exchange resin as shell；
The preparation method of the composite material of core-shell structure includes the following steps:
(1) at room temperature, by mass ratio 0.005:1~0.05:1 of rare-earth salts and ethylene glycol, rare-earth salts alcohol suspension is configured, by sulphur ATS (Ammonium thiosulphate) is added in mass ratio 5:1~20:1 of ammonium thiosulfate and rare-earth salts, stirs 20~60min, is transferred to reaction kettle In, 36~60h is reacted at 160 DEG C, is cooled to room temperature, and washs filter cake with the deionized water of 100~500 times of rare earth salt qualities, 60 ~100 DEG C of vacuum drying 8~10h, 600~1200 DEG C of 4~12h of roasting obtain rare earth oxide；
(2) at room temperature, by mass ratio 0.005:1~0.01:1 of rare earth oxide and isopropanol, it is molten to configure rare earth oxide alcohol Liquid, then mass ratio 0.2:1~1:1 of silane coupling agent and rare earth oxide is pressed, silane coupling agent is added, is transferred to reaction kettle In, 12~36h is reacted at 120 DEG C, is cooled to room temperature, is washed filter with the deionized water of 200~500 times of rare-earth oxidation amount of substance Cake obtains hydrophobic rare earth oxide；
(3) at room temperature, styrene, divinylbenzene, pore-foaming agent and initiator are stirred evenly, is heated to 60~90 DEG C, obtained oily Liquid is mixed, mass ratio 0.01:1~0.05:1 of liquid is mixed by hydrophobic rare earth oxide and oil, hydrophobic rare-earth oxidation is added Object, 0.5~2h of ultrasonic disperse, is cooled to room temperature, and obtains composite oil phase reaction solution；Under nitrogen protection, it is reacted by composite oil phase Composite oil phase mixture is added to saturated sodium chloride solution by volume ratio 0.2:1~0.5:1 of liquid and saturated sodium chloride solution In, 60~80 DEG C are stirred and heated to, 2~5h of sustained response is warming up to boiling reflux, the reaction was continued 3~5h, cold filtration, Styrene resin fat complexes crude product is obtained, successively with the second alcohol and water of 10~100 times of styrene resin fat complexes crude product quality Filter cake is rinsed, 60~80 DEG C of 6~9h of vacuum drying obtain styrene resin fat complexes；
(4) at room temperature, by volume ratio 1:1~3:1 of dichloroethanes and chloromethyl ether, dichloroethanes-chloromethane ether mixture is configured, then By volume ratio 2:1~4:1 of methylene chloride and chloromethyl ether, methylene chloride is added, chloromethylation liquid is made, by styrene resin It is multiple that styrene resin obtained in step (3) is added in mass ratio 0.1:1~0.25:1 of fat complexes and chloromethylation liquid Object is closed, catalyst is added, and 40~60 DEG C are stirred to react 1~2h, and it is compound that chloromethyl resin is obtained by filtration in stirring 6~8h of swelling Object；
(5) at room temperature, the trimethylamine aqueous solution that configuration quality score is 20%~80%, by chloromethyl resin compound and three Chloromethyl resin compound made from step (4) is added in mass ratio 0.2:1~0.5:1 of methylamine water solution, using 0.5~ The Na of 1mol/L2CO3Aqueous solution adjusts the pH to 8~10 of mixed solution, is stirred to react 6~8h, filters, is washed to neutrality, obtains Macroporous anion exchange resin compound；
(6) sodium bicarbonate aqueous solution that configuration quality score is 5%~15% at room temperature, it is compound by macroporous anion exchange resin Large pore anion exchange tree obtained in step (5) is added in mass ratio 0.02:1~0.05:1 of object and sodium bicarbonate aqueous solution Fat complexes are stirred to react 6~8h, filtering, with the deionized water of 50~100 times of macroporous anion exchange resin compound quality Filter cake is washed, it, will by mass ratio 0.01:1~0.05:1 of macroporous anion exchange resin compound and sodium hydrate aqueous solution Obtained filter cake is added in the sodium hydrate aqueous solution that mass fraction is 30%~50%, and return stirring reacts 6~8h, mistake Filter washs filter cake, 60~80 DEG C of vacuum drying with the deionized water of 50~100 times of macroporous anion exchange resin compound quality 6~9h obtains nuclear grade ion-exchange resins base composite material of core-shell structure.
2. nuclear grade ion-exchange resins base composite material of core-shell structure according to claim 1, which is characterized in that described light Rare earth oxide is selected from one of cerium oxide, lanthana and praseodymium oxide.
3. nuclear grade ion-exchange resins base composite material of core-shell structure according to claim 1, which is characterized in that step (1) in, the rare-earth salts is one of cerous nitrate, lanthanum nitrate, praseodymium nitrate.
4. nuclear grade ion-exchange resins base composite material of core-shell structure according to claim 1, which is characterized in that step (2) in, the silane coupling agent is one of KH551, KH171, KH172.
5. nuclear grade ion-exchange resins base composite material of core-shell structure according to claim 1, which is characterized in that step (3) in, the oil mixes the constituent content of liquid are as follows: 40~50 parts of styrene, 5~10 parts of divinylbenzene, pore-foaming agent 1.5~ 3 parts and 0.2~1 part of initiator.
6. nuclear grade ion-exchange resins base composite material of core-shell structure according to claim 1 or 5, which is characterized in that step Suddenly in (3), the pore-foaming agent is ethyl alcohol, butanol or isopropanol, and initiator is cyclohexanone peroxide, dibenzoyl peroxide, mistake Aoxidize one of two carbonic acid diisobutyl esters.
7. nuclear grade ion-exchange resins base composite material of core-shell structure according to claim 1, which is characterized in that step (4) in, the catalyst is SbCl5Or ZnCl2, the additive amount of catalyst be styrene resin fat complexes additional amount 1~ 1.5%.
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