CN109896578A - A kind of solid absorbent materials and its preparation method and application - Google Patents
A kind of solid absorbent materials and its preparation method and application Download PDFInfo
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- CN109896578A CN109896578A CN201910299294.5A CN201910299294A CN109896578A CN 109896578 A CN109896578 A CN 109896578A CN 201910299294 A CN201910299294 A CN 201910299294A CN 109896578 A CN109896578 A CN 109896578A
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Abstract
The invention belongs to technical field of radioactive wastewater treatment, it is related to a kind of solid absorbent materials and its preparation method and application.The solid absorbent materials contain the extractant of structure shown in formula (a) or formula (b).Solid absorbent materials of the invention can have preferable absorption property by the actinide ion and lanthanide ion of right+3 ,+4 ,+6 valence state (wherein+6 valence states are Actinyl ion) in wider Acidity Range.
Description
Technical field
The invention belongs to technical field of radioactive wastewater treatment, it is related to a kind of solid absorbent materials and preparation method thereof and uses
On the way.
Background technique
Currently, nuclear technology relevant to radionuclide has obtained extensively in the energy, military affairs, medical treatment and field of scientific study
General application.But in multiple links of the relevant Application of Nuclear Technology of radionuclide, such as uranium mining and smelting, element manufacture, weary
There may be the waste water containing radionuclide during fuel post-processing, nuclear waste transmutation；Meanwhile nuclear weapon explode or core
During facility operation, there are also radionuclides to be released in environment.And in these radionuclides, actinium series and group of the lanthanides
Element accounts for sizable a part.
The α particle-emitting nuclides that Spent Radioactive water process and ENVIRONMENTAL RADIOCHEMISTRY are concerned about very much be all more actinides or
Its daughter.Chromatography method is widely used in Spent Radioactive water process and Environmental Radioactive Sample separation, and chromatograph
The basis of separation method is solid absorbent materials.
In acidic solution system, lanthanide series exists in the form of+trivalent metal ion mostly, and actinides will
Complicated is more, and relatively conventional ionic valence condition has+3 (such as Am3+) ,+4 (such as Pu4+) ,+5 (such as NpO2 +) and+6 (such as UO2 2+And PuO2 2 +) etc..
Up to the present, the scientific worker of countries in the world, which has developed, some can be used for actinides and lanthanide series
Isolated solid absorbent materials mainly include following 4 seed type:
(1) ion exchange resin.As respectively with-SO3H and-COOH is the highly acid and Subacidity cation of functional group
Exchanger resin and strong-base anion-exchange resin etc.；
(2) extration resin.Such as using tributyl phosphate as the TBP resin of functional reagent, with di-(2-ethylhexyl)phosphoric acid ester
For the P204 resin etc. of functional reagent；
(3) chelating resin.The chelating resin and other chelating resins of similar ethylenediamine tetra-acetic acid；
(4) natural adsorbent material.Such as bentonite, zeolite, chitosan, cellulose.
But it up to the present, (can be put from the aqueous solution of wider Acidity Range there is no a kind of ideal solid absorbent materials
Penetrating property waste water or environmental sample lysate) in selective absorption majority valence state actinides and lanthanide series.
Summary of the invention
Primary and foremost purpose of the invention is to provide a kind of solid absorbent materials, with can be in wider Acidity Range to actinium series
Ion and lanthanide ion have preferable absorption property.
In order to achieve this, the present invention provides a kind of solid absorbent materials, the solid phase in the embodiment on basis
Adsorbent material contains extractant (the 3- oxa--penta two with Asymmetrical substitute alkyl of the structure as shown in following formula (a) or formula (b)
Amides compound),
Wherein:
R1For methyl or ethyl；
R2For alkyl more than 4 carbon.
A second object of the present invention is to provide a kind of preparation method (infusion process) of solid absorbent materials as described above,
Can preferably prepare solid absorbent materials as described above, preparing resulting solid absorbent materials can be in wider acidity
There is preferable absorption property to actinide ion and lanthanide ion in range.
In order to achieve this, the present invention provides a kind of solid absorbent materials as described above in the embodiment on basis
Preparation method, the preparation method includes the following steps:
(1) solution of the extractant is uniformly mixed with support；
(2) solvent flashing obtains the solid absorbent materials.
In a preferred embodiment, the present invention provides a kind of preparation side of solid absorbent materials as described above
Method, wherein in step (1), the solution of the extractant is the organic solvent solution of extractant, and the organic solvent is low
Boiling point organic diluent is selected from one or more of methanol, ethyl alcohol, acetone, methylene chloride；
The support is the composite organic-inorganic material that porous polymer microsphere or organic reagent are modified, selected from more
Hole polystyrene bead, microporous polyacrylate bead, porous styrene-methacrylate copolymer bead, chain alkyl
One or more of the macro porous silica gel of surface modification, macro porous silica gel of polymer overmold；
The mass ratio of the extractant and the support is 1:100-1:1.
In a preferred embodiment, the present invention provides a kind of preparation side of solid absorbent materials as described above
Method, wherein in step (2), the solvent flashing uses rotary evaporation in vacuo, infrared lamps, low temperature drying and/or nature
The method of placement.
Third object of the present invention is to provide the preparation methods of another solid absorbent materials as described above (to suspend poly-
Legal (extration resin method)), can preferably prepare solid absorbent materials as described above, prepare resulting solid phase adsorption material
Material can have preferable absorption property to actinide ion and lanthanide ion in wider Acidity Range.
In order to achieve this, the present invention provides another solid phase adsorption material as described above in the embodiment on basis
(the method can only be used to the adsorbent material for preparing support as polymer globules to the preparation method of material, and cannot prepare support
For the adsorbent material of composite organic-inorganic material), the preparation method includes the following steps:
(1) monomer solution of styrene, divinylbenzene and methacrylate is mixed in proportion, adds benzoyl peroxide
Or azo diisopropyl nitrile is as initiator (dosage be about monomer gross mass 0.5%), and (extractant matter in proportion as needed
The ratio of amount and monomer gross mass is between 1 to 100 to 1 to 1) extractant of structure shown in addition formula (a) or formula (b) (has
Asymmetry four replaces 3- oxa--glutaramide of structure), it stirs evenly；
(2) gelatin is dissolved in boiling water, calcium carbonate and dodecyl sodium sulfate is added, be uniformly mixed；
(3) step (1) acquired solution is added in mixed liquor obtained by step (2), and appropriate polyvinyl alcohol is added, sufficiently stirred
45-65 DEG C is heated under the conditions of mixing, constant temperature is heated to 80-95 DEG C after a certain period of time and keeps certain time, obtains comprising extraction
Take the polymer globules of agent；
(4) polymer globules are washed with deionized 5-10 times after cooling down, until cleaning clarification of water；
(5) polymer globules filtered, dried to get the solid absorbent materials.In a kind of preferred embodiment
In, the present invention provides the preparation method of another solid absorbent materials as described above, wherein in step (1), the benzene second
The mixing mass ratio of alkene and divinylbenzene is 3:1-8:1, and mass content of the methacrylate in monomer is less than 30%.
In a preferred embodiment, the present invention provides the preparation side of another solid absorbent materials as described above
Method, wherein in step (2), gelatin is in the mass content in mixed liquor between 0.4%-2.0%, and calcium carbonate is in mixed liquor
Mass content between 0.01%-0.2%, mass content of the dodecyl sodium sulfate in mixed liquor 0.01%-0.1% it
Between.
In a preferred embodiment, the present invention provides the preparation side of another solid absorbent materials as described above
Method, wherein in step (3),
The time of constant temperature is 15-30 minutes after being stirred and heated to 45-65 DEG C；
The time kept after being heated to 80-95 DEG C is 1.5-4.0 hours.
In a preferred embodiment, the present invention provides the preparation side of another solid absorbent materials as described above
Method, wherein in step (4),
The cooling is to be down to room temperature to 50 DEG C.
Fourth object of the present invention is to provide a kind of purposes of solid absorbent materials as described above, with can be better
Using solid absorbent materials as described above.
In order to achieve this, the present invention provides a kind of solid absorbent materials as described above in the embodiment on basis
For the selective absorption actinium series from solution and the purposes of lanthanide ion.The beneficial effects of the present invention are of the invention
Solid absorbent materials can in wider Acidity Range right+3 ,+4 ,+6 valence state (wherein+6 valence states are Actinyl ion) actinium series
Ion and lanthanide ion have preferable absorption property.
Solid absorbent materials of the invention are right within the scope of wider nitric acid and concentration of hydrochloric acid+actinium series and group of the lanthanides of trivalent state
The actinide ion of ion and+4 valence states has very strong adsorption capacity, can be used for from acid solution or the higher solution of salt content
The actinium series and lanthanide metal ion of+3 ,+4 valence states of middle absorption.In addition, solid absorbent materials of the invention are to Actinyl ion (such as UO2 2 +Ion) also there is stronger adsorption capacity.
Therefore, adsorbent material low level waste water processing and radiochemical analysis (americium in such as large volume lysate in particular embodiments
With the enrichment or separation of plutonium) in have preferable application prospect.
Detailed description of the invention
Fig. 1 is the relational graph of embodiment 1 resulting distribution coefficient and acid concentration.
Fig. 2 is the relational graph of embodiment 2 resulting distribution coefficient and acid concentration.
Specific embodiment
A specific embodiment of the invention is further illustrated with attached drawing with reference to embodiments.
Embodiment 1: the preparation and detection (one) of solid absorbent materials
With N, N '-dimethyl-N, N '-dioctyl -3- oxa--glutaramide is extractant, with Amberlite XAD7HP
Solid absorbent materials are prepared for support, and measure point of its adsorbing metal ions from nitric acid solution by Staticadsorption experiment
Distribution coefficient.
Preparation process is as follows:
(1) by the N of 7.0g, N '-dimethyl-N, N '-dioctyl -3- oxa--glutaramide (DMDODGA) is dissolved in 40mL first
In alcohol；
(2) by dried to the 20-60 mesh partial size of constant weight Amberlite XAD7HP particle be packed into 250mL single port it is flat
In flask, it is put into the magneton of polytetrafluoroethylene (PTFE) cladding；
(3) solution is added dropwise under the conditions of electromagnetic agitation and is entered in flask, stirred 30 minutes；
At (4) 40 DEG C, rotary evaporation to constant weight is to get target solid absorbent materials, the wherein mass content of DMDODGA
35.0%.
Eu in prepared solid absorbent materials absorption various concentration nitric acid solution is tested using Staticadsorption experiment3+、Np4 +And UO2 2+The performance of ion.Distribution coefficient (Kd) calculated as the following formula:
Wherein, CiAnd CeThe concentration of metal ion in solution, V after respectively originating and balanceaFor the volume of solution, msFor
The quality of solid phase material.
25.0 ± 0.2 DEG C of constant temperature gas bath concussions, control liquid-solid ratio50 between 100mL/g, absorption front and back solution
The concentration using plasma inductive coupling of middle Eu and U-mass spectrum (ICP-MS) measurement, before and after absorption in solution239Np specific activity
It is measured using high-purity oleic acid.Gained distribution coefficient is as shown in Figure 1.From the figure:
Within the scope of 0.05mol/L to 10.0mol/L concentration of nitric acid, which adsorbs typical lanthanide ion Eu3+From
The distribution coefficient of son is all larger than 1.0 × 106ML/g material, in view of the similitude of trivalent actinium series and group of the lanthanides chemical property, it is contemplated that
Also there is very strong adsorption capacity for trivalent actinide ion.
In 0.5mol/L nitric acid solution, the adsorbent material is to Np4+The distribution coefficient of ion is greater than 1.0 × 105ML/g material；
In 1.0mol/L nitric acid solution, the adsorbent material is to Np4+The distribution coefficient of ion is greater than 2.0 × 107ML/g material；Concentration of nitric acid
When between 2.0mol/L and 10.0mol/L, the adsorbent material is in aqueous solution to Np4+The distribution coefficient of ion be greater than 5.0 ×
107ML/g material.
For UO2 2+Ion, maximum allocated coefficient is up to 3.0 × 103It is more than mL/g material.
These statistics indicate that, prepared adsorbent material is to trivalent actinium series/lanthanide ion in nitric acid solution, tetravalence actinium series
Ion, sexavalence Actinyl ion have very strong adsorption capacity, are expected to be used for adsorbing separation actinium series/group of the lanthanides from nuclear industry acid waste liquid
Element.
Embodiment 2: the preparation and detection (two) of solid absorbent materials
With N, N '-dimethyl-N, N '-dioctyl -3- oxa--glutaramide is extractant, with styrene and divinyl
Benzene is that the initial monomers of support prepare solid absorbent materials, and measures it from hydrochloric acid solution by Staticadsorption experiment and adsorb
The distribution coefficient of metal ion.
Preparation process is as follows:
15.0g styrene monomer and 10.0g divinylbenzene monomer are uniformly mixed, it is different that the azo two of 0.5g after purification is added
Propionitrile (ALBN) is used as initiator, adds 15.0g N, N '-dimethyl-N, N '-dioctyl -3- oxa--glutaramide
(DMDODGA), it stirs evenly as oily phase.Separately 6.0g gelatin is dissolved in 500mL boiling water, then be added 0.5g calcium carbonate and
0.05g Triton X-100 is used as water phase after mixing, its temperature is made to be maintained at 45 DEG C.Oil is added in water phase, is stirred
It mixes and is warming up to 80 DEG C after twenty minutes, isothermal reaction is warming up to 90 DEG C after 6 hours, obtain polymer globules.50 DEG C are cooled to, is poured out
Solution, with mutually synthermal deionized water repeatedly cleaning cleaning polyalcohol bead until cleaning clarification of water.Bead suction filtration, low temperature is true
Sky is dry to constant weight, obtains 32.0g white globules, as target solid absorbent materials, particle size range 0.10-0.50mm,
The degree of cross linking is 20%, and wherein the mass content of DMDODGA is 42.2%.
At 25.0 ± 0.2 DEG C, the material is measured in various concentration hydrochloric acid solution also with Staticadsorption experiment and is inhaled
The performance of attached Eu (III) and U (VI), the calculating of distribution coefficient and the method for measurement of concentration of metal ion are same as Example 1.Institute
It is as shown in Figure 2 to obtain distribution coefficient.From the figure:
Rise with acidity, adsorbent material is to Eu in hydrochloric acid solution3+The distribution coefficient of ion rises, in concentration of hydrochloric acid
Reach between 2.0mol/L and 6.0mol/L maximum (in 4.0mol/L hydrochloric acid solution, Eu in solution after material absorption3+Concentration
It detects and limits lower than method, distribution coefficient is greater than 5.0 × 107ML/g material)；
For UO2 2+Ion, maximum allocated coefficient is up to 8.0 × 103It is more than mL/g material.
These statistics indicate that, which also has very strong adsorption capacity to actinium series/lanthanide ion in hydrochloric acid solution.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.If in this way, belonging to the model of the claims in the present invention and its equivalent technology to these modifications and changes of the present invention
Within enclosing, then the present invention is also intended to include these modifications and variations.Above-described embodiment or embodiment are only to the present invention
For example, the present invention can also be implemented with other ad hoc fashions or other particular form, without departing from of the invention
Main idea or substantive characteristics.Therefore, the embodiment of description is regarded as illustrative and non-limiting in any way.This
The range of invention should be illustrated that any variation equivalent with the intention and range of claim also should include by appended claims
Within the scope of the invention.
Claims (10)
1. a kind of solid absorbent materials, it is characterised in that: the solid absorbent materials contain as shown in following formula (a) or formula (b)
The extractant of structure,
Wherein:
R1For methyl or ethyl；
R2For alkyl more than 4 carbon.
2. a kind of preparation method of solid absorbent materials according to claim 1, which is characterized in that the preparation method
Include the following steps:
(1) solution of the extractant is uniformly mixed with support；
(2) solvent flashing obtains the solid absorbent materials.
3. preparation method according to claim 2, it is characterised in that: in step (1), the solution of the extractant is extraction
The organic solvent solution of agent is taken, the organic solvent is low boiling point organic diluent, is selected from methanol, ethyl alcohol, acetone, dichloromethane
One or more of alkane；
The support is the composite organic-inorganic material that porous polymer microsphere or organic reagent are modified, selected from porous poly-
Styrene bead, microporous polyacrylate bead, porous styrene-methacrylate copolymer bead, chain alkyl surface
One or more of the macro porous silica gel of modification, macro porous silica gel of polymer overmold；
The mass ratio of the extractant and the support is 1:100-1:1.
4. preparation method according to claim 2, it is characterised in that: in step (2), the solvent flashing uses vacuum
Rotary evaporation, infrared lamps, low temperature drying and/or the method placed naturally.
5. a kind of preparation method of solid absorbent materials according to claim 1, which is characterized in that the preparation method
Include the following steps:
(1) monomer solution of styrene, divinylbenzene and methacrylate is mixed in proportion, adds benzoyl peroxide or idol
Nitrogen diisopropyl nitrile is proportionally added into the extractant of structure shown in formula (a) or formula (b) as initiator as needed, and stirring is equal
It is even；
(2) gelatin is dissolved in boiling water, calcium carbonate and dodecyl sodium sulfate is added, be uniformly mixed；
(3) step (1) acquired solution is added in mixed liquor obtained by step (2), and appropriate polyvinyl alcohol is added, item is sufficiently stirred
45-65 DEG C is heated under part, constant temperature is heated to 80-95 DEG C after a certain period of time and keeps certain time, obtains comprising extractant
Polymer globules；
(4) polymer globules are washed with deionized 5-10 times after cooling down, until cleaning clarification of water；
(5) polymer globules filtered, dried to get the solid absorbent materials.
6. preparation method according to claim 5, it is characterised in that: in step (1), the styrene and divinylbenzene
Mixing mass ratio be 3:1-8:1, mass content of the methacrylate in monomer is less than 30%.
7. preparation method according to claim 5, it is characterised in that: in step (2), quality of the gelatin in mixed liquor contains
Amount between 0.4%-2.0%, calcium carbonate in the mass content in mixed liquor between 0.01%-0.2%, dodecyl sodium sulfonate
Sodium is in the mass content in mixed liquor between 0.01%-0.1%.
8. preparation method according to claim 5, it is characterised in that: in step (3),
The time of constant temperature is 15-30 minutes after being stirred and heated to 45-65 DEG C；
The time kept after being heated to 80-95 DEG C is 1.5-4.0 hours.
9. preparation method according to claim 5, it is characterised in that: in step (4),
The cooling is to be down to room temperature to 50 DEG C.
10. a kind of solid absorbent materials according to claim 1 are used for selective absorption actinium series and group of the lanthanides member from solution
The purposes of plain ion.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113621175A (en) * | 2021-08-13 | 2021-11-09 | 中国科学院化学研究所 | Efficient isotactic polypropylene beta-crystal form nucleating agent and preparation method and application thereof |
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| CN101139418A (en) * | 2007-07-19 | 2008-03-12 | 四川大学 | Elution-extracting resin using amide compound as extracting agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101139418A (en) * | 2007-07-19 | 2008-03-12 | 四川大学 | Elution-extracting resin using amide compound as extracting agent and preparation method thereof |
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| XIUJING PENG等: "Separation of Pr(III) and Fe(III) by unsymmetrical diglycolamides from nitric acid media", 《SEPARATION AND PURIFICATION TECHNOLOGY》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113621175A (en) * | 2021-08-13 | 2021-11-09 | 中国科学院化学研究所 | Efficient isotactic polypropylene beta-crystal form nucleating agent and preparation method and application thereof |
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