CN103788301A - Preparation method of chelation microspheres for adsorbing neodymium - Google Patents
Preparation method of chelation microspheres for adsorbing neodymium Download PDFInfo
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- CN103788301A CN103788301A CN201410037718.8A CN201410037718A CN103788301A CN 103788301 A CN103788301 A CN 103788301A CN 201410037718 A CN201410037718 A CN 201410037718A CN 103788301 A CN103788301 A CN 103788301A
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- microballoon
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Abstract
The invention belongs to the technical field of functional high-molecular materials, and particularly relates to a preparation method of chelation microspheres for adsorbing neodymium. With polystyrene (PS) microspheres as a matrix, the method comprises the following steps: grafting the microspheres with glycidyl methacrylate (GMA) containing a functional epoxy group by a process of cobalt-source gamma ray triggering radiation grafting; and preparing the amino-containing chelation microspheres through amination. The method has the advantages of simple synthesis steps and cheap and easily-available raw materials; the synthesized microspheres with a chelation function have the advantages of relatively good chemical and mechanical stability, perfect coordination complexing capacity on neodymium ions, good selectivity, large adsorption capacity, easy regeneration and reusability, and can be applied to selective separation of other minor actinides.
Description
Technical field
The preparation method who the present invention relates to a kind of neodymium ion absorption chelating microballoon, belongs to functional high molecule material technical field.
Background technology
The maximum use of neodymium is to prepare Nd-Fe-Bo permanent magnet material, and neodymium iron boron magnetic body magnetic energy product is high, is known as the present age " king of permanent magnetism ", is widely used in the industry such as electronics, machinery with its excellent performance.Neodymium also can be made alloy material and be applied to space industry.For the research of reclaiming neodymium from solution, scientific research personnel has done a lot of significant explorations.Traditional method comprises the precipitator method, absorption method, solvent extration etc.Because character between rare earth element is very similar, be difficult to effective separation, the novel material day of therefore finding a kind of effective separation, purification neodymium element is aobvious important.Carry out adsorbing metal ions with functional polymer, loading capacity is large, easy and simple to handle.The rear functional polymer of adsorbing metal ions can be used acidity or basic solution processing, and metal ion disengages, and macromolecular material is reusable again.The polymer with difference in functionality base has different adsorptive poweies to different metals.Due to give electronics atom as oxygen, nitrogen, sulphur etc. with metal implement for coordination binding ability, the sorbent material that the functional polymer that contains these atoms is chosen as metal ion is a comparatively active research field in recent years.
The development of nuclear energy makes radwaste increasing.To reach 2000t to the year two thousand twenty spent fuel accumulative total, after this will produce every year about 1000t spent fuel.Can be in time, these high-level wastes of safe disposal, be to be related to the unavoidable significant problem that can China's nuclear undertaking Sustainable development.The ionic radius of the long lifetime trivalent Minor actinides existing in spent fuel is close to neodymium ion radius, Crystallochemical Properties is also similar, radiological hazard when avoiding experimental implementation, therefore the trivalent actinides in conventional neodymium ion simulated high-level radioactive waste, use chelating microballoon so prepare neodymium ion absorption in the present invention, can also be used in the selective separation aspect of spent fuel aftertreatment field Minor actinides.
Summary of the invention
The object of the invention is to utilize method for radio-grafting to prepare a kind of for adsorbing the chelating microballoon of neodymium, the superiority such as the method has controlled, simple to operate and graft product is pure; The chelating microballoon that it obtains, is the Polystyrene chelating microballoon of a kind of amino-contained functional group, and its stable performance, chelating capacity are large, and easily regeneration, has good mechanical property.
The present invention first introduces glycidyl methacrylate by mutual radiation grafting on cheap polystyrene microsphere, then prepares neodymium ion chelate sorbent by the addition reaction of epoxy group(ing) and aminated compounds, and reaction equation is as follows:
Concrete steps are as follows:
(1) will, through pretreated PS microballoon, glycidyl methacrylate solution, tetrahydrofuran (THF) and stopper, after mixing, under inert atmosphere, be placed in
60the indoor gamma-ray irradiation that carries out in Co source; After reaction finishes, suction filtration, solvent wash obtain grafted polystyrene microballoon; Wherein: the solvent in described glycidyl methacrylate solution is tetrahydrofuran (THF), its concentration of volume percent is 10-20%, and the mass ratio of described glycidyl methacrylate, PS microballoon and stopper is (20-40): (60-80): (0-2);
(2) grafted polystyrene microballoon obtained above and diethylenetriamine are carried out to amination reaction at 105-120 ℃, the reaction times is 12-36h, after reaction finishes, and suction filtration, washing, dries and obtains chelating microballoon; The mass ratio of wherein said grafted polystyrene microballoon and diethylenetriamine is 1:(2-5).
In above-mentioned steps (1), described PS microballoon cleans, is dried and carries out pre-treatment with acetone; Described inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
In above-mentioned steps (1), in described glycidyl methacrylate solution, solvent is tetrahydrofuran (THF).
In above-mentioned steps (1), the total dose of gamma-ray irradiation is 5-30kGy, and radiation dose rate is 0.8kGy/h.
In above-mentioned steps (1), when washing, solvent adopts N, one or more in N – dimethyl formamide, methyl alcohol or tetrahydrofuran (THF).
The present invention also provide a kind of utilize that above-mentioned preparation method obtains for adsorbing the chelating microballoon of neodymium.
While the chelating microballoon preparing being carried out to chelating absorption for the neodymium ion aqueous solution in the present invention, appropriate pH value is 1.06-2.80; The suitable concentration of neodymium ion is between 0.05-100ppm.
Beneficial effect of the present invention is:
(1) simple to operate, raw material is cheap and easy to get; When mutual radiation grafting, can, by controlling irradiation dose and monomer concentration, change flexibly the percentage of grafting of monomer, thereby regulate the introduction volume of epoxide group on grafted chain.
(2) adopt tetrahydrofuran (THF) as graft reaction solvent, it both had very high mutual solubility with monomer (glycidyl methacrylate), again can good swelling body material polystyrene microsphere, thereby contribute to accelerate the rate of diffusion of monomer to matrix, in improving percentage of grafting, be conducive to prepare the chelating microballoon that graft component is evenly distributed.
(3) the synthetic stable performance of chelating microballoon, chelating capacity is large, and selectivity is good, and easily regeneration, has good mechanical property.Except neodymium ion is had to excellent chelating absorption property, can also be used for the selective separation of spent fuel aftertreatment field time actinium series radionuclide; The inventive method is not only a kind of novel method, simultaneously also for low cost recovering rare earth element provides new approaches.
Accompanying drawing explanation
Fig. 1 is that stopper copper sulfate content affects figure to percentage of grafting.
Fig. 2 is chelating microballoon loading capacity figure to neodymium ion, cadmium ion in different pH value situations that this invention makes.
Fig. 3 is that neodymium ion starting point concentration is on the figure that affects on chelating microballoon loading capacity.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
1) by polystyrene microsphere (d
50=600 μ m), with acetone abundant washing by soaking under the state stirring, are dried to constant weight.Sample after weighing is put into 100ml ground graft reaction container, then to the GMA tetrahydrofuran solution and the copper sulfate that add 15%vol in container, wherein: the mass ratio of GMA tetrahydrofuran solution, polystyrene microsphere and copper sulfate is 10:30:1; Repeatedly to reaction vessel vacuum nitrogen filling gas, get rid of the air on solution inside and top again.The ground stopper that screws reaction vessel, is placed in
60the indoor gamma-ray irradiation that carries out in Co source.Total dose 30kGy, radiation dose rate is 0.8kGy/h;
2) after graft reaction completes, polystyrene microsphere and graft reaction solution are taken out from reaction vessel, decompress filter is removed graft reaction solution, first use N, N – dimethyl formamide washing grafted polystyrene microballoon, then under the state of being used the mixing solutions (volume ratio 1:1) of methyl alcohol and tetrahydrofuran (THF) to stir, soak 12 hours, to remove microsphere surface homopolymer;
3) the grafted polystyrene microballoon that is 1:4 by mass ratio and diethylenetriamine mass ratio are for carrying out aminating reaction, and the reaction times is 24h, and temperature of reaction is 115 ℃, make the epoxide group on grafted polystyrene microballoon be transformed into secondary amine group.After reaction finishes, amination reaction solution is removed in pressure filtration, after washing, oven dry, obtains chelating microballoon.The particle diameter of microballoon is 700-920 μ m, and 67.2% epoxide group has been converted to secondary amine group.Examination of infrared spectrum shows, 982,845cm
-1place
a little less than the charateristic avsorption band of group becomes very, at 1121cm
-1having there is C-N stretching vibration peak absorption peak in place, proves that the epoxy group(ing) on grafting microballoon with diethylenetriamine, amination reaction has occurred.
In the reaction of mutual radiation solution graft copolymerization, often need in grafting system, add stopper to suppress homopolymerization.Prepare on the basis of chelating microballoon in method described in employing embodiment 1 and step, investigated the affect rule of stopper consumption on percentage of grafting, result as shown in Figure 1.Stopper shared weight percentage in grafting system is 0-1%, and irradiation dose is 30kGy, and solvent is THF, and the volumn concentration of monomer in solvent is 15%.
The chelating microballoon that employing embodiment 1 makes is under different condition, to adsorbing containing the aqueous solution of neodymium ion and cadmium ion, to investigate the adsorption selectivity of chelating microballoon in the time that coexisting ion exists.Concrete grammar is: get after chelating microballoon is accurately weighed and put into 50ml vial, then add containing Nd
3+, Cd
2+mixed aqueous solution, volume is 25mL, Nd
3+, Cd
2+concentration be 5ppm.Solution acidity is regulated by the hydrochloric acid of 0.1mol/L, regulates pH value between 1.06-2.8.In every ml soln, add 7.5mg chelating microballoon, vial is placed on vibrator to 25 ℃ of isothermal vibrations 1 hour, filtration under diminished pressure takes out chelating microballoon, then uses inductive coupling plasma emission spectrograph (ICP) to measure in solution and remains Nd
3+, Cd
2+concentration, thereby calculate chelating microballoon maximum adsorption capacity to neodymium ion in the situation that of different pH that this invention makes.Figure 2 shows that the chelating microballoon making loading capacity figure to neodymium ion, cadmium ion (Q is loading capacity) in different pH value situations.
It is 0.887mg/g to the maximum adsorption capacity of neodymium ion in the situation that of pH=2.2, much larger than the maximum adsorption capacity 0.143mg/g to cadmium ion under similarity condition, to Nd
3+show good adsorption selectivity.
The chelating microballoon that has adsorbed neodymium ion or cadmium ion can be regenerated by acid method, concrete steps are: the salpeter solution blend that is 1mol/L the microballoon after chelated metal ions and concentration, under whipped state, carry out desorption experiment, the time is 2h, makes metal ion be converted into salt soluble in water and desorb.Repeatedly carry out several times above-mentioned absorption-desorption experiment, result shows, adsorbs the chelating microballoon obtaining the in the situation that of above-mentioned pH=2.2, still keeps good adsorptive power after regenerating, after 3 absorption-desorption circulations, the adsorptive capacity of chelating microballoon only reduces by 1.6%.
Determine on the basis of optimal adsorption acidity in above-mentioned Static Adsorption test, carry out dynamic column adsorption test.Concrete operation step is: accurately takes the chelating microballoon of 0.3g, is packed in glass adsorption column, and the high 20mm of post, diameter 27mm, 60ml, the neodymium ion aqueous solution of the different concns of pH=2.2 is poured in 100ml constant pressure funnel.Then dropping funnel ground place and the tangent merging of ground of adsorption column upper end are screwed to check system resistance to air loss.Open the glass cock on separating funnel, control solution flow rate is 3ml/min, measures Concentration of Neodymium Ion in Czochralski, thereby calculate the chelating microballoon loading capacity under different neodymium ion starting point concentrations after effluent liquid collection with ICP, and result as shown in Figure 3.
Work as Nd
3+starting point concentration while being 100ppm, chelating microballoon is to Nd
3+dynamic adsorption capacity Q be 17.58mg/g.
Claims (7)
1. for adsorbing the preparation method of chelating microballoon for neodymium, it is characterized in that, concrete steps are as follows:
(1) will, after pretreated PS microballoon, glycidyl methacrylate solution and stopper mix, under inert atmosphere, be placed in
60the indoor gamma-ray irradiation that carries out in Co source; After reaction finishes, suction filtration, solvent wash obtain grafted polystyrene microballoon; Wherein: the solvent in described glycidyl methacrylate solution is tetrahydrofuran (THF), its concentration of volume percent is 10-20%, described glycidyl methacrylate solution, the mass ratio of PS microballoon and stopper is (20-40): (60-80): (0-2);
(2) grafted polystyrene microballoon obtained above and diethylenetriamine are carried out to amination reaction at 105-120 ℃, the reaction times is 12-36h, after reaction finishes, and suction filtration, washing, dries and obtains chelating microballoon; The mass ratio of wherein said grafted polystyrene microballoon and diethylenetriamine is 1:(2-5).
2. preparation method according to claim 1, is characterized in that: in step (1), described PS microballoon cleans, is dried and carries out pre-treatment with acetone; Described inert atmosphere is nitrogen atmosphere or argon gas atmosphere; Described stopper is copper sulfate.
3. preparation method according to claim 1, is characterized in that: in step (1), the total dose of gamma-ray irradiation is 5-30kGy, and radiation dose rate is 0.8kGy/h.
4. preparation method according to claim 1, is characterized in that: in step (1), when washing, solvent adopts N, one or more in N – dimethyl formamide, methyl alcohol or tetrahydrofuran (THF).
5. obtain according to the preparation method one of claim 1-4 Suo Shu for adsorbing the chelating microballoon of neodymium.
6. for adsorbing the application of chelating microballoon for neodymium, it is characterized in that: when application, in its solution, Concentration of Neodymium Ion in Czochralski is 0.05-100ppm; PH is between 1.06-2.80.
7. according to claim 6 for adsorbing the application of chelating microballoon of neodymium, it is characterized in that: its pH value is 2.2.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105478094A (en) * | 2015-12-25 | 2016-04-13 | 四川大学 | Aminated poly-glycidyl methacrylate crosslinked composite microsphere and preparation method as well as application thereof |
| CN109265613A (en) * | 2018-08-20 | 2019-01-25 | 南通乐道环保技术有限公司 | A kind of functional polystyrene microballoon and its preparation method and application |
| CN110290853A (en) * | 2016-10-12 | 2019-09-27 | Pq公司 | For carrying out the stable immobilization amine sorbent of REE and heavy metal recovery from fluid supply |
| CN115141319A (en) * | 2022-06-27 | 2022-10-04 | 厦门大学 | Engineered radioactive polymer microsphere, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718910A (en) * | 2012-04-23 | 2012-10-10 | 苏州异导光电材料科技有限公司 | Preparation method of crosslinked polystyrene microsphere |
-
2014
- 2014-01-26 CN CN201410037718.8A patent/CN103788301A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718910A (en) * | 2012-04-23 | 2012-10-10 | 苏州异导光电材料科技有限公司 | Preparation method of crosslinked polystyrene microsphere |
Non-Patent Citations (1)
| Title |
|---|
| ZU JIANHUA,ET AL.: "Amination of glycidyl methacrylate-grafted polystyrene particles and their adsorption capacity for Nd3+ and Cd2+", 《IRANIAN POLYMER JOURNAL》, vol. 22, no. 4, 19 February 2013 (2013-02-19), pages 259 - 265, XP035361023, DOI: doi:10.1007/s13726-013-0123-9 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105478094A (en) * | 2015-12-25 | 2016-04-13 | 四川大学 | Aminated poly-glycidyl methacrylate crosslinked composite microsphere and preparation method as well as application thereof |
| CN105478094B (en) * | 2015-12-25 | 2018-04-20 | 四川大学 | Amination poly (glycidyl methacrylate) crosslinking complex microsphere and preparation method and application |
| CN110290853A (en) * | 2016-10-12 | 2019-09-27 | Pq公司 | For carrying out the stable immobilization amine sorbent of REE and heavy metal recovery from fluid supply |
| CN110290853B (en) * | 2016-10-12 | 2023-05-16 | Pq公司 | Stable immobilized amine sorbents for REE and heavy metal recovery from liquid sources |
| CN109265613A (en) * | 2018-08-20 | 2019-01-25 | 南通乐道环保技术有限公司 | A kind of functional polystyrene microballoon and its preparation method and application |
| CN109265613B (en) * | 2018-08-20 | 2021-03-19 | 南通乐道环保技术有限公司 | Functionalized polystyrene microsphere and preparation method and application thereof |
| CN115141319A (en) * | 2022-06-27 | 2022-10-04 | 厦门大学 | Engineered radioactive polymer microsphere, preparation method and application thereof |
| US11865196B2 (en) | 2022-06-27 | 2024-01-09 | Xiamen University | Engineered radioactive polymeric microsphere, and preparation and application thereof |
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Application publication date: 20140514 |