CN109616234A - A method of for separating and/or extracting radioactive metal cation - Google Patents
A method of for separating and/or extracting radioactive metal cation Download PDFInfo
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- CN109616234A CN109616234A CN201811382375.3A CN201811382375A CN109616234A CN 109616234 A CN109616234 A CN 109616234A CN 201811382375 A CN201811382375 A CN 201811382375A CN 109616234 A CN109616234 A CN 109616234A
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
This application discloses a kind of methods for separating and/or extracting radioactive metal cation, ion-exchanger is placed in the liquid containing radioactive metal cation, contact is no less than 5min at 20~80 DEG C, and the ion-exchanger capture separates the radioactive metal cation.This method is when removing radioactive metal cation, the advantages of showing fast capture isotopic ion speed, high adsorption capacity, highly selective, excellent resistance to β and gamma-ray irradiation, high removal rate, low residual volume, residual volume reaches the World Health Organization (WHO) water quality standard for drinking water, and can be by cheap and simple, environmental-friendly method by [Sn3S7]n 2n‑Radioactive metal cation in two-dimensional framework material elutes, and is of great significance for the radioactive metal cation for efficiently removing and recycling in water environment.
Description
Technical field
This application involves a kind of methods for separating and/or extracting radioactive metal cation, belong to environmental protection neck
The processing technique of cationic water containing radioactive metal in domain.
Background technique
Energy and environment are always the big hot issue of today's society two.Due to the non-renewable of fossil energy itself and
Using inevitable problem of environmental pollution in the process, sight is aimed at the new energies such as nuclear energy, solar energy, wind energy by the mankind.Its
Middle nuclear energy is considered a kind of efficient and clean energy, and the favor by many countries.On November 2nd, 2007, China's publication
" nuclear power Long-and Medium-term Development plans (2005-2020) ", indicates that China's nuclear power developing policy is adjusted to by " optimum development "
" actively development ".But acceptance level of the people for nuclear energy and the processing capacity to nuclear waste are closely related.Radioactive nucleus is useless
The processing of object You Yiqi solution is the most intractable.Nuclear waste, which is dealt with improperly, to bring radioactive pollution to environment, these pollutions are held
Continuous period is long, refractory reason, and consequence is serious, can generate grave danger to the survival and development of the mankind, thus to nuclear waste
Be treated as one of top-priority key factor of the further development need of nuclear power industry.In nuclear waste after dilution, put
Penetrating property133Ba2+The half-life period of ion is about 10.7, is most dangerous one of harmful components as gamma-ray radioactive source.Separately
Outside, high temperature, highly acid nuclear waste reacted with container generate radioactivity63Ni2+、60Co2+Ion is as β and gamma-ray radiation
Source also results in threat to environment.The World Health Organization (WHO) provides Ba in drinking water2+、Ni2+The maximum concentration of ion is distinguished
For 0.7ppm, 0.07ppm.It is worth noting that, Ba2+Ion has and radioactivity226Ra2+The similar ionic diameter of ion and from
Sub- exchange features, therefore Ba2+Ion often can be used as the bigger radioactivity of toxicity226Ra2+Ion (half-life period is 1600 ± 7 years) replaces
For object.Therefore, these radioactive metal cations are effectively removed to human health, environmental protection and heat recovery to Guan Chong
It wants.
The mode for removing from waste water and recycling metal ion mainly has: the precipitation method, liquid-liquid extraction method, absorption method, ion
Exchange process etc..Its ion exchange methods attracts attention due to the advantages such as its operation is convenient, inexpensive, efficient.Currently, applied to going
Except Ba2+(radioactivity226Ra2+The substitute of ion) ion-exchanger mainly include zeolite, clay, titanate nano material,
Niobic acid salt material etc., but current material the disadvantages of that there are adsorbances is low, poor selectivity.On the other hand, Ni is removed2+、Co2+'s
Ion exchange/adsorbent material mainly includes zeolite, clay, active carbon etc., is primarily present poor selectivity, residual volume is not up to
The problems such as drinking water standard of WHO.Therefore need to develop one kind can in waste liquid low cost, efficiently removal and recycling Ra2+、
Ba2+、Ni2+、Co2+The method of equal radioactive metals cation.
Summary of the invention
According to the one aspect of the application, provide a kind of for separating and/or extracting the side of radioactive metal cation
Method utilizes cheap [Sn3S7]n 2n-Two-dimensional framework material efficiently removes and recycles radioactive metal cation, as ion exchange
Agent handles waterborne radioactivity metal cation, then is eluted by cheap and simple, environmental-friendly method, and utilized
The material has carried out ion exchange column experiment.This method shows capture radiation when removing radioactive metal cation
Property ion velocity is fast, high adsorption capacity, highly selective, excellent resistance to β and gamma-ray irradiation, high removal rate, low residual volume it is excellent
Point, residual volume reaches the World Health Organization (WHO) water quality standard for drinking water, and can pass through cheap and simple, environmental-friendly side
Method is by [Sn3S7]n 2n-Radioactive metal cation in two-dimensional framework material elutes, for efficiently removing and recycling water ring
Radioactive metal cation in border is of great significance.
[the Sn that the removal of the radioactive metal cation and recovery method are utilized3S7]n 2n-The knot of two-dimensional framework material
Structure is made of tin and sulphur, and component is simply uniform, has strong parent with excellent radioresistance, and to radioactive metal cation
With power and highly selective.
The method for separating and/or extracting radioactive metal cation, which is characterized in that by ion-exchanger
It is placed in the liquid containing radioactive metal cation, contact is no less than 5min at 20~80 DEG C, and the ion-exchanger is caught
Obtain the separation radioactive metal cation;
The radioactive metal cation includes Ra2+、Ba2+、Ni2+、Co2+;
The ion-exchanger, which contains, has two-dimentional electronegativity [Sn3S7]n 2n-The crystalline material of skeleton;
The crystalline material has molecular formula as follows:
R1 xR2 2-xSn3S7·y[H2O]
Wherein, R1、R2Independently selected from least one of organoammonium ions;X=0~2, y >=0.
Optionally, the crystalline material belongs to monoclinic system, space group C2/c, and cell parameter is a=22.5~22.6,
B=13.0~13.1,β=101.2~101.3 °, Z=8.
Optionally, the R1、R2Independently selected from dimethyl ammonium ion, ethylammonium ions, trimethyl ammonium ion at least
It is a kind of.
Optionally, described that there is two-dimentional electronegativity [Sn3S7]n 2n-The crystalline material of skeleton is [Me2NH2]4/3[Me3NH]2/ 3Sn3S7·1.25H2O.Described has two-dimentional electronegativity [Sn3S7]n 2n-The crystalline material of skeleton there is tin and sulphur to form electricity negative
Property two-dimensional layer skeleton structure, be easy to exchange organic amine cation R1、R2Positioned at the feature of the interlayer of two-dimensional layer skeleton.
All Sn atoms are all pentacoordinate in two-dimensional layer microcellular structure, and the trigonal biyramid coordination to form distortion is coordinated with sulphur atom
Configuration, the secondary building unit of composition are [Sn3S7];[Sn3S7] respectively with three [Sn around3S7] mutual by way of total side
Connection is formed in parallel with the face ab bi-dimensional cellular shape extension anion frame structure [Sn3S7]n 2n-, interlamellar spacing is
Wherein, diformazan ammonium ion is expressed as [Me2NH2]+, structural formula are as follows:
Wherein, trimethylammonium ion is expressed as [Me3NH]+, structural formula are as follows:
[Sn above3S7]n 2n-Only herein described [the Sn of the compound of skeleton3S7]n 2n-The typical generation of two-dimensional framework material
Table, herein described [Sn3S7]n 2n-Two-dimensional framework material is not limited to this.The removal and recycling of the radioactive metal cation
[the Sn that method is utilized3S7]n 2n-Its preparation method of two-dimensional framework material is referring to Chinese invention patent, Publication No.
CN104399538。
Optionally, the temperature of the contact is 20~30 DEG C.
Optionally, the temperature of the contact is 25 DEG C.
Optionally, the time of the contact is 5~10min.
Optionally, the ion-exchanger has quick dynamics removal ability to radioactive metal cation,
Reach the adsorption equilibrium to radioactive metal cation in 5min.
Optionally, the ion-exchanger has high adsorbance to radioactive metal cation, to radioactivity Ba2+
(radioactivity226Ra2+The substitute of ion), Ni2+、Co2+For ion, adsorbance respectively reach 289.04mg/g,
83.64mg/g、51.98mg/g。
Optionally, the ion adsorbent has high selectivity to radioactive metal cation, to radioactivity Ba2+From
For son, the removal of radioactive metal cation and recovery method are to Ba in simulated groundwater environment2+It still keeps high
Removal rate and the residual volume for reaching WHO drinking water standard.
Optionally, the radioactive metal cation includes226Ra2+、133Ba2+、63Ni2+、60Co2+。
Optionally, the liquid containing radioactive metal cation is passed through into the ion exchange containing the ion-exchanger
Column, the ion-exchanger capture separate the radioactive metal cation.
Optionally, described that there is two-dimentional electronegativity [Sn3S7]n 2n-The crystalline material of skeleton 200kGy intensity β and
After the gamma-ray irradiation of 200kGy intensity, to the capture rate of radioactive metal cation 99% or more.
Optionally, the ion exchange column uses [Sn3S7]n 2n-Two-dimensional framework material filling, to radioactive metal cation
With excellent removal ability, to Ba2+、Ni2+、Co2+For the mixed aqueous solution of ion is handled, when the mixing of processing
When solution reaches 1100 times of bed volumes, Ba2+、Ni2+、Co2+Still > 99%, residual concentration still reaches WHO to the removal rate of ion
To the standard of drinking water.
Optionally, after the ion-exchanger capture separates the radioactive metal cation, then inorganic salt solution is used
Elution.
Optionally, the inorganic salt solution is KCl aqueous solution.
Optionally, the ion exchange column uses [Sn3S7]n 2n-Two-dimensional framework material filling, exchange radioactive metal sun from
It, can be by cheap and simple, environmental-friendly method by [Sn after son3S7]n 2n-Radioactive metal cation in two-dimensional framework material
It elutes, to exchange Ba2+[Sn after ion3S7]n 2n-For two-dimensional framework material, contained Ba2+Ion can utilize KCl etc.
Inorganic salt solution elutes recycling completely.
Optionally, it includes ion exchange and/or suction that the ion-exchanger capture, which separates the radioactive metal cation,
Attached effect.It is organic amine cation R between the two-dimensional layer skeleton structure of the application intermediate ion exchanger1、R2, with radiogold
Belong to cation and carries out ion exchange;Ion-exchanger is two-dimensional layer microcellular structure, can effectively capture radioactive metal sun
Ion.Ion exchange and suction-operated separate radioactivity to capture133Ba2+Ion (radioactivity226Ra2+The substitution of ion
Object) adsorbance and absorption limit have a significant impact, the physical chemistry work depending on ion-exchanger and radioactive metal cation
With.
The beneficial effect that the application can generate includes:
1) method for separating and/or extracting radioactive metal cation provided herein, this method are removing
When radioactive metal cation, show that capture isotopic ion speed is fast, high adsorption capacity, highly selective, excellent resistance to β and γ
The advantages of x ray irradiation x, high removal rate, low residual volume, residual volume reach the World Health Organization (WHO) water quality standard for drinking water,
And it can be by cheap and simple, environmental-friendly method by [Sn3S7]n 2n-Radioactive metal cation in two-dimensional framework material
It elutes, is of great significance for the radioactive metal cation for efficiently removing and recycling in water environment;
2) method for separating and/or extracting radioactive metal cation provided herein, to radioactive metal
Cation has quick dynamics removal ability, and the adsorption equilibrium to radioactive metal cation is reached in 5min;
3) method for separating and/or extracting radioactive metal cation provided herein, to radioactive metal
Cation has high adsorbance, to radioactivity Ba2+、Ni2+、Co2+For ion, adsorbance is respectively reached
289.04mg/g,83.64mg/g,51.98mg/g;
4) method for separating and/or extracting radioactive metal cation provided herein, to radioactive metal
Cation has high selectivity, to radioactivity Ba2+For ion, in simulated groundwater environment the radioactive metal sun from
The removal of son and recovery method are to Ba2+It still keeps high removal rate and reaches the residual volume of WHO drinking water standard;
5) method for separating and/or extracting radioactive metal cation provided herein utilizes [Sn3S7]n 2n-
The ion exchange column of two-dimensional framework material filling has excellent removal ability to radioactive metal cation, to Ba2+、Ni2 +、Co2+For the mixed aqueous solution of ion is handled, when the mixed solution of processing reaches 1100 times of bed volumes, Ba2+、Ni2 +、Co2+Still > 99%, residual concentration still reaches WHO to the standard of drinking water to the removal rate of ion;
6) method for separating and/or extracting radioactive metal cation provided herein, [Sn3S7]n 2n-Two dimension
It, can be by cheap and simple, environmental-friendly method by [Sn after framework material exchanges radioactive metal cation3S7]n 2n-Two-dimentional bone
Radioactive metal cation in frame material elutes, to exchange Ba2+[Sn after ion3S7]n 2n-Two-dimensional framework material is
Example, contained Ba2+Ion can elute completely recycling using inorganic salt solutions such as KCl.
Detailed description of the invention
Fig. 1 is the X-ray powder diffraction comparison diagram of sample 1# experiment and the simulation of sample 1# mono-crystalline structures in embodiment 1.
Fig. 2 is the exchange kinetics test data of sample 1# removal and recycling radioactive metal cation in embodiment 1,
In (a), (b), (c) be respectively sample 1# removal Ba2+、Ni2+、Co2+The dynamic experiment result of ion.
Fig. 3 is the Adsorption Model test data of sample 1# removal and recycling radioactive metal cation in embodiment 1, wherein
(a) Ba is removed for sample 1#2+The Adsorption Model experimental result of ion;(b) Ni is removed for sample 1#2+、Co2+The absorption mould of ion
Type experimental result.
Fig. 4 is the x-ray photoelectron spectroscopy point of sample 1# removal and recycling radioactive metal cation front and back in example 1
Analysis figure, wherein (a) is that sample 1# removes Ba2+、Ni2+、Co2+The x-ray photoelectron spectroscopy figure of front and back N atom;It (b) is sample 1#
Remove Ba2+、Ni2+、Co2+The x-ray photoelectron spectroscopy figure of S atom in front and back and BaS sample.
Fig. 5 is the distribution coefficient and removal ability test for applying sample 1# removal and recycling radioactive metal cation in example 1,
Wherein (a) be predose after remove Ba2+、Ni2+、Co2+The distribution coefficient of ion;It (b) is removal ability experimental result.
Fig. 6 is that sample 1# simulates ion exchange column to mixing Ba in Application Example 12+、Ni2+、Co2+Solion
Removal rate figure.
Fig. 7 is to apply in example 1 to wash in elution experiments after the ion exchange of sample 1# removal and recycling radioactive metal cation
The energy spectrum diagram of the Ba of de- front and back, wherein (a) is the energy spectrum diagram of sample 1#-Ba;It (b) is the energy spectrum diagram of sample 1#-Ba- elution.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, the raw material in embodiments herein is bought by commercial sources.
Analysis method is as follows in embodiments herein:
Atomic absorption spectrum and inductively coupled plasma atomic emission are filled in Thermo 7400 and XSerise II respectively
Set progress.
Energy dispersion X-ray composes (EDS) test in JEOL JSM-6700F scanning electron microscope and HITACHI FE-SEM
It is carried out on SU8010 machine.
X-ray powder diffraction material phase analysis (XRD) is penetrated in 30kV, the Miniflex II type X in Rigaku company of 15mA
It is carried out on line diffractometer, Cu target, K α radiation source
X-ray photoelectron spectroscopy analysis (XPS) records on ESCALAB 250Xi xps energy spectrum instrument.
The experiment of β x ray irradiation x is to provide the electron beam that energy is 1.2MeV by electron accelerator to irradiate, and gamma-ray irradiation is real
Test be by60The source Co (2.22 × 1015Bq) energy exposure is provided.
Embodiment 1
[Sn3S7]n 2n-The preparation of two-dimensional framework material is real in the Chinese patent application with reference to Publication No. CN104399538
Apply the example 1, [Sn of selection3S7]n 2n-Two-dimensional framework material is compound [Me2NH2]4/3[Me3NH]2/3Sn3S7·1.25H2O, only
For herein described [Sn3S7]n 2n-The Typical Representative of two-dimensional framework material, herein described [Sn3S7]n 2n-Two-dimensional framework material is not
It is confined to this.[Me2NH2]4/3[Me3NH]2/3Sn3S7·1.25H2The synthetic method of O (sample 1#) specifically:
Tin source, sulphur source, dimethylamine agueous solution and water are uniformly mixed by certain molar ratio, sealed after being sufficiently stirred at room temperature
Entering in the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE), certain temperature isothermal reaction is naturally cooling to room temperature afterwards for a period of time,
After sufficiently washing by gained sample filtering and with distilled water, ethyl alcohol, being dry, [Me can be obtained2NH2]4/3[Me3NH]2/3Sn3S7·
1.25H2O (sample 1#).See Table 1 for details for the type and proportion of raw material, reaction temperature and time, yield.
Table 1
Yield=(quality of gained sample 1#) ÷ (molal quantity 3 × product theory of ÷ molecular weight of tin element in tin source) ×
100%.
Sample 1# crystal structure is analyzed using X-ray powder diffraction, as a result as shown in Figure 1, as seen from the figure,
The mono-crystalline structures simulation powder of sample 1# and sample 1# compares preferably, it was demonstrated that synthesis gained sample 1# is pure phase.
Embodiment 2 utilizes [Sn3S7]n 2n-The exchange of the removal of two-dimensional framework material and recycling radioactive metal cationic processes
Kinetic test
Sample 1# is to Ba2+、Ni2+、Co2+The exchange kinetics experiment specific step of ion are as follows: the powder sample 1# after grinding
Respectively to the Ba of certain initial concentration2+、Ni2+、Co2+The aqueous solution of ion is at 25 DEG C, V (liquor capacity): m (exchanger quality)
Under the conditions of=1000mL/g, supernatant measurement wherein ion concentration is taken respectively at regular intervals.As a result as shown in Fig. 2, by
Figure can be seen that sample 1# to Ba2+、Ni2+、Co2+The exchange of ion can reach balance within 5min, and residual volume reaches
Standard of the WHO to drinking water.
Embodiment 3 utilizes [Sn3S7]n 2n-The absorption of the removal of two-dimensional framework material and recycling radioactive metal cationic processes
Model measurement
Sample 1# is to Ba2+、Ni2+、Co2+The Adsorption Model experiment specific step of ion are as follows: 1# pairs of the powder sample after grinding
The Ba of different initial concentrations2+、Ni2+、Co2+Deionized water solution is at 25 DEG C, V (liquor capacity): m (exchanger quality)=1000mL/
It is exchanged under the conditions of g for 24 hours, supernatant liquor and initial soln is taken to measure wherein ion concentration.As a result as shown in figure 3, can be seen by figure
Out, sample 1# is to Ba2+、Ni2+、Co2+The adsorbance of ion can respectively reach 289.04mg/g, 83.64mg/g, 51.98mg/g.
Sample 1# is to Ba2+The adsorbance of ion has reached the 148% of theoretical value.Using x-ray photoelectron spectroscopy to exchange
Ba2+、Ni2+、Co2+Sample 1# before and after ion is analyzed, and as shown in Fig. 4 (a), exchanges Ba2+、Ni2+The N of sample 1# after ion
The characteristic peak of atom disappears, and exchanges Co2+The characteristic peak of the N atom of sample 1# obviously weakens after ion, shows in sample 1#
Organoammonium ions can be by Ba2+、Ni2+Ion complete exchange, by Co2+Ion only partially exchanges;As shown in Fig. 4 (b), Ba is exchanged2+
There is the characteristic peak of apparent BaS in sample 1# after ion, shows the S on sample 1# frame2-To Ba2+There are stronger for ion
Affinity, sample 1# is to Ba2+The presence that is partly due to strong adsorption effect of the adsorbance of ion beyond theoretical value.
Sample 1# can effectively remove radioactivity Ba2+And the radioactive nucleus waste liquid of highly acid reacts generation with container
Radioactivity Ni2+、Co2+, reached to Ba2+Comprehensive removal of radiation pollution;Ba2+Ion has and Ra2+The similar ion of ion
Diameter and ionic exchange characteristics, therefore Ba2+Ion often can be used as the bigger radioactivity Ra of toxicity2+(half-life period is 1600 ± 7 to ion
Year) substitute, therefore it can be proved to Ra2+Effectively remove effect.
Embodiment 4 utilizes [Sn3S7]n 2n-The selection of the removal of two-dimensional framework material and recycling radioactive metal cationic processes
Property removal ability test
Specific experiment step be grinding after powder sample 1# to simulated groundwater solution at 25 DEG C, V (liquor capacity): m
It is exchanged for 24 hours under the conditions of (exchanger quality)=1000mL/g, supernatant liquor and initial soln is taken to measure wherein ion concentration, test
As a result see Table 2 for details:
Table 2
The result shows that (the high concentration K in simulated groundwater environment+、Na+、Ca2+、Mg2+Competing ions presence), sample 1#
To Ba2+The removal rate of ion still reaches 85.93%, and Ba2+The residual concentration of ion reaches WHO to drink down to 0.386ppm
With Ba in water2+The standard (0.7ppm) of ion concentration.
Before and after 5 high intensity radiation of embodiment, [Sn is utilized3S7]n 2n-The removal of two-dimensional framework material and recycling radioactive metal sun
The distribution coefficient and removal ability of ion method are tested
Specific experiment step are as follows: powder sample 1# after grinding and its after 200kGy β or 200kGy gamma-ray irradiation it is right
Ba2+、Ni2+、Co2+The mixed aqueous solution of ion is under the conditions of 25 DEG C, V (liquor capacity): m (exchanger quality)=1000mL/g
Exchange for 24 hours, takes supernatant liquor and initial soln to measure wherein ion concentration.As a result as shown in figure 5, as seen from the figure, sample
1# is after 200kGy β or 200kGy γ irradiation to Ba2+、Ni2+、Co2+Ion still keeps high distribution coefficient (Kd) and removal
Rate illustrates that ion-exchanger provided herein has excellent irradiation stability, after high-intensitive β and gamma-ray irradiation
To radioactivity Ba2+、Ni2+、Co2+Ion still has stronger removal ability and high selectivity.
Embodiment 6 simulates ion exchange column application
Preparing packed heights with about 3.1 grams of sample 1# in the Flash chromatography column that an internal diameter is 13.4 millimeters is 2 centimetres
Ion exchange column.With the Ba of the treatment on ion exchange columns certain volume2+、Ni2+、Co2+Mixed solution is spaced different filtrate volumes
Collect the solution at column outlet, sample detection Ba therein2+、Ni2+、Co2+Ion concentration.
Fig. 6 is to fill 3.1 grams of sample 1#, the Ba of 1100 times of bed volumes of coprocessing in simulation ion exchange column experiments2+、
Ni2+、Co2+Mixed solution, Ba2+、Ni2+、Co2+The removal rate of ion is positively retained at 99% or so, it is notable that works as processing
Mixed solution when being more than 3L, Ba2+、Ni2+、Co2+The removal rate of ion can still respectively reach 99.74%, 99.30%,
99.65%, Ba2+、Ni2+、Co2+The residual concentration of ion can still reach respectively down to 2.33ppb, 6.24ppb, 3.25ppb
Standard of the WHO to drinking water.
Embodiment 7 utilizes [Sn3S7]n 2n-The ion of the removal of two-dimensional framework material and recycling radioactive metal cationic processes
Elution experiments after exchange
Sample 1#20mg obtained in Example 1 is placed in 20mL and contains 3000ppm Ba2+In the aqueous solution of ion, 25
Magnetic agitation for 24 hours, obtains Ba under the conditions of DEG C2+Product after ion exchange is denoted as sample 1#-Ba.Sample 1#-Ba is placed in 0.5M
Magnetic agitation 12h under the conditions of 25 DEG C, obtains Ba in KCl solution2+Product after ion elution is denoted as sample 1#-Ba- elution.It will
Sample 1#-Ba and sample 1#-Ba- elution carries out EDS test, elutes as Fig. 7 is shown by KCl, the barium element in sample 1#-Ba
It is washed away completely.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of method for separating and/or extracting radioactive metal cation, which is characterized in that ion-exchanger to be placed in
In liquid containing radioactive metal cation, contact is no less than 5min, the ion-exchanger capture point at 20~80 DEG C
From the radioactive metal cation;
The radioactive metal cation includes Ra2+、Ba2+、Ni2+、Co2+;
The ion-exchanger, which contains, has two-dimentional electronegativity [Sn3S7]n 2n-The crystalline material of skeleton;
The crystalline material has molecular formula as follows:
R1 xR2 2-xSn3S7·y[H2O]
Wherein, R1、R2Independently selected from least one of organoammonium ions;X=0~2, y >=0.
2. the method according to claim 1, wherein the crystalline material belongs to monoclinic system, space group C2/
C, cell parameter are a=22.5~22.6, b=13.0~13.1, c=β=101.2~101.3 °, Z=
8。
3. application according to claim 1, which is characterized in that the R1、R2Independently selected from dimethyl ammonium ion, ethyl
At least one of ammonium ion, trimethyl ammonium ion.
4. the method according to claim 1, wherein described have two-dimentional electronegativity [Sn3S7]n 2n-The crystalline substance of skeleton
Body material is [Me2NH2]4/3[Me3NH]2/3Sn3S7·1.25H2O。
5. the method according to claim 1, wherein the temperature of the contact is 20~30 DEG C.
6. the method according to claim 1, wherein the time of the contact is 5~10min.
7. the method according to claim 1, wherein the radioactive metal cation includes226Ra2+、133Ba2+
、63Ni2+、60Co2+。
8. the method according to claim 1, wherein described have two-dimentional electronegativity [Sn3S7]n 2n-The crystalline substance of skeleton
Body material exists to the capture rate of radioactive metal cation after the gamma-ray irradiation of the β and 200kGy intensity of 200kGy intensity
99% or more.
9. the method according to claim 1, wherein by the liquid containing radioactive metal cation by containing
The ion exchange column of the ion-exchanger, the ion-exchanger capture separate the radioactive metal cation;
Preferably, it after ion-exchanger capture separates the radioactive metal cation, then is eluted with inorganic salt solution.
10. the method according to claim 1, wherein ion-exchanger capture separation radioactivity133Ba2+Packet
Include ion exchange and suction-operated, capture separation radioactivity63Ni2+、60Co2+It only include ion exchange.
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