CN108380169B - Layered metal sulfide NaInS for removing radionuclide U (VI)2And preparation thereof - Google Patents
Layered metal sulfide NaInS for removing radionuclide U (VI)2And preparation thereof Download PDFInfo
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- CN108380169B CN108380169B CN201810142574.0A CN201810142574A CN108380169B CN 108380169 B CN108380169 B CN 108380169B CN 201810142574 A CN201810142574 A CN 201810142574A CN 108380169 B CN108380169 B CN 108380169B
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- 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
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- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
Abstract
The invention belongs to the technical field of preparation of cation exchangers, and particularly relates to a layered metal sulfide NaInS for removing radionuclides U (VI)2And preparation. NaCl is used as a molten salt system, indium powder, high-purity sulfur and sodium sulfide nonahydrate are used as precursors, and porous metal sulfide NaInS is obtained by roasting at 825 DEG C2. The method is simple and quick, green and environment-friendly, and the precursor is cheap; the NaInS obtained2Due to the large amount of exchangeable Na contained between layers+The material has the advantages of rapid adsorption capacity and high adsorption capacity for radioactive uranyl, wide pH operation range and high tolerance to high salt concentration; the layered metal sulfide NaInS prepared by the preparation method of the invention2Has wide application prospect in the aspect of enriching uranyl.
Description
Technical Field
The invention belongs to the technical field of preparation of cation exchangers, and particularly relates to a layered metal sulfide NaInS for removing radionuclides U (VI)2And preparation.
Background
In the last two decades, 9 nuclear power stations which are put into operation in China generate 470 million tons of spent fuel every year, and the number of the spent fuel in China is estimated to reach 1 million tons and continuously increases at the speed of more than 1000 tons every year in 202012kg, at a concentration of about 3ppb, which can provide thousands of years of nuclear fuel use. At present, ionic Na coexisting in seawater+、Mg2+、Ca2+、Cl-、
、
The adverse factors of complex types, high content and the like restrict the efficiency and the cost of extracting uranium from seawater.
The adsorption method is one of the most suitable methods for extracting uranium from seawater, and the adsorption material with good selectivity and high adsorption efficiency is the best material for extracting uranium from seawater. However, physical surface adsorption and precipitation reduction are limited by surface processes and are easily oxidized by oxidizing agents, hindered and inhibited by contaminants. The adsorption effect of the inorganic ion exchanger depends on the overall properties of the material, the adsorption effect is not limited by surface technology, and the inorganic ion exchanger has better heat resistance, radioactivity resistance, mechanical strength and the like, so that the inorganic ion exchanger has unique advantages in the treatment of radioactive wastes. The traditional ion exchange materials mainly comprising oxides, such as montmorillonite, zeolite, resin and the like, have the problems of low selectivity and easy protonation at low pH value, and have limited adsorption capacity to radionuclides. According to the soft and hard acid-base principle, the sulfur atom is a soft base, and
and
considered as hard cations, these cations are theoretically more prone to combine with sulfur atoms to form strong covalent bonds, and chalcogenides can effectively adsorb u (vi) and sr (ii). At present, only sulfide minerals such as FeS can remove uranyl by the soft ligand, and the main mechanism for removing uranyl is to reduce hexavalent uranyl to form precipitate U3O8However, in order to ensure the efficient removal rate, the surface of the adsorbent of this type needs to be continuously polished, so that the practical application thereof is limited.
In recent years, layered metal chalcogenide A having ion exchange propertiesxMQ2Wherein A is alkali metal ion, M is transition metal of 4, 5, 6 subgroup early, Q is S, Se, Te, because it has low cost, stable in aqueous solution, pH application range is wide, adsorption capacity is high, anti-interference ion ability advantage such as being strong, used for separation enrichment and safe processing research of radionuclide, however these materials are not suitable for the practical application because of unstable easy hydrolysis. Previously reported layered metal sulfide KMS-1 (K)2xMnxSn3-xS6(x ═ 0.5-0.95)) and KMS-2 (K)2xMgxSn3-xS6(x ═ 0.5-1)) has a technical problem that the raw material is complicated, the structure is complicated, the active site is exposed only on the surface, and the adsorption capacity to u (vi) is low.
Therefore, the synthesis of the novel layered metal sulfide with excellent structure and stable surface property is the key for realizing the rapid and efficient removal of the radioactive nuclide in the water body in the complex environment.
Disclosure of Invention
The invention aims to provide a layered metal sulfide NaInS for removing radionuclide U (VI)2The preparation method comprises the following specific technical scheme:
layered metal sulfide NaInS for removing radionuclide U (VI)2From InS with a layered octahedral structure2 -And Na which can be exchanged between layers+The composition and the structure are simple, and the saturated adsorption capacity to U (VI) can reach 863.94mg g-1。
The layered metal sulfide NaInS2The preparation method takes indium powder, sulfur powder and sodium sulfide nonahydrate after vacuum drying as raw materials, takes sodium chloride molten salt as a solid solvent, and is roasted in inert atmosphere; the method specifically comprises the following steps:
(1) vacuum drying sodium sulfide nonahydrate, naturally cooling, and preserving under inert atmosphere;
(2) mixing the sodium sulfide nonahydrate obtained in the step (1) with indium powder, sulfur powder and sodium chloride in an inert atmosphere, grinding, drying and roasting;
(3) the calcined solid powder was washed and dried in vacuo.
The temperature of the sodium sulfide nonahydrate vacuum drying is 100-120 ℃, and the drying time is 6-12 h.
The molar ratio of the sodium sulfide nonahydrate to the indium powder to the sulfur powder to the sodium chloride is (1-2): 1, (2-4): 4.
The roasting temperature is 825-900 ℃ and the roasting time is 4-6 h.
And (3) the detergent is deionized water and ethanol, the drying temperature is 40-60 ℃, and the drying time is 6-12 h.
The inert atmosphere is Ar and N2Or He.
The invention has the beneficial effects that:
(1) the invention provides a layered metal sulfide NaInS2The molten salt synthesis method only takes indium powder, elemental sulfur powder and sodium sulfide as precursors and molten salt sodium chloride as a solid solvent, and the high-temperature roasting is carried out in an inert atmosphere; compared with the traditional wet chemical method, the molten salt method is not limited by water and organic solvents; compared with the preparation of U (VI) adsorbing materials in other seawater, the preparation method is simpler, quicker and more effective, the U (VI) adsorbing materials with uniform size and good dispersibility can be obtained by only one-step reaction, and the method has the advantages of convenient operation, easily obtained raw materials and low production cost, and is beneficial to industrial popularization;
(2) the layered metal sulfide NaInS prepared by the preparation method of the invention2The pure layered metal sulfide has the advantages of uniform nano-particles, good dispersibility, high crystallinity and simple structure, and contains abundant exchangeable Na between layers+Has high capturing and adsorbing capacity for radioactivity U (VI).
(3) The invention provides a layered metal sulfide NaInS2Has high selectivity, large U (VI) adsorption amount, wide pH range and no high concentration Ca2+Interference, simple and controllable operation and the like, and is suitable for the high-efficiency and rapid adsorption of U (VI) in drinking water, seawater and other complex water systems; the problems of low adsorption performance, narrow pH operation range, poor high-concentration brine tolerance and the like of the existing U (VI) adsorption material are solved.
Drawings
FIG. 1 is a drawing of the present inventionExample 1 preparation of the resulting layered Metal sulfide NaInS2A characterization map of the solid powder; wherein, a) is a scanning electron microscope picture, b) is a transmission electron microscope picture, and c) is an X-ray energy dispersion spectrum;
FIG. 2 shows the layered metal sulfide NaInS prepared in example 1 of the present invention2Adsorption of N by solid powder2The adsorption isotherm and pore size distribution diagram of (1), wherein 2-a is the adsorption isotherm map and 2-b is the pore size distribution diagram;
FIG. 3 the layered metal sulfide NaInS prepared in example 1 of the present invention2The solid powder absorbs X-ray diffraction spectrum and infrared spectrum before and after U (VI), wherein 3-a is X-ray diffraction spectrum, and 3-b is infrared spectrum.
FIG. 4 shows the layered metal sulfide NaInS prepared in example 1 of the present invention2Map of adsorption effect on radionuclide U, wherein 4-a is NaInS2Adsorption kinetics curves for U (VI), pH vs. NaInS 4-b2Influence of the adsorption of U (VI), 4-c being Ca2+Concentration pair Kd U(mg/L) Effect of the distribution coefficient, 4-d is the temperature difference, U (VI) in NaInS2Adsorption isotherm above;
FIG. 5 shows the layered metal sulfide NaInS prepared in example 1 of the present invention2A thermodynamic fit curve to the adsorption of radionuclide u (vi);
FIG. 6 shows the layered metal sulfide NaInS prepared in example 1 of the present invention2The performance of adsorbing radioactive nuclides U (VI) in different water systems.
Detailed Description
The invention provides a layered metal sulfide NaInS for removing radionuclide U (VI)2And the preparation, the invention is further explained by combining the attached drawings and the embodiment.
Example 1
Preparation of layered Metal sulfide NaInS2The method comprises the following specific steps:
(1) weighing 0.48g of sodium sulfide nonahydrate, drying at 100 ℃ for 12h by using a vacuum drying oven, and naturally cooling to obtain Na without crystal water2S, in a glove boxStoring under Ar;
(2) na obtained in the step (1)2Grinding and stirring S, 0.126g of indium powder, 0.128g of high-purity sulfur and 0.234 g of sodium chloride in a glove box under an argon atmosphere, and stirring uniformly, wherein H is arranged in the glove box2O、O2The concentration is less than 1ppm, the mixture is placed in a ceramic crucible with the thickness of 7m L,
(3) heating in a tubular furnace at a heating rate of 5 ℃/min, and continuously roasting for 4h at 825 ℃ under the protection of Ar;
(4) naturally cooling the solid powder obtained in the step (3), washing the solid powder with deionized water and ethanol for three times respectively until the supernatant is nearly neutral, and removing impurities; then the mixture is dried in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the light yellow layered metal sulfide NaInS2And (3) solid powder.
FIG. 1-a and FIG. 1-b are respectively a metal sulfide NaInS prepared by the method2Scanning electron micrographs and Transmission electron micrographs of the solid powder from FIGS. 1-a and 1-b show that the NaInS prepared2The dispersion was uniform and no blocky structure was present. FIG. 1-c shows NaInS after U (VI) adsorption2The energy dispersion spectrum of the X-ray can obtain NaInS2Middle and most part of Na+By U (VI), indicating NaInS2Interlayer of Na+An ion exchange reaction with U (VI) takes place.
FIG. 2-a shows the prepared metal sulfide NaInS2N of solid powder2Isothermal adsorption Curve, from 2-a, the metal sulfide NaInS2The specific surface area of the solid powder was 12m2G, much greater than commercial NaInS2Specific surface area of (A), (B)<1.0m2G), is more beneficial to improving NaInS2The contact area with U (VI) promotes the ion exchange reaction and enhances the adsorption performance; FIG. 2-b shows the prepared metal sulfide NaInS2Pore size distribution of solid powder, NaInS can be seen from the figure2The aperture of the solid powder is distributed between 10nm and 100nm, namely, mesopores and macropores exist, and the existence of the composite aperture improves NaInS2Probability of collision and contact with U (VI), and thus into InS2 -Interlaminar, and Na+Ion exchange is performed.
FIGS. 3-a and 3-b show NaInS before and after U (VI) adsorption2X-ray diffraction pattern and infrared spectrum of the solid powder. As can be seen from FIG. 3-a, NaInS was prepared2The crystallinity is good, and no impurity peak exists; after adsorbing U (VI), the (003) interplanar spacing was found to be large, indicating that the U (VI) ions entered the NaInS2Interlamination; and at 924cm from the IR spectrum 3-b-1Can observe [ O ═ U-VI＝O]2+Antisymmetric vibrational peaks, which indicate that U (VI) not only has NaInS2Between layers, also adsorbing NaInS2Of (2) is provided.
Example 2
Detection of the layered Metal sulfide NaInS prepared in example 12The specific operation of the adsorption effect on the radioactive nuclide U (VI) is as follows:
(1) sequentially adding NaInS into a polyethylene centrifugal tube2UO containing radionuclide U (VI)2(NO3)2·6H2O solution and containing Ca2+,Mg2+,K+And Na+An electrolyte solution of plasma;
(2) with 0.4 mol/L NaNO3Adjusting the ionic strength with trace amounts of HNO3Or NaOH solution is used for adjusting the pH value of the system to 4.0;
(3) then fully oscillating the uniformly mixed suspension on an oscillator, and after the suspension is contacted for 12 hours and the adsorption reaches the balance, carrying out centrifugal separation at the rotating speed of 9000rpm so as to separate solid from liquid;
(4) a volume of the supernatant was taken and the concentration of U (VI) in the supernatant was determined by inductively coupled plasma mass spectrometry.
FIG. 4-a is NaInS2Adsorption kinetics curves for U (VI); as can be seen from fig. 4-a, at pH 4.0, u (vi) is at NaInS2The adsorption equilibrium adsorption efficiency reaches 98 percent within the last 30 min.
Under the same operation as described above, the layered metal sulfide NaInS obtained in example 1 was detected2At different pH and different CaCl2The detection results of the change of the adsorption behavior of the radionuclide U under the concentration and different temperatures are respectively shown in FIGS. 4-b, 4-c and 4-d;
4-b is NaInS with different PH pairs2Influence of adsorption U (VI) effect; as can be seen from fig. 4-b, NaInS ranges from PH 4.0 to 9.02The adsorption rate of U (VI) is kept above 80 percent, compared with the traditional oxygen-containing ion exchanger, NaInS2Containing soft basic sites S2-The ligand has weak affinity to hard hydrogen ions in the water body; thus, NaInS2The adsorbent shows better adsorption performance under acidic conditions.
4-c is Ca2+Concentration pair Kd U(mg/L) influence of the distribution coefficient, as can be seen from FIG. 4-c, when the Ca/U molar ratio is 1.5 × 103～6×104Then, NaInS2Exhibits a good distribution coefficient Kd UIs 1.04 × 103-2.32×104I.e. NaInS2Shows to Ca2+Higher tolerance.
4-d are different temperatures, U (VI) in NaInS2Adsorption isotherm above; as can be seen from FIG. 4-d, at 293K, 313K, 333K, NaInS2The saturated adsorption amounts to U (VI) were 699.72 mg g-1、804.44mg g-1、863.94mgg-1That is, increasing the temperature can promote U (VI) in NaInS2Ion exchange of (2); in addition, for NaInS in FIG. 4-d2Performing model fitting on the adsorption isotherms of U (VI) to obtain NaInS2The adsorption to U (VI) conforms to the L angmuir model, which demonstrates NaInS2The active sites on the surface are adsorbed equally to U (VI) and belong to monolayer adsorption.
To U (VI) in NaInS2Performing thermodynamic fitting on the ion exchange solution, and specifically obtaining U (VI) in NaInS as shown in FIG. 52The above ion exchange process belongs to spontaneous endothermic reaction, so that U (VI) can be promoted in NaInS under high temperature condition2Ion exchange of (A) with U (VI) and NaInS2The interaction provides a thermodynamic basis.
Therefore, the layered metal sulfide NaInS prepared by the preparation method2The adsorption rate to the radionuclide U reaches 98 percent, the adsorption rate in a wider PH range of 4.0-9.0 can reach more than 80 percent, and the adsorption rate is not influencedCa with higher content of electrolyte cation in water2+The method has the advantages of obvious adsorption effect, wide applicable environment and few interference factors.
Example 3
The layered metal sulfide NaInS prepared in example 12The adsorption experiment device is used for adsorption experiments of ultrapure water, tap water and seawater polluted by radioactive wastewater uranyl.
Wherein the ultrapure water is a water system with almost completely removed conductive electrolyte at 25 deg.C, the resistivity reaches 18.25M Ω cm, the drinking water is obtained from drinking water, and is directly used in adsorption experiment without filtration, the seawater is obtained from water area near six horizontal islands in Zhoushan city, Zhejiang province, and the operation is carried out by respectively polluting the above solutions with 30ppb uranyl, and adding 1.0 g/L of NaInS2After stirring for 24 hours, the supernatant was assayed for the concentration of U (VI) by the same method as in example 1.
The results of detection of the electrolyte cations and the change in pH before and after the ultrapure water, the tap water, and the seawater are shown in table 1:
TABLE 1U (VI) in ultrapure water, contaminated Drinking Water and seawater in NaInS2Upper adsorption experiment
Different water systems to U (VI) in NaInS2The effect of the adsorption is shown in FIG. 6. it can be seen from FIG. 6 that Na contained in various electrolyte cations+、K+、Mg2+And Ca2+In the complex water system of (1), NaInS2The adsorption capacity to U (VI) is still kept high, and the method has potential industrial application value.
Claims (6)
1. Layered metal sulfide NaInS for removing radionuclide U (VI)2The method for preparing (1) is characterized in that,
the preparation method comprises the steps of roasting indium powder, sulfur powder and vacuum-dried sodium sulfide nonahydrate serving as raw materials in an inert atmosphere by using sodium chloride molten salt as a solid solvent; the method specifically comprises the following steps:
(1) drying sodium sulfide nonahydrate in vacuum, and preserving under inert atmosphere;
(2) mixing the sodium sulfide nonahydrate obtained in the step (1) with indium powder, sulfur powder and sodium chloride in an inert atmosphere, grinding, drying and roasting;
(3) washing the roasted solid powder, and drying in vacuum;
the NaInS2From InS with a layered octahedral structure2 -And Na which can be exchanged between layers+And (4) forming.
2. The method as claimed in claim 1, wherein the temperature for vacuum drying of the sodium sulfide nonahydrate is 100-120 ℃ and the drying time is 6-12 h.
3. The preparation method according to claim 1, wherein the molar ratio of the sodium sulfide nonahydrate to the indium powder to the sulfur powder to the sodium chloride is (1-2: 1 (2-4): 4.
4. The preparation method as claimed in claim 1, wherein the calcination temperature is 825-900 ℃ and the calcination time is 4-6 h.
5. The preparation method according to claim 1, wherein the detergent in the step (3) is deionized water or ethanol, the drying temperature is 40-60 ℃, and the drying time is 6-12 h.
6. The method according to claim 1, wherein the inert atmosphere is Ar or N2Or He.
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| JP2004008922A (en) * | 2002-06-06 | 2004-01-15 | Japan Science & Technology Corp | Visible light responsive sulfide photocatalyst for producing hydrogen from water |
| CN101054198A (en) * | 2007-05-17 | 2007-10-17 | 上海交通大学 | Method for preparing monodisperse ternary sulfide CuInS2 |
| CN102229470A (en) * | 2011-04-15 | 2011-11-02 | 河南大学 | Method of preparing CuInS2 film by wet chemical process |
| CN105271372A (en) * | 2015-10-27 | 2016-01-27 | 南昌航空大学 | Method for preparing one-dimensional disc-shaped nano indium sulfide particles with organic molten salt method |
| CN106145182A (en) * | 2015-03-18 | 2016-11-23 | 陈莹 | A kind of NaInS2nanometer sheet acanthosphere |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004008922A (en) * | 2002-06-06 | 2004-01-15 | Japan Science & Technology Corp | Visible light responsive sulfide photocatalyst for producing hydrogen from water |
| CN101054198A (en) * | 2007-05-17 | 2007-10-17 | 上海交通大学 | Method for preparing monodisperse ternary sulfide CuInS2 |
| CN102229470A (en) * | 2011-04-15 | 2011-11-02 | 河南大学 | Method of preparing CuInS2 film by wet chemical process |
| CN106145182A (en) * | 2015-03-18 | 2016-11-23 | 陈莹 | A kind of NaInS2nanometer sheet acanthosphere |
| CN105271372A (en) * | 2015-10-27 | 2016-01-27 | 南昌航空大学 | Method for preparing one-dimensional disc-shaped nano indium sulfide particles with organic molten salt method |
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