CN114956172B - Magnesium vanadate adsorbent for targeting strontium ions and cesium ions, and preparation method and application thereof - Google Patents

Magnesium vanadate adsorbent for targeting strontium ions and cesium ions, and preparation method and application thereof Download PDF

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CN114956172B
CN114956172B CN202210548604.4A CN202210548604A CN114956172B CN 114956172 B CN114956172 B CN 114956172B CN 202210548604 A CN202210548604 A CN 202210548604A CN 114956172 B CN114956172 B CN 114956172B
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adsorbent
strontium
cesium
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CN114956172A (en
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李柔遊
杨赞禾
韩昌明
潘健玉
张衡
王欣鹏
叶海梅
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Guangxi University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/006—Radioactive compounds
    • 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

Abstract

The invention provides a magnesium vanadate adsorbent targeting strontium ions and cesium ions, and a preparation method and application thereof, and belongs to the technical field of adsorption materials. Adding water into vanadium pentoxide, stirring and fully mixing, and then adding hydrogen peroxide for dissolution to obtain a solution A; dissolving magnesium acetate tetrahydrate in water, slowly adding the solution A, stirring while adding, transferring to a reaction kettle for hydrothermal reaction at 120-180 ℃ for 12-24 hours; and taking out and centrifuging after the hydrothermal reaction is finished, and drying to obtain the magnesium vanadate adsorbent targeting strontium ions and cesium ions. The method provided by the invention is simple and convenient to operate, and the prepared magnesium vanadate adsorbent has good adsorption performance on strontium ions and cesium ions in the radioactive nuclear wastewater.

Description

Magnesium vanadate adsorbent for targeting strontium ions and cesium ions, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of adsorption materials, and particularly relates to a magnesium vanadate adsorbent for targeting strontium ions and cesium ions.
Background
The radioactive elements are derived from human radioactive wastes from nuclear power plants and reprocessing, spent fuel, nuclear weapons, wherein 137 Cs and 90 sr is a common and most dangerous radionuclide, and their half-life is as long as about 30 years. For example, in Fudawn nuclear power accident, the radioactive strontium and cesium in underground seeping water are measured to be seriously out of standard, but the concentration of the element strontium and cesium is extremely low, and the concentration of coexisting sodium ions is up to about 10 4 ppm, and alsoContains Cl, K, ca, mg, fe, ni, al ions and other impurity components, and increases the treatment difficulty of wastewater. Therefore, efficient selective removal of extremely low concentrations of the radioactive elements strontium, cesium from highly salty wastewater of extremely complex and diverse composition and properties is a key to technical development. The method for removing the radionuclide Sr/Cs comprises chemical precipitation, solvent extraction, membrane treatment, biological treatment and adsorption. The method for treating radioactive wastewater by adsorption has the advantages of simple process, high removal rate, low cost and high decontamination coefficient.
Chinese patent application 201610832559.X proposes a method for preparing a hybrid membrane for removing strontium ions from radioactive wastewater. Adding a chitosan-epichlorohydrin crosslinked product and a metallic titanium-based precursor into a polyvinyl alcohol aqueous solution to obtain a coating solution, coating the coating solution on a support to obtain a membrane, separating the membrane from the support, and drying to obtain a hybrid membrane without the support, or separating the membrane from the support and drying to obtain a hybrid membrane with the support; or dissolving the film coating liquid with a solvent, and then coating the film on the support to obtain a film, and separating the film from the support to obtain the hybrid film without the support. The hybrid membrane prepared by the method has the advantages of low adsorption capacity, complicated operation process, incomplete strontium ion treatment, limited application value and difficulty in meeting the actual requirements of large-scale industrial radioactive wastewater treatment.
Chinese patent application 201510880941.3 proposes a method for preparing a magnetic cesium ion adsorbent, comprising the steps of: A. preparing amino ferroferric oxide; B. mixing the carboxylated crown ether derivative with a condensing agent to obtain a first mixture; C. placing the first mixture into a solvent, stirring, adding amino ferroferric oxide into the solvent, and reacting for 1h at 40-80 ℃ to obtain a second mixture; wherein the solvent is used for dissolving the carboxylated crown ether derivative and the condensing agent; D. and carrying out solid-liquid separation on the second mixture to obtain a first solid phase, and cleaning and drying the first solid phase to obtain the cesium ion adsorbent. The magnetic cesium ion adsorbent prepared by the method has low adsorption capacity, complex operation process and limited application value, and is difficult to meet the actual requirements of large-scale industrial radioactive wastewater treatment.
Chinese patent application 201510263702.3 proposes an iron-based nano alloy and application thereof in cesium adsorption, wherein a liquid-phase chemical reduction method is used for preparing a ferrophosphorus nano alloy material, and the ferrophosphorus nano alloy material has the characteristics of simple preparation process, acid resistance, radiation resistance and easy recovery. But has lower adsorption capacity and limited application value, and is difficult to meet the actual requirements of large-scale industrialized radioactive wastewater treatment.
Vanadate is a layered compound, based on VO 6 The octahedron has shared edges, and the interlayer is composed of exchangeable charge compensation ions, so that the layered vanadate is more stable under the acidic condition. And has better chemical stability and thermal stability compared with organic resin. However, many inorganic ion adsorbents at present have many problems such as low adsorption capacity, slow equilibrium time and weak selectivity.
Therefore, the vanadate adsorbent with high efficiency and large capacity is developed, and has high application value for treating strontium and cesium in radioactive wastewater.
Disclosure of Invention
The invention aims to provide a target strontium ion and cesium ion adsorption material, a preparation method and application thereof, wherein the target strontium ion/cesium ion can effectively adsorb strontium ions and cesium ions from radioactive nuclear wastewater, solid-liquid separation is easy, and meanwhile, the preparation method has the advantages of simple steps and convenience in operation.
In order to achieve the above object, the present invention provides a method for preparing a magnesium vanadate adsorbent targeting strontium ions and cesium ions, comprising the steps of:
(1) Adding water into vanadium pentoxide, stirring and dissolving, and adding 30% of hydrogen peroxide by mass fraction for dissolving to obtain a solution A;
(2) Dissolving magnesium acetate tetrahydrate in water, slowly adding the solution A, stirring while adding, transferring to a reaction kettle for hydrothermal reaction at 120-180 ℃ for 12-24 hours; and taking out and centrifuging after the hydrothermal reaction is finished, and drying to obtain the magnesium vanadate adsorbent targeting strontium ions and cesium ions.
As a preferred technical scheme, the molar ratio of vanadium pentoxide, water and hydrogen peroxide in the step (1) is 1-4:0.8889:0.0039.
as the optimization of the technical scheme, in the step (1), a magnetic stirrer is adopted for stirring, the speed is 100-200r/min, and the stirring time is 30-60min.
As a preferred technical scheme, the molar ratio of magnesium acetate tetrahydrate to water in the step (2) is 1:0.5555-1.
As the optimization of the technical scheme, in the step (2), a magnetic stirrer is adopted for stirring, the speed is 200-300r/min, and the stirring time is 0.5-1h.
As a preference of the technical scheme, the reaction time in the oven in the step (2) is 12-24 h.
As the optimization of the technical scheme, the rotating speed of the centrifugal machine in the centrifugal process in the step (2) is 5000-8000r/min, and the centrifugal time is 10-20min.
As the optimization of the technical scheme, the drying temperature in the step (2) is 70-80 ℃ and the drying time is 10-12h.
The magnesium vanadate adsorbent targeting strontium ions and cesium ions, which is obtained by adopting the preparation method, has the characteristics of high efficiency, large capacity and selective adsorption.
The magnesium vanadate adsorbent for targeting strontium ions and cesium ions can be applied to strontium ion and cesium ion adsorption.
The magnesium vanadate adsorbent of the invention adsorbs strontium ions, the magnesium vanadate adsorbent of targeted strontium ions and cesium ions is added into a strontium ion solution with the concentration of 50-500mg/L, the pH value is adjusted to 2, and the magnesium vanadate adsorbent adsorbs 25-120min at normal temperature; the adding amount of the adsorbent is 1-2g of the adsorbent per liter of the strontium ion solution.
The magnesium vanadate adsorbent of the invention adsorbs cesium ions, wherein the magnesium vanadate adsorbent of targeted strontium ions and cesium ions is added into cesium ion solution with the concentration of 50-500mg/L, the pH value is adjusted to 4, and the cesium ion solution is adsorbed for 5-30min at normal temperature; the amount of the adsorbent added is 1-2g of adsorbent per liter of cesium ion solution.
The principle of the invention is as follows: firstly, dissolving vanadium pentoxide by utilizing hydrogen peroxide, then slowly dripping a magnesium acetate tetrahydrate solution into the solution, inserting magnesium ions and water molecules between the vanadium pentoxide layers, expanding the interlayer spacing, putting a magnesium vanadate adsorption material targeting strontium ions and cesium ions into nuclear discharge wastewater, combining the strontium ions and the cesium ions into the material through electrostatic action and ion exchange, and eluting the magnesium vanadate adsorption material after adsorbing the cesium ions by using a sodium chloride solution to achieve the purpose of cesium ions.
The invention has the following beneficial effects:
1. the raw materials of the invention have rich sources, low price and certain economic advantages, and the preparation method is simple, the operation difficulty is low and the danger is low; the experimental raw materials and byproducts adopted in the invention have low harm to human bodies and environment, and are environment-friendly.
2. The magnesium vanadate adsorbent for targeting strontium ions and cesium ions can adsorb more than 250mg/g of strontium ions and cesium ions, and can adsorb cesium ions quickly, saturated adsorption can be realized in a shorter time of 5 minutes, and the adsorption selectivity to cesium ions is strong.
3. The magnesium vanadate adsorbent for targeting strontium ions and cesium ions can effectively adsorb strontium ions and cesium ions from radioactive nuclear wastewater, and is easy for solid-liquid separation. And the magnesium vanadate adsorbent after cesium ion adsorption can be regenerated through 5 times of circulation, and has the advantages of economy and high efficiency.
4. The magnesium vanadate adsorbent disclosed by the invention is used for treating Sr in polluted water bodies under different environments 2+ And Cs + The removal rate can reach more than 95%, and the applicability is wide.
Drawings
FIG. 1 is an XRD pattern of a strontium ion-and cesium ion-targeted magnesium vanadate adsorbent obtained in example 1.
FIG. 2 is a TG-DSC analysis of magnesium vanadate adsorbent targeting strontium ions and cesium ions obtained in example 1.
FIG. 3 is a surface SEM image of the magnesium vanadate adsorbent of example 1 before it is not adsorbed.
FIG. 4 is a surface energy spectrum (EDS) of the magnesium vanadate adsorbent of example 1 before adsorption.
Fig. 5 is a surface SEM image of the magnesium vanadate adsorbent of example 1 after adsorption of strontium ions.
FIG. 6 is a surface energy spectrum (EDS) of the magnesium vanadate adsorbent of example 1 after adsorption of strontium ions.
Fig. 7 is a surface SEM image of the magnesium vanadate adsorbent in example 1 after cesium ions are adsorbed.
FIG. 8 is a surface energy spectrum (EDS) of the magnesium vanadate adsorbent of example 1 after cesium ions are adsorbed.
FIG. 9 is a graph showing the relationship between pH and the adsorption capacity of magnesium vanadate adsorbent for strontium ions in example 1.
FIG. 10 is a graph showing the relationship between pH and cesium ion adsorption capacity of magnesium vanadate adsorbent in example 1.
FIG. 11 is a graph of contact time versus adsorption capacity of magnesium vanadate adsorbent for strontium ions in example 1.
FIG. 12 is a graph showing the relationship between the contact time and the adsorption capacity of cesium ions by the magnesium vanadate adsorbent in example 1.
FIG. 13 is a graph of initial concentration versus adsorption capacity of magnesium vanadate adsorbent for strontium ions in example 1.
FIG. 14 is a graph of initial concentration versus cesium ion adsorption capacity of magnesium vanadate adsorbent in example 1.
FIG. 15 is the effect of coexistence of competing cations on adsorption of strontium cesium ions by magnesium vanadate adsorbent in example 1.
FIG. 16 shows the removal rate of the magnesium vanadate adsorbent in example 1 for adsorbing strontium cesium ions in four different water bodies.
FIG. 17 is a graph showing the analysis efficiency of magnesium vanadate adsorbent against cesium ions by using different analysis solutions in example 1.
FIG. 18 is a graph showing the relationship between the number of cycles of cesium ion adsorption by the magnesium vanadate adsorbent and the adsorption capacity and analysis efficiency in example 1.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention. The present invention will be described in detail by examples.
Example 1
The preparation method of the magnesium vanadate adsorbent for targeting strontium ions and cesium ions comprises the following steps:
1) 2mmol of vanadium pentoxide was mixed with 16mL of deionized water, stirred for 30min using a magnetic stirrer (rotation speed 100 r/min), and dissolved by adding 4mL of hydrogen peroxide (30% mass fraction).
2) 1mmol of magnesium acetate tetrahydrate is dissolved in 10mL of water, and then the solution is slowly dripped into hydrogen peroxide to dissolve vanadium pentoxide solution by using a rubber head dropper, and the solution is stirred for 60min by using a magnetic stirrer (rotating speed is 200 r/min) while dripping. Transferring the mixture to a polytetrafluoroethylene-lined reaction kettle, reacting at 180 ℃ for 24 hours, taking out and centrifuging (the rotating speed is 8000 r/min) for 10 minutes, and drying at 70 ℃ for 12 hours to obtain the magnesium vanadate adsorbent targeting strontium ions and cesium ions.
Example 2
The preparation method of the magnesium vanadate adsorbent for targeting strontium ions and cesium ions comprises the following steps:
1) 1mmol of vanadium pentoxide was mixed with 16mL of deionized water, stirred for 60min using a magnetic stirrer (rotation speed 100 r/min), and dissolved by adding 4mL of hydrogen peroxide (30% mass fraction).
2) 2mmol of magnesium acetate tetrahydrate was dissolved in 10mL of water, and the solution was slowly dropped into the solution 1) by a rubber head dropper, and stirred with a magnetic stirrer (rotation speed 300 r/min) for 30min. Transferring the mixture to a polytetrafluoroethylene-lined reaction kettle, reacting at 160 ℃ for 48 hours, taking out and centrifuging (the rotating speed is 5000 r/min) for 20 minutes, and drying at 70 ℃ for 12 hours to obtain the magnesium vanadate adsorbent targeting strontium ions and cesium ions.
Example 3
The preparation method of the magnesium vanadate adsorbent for targeting strontium ions and cesium ions comprises the following steps:
1) 3mmol of vanadium pentoxide was mixed with 16mL of deionized water, stirred for 30min using a magnetic stirrer (rotation speed 200 r/min), and dissolved by adding 4mL of hydrogen peroxide (30% mass fraction).
2) 3mmol of magnesium acetate tetrahydrate was dissolved in 10mL of water, and the solution was slowly dropped into the solution 1) by a rubber head dropper, and stirred with a magnetic stirrer (rotation speed 300 r/min) for 45min. Transferring the mixture to a polytetrafluoroethylene-lined reaction kettle, reacting at 200 ℃ for 48 hours, taking out and centrifuging (the rotating speed is 6000 r/min) for 15 minutes, and drying at 80 ℃ for 10 hours to obtain the magnesium vanadate adsorbent targeting strontium ions and cesium ions.
Example 4
The preparation method of the magnesium vanadate adsorbent for targeting strontium ions and cesium ions comprises the following steps:
1) 2mmol of vanadium pentoxide was mixed with 16mL of deionized water, stirred for 45min using a magnetic stirrer (rotation speed 200 r/min), and dissolved by adding 4mL of hydrogen peroxide (30% mass fraction).
2) 4mmol of magnesium acetate tetrahydrate was dissolved in 10mL of water, and the solution was slowly dropped into the solution 1) by a rubber head dropper, and stirred with a magnetic stirrer (rotation speed 250 r/min) for 45min. Transferring the mixture to a polytetrafluoroethylene-lined reaction kettle, reacting at 150 ℃ for 24 hours, taking out and centrifuging (the rotating speed is 8000 r/min) for 10 minutes, and drying at 80 ℃ for 10 hours to obtain the magnesium vanadate adsorbent targeting strontium ions and cesium ions.
Example 5
The preparation method of the magnesium vanadate adsorbent for targeting strontium ions and cesium ions comprises the following steps:
1) 3mmol of vanadium pentoxide was mixed with 16mL of deionized water, stirred for 45min using a magnetic stirrer (rotation speed 150 r/min), and dissolved by adding 4mL of hydrogen peroxide (30% mass fraction).
2) 1mmol of magnesium acetate tetrahydrate was dissolved in 10mL of water, and the solution was slowly dropped into the solution 1) by a rubber head dropper, and stirred with a magnetic stirrer (rotation speed 250 r/min) for 30min. Transferring the mixture to a polytetrafluoroethylene-lined reaction kettle, reacting at 180 ℃ for 32 hours, taking out and centrifuging (the rotating speed is 5000 r/min) for 20 minutes, and drying at 75 ℃ for 11 hours to obtain the magnesium vanadate adsorbent targeting strontium ions and cesium ions.
Example 6
The preparation method of the magnesium vanadate adsorbent for targeting strontium ions and cesium ions comprises the following steps:
1) 1mmol of vanadium pentoxide was mixed with 16mL of deionized water, stirred for 60min using a magnetic stirrer (rotation speed 150 r/min), and dissolved by adding 4mL of hydrogen peroxide (30% mass fraction).
2) 4mmol of magnesium acetate tetrahydrate was dissolved in 10mL of water, and the solution was slowly dropped into the solution 1) by a rubber head dropper, and stirred with a magnetic stirrer (rotation speed 200 r/min) for 45min. Transferring the mixture to a polytetrafluoroethylene-lined reaction kettle, reacting at 200 ℃ for 48 hours, taking out and centrifuging (the rotating speed is 5000 r/min) for 10 minutes, and drying at 75 ℃ for 11 hours to obtain the magnesium vanadate adsorbent targeting strontium ions and cesium ions.
And (3) material performance detection:
1. the magnesium vanadate adsorbent targeting strontium ions and cesium ions obtained in example 1 was subjected to X-ray spectroscopy to obtain fig. 1. From fig. 1, it can be seen that the sample obtained by the hydrothermal reaction is different from any reactant before the reaction, which shows that a new magnesium vanadate material is formed after intercalation of magnesium ion into vanadium pentoxide.
2. Thermogravimetric analysis was performed on the magnesium vanadate adsorbent targeting strontium ions and cesium ions obtained in example 1 to obtain TG-DSC analysis chart 2. As can be seen from fig. 2, 9.764% mass loss occurs at room temperature to 100 ℃, which can be attributed to loss of adsorbed water on the sample surface, 6.678% mass loss occurs between 100 ℃ and 400 ℃, due to loss of structural water or crystallization inside the magnesium vanadate adsorbent.
3. Adsorption experiment of strontium ion and cesium ion
(1) PH experiment
Sr is regulated by hydrochloric acid and sodium hydroxide 2+ And Cs + The pH of the solution, 0.01g of the magnesium vanadate adsorbent of the invention was weighed in this experiment and added to 10mL of 10, 500mg/L Sr with pH of 2, 3, 4, 5, 6, 7, 8, 9, 10, respectively 2+ And Cs + In solution, the effect of pH was investigated. Adsorption conditions: the temperature is 25 ℃, the adsorption time is 2 hours, and the oscillation rate is 120r/min.
Experiments at different pH values were recorded in table 1 and generated in fig. 9: fig. 10, which is a graph of pH versus adsorption capacity of magnesium vanadate adsorbent for adsorbing strontium ions: the pH is plotted against the adsorption capacity of the magnesium vanadate adsorbent for cesium ions.
TABLE 1 adsorption amount of strontium ions and cesium ions by magnesium vanadate adsorbents at different pH values
As is clear from table 1, fig. 8 and fig. 9, the magnesium vanadate adsorbent showed the maximum adsorption amount of strontium ions at ph=2, which is as high as 258.79mg/g, and the adsorption capacities of strontium ions at other pH values were not very different. The magnesium vanadate adsorbent has the maximum cesium ion adsorption capacity at the pH value of=4, can reach 266.55mg/g, and has higher adsorption performance in a wide range of pH values of=3-10.
(2) Adsorption time
The experiment respectively measures 0.01g of magnesium vanadate adsorbent and adds the magnesium vanadate adsorbent into 10mL of Sr with 500mg/L 2+ And Cs + In the solution, the adsorption of magnesium vanadate on Sr is explored under the conditions of 30s, 1min, 1.5min, 2min, 3min, 4min, 5min, 10min, 30min, 60min and 120min 2+ And Cs + Is a natural gas, and is an adsorption effect of the catalyst. Adsorption kinetics models are also discussed. Sr (Sr) 2+ Adsorption conditions of (2): ph=2, cs + Adsorption conditions of (2): ph=4, temperature 25 ℃, and oscillation rate 120r/min, giving fig. 11 and 12.
As shown in fig. 11, the adsorption equilibrium time for the magnesium vanadate adsorbent to adsorb strontium ions was 1h, and as shown in fig. 12, the adsorption equilibrium time for adsorbing cesium ions was 5min.
(3) Initial concentration
In the experiment, 0.01g of magnesium vanadate adsorbent is respectively weighed and added into 10mL of Sr2+ and Cs+ solutions with initial concentrations of 50mg/L, 100mg/L, 150mg/L, 200mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L and 800mg/L respectively, the influence of the initial concentrations is explored, and a temperature-equivalent adsorption model is studied. Adsorption conditions of sr2+: ph=2, cs + Adsorption conditions of (2): ph=4, temperature 25 ℃, and oscillation rate 120r/min, giving fig. 13 and 14.
As can be seen from fig. 13, as the initial concentration of strontium ions increases, the adsorption capacity of magnesium vanadate continues to increase, and after that, the adsorption capacity increases slowly. As can be seen from fig. 14, the adsorption capacity of cesium ions also increases with the initial concentration, and eventually reaches the adsorption equilibrium, and the isotherm is used to investigate the maximum adsorption capacity.
(4) Co-existing ion competitive adsorption
For Sr 2+ And Cs + Adsorption exploration in other coexisting ion solutions is performed to help understand the Sr of different ion pairs 2+ And Cs + Is a competitive adsorption effect of (a). In the experiment, 0.01g of magnesium vanadate adsorbent is respectively weighed and added into Na with the coexisting ion concentration of 1mmol/L + 、K + 、Ca 2+ 、Mg 2+ 、Cu 2+ 、Zn 2+ 、Mn 2+ 、Sr 2+ 、Cs + Is a solution of (a) and (b). Adsorption conditions: ph=4, temperature 25 ℃, solution volume 10mL, shake rate 120r/min, giving fig. 15.
As can be seen from FIG. 15, the partition coefficient of magnesium vanadate to cesium ions in the mixed solution of plural competing ions was 10 4 Above, this indicates that it shows extremely high selectivity for cesium ions in solution. Thus, in systems where there are a variety of contaminants ex vivo, the adsorbents of the present invention preferentially adsorb cesium ions.
(5) Real water body
The experiment adopts four different water bodies of laboratory pure water, tap water, lake water and sea water to respectively prepare 10mg/L Sr 2+ And Cs + A solution. Adsorption conditions: the temperature was 25℃and the solution volume was 10mL, and the shaking rate was 120r/min, giving FIG. 16.
From fig. 16, it is clear that the magnesium vanadate adsorbent can achieve a removal rate of 95% or more for any contaminated water body.
(6) Cyclic regeneration experiments
The regeneration of the adsorbent refers to that on the premise that the original structure is not destroyed, the ions on the surface of the adsorbent are released into the solution by a physical or chemical method, and the adsorption performance of the adsorbent is recovered. The desorbing agent adopted in the experiment is hydrochloric acid solution, sodium chloride solution, EDTA-2Na solution and the like with a certain concentration. Specifically, up water, 0.01mol/L and 0.015mol/L HCl solution, 0.05mol/L and 0.01mol/L EDTA-2Na solution, and 2mol/L and 5mol/L sodium chloride solution were used to obtain FIG. 17.
As is clear from FIG. 17, the 5mol/L sodium chloride solution had the best resolution, and reached a resolution of 99.58%. Therefore, the solution is selected as the subsequent adsorption pair resolving agent, the resolving rate is above 90%, and the adsorption capacity still maintains higher performance after 5 times of circulation, as shown in fig. 18.
4. The adsorption material which does not adsorb strontium ions and cesium ions, the material which adsorbs strontium ions and the material which adsorbs cesium ions are all observed by using a Scanning Electron Microscope (SEM), and the obtained microscopic morphologies are respectively shown in figure 3 and figure 5, and the microscopic morphologies of the material after adsorbing strontium ions are basically maintained unchanged and are relatively stable.
5. The energy spectrum detection of the adsorption material which does not adsorb strontium ions and cesium ions, the material which adsorbs strontium ions and the material which adsorbs cesium ions is carried out to obtain fig. 6-8, and it is known that strontium cesium ions are uniformly distributed on the surface of the magnesium vanadate adsorbent after adsorbing strontium ions and cesium ions, and radioactive strontium cesium ions are not separated from the adsorbent in the high-speed centrifugal separation process.

Claims (7)

1. The application of the magnesium vanadate adsorbent for targeting strontium ions and cesium ions in the adsorption of the strontium ions and the cesium ions is characterized in that the preparation method of the magnesium vanadate adsorbent comprises the following steps:
(1) Adding water into vanadium pentoxide, stirring and dissolving, and adding 30% of hydrogen peroxide by mass fraction for dissolving to obtain a solution A; the molar ratio of the vanadium pentoxide to the water to the hydrogen peroxide is 1-4:0.8889: 0.0039;
(2) Dissolving magnesium acetate tetrahydrate in water, slowly adding the solution A, stirring while adding, transferring to a reaction kettle for hydrothermal reaction at 120-180 ℃ for 12-24 hours; and taking out and centrifuging after the hydrothermal reaction is finished, and drying to obtain the magnesium vanadate adsorbent targeting strontium ions and cesium ions.
2. The use of magnesium vanadate adsorbent for targeting strontium ions and cesium ions according to claim 1, wherein in step (1), a magnetic stirrer is used for stirring at a speed of 100-200r/min and for a stirring time of 30-60min.
3. Use of a magnesium vanadate adsorbent targeting strontium and cesium ions according to claim 1, for the adsorption of strontium and cesium ions, characterized in that: in the step (2), the molar ratio of the magnesium acetate tetrahydrate to the water is 1:0.5555-1.
4. The use of magnesium vanadate adsorbent for targeting strontium ions and cesium ions according to claim 1, wherein in step (2), a magnetic stirrer is used for stirring at a speed of 200-300r/min for 0.5-1h; the rotation speed of the centrifugal machine is 5000-8000r/min in the centrifugal process, and the centrifugal time is 10-20min; the drying temperature is 70-80 ℃ and the drying time is 10-12h.
5. The method of any one of claims 1-4 to provide a magnesium vanadate adsorbent targeted to strontium ions and cesium ions, wherein the adsorbent is characterized by sea urchin shape.
6. The use of the magnesium vanadate adsorbent for targeting strontium ions and cesium ions in the adsorption of strontium ions and cesium ions according to claim 1, wherein the magnesium vanadate adsorbent for targeting strontium ions and cesium ions is added into a strontium ion solution with the concentration of 50-500mg/L, the pH value is adjusted to 2, and the magnesium vanadate adsorbent is adsorbed for 25-120min at normal temperature; the adding amount of the adsorbent is 1-2g of the adsorbent per liter of the strontium ion solution.
7. The use of magnesium vanadate adsorbent for targeting strontium ions and cesium ions in the adsorption of strontium ions and cesium ions according to claim 1, wherein the magnesium vanadate adsorbent for targeting strontium ions and cesium ions is added into cesium ion solution with the concentration of 50-500mg/L, the pH value is adjusted to 4, and the adsorption is carried out for 5-30min at normal temperature; the amount of the adsorbent added is 1-2g of adsorbent per liter of cesium ion solution.
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CN106830078A (en) * 2017-02-28 2017-06-13 嘉兴学院 A kind of vanadic anhydride micron order film and preparation method thereof
CN109809485A (en) * 2018-12-13 2019-05-28 南京林业大学 A kind of height ratio capacity hydration vanadic acid magnesium and the preparation method and application thereof
CN112093821A (en) * 2020-09-16 2020-12-18 黑龙江大学 Preparation method of spinel magnesium vanadate microspheres

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015129941A1 (en) * 2014-02-28 2015-09-03 주식회사 지오엔 Vanadosilicate having hexadeca-coordinated cs+ ions and use thereof
CN105032341A (en) * 2015-08-28 2015-11-11 中国能源建设集团广东省电力设计研究院有限公司 Inorganic material for treating waste water with cesium, strontium and cobalt and preparation method of inorganic material
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CN109809485A (en) * 2018-12-13 2019-05-28 南京林业大学 A kind of height ratio capacity hydration vanadic acid magnesium and the preparation method and application thereof
CN112093821A (en) * 2020-09-16 2020-12-18 黑龙江大学 Preparation method of spinel magnesium vanadate microspheres

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