CN113797892B - Application of mineral-based Yolk-shell composite microsphere in adsorption of iodine ions in radioactive water - Google Patents
Application of mineral-based Yolk-shell composite microsphere in adsorption of iodine ions in radioactive water Download PDFInfo
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- CN113797892B CN113797892B CN202111130356.3A CN202111130356A CN113797892B CN 113797892 B CN113797892 B CN 113797892B CN 202111130356 A CN202111130356 A CN 202111130356A CN 113797892 B CN113797892 B CN 113797892B
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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- 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
- B01J20/28—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
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of sewage treatment, and discloses an application of mineral-based Yolk-shell composite microspheres in adsorbing iodide ions in radioactive water, wherein the composite microspheres are prepared by using attapulgite minerals as matrix materials, alcohol esters as cross-linking agents and amino esters as polymerization monomers in N 2 Mixing the mixture with attapulgite suspension under protection to prepare a Pickling emulsion, carrying out polymerization reaction under illumination, and removing internal organic matters by calcining to prepare the micron-sized mineral-based hollow porous amino polymeric microspheres; dispersing the mineral-based hollow porous amino polymeric microspheres in an organic solvent by a double-solution dipping-reduction method, adding a copper sulfate solution for dipping, and reducing by a reducing agent to form Cu or Cu-based hollow porous amino polymeric microspheres 2 O is the mineral-based Yolk-shell composite microsphere of the inner core. Compared with the traditional adsorbent, the invention improves the iodine adsorption capacity and selectivity and can effectively remove the radioactive iodine in the wastewater.
Description
Description of the division
The invention discloses a preparation method of a mineral-based Yolk-shell composite microsphere, which is applied for the application of the mineral-based Yolk-shell composite microsphere in adsorbing iodine ions in radioactive water, wherein the application is 5/9/2019, the application number is 2019103854711.
Technical Field
The invention relates to the technical field of sewage purification treatment in environmental protection, in particular to a method for purifying sewage by Cu or Cu-Cu 2 The application of the mineral-based Yolk-shell composite microsphere with O as an inner core and a mineral-based polymer as a shell in adsorbing iodine ions in radioactive water is provided.
Background
With the vigorous development of Chinese economy and the increasing prominence of environmental problems, the nuclear power industry has become an important development strategy in China, and the total amount of nuclear power operation and installation in China is expected to reach 88 GW in 2020. Effectively solves the following radiation pollution and has important significance for the safe use of nuclear energy. Radioiodine is often used as a breakage monitoring indicator for nuclear fuel element cladding and as a signal nuclide for environmental monitoring after nuclear explosion, and is one of the necessary products of nuclear fission. Therefore, the efficient removal of liquid-phase radioactive iodine is a key scientific problem to be solved for nuclear power safety utilization.
The technology of chemical precipitation, porous material adsorption, ion exchange, membrane separation and the like can be used for removing liquid radioactive iodine. The metal materials used in chemical precipitation are expensive and tend to cause secondary pollution of heavy metals. The selective adsorption efficiency of porous materials in complex environments is difficult to ensure. The ion exchange technology is also prone to secondary pollution due to the use of organic or inorganic solvents. Membrane separation technology has good removal efficiency, but is expensive to operate.
The preparation of the composite material with the Yolk-shell structure is generally divided into a hard template method, a soft template method, a template-free method and a 'core-in-shell' method. In the conventional template sacrificial method (hard template method, soft template method), multi-step pyrolysis, chemical etching or solvent extraction is generally required to remove the pre-deposited intermediate shell layer, and the synthesis process is difficult to effectively control and is easy to influence the activity of the core. The template-free method generally utilizes Ostwald curing, kirkendall effect and the like to create a hollow structure, but the method is only suitable for special metal or metal sulfide and oxide systems, and the morphology and the size of the obtained material are difficult to regulate.
Disclosure of Invention
The invention aims to: aiming at the problems existing in the prior art, the invention provides an application of mineral-based Yolk-shell composite microspheres in adsorbing iodine ions in radioactive water and in adsorbing electric ions in radioactive water, wherein mineral-based polymer eggshells are utilized to physically adsorb liquid-phase radioactive pollutants, and Cu or Cu-Cu is utilized 2 The O inner core selectively adsorbs radioactive iodine, so that compared with the traditional adsorbent, the iodine adsorption capacity and selectivity are improved, and technical reference is provided for removing radioactive iodine in wastewater.
The technical scheme is as follows: the invention provides an application of mineral-based Yolk-shell composite microspheres in adsorbing iodine ions in radioactive water, and a preparation method of the mineral-based Yolk-shell composite microspheres comprises the following steps: s1: dispersing attapulgite in deionized water to obtain a suspension; s2: respectively adding diethylaminoethyl methacrylate and ethylene glycol dimethacrylate into the suspension, then adding paraxylene and photoinitiator, stirring uniformly, and adding the mixture into N 2 Under the protection condition, the mineral-based hollow porous amino polymeric microspheres are obtained by utilizing ultraviolet irradiation reaction for a certain time, centrifugally filtering, washing with water and calcining; s3: dispersing the mineral-based hollow porous amino polymeric microspheres in normal hexane solution, dropwise adding copper nitrate solution, fully stirring, and then adding the solution into N 2 Under the protection of gas, naBH is added dropwise 4 After the solution is fully reacted by magnetic stirring, centrifugally filtering and washing the solution to obtain Cu or Cu-Cu containing solution 2 Mineral-based Yolk-shell composite microspheres with O cores; s4: and drying the mineral-based Yolk-shell composite microsphere in a vacuum drying oven at 50 ℃ for 10 h.
Preferably, in the step S2, the mass ratio of the attapulgite, diethylaminoethyl methacrylate, ethylene glycol dimethacrylate, paraxylene and the photoinitiator in each liter of water is 1: 1-15: 1-15: 20-40: 0.2 to 1.0.
Preferably, in the step S4, the mass ratio of the mineral-based hollow porous amine-based polymeric microsphere, copper nitrate, reducing agent and organic solvent is 1:0.01 to 0.10:0.001 to 0.010: 20-40.
Preferably, in the step S3, the time for the light irradiation of the locking emulsion is 50-70 min.
Preferably, in the step S3, the calcination temperature after centrifugal filtration and water washing is 200-400 ℃ and the calcination time is 2.5-3.5 h.
In the S4, the reducing agent is NaBH 4 Solutions or hydrazine hydrate.
The invention also provides application of the mineral-based Yolk-shell composite microsphere in adsorbing iodine ions in radioactive water.
Preferably, the concentration of iodide ions in the radioactive water is 0.1-1.0 mM; the adding amount of the mineral-based Yolk-shell composite microsphere in the radioactive water body is 0.25-2 g.L －1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably 1 g.L －1 。
Preferably, the temperature of the mineral-based Yolk-shell composite microsphere when being adsorbed in the radioactive water body is 25-50 ℃ and the adsorption time is 5-30 min.
Preferably, the mineral-based Yolk-shell composite microsphere is adsorbed in the radioactive water in the following manner: and the opening is communicated with air.
The beneficial effects are that: the invention uses attapulgite mineral with good stability, low price and large specific surface as a matrix material, alcohol ester as a cross-linking agent and amino ester as a polymerization monomer, and uses the mixture in N 2 Mixing the mixture with an attapulgite suspension under the protection of air blowing to prepare a Pickling emulsion, carrying out polymerization reaction under the irradiation of visible light, and removing internal organic matters by vacuum calcination to form the mineral-based hollow porous amino polymeric microspheres with the micron size; dispersing the mineral-based hollow porous amino polymeric microspheres in an organic solvent by a double-solution dipping-reduction method, adding a copper sulfate solution for dipping, and reducing by a reducing agent to form Cu or Cu-based hollow porous amino polymeric microspheres 2 Ore with O as coreAnd (3) the matrix Yolk-shell composite microsphere.
As shown in FIG. 10, the prepared mineral-based Yolk-shell composite microsphere is used for adsorbing iodine ions in radioactive water, and low-concentration iodine in a solution is enriched by virtue of charge characteristics of amine groups in a mineral-based shell (I － 、I 2 ) The concentration of radioactive iodine in the solution takes the mineral-based Yolk-shell composite microsphere as the center to be distributed in a gradient manner, and Cu in the inner core are utilized 2 Reaction of the compact layer of CuO on the O surface to generate Cu 2 O reacts with iodide ion to generate cuprous iodide, and then is physically adsorbed with I 2 Copper triiodide is formed. In the adsorption process, the radioactive iodine outside the shell is continuously enriched into the shell due to the consumption of the radioactive iodine in the shell, so that the ultrahigh adsorption efficiency of the low-concentration radioactive iodine is realized. Because the reaction product is in the inner core of the mineral-based Yolk-shell composite microsphere structure, the polymeric shell can fix the inner core reaction product, can effectively reduce the direct irradiation of natural light on the adsorbed product, and can adsorb a small amount of decomposed iodine, thereby effectively avoiding the radioactive iodine from escaping from the composite microsphere. Therefore, the mineral-based Yolk-shell composite microsphere is expected to efficiently remove low-concentration radioactive iodine in a solution.
Compared with the prior art, the method has the remarkable advantages that: (1) The method adopts a simple hydrothermal synthesis method, has simple process, short synthesis time, low-cost and easily obtained raw materials, is nontoxic, and is Cu or Cu-Cu 2 The preparation of the O core-shell structure material provides a new method; (2) Synthetic Cu or Cu-Cu 2 The morphology and the content of elemental copper of the mineral-based Yolk-shell composite microsphere with the O core-shell structure can be adjusted. (3) The shell-in-shell nucleation method is used for preparing the shell and then immersing and nucleating, the process is simple, and the activity and the maximum functionalization of the core are facilitated.
Drawings
FIG. 1 is an SEM spectrum of mineral-based Yolk-shell composite microspheres prepared in embodiment 1;
FIG. 2 is an SEM spectrum of mineral-based Yolk-shell composite microspheres prepared in embodiment 1;
FIG. 3 is an XRD spectrum of the mineral-based Yolk-shell composite microsphere prepared in embodiment 1;
FIG. 4 is an adsorption graph of mineral-based Yolk-shell composite microspheres prepared in embodiment 1;
FIG. 5 is an SEM spectrum of mineral-based Yolk-shell composite microspheres prepared in embodiment 2;
FIG. 6 is an XRD spectrum of the mineral-based Yolk-shell composite microsphere prepared in embodiment 2;
FIG. 7 is an adsorption graph of mineral-based Yolk-shell composite microspheres prepared in embodiment 2;
FIG. 8 is an SEM spectrum of mineral-based Yolk-shell composite microspheres prepared in embodiment 3;
FIG. 9 is an adsorption graph of mineral-based Yolk-shell composite microspheres prepared in embodiment 3;
FIG. 10 is a schematic diagram of efficient adsorption of low concentration radioiodine by mineral-based Yolk-shell composite microspheres.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
Embodiment 1:
dispersing 0.3 g attapulgite in 20 mL deionized water to obtain suspension, adding 2.0 g diethylaminoethyl methacrylate and 1.0 g ethylene glycol dimethacrylate into the suspension, respectively, and adding 8 g paraxylene and 0.16 g 819 TM Magnetically stirring the photoinitiator for 5 min to obtain a Pickling emulsion, and then adding the Pickling emulsion into N 2 Under the protection condition, the light-irradiation Pickling emulsion polymerization reaction 1 h is carried out, centrifugal filtration is carried out, the mixture is washed with water for three times, and then calcined at 200 ℃ for 3 h, thus obtaining the mineral-based hollow porous amino polymeric microsphere for standby.
Dispersing 1g hollow porous amino polymeric microsphere in 30 mL N-hexane solution, adding 1 mL 0.15M copper nitrate solution dropwise into the suspension, stirring thoroughly 1 h, and adding N 2 Under the protection of gas, 1 mL of 0.10M NaBH is added dropwise 4 And (3) magnetically stirring the solution for 30 min, centrifugally filtering, washing for three times to obtain the mineral-based Yolk-shell composite microsphere with the Cu inner core, and finally drying the mineral-based Yolk-shell composite microsphere in a vacuum drying oven at 50 ℃ for 10 h.
The morphology of the mineral-based Yolk-shell composite microsphere prepared by the embodiment is observed through SEM. FIG. 1 illustrates the morphology of the prepared mineral-based Yolk-shell composite microsphere as a micron-sized spherical structure. The electron microscope image (FIG. 2) after breakage illustrates that the product is a Yolk-shell structure. According to XRD test, the diffraction peak of the wide-angle part is shown as the product of elemental copper and attapulgite, and the diffraction peak is very clear and sharp.
50 mg of the mineral-based Yolk-shell composite microsphere prepared above is added into 50 mL of 1.0 mM of solution simulating radioactive iodide ions, and after being adsorbed for 10 min at normal temperature, the solution is filtered to measure the concentration of residual iodide ions in the solution. The adsorption result in fig. 4 shows that the mineral-based Yolk-shell composite microsphere reaches adsorption equilibrium within 5 min, and the adsorption efficiency can reach 85%.
Embodiment 2:
dispersing 0.3 g attapulgite in 20 mL deionized water to obtain suspension, adding 1.5 g diethylaminoethyl methacrylate and 1.5 g ethylene glycol dimethacrylate into the suspension, respectively, and adding 6 g paraxylene and 0.20 g 819 TM Magnetically stirring the photoinitiator for 5 min to obtain a Pickling emulsion, and then adding the Pickling emulsion into N 2 Under the protection condition, the light-irradiation Pickling emulsion polymerization reaction 1 h is carried out, centrifugal filtration is carried out, the mineral-based hollow porous amino polymerization microsphere is obtained for standby after three times of water washing and calcination at 300 ℃ for 3 h.
Dispersing 1g hollow porous amino polymeric microsphere in 20 mL N-hexane solution, adding 1 mL 0.30M copper nitrate solution dropwise into the suspension, stirring thoroughly 1 h, and adding N 2 Under the protection of gas, 1 mL of 0.05M NaBH is added dropwise 4 Magnetically stirring the solution for 30 min, centrifuging, filtering, and washing with water for three times to obtain Cu-Cu alloy 2 And finally, drying the mineral-based Yolk-shell composite microsphere in a 50 ℃ vacuum drying oven for 10 h.
The morphology of the mineral-based Yolk-shell composite microsphere prepared by the embodiment is observed through SEM. Fig. 5 illustrates the morphology of the product as a micron-sized spherical structure. XRD test shows that the diffraction peaks at the wide angle part show that the products are elemental copper, cuprous oxide and attapulgite.
50 mg of the mineral-based Yolk-shell composite microsphere prepared above is added into 50 mL of 1.0 mM of solution simulating radioactive iodide ions, and after being adsorbed for 10 min at normal temperature, the solution is filtered to measure the concentration of residual iodide ions in the solution. The adsorption result in FIG. 7 shows that the mineral-based Yolk-shell composite microsphere reaches adsorption equilibrium within 5 min, and the adsorption efficiency can reach 80%.
Embodiment 3:
dispersing 0.3 g attapulgite in 20 mL deionized water to obtain suspension, adding 1.0 g diethylaminoethyl methacrylate and 2.0 g ethylene glycol dimethacrylate into the suspension, respectively, and adding 10 g paraxylene and 0.12 g 819 TM Magnetically stirring the photoinitiator for 5 min to obtain a Pickling emulsion, and then adding the Pickling emulsion into N 2 Under the protection condition, the light-irradiation Pickling emulsion polymerization reaction 1 h is carried out, centrifugal filtration is carried out, the mixture is washed with water for three times, and then calcined at 400 ℃ for 3 h, thus obtaining the mineral-based hollow porous amino polymeric microspheres for standby.
Dispersing 1g hollow porous amino polymeric microsphere in 40 mL N-hexane solution, adding 1 mL 0.18M copper nitrate solution dropwise into the suspension, stirring thoroughly 1 h, and adding N 2 Under the protection of gas, 1 mL of 0.10M NaBH is added dropwise 4 Magnetically stirring the solution for 30 min, centrifuging, filtering, and washing with water for three times to obtain Cu-Cu alloy 2 And finally, drying the mineral-based Yolk-shell composite microsphere in a 50 ℃ vacuum drying oven for 10 h.
The morphology of the mineral-based Yolk-shell composite microsphere prepared by the embodiment is observed through SEM. Fig. 8 illustrates the morphology of the product as a micron-sized spherical structure.
50 mg of the mineral-based Yolk-shell composite microsphere prepared above is added into 50 mL of 1.0 mM of solution simulating radioactive iodide ions, and after being adsorbed for 10 min at normal temperature, the solution is filtered to measure the concentration of residual iodide ions in the solution. The adsorption result in FIG. 9 shows that the mineral-based Yolk-shell composite microsphere reaches adsorption equilibrium within 5 min, and the adsorption efficiency can reach 77.5%.
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. The application of the mineral-based Yolk-shell composite microsphere in adsorbing iodine ions in radioactive water is characterized in that the preparation method of the mineral-based Yolk-shell composite microsphere comprises the following steps:
s1: dispersing attapulgite in deionized water to obtain a suspension;
s2: respectively adding diethyl aminoethyl methacrylate and ethylene glycol dimethacrylate into the suspension, then adding paraxylene and a photoinitiator, and uniformly stirring to obtain a Picking emulsion;
s3: at N 2 Under the protection condition, carrying out light irradiation on the Pickling emulsion polymerization reaction for a certain time, centrifugally filtering, washing with water, and calcining to obtain the mineral-based hollow porous amino polymeric microspheres;
s4: dispersing the mineral-based hollow porous amino polymeric microspheres in an organic solvent, dropwise adding a copper nitrate solution, fully stirring, and then adding the solution into N 2 Under the protection of gas, dropwise adding a reducing agent, magnetically stirring for full reaction, and centrifugally filtering and washing to obtain Cu or Cu-Cu alloy 2 Mineral-based Yolk-shell composite microspheres with O cores;
s5: and drying the mineral-based Yolk-shell composite microsphere in a vacuum drying oven at 50 ℃ for 10 h.
2. The use of mineral-based Yolk-shell composite microspheres according to claim 1 for adsorbing iodide ions in radioactive water, wherein in S2, the mass ratio of attapulgite, diethylaminoethyl methacrylate, ethylene glycol dimethacrylate, paraxylene and photoinitiator in each liter of water is 1: 1-15: 1-15: 20-40: 0.2 to 1.0.
3. The use of the mineral-based Yolk-shell composite microsphere according to claim 1, wherein in S4, the mass ratio of the mineral-based hollow porous amine-based polymeric microsphere, copper nitrate, reducing agent and organic solvent is 1:0.01 to 0.10:0.001 to 0.010: 20-40.
4. Use of mineral-based Yolk-shell composite microspheres according to any one of claims 1 to 3 for adsorbing iodide ions in radioactive water, wherein in S3 the time of the light-illuminated jacking emulsion reaction is 50-70 min.
5. The use of the mineral-based Yolk-shell composite microsphere according to any one of claims 1 to 3 for adsorbing iodine ions in radioactive water, wherein in S3, the calcination temperature after centrifugal filtration and water washing is 200-400 ℃ and the calcination time is 2.5-3.5 h.
6. Use of mineral-based Yolk-shell composite microspheres according to any one of claims 1-3 for adsorbing iodide ions in radioactive water, characterized in that in S4 the reducing agent is NaBH 4 Solutions or hydrazine hydrate.
7. Use of mineral-based Yolk-shell composite microspheres according to any one of claims 1-3 for adsorbing iodide ions in radioactive water, wherein in S4 the organic solvent is n-hexane.
8. The use of mineral-based Yolk-shell composite microspheres according to any one of claims 1 to 3 for adsorbing iodide ions in radioactive water, wherein the concentration of iodide ions in radioactive water is 0.1-1.0 mM; the adding amount of the mineral-based Yolk-shell composite microsphere in the radioactive water body is 0.25-2 g.L －1 。
9. The application of the mineral-based Yolk-shell composite microsphere in adsorbing iodine ions in radioactive water, which is characterized in that the temperature of the mineral-based Yolk-shell composite microsphere in adsorbing the radioactive water is 25-50 ℃ and the adsorption time is 5-30 min.
10. The use of mineral-based Yolk-shell composite microspheres according to claim 8 for adsorbing iodide ions in radioactive water, wherein the mineral-based Yolk-shell composite microspheres are adsorbed in the radioactive water in the following manner: and the opening is communicated with air.
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