CN109174060B - Phosphonic acid group-containing chelate resin and method for separating and enriching thorium under high acidity - Google Patents
Phosphonic acid group-containing chelate resin and method for separating and enriching thorium under high acidity Download PDFInfo
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- CN109174060B CN109174060B CN201811122218.9A CN201811122218A CN109174060B CN 109174060 B CN109174060 B CN 109174060B CN 201811122218 A CN201811122218 A CN 201811122218A CN 109174060 B CN109174060 B CN 109174060B
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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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- 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
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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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
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Abstract
The invention relates to a phosphonic acid group-containing chelating resin, which is prepared by adopting the solvent thermal polymerization of hydrogen phosphate di (methacryloyloxyethyl) ester, and the preparation method comprises the following steps: adding 0.5-2 g of hydrogen phosphate di (methacryloyloxyethyl) ester and 0.05g of azobisisobutyronitrile into 1-15ml of organic solvent, stirring for 1-3H at 25 ℃, adding the solution into a hydrothermal reaction kettle, reacting for 24H at 100 ℃, taking out, opening the kettle, removing the organic solvent through rotary evaporation, drying for 12-24H under vacuum at 45 ℃ to obtain phosphonic acid group-containing chelate resin, separating and enriching thorium by the phosphonic acid group-containing chelate resin at high acidity, and adjusting H of the thorium-containing aqueous solution to be treated+And (3) adding a chelating resin adsorbent containing phosphonic acid groups into the solution with the concentration of 1-8 mol/L, and oscillating and adsorbing the solution. The chelating resin containing phosphonic acid groups prepared by the invention has the advantages of simple preparation method, simple and convenient operation, less by-products, reusability and the like.
Description
Technical Field
The invention relates to the technical field of thorium adsorption, in particular to a phosphonic acid group-containing chelate resin and a method for separating and enriching thorium under high acidity.
Background
Nuclear power generation is a new energy source for economy, cleanliness and high efficiency. Uranium is an important nuclear fuel resource, but the uranium resource in China is relatively lack, so that the demand of future nuclear power development is difficult to meet. Thorium is another most important nuclear energy resource except uranium, and the stock of thorium resources which are already proved in China accounts for the second place of the world. Meanwhile, thorium-containing radioactive wastewater is generated in the development and utilization process of thorium resources, so that the ecological environment is seriously polluted. From the development and utilization of thorium resources and from the viewpoint of environmental protection, it is necessary and urgent to research a high-efficiency separation and enrichment technology of thorium.
The current methods for separating and enriching thorium mainly comprise liquid-liquid extraction, liquid membrane extraction, ion exchange, extraction chromatography, solid phase extraction technology and the like. Compared with other methods, the solid phase extraction technology has attracted increasing attention because of its advantages of wide material source, low cost, high selectivity, simple operation, low energy consumption, high speed, large capacity, etc. At present, materials for separating and enriching thorium mainly comprise carbon materials, silicon materials, polymer materials, magnetic materials, biomass materials and the like. No matter development and utilization of thorium resources or treatment of thorium-containing wastewater, the acidity of a system is very high (generally a high-acidity system of 1-4 mol/L), most of adsorbing materials reported in literature at present have good adsorption performance on thorium ions at a pH value of about 3, and the adsorption capacity on thorium is very low at a high acidity. The adsorption materials mainly rely on functional groups such as phosphonic acid groups, phosphate esters, carboxyl groups, hydroxyl groups, amino groups, amidoxime groups and the like on the surfaces of the adsorption materials to realize the separation and enrichment of thorium. Most of the functional groups are introduced by a post-grafting method, and the number of the functional groups introduced by the post-grafting method is extremely limited, so that the adsorption capacity of the materials on thorium at high acidity is influenced to a great extent.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provide a chelating resin containing phosphonic acid groups and a method for separating and enriching thorium at high acidity.
One of the objects of the present invention is to provide a phosphonic acid-containing chelate resin;
the second purpose of the invention is to provide the application of chelating resin containing phosphonic acid group as an adsorbent;
the invention also aims to provide the application of chelating resin containing phosphonic acid groups as an adsorbent for adsorbing thorium under high acidity;
the fourth purpose of the invention is to provide a method for adsorbing thorium by using chelate resin containing phosphonic acid groups under high acidity;
one of the objects of the invention is achieved by:
a phosphonic acid group-containing chelating resin is prepared by the following steps:
adding 0.5-2 g of hydrogen phosphate di (methacryloyloxyethyl) ester and 0.05g of azobisisobutyronitrile into 1-15ml of an organic solvent, stirring for 1-3 h at 25 ℃, adding the solution into a hydrothermal reaction kettle, reacting for 24h at 100 ℃, taking out, opening the kettle, removing the organic solvent through rotary evaporation, and drying in vacuum for 12-24 h at 45 ℃ to obtain the phosphonic acid group-containing chelate resin, wherein the mass number and the volume number are adjusted in proportion;
further, the organic solvent is acetone, ethyl acetate, tetrahydrofuran or ethanol
Further, the phosphorus content of the chelating resin containing phosphonic acid groups is 10-15% by mass.
The second purpose of the invention is realized by the following steps:
a polymeric adsorbent for separating and enriching thorium under high acidity is prepared from chelating resin containing phosphonic acid group prepared by solvent thermal polymerization method, and the chelating group is phosphonic acid group.
The third purpose of the invention is realized by the following steps:
an application of chelating resin containing phosphonic acid group as polymeric adsorbent for adsorbing thorium under high acidity.
The fourth purpose of the invention is realized by the following steps:
a method for adsorbing thorium by using chelating resin containing phosphonic acid groups under high acidity comprises the following steps:
adjusting the H of the aqueous thorium-containing solution to be treated+The concentration is 1-4 mol/L, and then the solution is addedAnd (2) oscillating and adsorbing the phosphonic acid-based chelating resin adsorbent, wherein the concentration of the thorium-containing aqueous solution is 50-200 mg/L, and the volume of the thorium-containing aqueous solution and the mass ratio of the adsorbent are 25 mL: 0.010g, the adsorption temperature is 5-45 ℃, the adsorption time is 0.5-24 h, and the oscillation speed is 135 r/min.
Further, the adsorption temperature is preferably 25 ℃, and the adsorption time is preferably 3 hours.
Further, the adjustment H+At the concentration value, 12mol/L HNO was used3The solution, a 1mol/L NaOH solution and a 5mol/L NaOH solution.
The main inventor of the invention is continuously innovated in the field, such as ZL 201610095125.6 entitled 2017.11.10 'a mesoporous chelating resin containing phosphorus-oxygen functional groups and a method for separating and enriching uranium', and ZL201611061801.4 entitled 2018.07.24 'a nitrogen-containing porous polymer chelating resin and a method for preparing and treating uranium-containing wastewater'. It should be noted, however, that the present invention has the following significant differences and improvements over the art in grant numbers ZL 201610095125.6 and ZL 201611061801.4: the objects of the first adsorption are different. The method is mainly used for extracting thorium ions in an aqueous solution, and the technologies with the granted patent numbers of ZL 201610095125.6 and ZL201611061801.4 are mainly used for extracting the uranyl ions in the aqueous solution. Although uranium and thorium belong to actinides, their properties are very different; the preparation method is different. The technology of the granted patent No. ZL 201610095125.6 mainly adopts the solvent thermal copolymerization technology of vinyl phosphonic acid and other monomers such as ethylene glycol dimethacrylate to prepare the adsorbent, and the technology of the granted patent No. ZL201611061801.4 mainly adopts a post-modification method to prepare the nitrogen-containing porous polymer adsorbent. The content of functional groups of the adsorbents prepared by the two methods is low, and the adsorption capacity of the adsorbents is influenced to a great extent. The density of the organic phosphonic acid functional groups in the adsorbent prepared by adopting the solvothermal self-polymerization technology of the hydrogen phosphate di (methacryloyloxyethyl) ester is very high, and the adsorption content of the adsorbent to thorium can be improved to a great extent.
Compared with the prior preparation method for separating enriched thorium under high acidity, the technology of the invention also has the following progress:
at present, the adsorbents used for separating and enriching thorium under high acidity mainly comprise polymer materials, silicon materials, carbon materials and the like. Most of the adsorbing materials are prepared by a post-modification method, and the preparation method is to immobilize organic functional groups on the surface of an adsorbent through multi-step chemical reactions of the functional groups on the surface of a solid phase carrier and organic micromolecules, so that the distribution and introduction amount of the organic functional groups are low, and the adsorption capacity of the adsorbing materials on thorium under high acidity is also low. The invention can uniformly introduce a large amount of organic phosphonic acid into a polymer organic framework by a solvent thermal polymerization technology of the hydrogen phosphate di (methacryloyloxyethyl) ester, and can greatly improve the adsorption capacity of the organic phosphonic acid to thorium under high acidity.
In view of the above, the invention intends to combine the advantages of strong complexation of phosphonic acid groups to thorium and the solid-phase extraction technology, and prepares a polymer resin adsorption material with high adsorption capacity to thorium ions at high acidity by using the solvent thermal polymerization technology of di (methacryloyloxyethyl) hydrogen phosphate, and the adsorption material has the characteristics of high adsorption speed and high adsorption capacity at high acidity.
The invention has the beneficial effects that:
(1) the chelating resin containing phosphonic acid groups prepared by the invention has the advantages of simple preparation method, simple and convenient operation, less by-products, reusability and the like.
(2) The chelating resin containing phosphonic acid groups prepared by the invention has the characteristics of high adsorption quantity, high adsorption speed and the like on thorium ions in an aqueous solution under high acidity, and can effectively achieve the purposes of adsorption and recycling.
Detailed Description
The invention is further illustrated by the following specific examples. The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination between the specific embodiments. In particular the ratio of the stated mass number to volume number.
Example 1
Phosphonic acid group-containing chelate resins can be prepared by solvothermal methods, as a typical synthesis example: adding 0.5g of hydrogen phosphate di (methacryloyloxyethyl) ester and 0.05g of azobisisobutyronitrile into 5ml of tetrahydrofuran, stirring for 1h at 25 ℃, adding the solution into a hydrothermal reaction kettle, reacting for 24h at 100 ℃, taking out, opening the kettle, removing ethyl acetate through rotary evaporation, and drying in vacuum for 12h at 45 ℃ to obtain the phosphonic acid group-containing chelating resin 1.
Example 2
Phosphonic acid group-containing chelate resins can be prepared by solvothermal methods, as a typical synthesis example: adding 0.5g of hydrogen phosphate di (methacryloyloxyethyl) ester and 0.05g of azobisisobutyronitrile into 5ml of acetone, stirring for 1h at 25 ℃, adding the solution into a hydrothermal reaction kettle, reacting for 24h at 100 ℃, taking out, opening the kettle, removing ethyl acetate through rotary evaporation, and drying in vacuum for 12h at 45 ℃ to obtain the phosphonic acid group-containing chelating resin 2.
Example 3
Accurately transferring 25mL of 100mg/L thorium standard solution into a 150mL conical flask, and regulating the H content of the uranium solution by using 12mol/L nitric acid, 1mol/L NaOH solution and 5mol/L NaOH solution+Concentration of solution H+The concentration was 4 mol/L. 0.010g of adsorbent 1 was added and the mixture was adsorbed at 25 ℃ for 3 hours in a constant temperature shaker at 135 r/min. The resultant was separated by filtration, subjected to spectral analysis by ICP-OES, and the concentration of thorium ion in the filtrate was measured, and the adsorbed amount at this time was found to be 59.5mg/g by the equation (1).
The adsorption amount of thorium ions is calculated according to the following formula:
in the formula: q. q.se-amount adsorbed, mg/g; v-volume of solution, L; ce-equilibrium concentration of thorium ion solution, mg/L; c0-initial concentration of thorium ion solution, mg/L; m-mass of adsorbent, g.
Example 4
Accurately transferring 25mL of 100mg/L thorium standard solution into a 150mL conical flask, and regulating the H content of the uranium solution by using 12mol/L nitric acid, 1mol/L NaOH solution and 5mol/L NaOH solution+Concentration of solution H+The concentration is 2 mol/L. 0.010g of adsorbent 1 was added and the mixture was adsorbed at 25 ℃ for 3 hours in a constant temperature shaker at 135 r/min. The resultant was separated by filtration, and subjected to spectral analysis by ICP, whereby the concentration of thorium ion in the filtrate was measured, and the adsorbed amount at this time was calculated to be 85.2mg/g by the following formula (1).
Example 5
Accurately transferring 25mL of 150mg/L thorium standard solution into a 150mL conical flask, and regulating the H content of the uranium solution by using 12mol/L nitric acid, 1mol/L NaOH solution and 5mol/L NaOH solution+Concentration of solution H+The concentration was 4 mol/L. 0.010g of adsorbent 1 was added and the mixture was adsorbed at 25 ℃ for 3 hours in a constant temperature shaker at 135 r/min. The resultant was separated by filtration, subjected to spectral analysis by ICP-OES, and the concentration of thorium ion in the filtrate was measured, and the amount adsorbed at this time was calculated to be 75.5mg/g by the following equation (1).
Example 6
Accurately transferring 25mL of 150mg/L thorium standard solution into a 150mL conical flask, and regulating the H content of the uranium solution by using 12mol/L nitric acid, 1mol/L NaOH solution and 5mol/L NaOH solution+Concentration of solution H+The concentration was 4 mol/L. 0.010g of adsorbent 2 was added and the mixture was adsorbed at 25 ℃ for 3 hours in a constant temperature shaker at 135 r/min. The resultant was separated by filtration, subjected to spectral analysis by ICP-OES, and the concentration of thorium ion in the filtrate was measured, and the adsorbed amount at this time was calculated to be 62.5mg/g by the following formula (1).
Example 7
Accurately transferring 25mL of 100mg/L thorium standard solution into a 150mL conical flask, and regulating the H content of the uranium solution by using 12mol/L nitric acid, 1mol/L NaOH solution and 5mol/L NaOH solution+Concentration of solution H+The concentration is 2 mol/L. 0.010g of adsorbent 2 was added and the mixture was adsorbed at 25 ℃ for 3 hours in a constant temperature shaker at 135 r/min. The resultant was separated by filtration, subjected to spectral analysis by ICP-OES, and the concentration of thorium ion in the filtrate was measured, and the adsorbed amount at this time was calculated to be 78.5mg/g by the following formula (1).
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A phosphonic acid group-containing chelating resin is characterized in that a polymer adsorbent is prepared by adopting solvent thermal polymerization of di (methacryloyloxyethyl) hydrogen phosphate, and the preparation method comprises the following steps:
adding 0.5-2 g of hydrogen phosphate di (methacryloyloxyethyl) ester and 0.05g of azobisisobutyronitrile into 1-15ml of an organic solvent, stirring for 1-3 h at 25 ℃, adding the solution into a hydrothermal reaction kettle, reacting for 24h at 100 ℃, taking out, opening the kettle, removing the organic solvent through rotary evaporation, and drying in vacuum for 12-24 h at 45 ℃ to obtain the phosphonic acid group-containing chelate resin, wherein the mass number and the volume number are adjusted in proportion;
the mass percentage of phosphorus in the chelating resin containing phosphonic acid groups is 10-15%; the organic solvent is acetone, ethyl acetate, tetrahydrofuran or ethanol.
2. Use of a chelating resin containing phosphonic acid groups as defined in claim 1 as polymeric adsorbent for the separation and enrichment of thorium at high acidity.
3. Process for the separation and enrichment of thorium at high acidity using the phosphonic acid group-containing chelating resins as claimed in claim 1, characterized in that the H of the aqueous thorium-containing solution to be treated is adjusted+The concentration is 1-8 mol/L, then chelating resin containing phosphonic acid groups is added as an adsorbent, oscillation and adsorption are carried out, wherein the concentration of the thorium-containing aqueous solution is 50-200 mg/L, and the volume of the thorium-containing aqueous solution and the mass ratio of the adsorbent are 25 ml: 0.010g, the adsorption temperature is 5-45 ℃, the adsorption time is 0.5-24 h, and the oscillation speed is 135 r/min.
4. The method for separating and enriching thorium at high acidity by using the chelating resin containing phosphonic acid group as claimed in claim 3, characterized in that the adsorption temperature is 25 ℃ and the adsorption time is 3 h.
5. The method for separating and enriching thorium at high acidity with the chelating resin containing phosphonic acid group as claimed in claim 3, characterized in that 12mol/L HNO is used3Solution, 1mol/L NaOH solution and 5mol/L NaOH solution+And (4) concentration.
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| CN109970913B (en) * | 2019-03-28 | 2021-02-19 | 广西大学 | Resin preparation method based on BMAOP and application thereof in scandium-zirconium separation |
| CN110813255B (en) * | 2019-12-03 | 2022-06-03 | 东华理工大学 | Method for preparing, separating and enriching uranium by using dual-functionalized polymer chelate resin |
| CN111171208B (en) * | 2020-03-02 | 2022-05-06 | 东华理工大学 | Polyamidoxime group chelate resin for extracting uranium from seawater and preparation method thereof |
| CN114700051A (en) * | 2022-04-05 | 2022-07-05 | 兰州大学 | Method for adsorbing Np (IV) and Pu (IV), resin and preparation method thereof |
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