CN114887603A - Resin for adsorbing Sr-90 and preparation method thereof - Google Patents
Resin for adsorbing Sr-90 and preparation method thereof Download PDFInfo
- Publication number
- CN114887603A CN114887603A CN202210658461.2A CN202210658461A CN114887603A CN 114887603 A CN114887603 A CN 114887603A CN 202210658461 A CN202210658461 A CN 202210658461A CN 114887603 A CN114887603 A CN 114887603A
- Authority
- CN
- China
- Prior art keywords
- resin
- adsorbing
- crown
- mixture
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3071—Washing or leaching
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
-
- 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 discloses a resin for adsorbing Sr-90 and a preparation method thereof. The Sr-90 adsorbing resin comprises a support and an extracting agent loaded on the support, wherein the support has a structure shown in the formula, the extracting agent loaded on the support is crown ether capable of adsorbing Sr-90, and the preferred crown ether is dicyclohexyl-18-crown-6. The preparation method is simple, and compared with the current commercial resin, the obtained resin has the advantages of lower cost, high selectivity, high adsorption capacity, stability in a high-acid medium and high thermal stability, and is expected to realize home-made substitution.
Description
Technical Field
The invention relates to a resin and a preparation method thereof, in particular to a resin for adsorbing Sr-90 and a preparation method thereof.
Background
Sr-90 is an important mitogen with a long half-life inThe environmental monitoring and radioactive safety assessment process is concerned, and the separation and analysis of the environmental monitoring and radioactive safety assessment process are always a hot problem in the field of environmental radiochemistry. The Sr-90 separating and purifying method mainly comprises an evaporation concentration method [1] Solvent extraction method [2] Chemical precipitation method [3] Ion exchange method [4] However, all the methods have certain disadvantages, such as large energy consumption and high cost of the evaporation concentration method; the solvent extraction method is easy to generate secondary pollution; the chemical precipitation method has low recovery rate and is easy to generate secondary pollution; the ion exchange method is easy to be pulverized and bonded and difficult to be regenerated. In contrast, the currently used solid phase extraction method is a recognized green and clean method due to the advantages of high adsorption capacity, high selectivity, good hydrodynamic property, no secondary pollution and the like [5] . However, the separation materials used in the current solid phase extraction methods have poor stability in high acid media, and mainly have the following problems: 1. the high acid environment has more strict requirements on the structural stability of the resin material, and the commercial organic polymer is not resistant to high acid and has poorer structural stability; 2. the functional group of the solid phase extraction resin is easy to protonate under the high acid environment, so that the separation performance is reduced, and the selective separation of target nuclide is difficult to realize. At present, commercial Sr resin produced by TRISKM company is most used in practice, but the Sr resin is expensive and has low absorption capacity, which results in high analysis cost [6] And also is not resistant to high acids.
[1] Ginger graduate, wind instrument, etc. Engineering of nuclear fuel reprocessing [ M ]. Beijing: atomic energy Press, 1995: 294-.
[2]D Deli,Law K,Liu Z,et al.Selective removal of 90 Sr and 60 Co from aqueous solution using N-aza-crown ether functional poly(NIPAM)hydrogels[J].Reactive&Functional Polymers,2012,72(6):414-419.
[3]Wu L,Wang Q,Zhang G.Removal of strontium from liquid waste using a hydraulic pellet co-precipitation microfiltration(HPC-MF)process[J].Desalination:The International Journal on the Science and Technology of Desalting and Water Purification,2014.
[4]Qi X H,Du K Z,Feng M L,et al.A two-dimensionally microporous thiostannate with superior Cs + and Sr 2+ ion-exchange property[J].J.mater.chem.a,2015,3(10):5665-5673.
[5]Horwitz E P,Dietz M L,Chiarizia R.The application of novel extraction chromatographic materials to the characterization of radioactive waste solutions[J].Journal of Radioanalytical&Nuclear Chemistry,1992,161(2):575-583.
[6]Yang A.Y.,Langmuir C.H.,Cai Y.,Michael P.,Goldstein S.L.,Chen Z.A subduction influence on ocean ridge basalts outside the Pacific subduction shield.Nature communications,2021,12,4757.。
Disclosure of Invention
The invention provides a Sr-90 adsorbing resin which can overcome the defects of the prior art and also provides a preparation method of the resin.
The Sr-90 adsorbing resin comprises a support body and an extracting agent loaded on the support body, wherein the support body has a structure shown in a formula 1,
preferably, the extraction agent loaded on the support in the Sr-90 adsorbing resin is crown ether capable of adsorbing Sr-90. More preferably, the crown ether of Sr-90 is dicyclohexyl-18-crown-6.
The preparation method of the Sr-90 adsorbing resin comprises the following steps: firstly, preparing micron-sized mesoporous silica particles coated by 3-aminopropyltriethoxysilane, then attaching a surface coating of Polyamide (PAMAM) dendritic polymer on the surfaces of the 3-aminopropyltriethoxysilane-coated micron-sized mesoporous silica particles, and then loading dicyclohexyl-18-crown-6 crown ether on the PAMAM dendritic surface coating in an impregnation mode. The principle is surface coating with PAMAM dendrimers by the michael reaction.
Preferably, the preparation method of the Sr-90 adsorbing resin is as follows:
(1) surface modification of silica particles
Dispersing micron-sized silicon dioxide particles in absolute ethyl alcohol, carrying out ultrasonic treatment by using an ultrasonic generator, adding 3-aminopropyltriethoxysilane into the mixture, then continuing to carry out full ultrasonic treatment, fully stirring the treated mixture, and fully cleaning the mixture by using absolute methyl alcohol to obtain 3-aminopropyltriethoxysilane modified micron-sized silicon dioxide particles;
(2) forming a coating on the surface of APTES modified micron-sized silica particles by using PAMAM dendritic polymer
Adding the product obtained in the last step into methyl acrylate/methanol solution, fully performing ultrasonic treatment on the suspension in room-temperature water bath, performing suction filtration, washing with methanol, and performing rotary evaporation on the product to remove excessive methyl acrylate/methanol attached to the surfaces of particles; then putting the mixture into an ethylenediamine/methanol solution, fully performing ultrasonic treatment in a room-temperature water bath, washing the product with a methyl acrylate/methanol solution, repeating the step for a plurality of times to obtain a required intermediate product, see formula 2,
(3) synthesis of Sr-90 adsorbing resin
And (3) taking 5g of the product obtained by the previous step, putting 2g of dicyclohexyl-18-crown-6 into absolute ethyl alcohol, fully oscillating to enable the dicyclohexyl and the crown-6 to be fully contacted, taking out, rotationally evaporating to remove the absolute ethyl alcohol and the crown ether, and drying in a vacuum drying oven at the temperature lower than 80 ℃ to obtain the final resin material.
The most preferred preparation method is:
in the step (1), 10g of 100-200 micron silicon dioxide particles are taken and dispersed in 50mL of absolute ethyl alcohol, 250mL of absolute ethyl alcohol is added, ultrasonic treatment is carried out on the mixture for 20min by an ultrasonic generator, 20mL of APTES is added, ultrasonic treatment is carried out for 10min, the mixture is stirred for 15 h, and the obtained product is washed by a small amount of absolute methyl alcohol for multiple times;
in step (2), 10g of the product obtained in step (1) was added to 400mL of a solution having a volume ratio of 1: 5, carrying out ultrasonic treatment on the suspension in a methyl acrylate/methanol solution at room temperature for 7 hours, then carrying out suction filtration and washing with methanol, and then carrying out rotary evaporation on the product to remove excessive methyl acrylate/methanol attached to the surfaces of the particles; in a 250mL volume ratio of 1: adding 80mL of ethylenediamine/methanol solution of 1 into the reaction product, carrying out ultrasonic reaction for 7 hours in a room-temperature water bath, washing by using the washing treatment mode, and repeating the step for at least three times;
in the step (3), 5g of the product obtained in the step (2) is added into 5mL of absolute ethyl alcohol in which 2g of dicyclohexyl-18-crown-6 (DtbuCH18C6) is dissolved, the mixture is shaken for 10 hours at 25 ℃, and after shaking, the mixture is taken out, rotated and evaporated to remove the absolute ethyl alcohol and crown ether, and then dried in a vacuum drying oven at 55 ℃.
The resin is a material formed by modifying the surface of a silicon oxide carrier, then coating the surface of the silicon oxide carrier with PAMAM polymer, and then impregnating crown ether on the surface of the silicon oxide carrier. During the preparation of the resin: 1. the properties of the silica (specific surface area, pore diameter, particle diameter) determine the particle diameter, functional group grafting ratio, etc. of the final resin; 2. the PAMAM can be more efficiently combined on the silicon substrate by modifying and activating the surface of the silicon substrate; 3. the final surface coating provides a stronger bond of the crown ether.
The advantages of the invention are shown in the following aspects:
1) the method can cover a mixed coating on the surface of the silicon oxide particles, increases the load amount of the crown ether along with the thickening of the coating, and plays a role in stabilizing the crown ether coating;
2) the preparation method is simpler and more convenient, and has lower cost than the current commercial resin;
3) the PAMAM dendritic mesoporous silicon dioxide strontium resin prepared by the method has high selectivity, high adsorption capacity, stability in a high-acid medium and high thermal stability, has performance superior to that of the current commercial product, and is expected to realize domestic substitution.
Drawings
FIG. 1 is a schematic representation of the impregnation of crown ether with silica-PAMAM particles according to the present invention;
FIG. 2 is a scanning electron micrograph of untreated silica particles of the present invention, wherein: a. full view, b. partial enlargement;
FIG. 3 is a scanning electron microscope image of the present invention in which a PAMAM coating is loaded on a silica substrate, wherein: a. full view, b. partial enlargement;
FIG. 4 is a scanning electron microscope image of the present invention in which a multi-layered PAMAM coating is loaded on a silica substrate, wherein: a. full view, b. partial enlargement;
FIG. 5 shows a resin DtbuCH18C6@ G according to the present invention 3 In a scanning electron micrograph, wherein: a. full view, b. partial enlargement;
FIG. 6 resin DtbuCH18C6@ G of the present invention 3 Scanning electron microscopy after 7M nitric acid immersion, wherein; a. full view, b. partial enlargement;
FIG. 7 is a drawing of the resin DtbuCH18C6@ G of the present invention 3 The corresponding element distribution diagram after Sr (II) is absorbed;
FIG. 8 is a graph of the infrared spectrum of the resin DtbuCH18C6 of the present invention after soaking in 1, 3, 5, 7, 9M nitric acid;
FIG. 9 is a resin DtbuCH18C6@ G of the present invention 3 Adsorption rate as a function of nitric acid concentration (C) [ solid-to-liquid ratio] ＝10g/L；C 0[Sr] ＝1ppm；t＝24h；T＝25.00℃)
FIG. 10 oscillation time pairs DtbuCH18C6@ G 3 Adsorption Rate Effect of adsorption Rate (C) [ solid-to-liquid ratio] ＝10g/L；C 0[Sr] 1 ppm; t is 25.00 ℃; acidity of nitric acid: 7M)
FIG. 11 DtbuCH18C6@ G at different initial concentrations of Sr ion 3 Adsorption Rate Change Pattern (C) [ solid-to-liquid ratio] ＝10g/L；t＝2h；
FIG. 12 DtbuCH18C6@ G at different temperatures 3 Adsorption Rate Change Pattern (C) [ solid-to-liquid ratio] ＝10g/L；C 0[Sr] 1 ppm; t is 2 h; acidity of nitric acid: 1M to 9M)
FIG. 13.DtbuCH18C6@ G 3 Selective adsorption of Sr (C) [ solid-to-liquid ratio] ＝10g/L；C 0[Sr] ＝1ppm；C 0[K，Cs，Mg，Ba] 10 ppm; t is 2 h; t is 25 ℃; acidity of nitric acid: 7M);
FIG. 14.DtbuCH18C6@ G 3 The initial concentration of Sr and the impurity of the resin is 1ppm at 10g/LEDS diagram after selective adsorption of Sr under nitric acid system with initial ion concentration of 10ppm and 7M
FIG. 15 shows the results of drying at different temperatures G 3 Resin adsorption rate as a function of acidity (C) [ solid-to-liquid ratio] ＝10g/L；C 0[Sr] 1 ppm; t is 2 h; t: 25 ℃; acidity of nitric acid: 1M to 8M).
Detailed Description
The invention is explained in detail below with reference to an embodiment.
Preparation of the resin
(1) Preparation of APTES coated micron-sized mesoporous silica particles
The surface modification of the silica particles was carried out with 3-Aminopropyltriethoxysilane (APTES) by the following steps: weighing 10g of 100-200 micron silica particles, dispersing the silica particles in 50mL of absolute ethyl alcohol, transferring the silica particles to a 500mL round-bottom flask, adding 250mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 30min by using an ultrasonic generator, adding 20mL of LAPTES at the 20 th min of ultrasonic treatment, and then carrying out ultrasonic treatment until the ultrasonic treatment is finished. The mixture was then stirred magnetically for 15 hours and the resulting product was washed with a small number of times with anhydrous methanol. Obtaining micron-sized silicon dioxide particles modified by APTES, namely APTES @ SiO 2 。
(2) Surface coating using PAMAM dendrimers
The principle is that the surface coating is carried out by using PAMAM dendritic polymer through Michael reaction, and APTES @ SiO obtained in the previous step is used 2 Also placed in a 500mL round bottom flask. Configuring 1000mL of the mixture with the volume ratio of 1: 5 to 400mL of the above solution, sonicating the suspension in a water bath at room temperature for 7 hours, suction filtering and washing with methanol after sonication, and then rotary evaporating the product to remove excess methyl acrylate/methanol adhering to the surface of the particles. Configuring a 250mL volume ratio of 1: and adding 80mL of ethylenediamine/methanol solution of 1 into the reaction product obtained in the previous step, carrying out ultrasonic reaction for 7 hours in a room-temperature water bath, and washing the product in the same manner. Repeating the above steps once to obtain a generation of product, and obtaining G 1 Repeating the above steps to obtain a secondary product G 2 Until the desired product algebra is reached, the invention relates toThe product G3 is synthesized by the following steps.
(3) Synthesis of Sr-90 resin
Accurately weighing 5gG 3 The product was placed in a 100mL centrifuge tube and 2g of bicyclohexane-18-crown-6 (DtbuCH18C6) was weighed out and dissolved in 5mL of absolute ethanol. This 5mL of ethanol was added to the centrifuge tube and mixed with G 3 Fully contacting, placing into a constant temperature oscillation box at 25 ℃ to oscillate for 10 hours, and loading crown ether in G by physical immersion 3 On the PAMAM dendritic surface coating. After the oscillation is finished, taking out the resin, performing rotary evaporation to remove absolute ethyl alcohol and crown ether, and then putting the resin into a vacuum drying oven for drying for 6 hours, wherein the temperature of the vacuum drying oven is 55 ℃ (lower than 80 ℃, and the temperature of the vacuum drying oven can be decomposed after being higher than 100 ℃), so that the resin is completely removed to obtain the final resin material which is named as DtbuCH18C6@ G 3 。
(II) material characterization:
(1) scanning electron microscopy: as can be seen from FIGS. 1 to 3, the morphology of the silica raw material is regular round spherical particles, a mixed coating is covered on part of the surface of the silica raw material modified by methyl acrylate and ethylenediamine, the coating is irregular and protruded, which indicates that the PAMAM coating is successfully loaded on the silica substrate, and the surface coating amount is gradually increased with the increase of generations (the resin material has the advantage that multiple coatings can be carried out, namely, the PAMAM coating is more and the final crown ether is more with the increase of the coating times). As can be seen in FIG. 4, G 3 After the crown ether is loaded, the ratio of the surface coating is increased, the shape is more regular and is closer to a dendritic shape, which shows that the crown ether is successfully loaded in the PAMAM coating, and simultaneously, the crown ether plays a role in stabilizing the coating and enabling the coating to be more orderly arranged. FIG. 5 shows DtbuCH18C6@ G 3 Comparing the full-looking surface image of the electron microscope after being soaked in 7M nitric acid for 24 hours at room temperature with the electron microscope image which is not soaked in the nitric acid, the PAMAM dendritic coating of the full-looking or the surface has no obvious change, and the resin can be preliminarily known to have certain acid resistance. FIG. 6 shows DtbuCH18C6@ G 3 The distribution diagram of four elements of C, N, O and Sr after Sr is adsorbed under the acidity condition of 7M nitric acid, the C element can be mainly distributed outside the particles, and the experiment utilizes methyl acrylateThe assumption of surface coating is made, and at the same time, a small part of C element is distributed in the particle interior due to the mesoporous structure of the silicon dioxide. Ethylenediamine is linked to methyl acrylate by the Michael reaction, which is well illustrated by the N element distribution diagram, which is consistent with the C element and contains less than C. DtbuCH18C6@ G 3 The O element(s) in (b) is derived primarily from the silica matrix and thus can be seen on the graph as enriched within the spherical particles, while the source of the O element(s) outside the particles is methyl acrylate and supported crown ether. The Sr element distribution diagram shows that the Sr element distribution diagram has no fixed distribution area, the Sr absorption is mainly dependent on the absorption capacity of the crown ether cavity, the Sr element distribution diagram is shown from the other side to be a crown ether site diagram, the mesoporous structure of the silicon dioxide enables the crown ether to enter the mesoporous structure for absorption, and the PAMAM coating on the particle surface provides a load point for the crown ether.
(2) Infrared spectrum (FT-IR): FIG. 7 shows DtbuCH18C6@ G 3 The infrared spectrogram after soaking in 1, 3, 5, 7 and 9M nitric acid shows that the chemical bond inside the resin is not changed after soaking in nitric acid with different concentrations, which indicates that the nitric acid cannot break the structure of the resin, according to the comparison of spectral lines, DtbuCH18C6@ G 3 Has excellent acid resistance.
(3) Specific surface area (BE T) analysis: SiO 2 2 ，G 1 ，G 3 ，DtbuCH18C6@G 3 Specific surface measurements were made and the results are shown in Table 1. As can be seen from the table, the mesoporous silica matrix has a larger specific surface area, and the specific surface area of the material gradually becomes smaller as the surface coating is continuously carried out, because the surface coating covers the mesoporous structure, so that the specific surface area of the material is reduced, and DtbuCH18C6@ G after the crown ether is loaded 3 The specific surface area is almost zero, which further demonstrates that the active sites on the surface of the modified support material of the invention are all occupied by crown ethers, which is why the resin has a high adsorption capacity.
TABLE 1 specific surface area (BET) measurement data
(III) testing of Properties
(4) Influence of acidity on adsorption rate: as can be seen from FIG. 8, the solid-to-liquid ratio was 10g/L, the temperature was 25 ℃ and the initial Sr concentration was 1ppm within the range of 0.5M to 8M in nitric acid acidity, and the adsorption rate increased with the increase in acidity. When the acidity is low, the adsorption capacity is weak, and when the acidity reaches 2M, the adsorption capacity is greatly improved. The maximum adsorption rate of 61% was reached at 7M nitric acid acidity and an equilibrium was reached, which is why subsequent experiments chose a system acidity of 7M. (Experimental conditions: solid-to-liquid ratio 10g/L, temperature 25 ℃, initial concentration of Sr 1ppm)
(5) Influence of shaking time on adsorption rate: oscillation time pair DtbuCH18C6@ G 3 The influence of Sr adsorption is shown in FIG. 9, the adsorption process is a relatively fast equilibrium reaction, and it can be seen that the adsorption rate can reach more than 50% of the maximum adsorption in ten minutes, indicating that the material has good adsorption kinetics. The adsorption rate rapidly rises to 50% in 1 hour, the adsorption rate is accelerated and slowed down in 1-2 hours, and the maximum adsorption rate reaches 61% in 2 hours, and the maximum adsorption rate is basically consistent with the maximum adsorption rate of the acidity of the 7M nitric acid. In the initial stage of adsorption within 1 hour, the surface of the adsorbent has a large amount of cavity crown ether, so that sufficient adsorption sites are provided, and the free Sr concentration on the surface is high, so that the adsorption rate is high. And the adsorption rate slows down with time within 1-2 hours and finally reaches the equilibrium because of the reduction of the cavity crown ether and the reduction of the surface Sr concentration.
(6) Influence of initial Sr (II) concentration on adsorption behavior: the influence of the initial Sr ion concentration on the adsorption capacity of the resin is shown in fig. 10, and it is understood from the graph that the adsorption rate gradually decreases as the initial Sr ion concentration increases. The adsorption capacity after fitting is 43mg/g, which is higher than 27mg/g of Sr special-effect resin.
(7) Influence of adsorption temperature on adsorption rate: as can be seen from fig. 11, temperature is a factor that affects the adsorption process of the resin, and the adsorption rate at high temperature is greater than that at lower temperature at the same acidity. At the same time, the high temperature brings the adsorption process to equilibrium more quickly, so that the adsorption process is an endothermic reaction. It is noted that temperature does not substantially affect the adsorption capacity of the resin, and the maximum adsorption rates at both temperatures are within the error of 61% of the theoretical maximum adsorption rate.
(8) Ion selectivity: FIG. 12 shows the selective adsorption of Sr by the resin under the conditions of solid-to-liquid ratio of 10G/L, acidity of 7M nitric acid, initial concentration of Sr of 1ppm, concentration of interfering cations of 10ppm, temperature of 25 ℃ and reaction time of 2h, and DtbuCH18C6@ G 3 The adsorption selectivity sequence for divalent metal ions is Sr 2+ >Ba 2+ >Cs 2+ >K 2+ >Mg 2+ Meanwhile, the adsorption rate is maintained at the theoretical maximum value of 61%, which shows that the impurity cations do not influence the adsorption capacity of Sr. K and Mg are not basically adsorbed by the resin, the interference capability is extremely weak, and Cs and Ba are slightly adsorbed along with Sr under the same adsorption condition, so that the resin is applied to pay extra attention to the two ions. FIG. 13 is an EDS diagram after selective adsorption of Sr by the resin under the acidity system of 10g/L, initial Sr concentration of 1ppm, initial impurity cation concentration of 10ppm and 7M nitric acid, and it can be seen that the adsorption amount of Sr by the resin is not greatly influenced by the influence of impurity cations.
(9) Thermal stability was investigated: FIG. 14 is a graph showing the initial concentration of Sr of 1ppm and the change of adsorption rate with nitric acid acidity after the resin is dried at 50 and 80 ℃ respectively. As can be seen from the figure, under most acidity conditions, the adsorption rate of the resin to Sr after being dried at 80 ℃ is lower than that under 50 ℃, and the maximum adsorption rate of the resin is consistent with that under normal temperature no matter at 50 ℃ or 80 ℃, so the resin has good thermal stability.
Claims (6)
1. The Sr-90 adsorbing resin comprises a support body and an extracting agent loaded on the support body, and is characterized in that the support body has a structure shown in the formula
2. The Sr-90 adsorbing resin according to claim 1, wherein the extractant supported on the support is crown ether capable of adsorbing Sr-90.
3. The Sr-90 adsorbing resin according to claim 2, wherein the crown ether capable of adsorbing Sr-90 as the extractant carried on the support is dicyclohexyl-18-crown-6.
4. The method for preparing the resin for adsorbing Sr-90 of claim 3, wherein the mesoporous silica particles are modified to prepare micron-sized mesoporous silica particles coated with 3-aminopropyltriethoxysilane, the surface coating of the polyamide dendrimer is attached to the surfaces of the micron-sized mesoporous silica particles coated with 3-aminopropyltriethoxysilane, and then the PAMAM dendrimer surface coating is loaded with the dicyclohexyl-18-crown-6 crown ether by immersion.
5. The method for preparing resin adsorbing Sr-90 according to claim 4, wherein:
(1) surface modification of silica particles
Dispersing micron-sized silicon dioxide particles in absolute ethyl alcohol, carrying out ultrasonic treatment by using an ultrasonic generator, adding 3-aminopropyltriethoxysilane into the mixture, then continuing to carry out full ultrasonic treatment, fully stirring the treated mixture, and fully cleaning the mixture by using absolute methyl alcohol to obtain 3-aminopropyltriethoxysilane modified micron-sized silicon dioxide particles;
(2) the polyamide dendritic polymer is used for forming a coating on the surface of APTES modified micron-sized silicon dioxide particles
Adding the product obtained in the last step into methyl acrylate/methanol solution, fully performing ultrasonic treatment on the suspension in room-temperature water bath, performing suction filtration, washing with methanol, and performing rotary evaporation on the product to remove excessive methyl acrylate/methanol attached to the surfaces of particles; then putting the mixture into an ethylenediamine/methanol solution, carrying out water bath at room temperature for sufficient ultrasound, and washing the product with a methyl acrylate/methanol solution to obtain a required intermediate product;
(3) synthesis of Sr-90 adsorbing resin
And (3) taking 5g of the product obtained by the previous step, putting 2g of dicyclohexyl-18-crown-6 into absolute ethyl alcohol, fully oscillating to enable the dicyclohexyl and the crown-6 to be fully contacted, taking out, rotationally evaporating to remove the absolute ethyl alcohol and the crown ether, and drying in a vacuum drying oven at the temperature lower than 80 ℃ to obtain the final resin material.
6. The method of claim 5, wherein:
in the step (1), 10g of 100-200 micron silicon dioxide particles are taken and dispersed in 50mL of absolute ethyl alcohol, 250mL of absolute ethyl alcohol is added, ultrasonic treatment is carried out on the silicon dioxide particles for 20min by an ultrasonic generator, 20mL of APTES is added, ultrasonic treatment is carried out for 10min again, the mixture is stirred for 15 hours, and the obtained product is washed by a small amount of absolute methyl alcohol for multiple times;
in the step (2), adding 8-12 g of the product obtained in the step (1) into 400mL of a mixture with a volume ratio of 1: 5, carrying out ultrasonic treatment on the suspension in a methyl acrylate/methanol solution at room temperature for 7 hours, then carrying out suction filtration and washing with methanol, and then carrying out rotary evaporation on the product to remove excessive methyl acrylate/methanol attached to the surfaces of the particles; in a 250mL volume ratio of 1: adding 80mL of ethylenediamine/methanol solution of 1 into the reaction product, carrying out ultrasonic reaction for 7 hours in a room-temperature water bath, washing by using the washing treatment mode, and repeating the step for at least three times;
in the step (3), 5g of the product obtained in the step (2) is added into 5mL of absolute ethyl alcohol in which 2g of dicyclohexyl-18-crown-6 (DtbuCH18C6) is dissolved, the mixture is shaken for 10 hours at 25 ℃, and after shaking, the mixture is taken out, rotated and evaporated to remove the absolute ethyl alcohol and crown ether, and then dried in a vacuum drying oven at 55 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210658461.2A CN114887603B (en) | 2022-06-12 | 2022-06-12 | Resin for adsorbing Sr-90 and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210658461.2A CN114887603B (en) | 2022-06-12 | 2022-06-12 | Resin for adsorbing Sr-90 and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114887603A true CN114887603A (en) | 2022-08-12 |
| CN114887603B CN114887603B (en) | 2023-08-18 |
Family
ID=82727288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210658461.2A Active CN114887603B (en) | 2022-06-12 | 2022-06-12 | Resin for adsorbing Sr-90 and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114887603B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117024642A (en) * | 2023-08-10 | 2023-11-10 | 兰州大学 | Scintillation resin with strontium-90 separation and detection functions and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5344623A (en) * | 1993-06-15 | 1994-09-06 | The United States Of America As Represented By The United States Department Of Energy | Process for the extraction of strontium from acidic solutions |
| US6511603B1 (en) * | 2000-10-24 | 2003-01-28 | Arch Development Corp. | Alkaline earth cation extraction from acid solution |
| CN101058065A (en) * | 2007-06-07 | 2007-10-24 | 浙江大学 | Adsorbent capable of separating heating element cesium and strontium at the same time and its preparation method and application |
| CN105478097A (en) * | 2015-12-25 | 2016-04-13 | 北京大学 | Strontium-yttrium separation resin as well as preparation and application thereof |
| RU2636482C1 (en) * | 2016-10-04 | 2017-11-23 | Николай Алексеевич Бежин | Method of producing sorbents based on media and crown ethers and 1,1,7-trihydrododecafluoroheptanol-1 as diluent |
| US20180345247A1 (en) * | 2017-06-06 | 2018-12-06 | Somaye Akbari | Modification of halloysite mineral adsorbent by dendritic polymer in convergent synthetic route and its application |
-
2022
- 2022-06-12 CN CN202210658461.2A patent/CN114887603B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5344623A (en) * | 1993-06-15 | 1994-09-06 | The United States Of America As Represented By The United States Department Of Energy | Process for the extraction of strontium from acidic solutions |
| US6511603B1 (en) * | 2000-10-24 | 2003-01-28 | Arch Development Corp. | Alkaline earth cation extraction from acid solution |
| CN101058065A (en) * | 2007-06-07 | 2007-10-24 | 浙江大学 | Adsorbent capable of separating heating element cesium and strontium at the same time and its preparation method and application |
| CN105478097A (en) * | 2015-12-25 | 2016-04-13 | 北京大学 | Strontium-yttrium separation resin as well as preparation and application thereof |
| RU2636482C1 (en) * | 2016-10-04 | 2017-11-23 | Николай Алексеевич Бежин | Method of producing sorbents based on media and crown ethers and 1,1,7-trihydrododecafluoroheptanol-1 as diluent |
| US20180345247A1 (en) * | 2017-06-06 | 2018-12-06 | Somaye Akbari | Modification of halloysite mineral adsorbent by dendritic polymer in convergent synthetic route and its application |
Non-Patent Citations (2)
| Title |
|---|
| A. ZHANG 等: "Kinetics of the adsorption of strontium(II) by a novel silica-based 4,4,(5)-di(tert-butylcyclohexano)-18-crown-6 extraction resin in nitric acid medium", JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY * |
| 何海峰 等: "聚酰胺胺改性纳米二氧化硅的研究进展", 材料导报 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117024642A (en) * | 2023-08-10 | 2023-11-10 | 兰州大学 | Scintillation resin with strontium-90 separation and detection functions and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114887603B (en) | 2023-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bai et al. | A novel functional porous organic polymer for the removal of uranium from wastewater | |
| Hu et al. | Selective separation and preconcentration of Th (iv) using organo-functionalized, hierarchically porous silica monoliths | |
| Yue et al. | Polymer-coated nanoporous carbons for trace seawater uranium adsorption | |
| Khdary et al. | Polymer-silica nanocomposite membranes for CO2 capturing | |
| Gan et al. | Synergistic action of multiple functional groups enhanced uranium extraction from seawater of porous phosphorylated chitosan/coal-based activated carbon composite sponge | |
| US9468923B2 (en) | Porous polymer networks and ion-exchange media and metal-polymer composites made therefrom | |
| CN107970878B (en) | Preparation method of phosphate group functionalized hollow mesoporous silica microspheres | |
| CN103946161A (en) | Complex comprising crystalline hybrid nanoporous material powder | |
| Zhou et al. | Modification of ZIF-8 on bacterial cellulose for an efficient selective capture of U (VI) | |
| Amesh et al. | Diethylenetriamine tethered mesoporous silica for the sequestration of uranium from aqueous solution and seawater | |
| CN114887603A (en) | Resin for adsorbing Sr-90 and preparation method thereof | |
| Zhang et al. | An imidazole functionalized porous organic polymer for the highly efficient extraction of uranium from aqueous solutions | |
| CN113842889A (en) | Microwave synthesis metal organic framework material DUT-5(Al) and synthesis method and application thereof | |
| CN113877549A (en) | Selective composite microsphere adsorption material and preparation method and application thereof | |
| CN110665482B (en) | Preparation method of chitosan composite microspheres for removing chromium and copper heavy metal ions | |
| US10086359B1 (en) | Adsorption material for removing chemical compounds from water and method of making the same | |
| CN106633215A (en) | Sulfonated beta-cyclodextrin-LDH complex and synthesis method thereof | |
| CN116219634A (en) | Preparation method of nanofiber membrane with covalent organic framework | |
| CN108250381B (en) | Preparation method and application of selenium-containing phenolic resin microspheres | |
| Marvaniya et al. | Polymeric nano-films with spatially arranged compartments for uranium recovery from seawater | |
| CN114832791A (en) | Nitrogen-doped zirconium-based organic metal framework adsorbent containing mixed ligand, preparation method and application | |
| CN115350689A (en) | Preparation method of IL @ MOF composite material and application of IL @ MOF composite material in gas adsorption separation | |
| CN107213877B (en) | Synthetic method of imprinted mesoporous material with high selectivity to bisphenol A | |
| Zhang et al. | Preparation of particle reusable heterogeneous catalyst Fe3O4/ATP for methylene blue decolorization. | |
| CN115739043B (en) | Triazine structure functionalized cationic organic polymer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |