CN114700051A - Method for adsorbing Np (IV) and Pu (IV), resin and preparation method thereof - Google Patents
Method for adsorbing Np (IV) and Pu (IV), resin and preparation method thereof Download PDFInfo
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- CN114700051A CN114700051A CN202210352260.XA CN202210352260A CN114700051A CN 114700051 A CN114700051 A CN 114700051A CN 202210352260 A CN202210352260 A CN 202210352260A CN 114700051 A CN114700051 A CN 114700051A
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- cmpo
- diisobutylaminocarbonyl
- phosphine oxide
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- 239000011347 resin Substances 0.000 title claims abstract description 96
- 229920005989 resin Polymers 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 11
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000011159 matrix material Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- HXZSFRJGDPGVNY-UHFFFAOYSA-N methyl(oxido)phosphanium Chemical compound C[PH2]=O HXZSFRJGDPGVNY-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000009755 vacuum infusion Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 46
- 238000000926 separation method Methods 0.000 abstract description 12
- 239000002253 acid Substances 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- SGZRFMMIONYDQU-UHFFFAOYSA-N n,n-bis(2-methylpropyl)-2-[octyl(phenyl)phosphoryl]acetamide Chemical compound CCCCCCCCP(=O)(CC(=O)N(CC(C)C)CC(C)C)C1=CC=CC=C1 SGZRFMMIONYDQU-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910052778 Plutonium Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 238000000638 solvent extraction Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000006399 behavior Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002901 radioactive waste Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000622 liquid--liquid extraction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 3
- -1 plutonium ions Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- OYEHPCDNVJXUIW-FTXFMUIASA-N 239Pu Chemical compound [239Pu] OYEHPCDNVJXUIW-FTXFMUIASA-N 0.000 description 1
- KWPGVWHAJORRAP-UHFFFAOYSA-N N,N-bis(2-methylpropyl)-1-[nonyl(phenyl)phosphoryl]formamide Chemical compound C(CCCCCCC)CP(C(N(CC(C)C)CC(C)C)=O)(C1=CC=CC=C1)=O KWPGVWHAJORRAP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
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- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000002927 high level radioactive waste Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002925 low-level radioactive waste Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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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
-
- 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
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
Abstract
The invention discloses a method for adsorbing radionuclide, and a resin preparation method used in the method. The resin is prepared by fully impregnating N-octyl phenyl-N, N-diisobutylaminocarbonyl methyl phosphine oxide and tributyl phosphate on CMPO @ XAD-7HP resin. The resin has high adsorption capacity for Np (IV) and Pu (IV), and can be used for high-efficiency separation of Np (IV) and Pu (IV) in a high-acid medium.
Description
Technical Field
The invention relates to a method for adsorbing radionuclide, resin used in the method and a preparation method of the resin, in particular to a method for adsorbing Np (IV) and Pu (IV), the resin and a preparation method thereof.
Background
The radioactive waste liquid contains a large amount of alpha radioactive nuclide, including various transuranics, such as237Np、238Pu、240Pu, etc., the half-life of the radionuclides is longer, and the subsequent treatment of the high level radioactive waste liquid is greatly influenced. At the same time as this is done,237Np、238pu has more purposes and can be used for manufacturing nuclear batteries on space detectors and nuclear power generation. The effective recovery and separation of Pu and Np are of great significance from the aspects of environment, safety, resource utilization and the like.
The common separation method for Pu and Np in the radioactive waste liquid mainly comprises a precipitation method, a liquid-liquid extraction method, a solid phase extraction method and the like. The precipitation method for separating Pu and Np is usually carried out by repeated precipitation and dissolution of bismuth phosphate, the operation is complicated, the reagent loss is excessive, and simultaneously a large amount of waste liquid is generated (reference: Zhang shou Hua, Shenwei, Liqiaozhen, Shenquan. bismuth phosphate precipitation carrier band-anion exchange method for measuring plutonium-239 [ J ]. atomic energy science in food, 1982(04):463 and 467. Meng et Shen, Lu Xiui, Lishun. experimental study for treating plutonium-containing waste water based on improved coprecipitation method [ J ]. nuclear fusion and plasma physics, 2019,39(02): 169). Phosphine and amide extractants are commonly used in liquid-liquid extraction, wherein the phosphine extractant octyl (phenyl) -N, N-diisobutylcarbamoyl methyl phosphine oxide (CMPO) has the best combination property, Pu and Np can be simultaneously separated (references: SenguptaA, Murali M S, Thulasidas S K, et al. solvent system connecting CMPO as the extractant in a two-dimensional mixture connecting N-side and isocatalytic for activating peptide purification run [ J ] hydrometallar, 2014,147: 228. Sun 233. Pan. O extraction monoamide back-extraction/alpha. spectroscopy analysis of low-level waste liquid [ 237 ] Np, (239+240) Pu, ((Cm) J. March. J. 12. Roman. P. 12. P. Np (VI), Pu (IV) and U (VI) with amines, BEHSO and CMPO from nitrile acid medium [ J ]. Radiochimica Acta,1996,73(4): 199-. However, the separation by liquid-liquid extraction method generates a large amount of organic waste, and the stripping and solution washing processes require a large amount of reagents and equipment, so that the treatment process and waste disposal costs are greatly increased, and the method is not an optimal method for separating Pu and Np. Solid phase extraction is a separation method developed by combining solid-liquid extraction and column liquid chromatography separation technology in recent years, and can be used for enrichment, concentration, purification and separation of target samples. Not only contains the advantages of the solvent extraction method, but also improves the disadvantages of the solvent extraction method in industrial application. The solid phase extraction is carried out by grafting various common extractants onto a solid phase material by the methods of Zhang A, Wei Y, Kumagai M, et al, A new partial process for high-level liquid chromatography using silica-substrate chemical chromatography [ J ]. Journal of Alloys and Compounds,2005,390(1-2): 275. 281. Zhang A, Wei Y, Kumagai M, et al. organic solvent synthesis of a novel silica-substrate organic solvent, N-dimethyl carbonate synthesis [ 463, J.: phosphor-amide synthesis, and Chemistry [ 72. gamma. ] 3. 13. 11. 9. Zhang A, Wei Y, Kumagai M, et al. organic solvent synthesis of a novel silica-substrate oxidation reaction [ 463. J. ]. 3. 13. 3. three. four. 3. four. three. eight. three. four. eight. three. four. three. four. three. four. three. four. three. four. three. four. three. four. The solid phase extraction has the advantages of high adsorption capacity, no secondary waste liquid generation and the like, so the method is widely applied to radionuclide separation. Triskm has developed a commercial TRU resin for the separation of Np (IV) and Pu (IV) which has a good separation effect on Np (IV) and Pu (IV), but the resin has a small particle size and is expensive (400 yuan/1 g) and cannot be used on a large scale.
Patent application 202111054476.X discloses a pyridine functional group-containing resin, a preparation method and an application thereof, the prepared resin contains a pyridine functional group, the pyridine functional group is a strongly basic anion exchange resin after quaternization, the quaternized pyridine functional group is a six-membered ring structure, the size is close to that of plutonium ions, a stable complex structure can be formed with the plutonium ions, and the plutonium can be separated from low-concentration radioactive waste liquid containing the plutonium.
Disclosure of Invention
The invention provides a method for adsorbing Np (IV) and Pu (IV), and an adsorption resin which has high adsorption capacity and high acid resistance, and particularly is superior to and can replace TRU resin.
The method for adsorbing Np (IV) and Pu (IV) uses a large-particle-size solid-phase resin which can replace the existing resin to extract the Np (IV) and Pu (IV) in a nitric acid extraction system, particularly in a high-acidity system, and the adopted resin is a modified CMPO @ XAD-7HP resin.
The modified CMPO @ XAD-7HP resin is prepared by fully impregnating N-octylphenyl-N, N-diisobutylaminocarbonyl methyl phosphine oxide and tributyl phosphate on CMPO @ XAD-7HP resin.
The preparation method of the modified CMPO @ XAD-7HP resin comprises the steps of soaking the CMPO @ XAD-7HP resin in an ethanol solution of N-octylphenyl-N, N-diisobutylaminocarbamyl methyl phosphine oxide and tributyl phosphate for full impregnation, removing ethanol, and drying to obtain a target product.
The preparation process includes soaking XAD-7HP solution with inorganic matter removed in ethanol solution of N-octyl phenyl-N, N-diisobutylaminocarbonyl methyl phosphine oxide and tributyl phosphate at room temperature, eliminating ethanol, washing with water and drying.
The preferred resin preparation method of the present invention is: weighing 5g of inert matrix XAD-7HP with the particle size of 0.5-1mm, putting the inert matrix XAD-7HP into a container, adding 50mL of methanol solution, oscillating for 30 minutes, repeating for 4-5 times, then washing with 5% by mass of hydrochloric acid and 50mL of 0.5mol/L of sodium hydroxide respectively, repeating the steps for 4-5 times, then washing with ultrapure water to be neutral, vacuum-filtering, and vacuum-drying the filtered resin at 60 ℃ for 24 hours; weighing 5g of the inert matrix XAD-7HP which is treated and dried according to the steps, putting the inert matrix XAD-7HP into a container, weighing 2g of the extracting agent N-octylphenyl-N, N-diisobutylaminocarbonyl methyl phosphine oxide and 3.14g of tributyl phosphate, adding the extracting agent N-octylphenyl-N, N-diisobutylaminocarbonyl methyl phosphine oxide and the 3.14g of tributyl phosphate into 25mL of absolute ethyl alcohol serving as a diluent, adding the absolute ethyl alcohol into the container, oscillating at room temperature for 24h, carrying out vacuum infusion at the temperature of 60 ℃, then removing the absolute ethyl alcohol, then dipping for 10-12h, washing for 5-6 times by using ultrapure water, and then carrying out vacuum drying to obtain the CMPO @ XAD-7HP resin.
The resin is a large-particle-size spherical material, has high adsorption capacity on Np (IV) and Pu (IV), can be used for high-efficiency separation of the Np (IV) and the Pu (IV) in a high-acid medium, and provides a new method, a new material and a new technology for extracting the Np (IV) and the Pu (IV) from radioactive waste liquid. Relevant experiments show that the resin of the invention has better performance than TRU resin and has great potential in replacing TRU resin which is a foreign product in a domestic product.
Drawings
FIG. 1 shows an infrared spectrum of a material according to the invention.
FIG. 2 is a scanning electron microscope of the material of the present invention.
FIG. 3 is a thermogravimetric plot of the material of the present invention.
FIG. 4 shows the comparison of the adsorption effect of the material of the present invention on Th (IV) adsorption with that of TRU resin.
FIG. 5 shows the effect of concentration on Th (IV) adsorption of the material of the invention.
FIG. 6 shows the adsorption kinetics of the material of the present invention when subjected to Th (IV) adsorption.
FIG. 7 shows the thermodynamics of adsorption when the material of the present invention is subjected to Th (IV) adsorption.
Detailed Description
The present invention uses CMPO as The main extractant in solid phase resin, and related studies show that The CMPO extractants have very similar extraction behavior and mechanism to Np (IV), Pu (IV) and Th (IV), while commercial TRU resins exhibit The same adsorption behavior to Np (IV), Pu (IV) and Th (IV) (refer to Philip Horwitz E, Diamond H, Martin KA. The extraction of selected interactions in The III (IV) and VI) oxidation states of hydrochloric acid by O π D (iB) CMPO. The TRUX-chlorine process [ J ]. Solvent extraction and exchange,1987,5(3 447) -. Because Np (IV) and Pu (IV) are not easy to obtain, Th (IV) is used as the analogues of Np (IV) and Pu (IV) in the experiment to explore the adsorption behavior of the analogues on the CMPO @ XAD-7HP resin, and thus reference is provided for the application of the resin in the separation of Np (IV) and Pu (IV).
The following are specific examples of the present invention.
Preparation method of (I) CMPO @ XAD-7HP resin
1) Purification of inert matrix XAD-7HP
5g of inert matrix XAD-7HP with the particle size of 0.5-1mm is weighed into a centrifuge tube, 50mL of methanol solution is added, the mixture is shaken for 30 minutes, and the process is repeated for 4-5 times. Then, the steps are repeated for 4 to 5 times by using 50mL of each of 5 percent hydrochloric acid and 0.5mol/L sodium hydroxide, so as to achieve the aim of removing inorganic matters in the matrix. Finally, washing the mixture to be neutral by using ultrapure water, and removing acid or alkali remained after washing. Vacuum filtration, the filtered resin at 60 ℃ vacuum drying for 24 h.
2) Preparation of large-particle-size CMPO @ XAD-7HP resin
5g of inert matrix XAD-7HP which is dried according to the steps is weighed and placed into a centrifuge tube, 2g of extracting agent N-octylphenyl-N, N-diisobutylaminocarbonyl methyl phosphine oxide (CMPO) and 3.14g of tributyl phosphate (TBP) are weighed and added into the centrifuge tube, and 25mL of absolute ethyl alcohol is used as a diluent. Shaking at room temperature for 24 hr, vacuum infusing at 60 deg.C, removing anhydrous ethanol, and soaking for 10-12 hr. The resin was washed 5-6 times with ultrapure water to give CMPO @ XAD-7HP resin, which was dried under vacuum for 24 h.
(II) characterization spectra of the inventive Material
Infrared spectrum: FIG. 1 is an infrared spectrum of XAD-7HP, CMPO @ XAD-7HP resin. By comparing the IR spectra of the inert matrix XAD-7HP with that of CMPO @ XAD-7 resin, it can be seen that XAD-7HP was 1738cm-1The peak is a stretching vibration peak of C ═ O in XAD-7HP, and the intensity of the peak is obviously reduced by comparison analysis, and the peak is possibly introduced into organic matters such as CMPO @ XAD-7HP to reduce peaks of some characteristic functional groups on XAD-7 HP. A study also found that 1210cm of IR spectrum of CMPO @ XAD-7HP resin-1A weak peak appears due to stretching vibration of the P ═ O group, 3430cm-1And 1028cm-1The appearance of the two peaks indicates that the CMPO and TBP are successfully impregnatedInto an inert matrix XAD-7 HP.
Scanning electron micrograph: and observing the change of the surface morphology of the resin before and after impregnation by using a scanning electron microscope. As can be seen from the attached FIG. 2, the impregnated CMPO @ XAD-7HP resin is consistent in morphology with the non-impregnated XAD-7HP inert matrix, and no significant change occurs before and after impregnation. While it can be seen from FIG. 2 (b) that there are a small number of agglomerates on the surface, the impregnation of CMPO and TBP into the inert matrix XAD-7HP has been successful by the impregnation method. FIG. 2 (d) shows the resin after absorbing Th (IV) under high acidity conditions, and by comparing FIG. 3 with FIG. 7, it can be seen that 4M HNO3The appearance of the CMPO @ XAD-7HP resin before and after adsorption is not changed under the condition, which shows that the CMPO @ XAD-7HP resin has better stability in a high-acid system.
Thermogravimetric curve: as shown in figure 3, the weight loss part of XAD-7HP in 30-100 ℃ is the water content in the resin; at about 160 ℃, CMPO @ XAD-7HP begins to lose weight, and the structure of XAD-7HP keeps stable, which indicates that the main functional group CMPO of the resin begins to decompose; XAD-7HP begins to lose weight at about 290 ℃, and the resin matrix structure is decomposed; the weight loss curves for XAD-7HP and CMPO @ XAD-7HP begin to coincide at around 340 deg.C, indicating that the CMPO has completely decomposed. Thermogravimetric analysis data show that the CMPO @ XAD-7HP has stable structure within 160 ℃ and can be applied to adsorption reaction in solution. The thermal stability of the resin CMPO @ XAD-7HP at 0-100 ℃ is higher.
(III) adsorption test
Comparison of the adsorption Effect of CMPO @ XAD-7HP with TRU resin: solid-to-liquid ratio of 5.0g/L, 0.5-10M HNO3The Th (IV) concentration of the solution was 100 ppb. FIG. 4 shows that the HNO is between 0.5 and 10M3Under the condition, the K of the CMPO @ XAD-7HP resin synthesized by the invention to Th (IV)dSignificantly higher than commercial TRU resins at acidity>3M HNO3Adsorption K of Th (IV) by CMPO @ XAD-7HP resindThe value is about one order of magnitude higher than the TRU resin. At the same time, the CMPO @ XAD-7HP resin is HNO with the acidity of 0.5-10M3In the range, excellent adsorption effect was exhibited for both th (iv) and the effect was far superior to that of the commercial TRU resin. Because the resin synthesized by the invention has the advantages of large particle size, high acid resistance, high adsorption performance and the like,the adsorption effect of the resin on Th (IV) can be greatly improved, and the adsorption capacity of the resin is obviously higher than that of commercial TRU resin, so that the resin has great potential in replacing commercial TRU resin in a home-made mode.
Comparison of the physicochemical properties of the existing commercial TRU resin with the CMPO @ XAD-7HP resin of the present invention: comparing the TRU resin with the CMPO @ XAD-7HP resin in particle size range, density, acid and alkali resistance range and maximum K for Th (IV)dValues, etc., and the results are shown in Table 1. By comparative analysis, it was found that the CMPO @ XAD-7HP resin exhibited a higher adsorption K to Th (IV) while possessing a large particle sizedThe value, which is comparable to commercial TRU resins in acid resistance, while the resin has a density greater than water, is effective in increasing the contact area with metal ions in aqueous solutions. From the above aspects, the CMPO @ XAD-7HP resins all exhibited excellent properties, even in terms of particle size, density and adsorption KdThe value is higher than that of the commercial TRU resin, and the method is expected to realize the replacement of the commercial TRU resin in a home-made mode.
TABLE 1 physicochemical Properties of TRU resin and CMPO @ XAD-7HP resin
Adsorption Performance on Th (IV) and Pu (IV) of CMPO @ XAD-7HP resin: FIG. 2 shows that the adsorption rates for Th (IV) and Pu (IV) of CMPO @ XAD-7HP resin are 99.74% and 99.20%, respectively. The resin shows good adsorption performance on Th (IV) and Pu (IV) and the adsorption effect is almost consistent, and further proves that the CMPO @ XAD-7HP resin has extremely similar adsorption behaviors on Th (IV) and Pu (IV) and provides strong evidence for experiments using Th (IV) as a substitute for subsequent experiments.
TABLE 2 adsorption Performance on Th (IV) and Pu (IV) of CMPO @ XAD-7HP resin
Initial concentration effects: solid-to-liquid ratio of 15.0g/L, 3M HNO3The Th (IV) concentration of the solution was 1 ppm. Adsorption isotherms were fitted using the Langmuir and Freundlich models, and the results are shown in figure 5, which fit more closely to the Langmuir model, indicating predominantly monolayer adsorption. The saturation adsorption capacity of Th (IV) on CMPO @ XAD-7HP resin was calculated by simulations to be 31.85mg/g at room temperature.
Adsorption kinetics: solid-to-liquid ratio of 15.0g/L, 3M HNO3The Th (IV) concentration of the solution was 1 ppm. The Th (IV) adsorption of the impregnated resin shows a rapid increasing trend along with the increase of the contact time, and the adsorption rate of the resin can reach about 90 percent at 15 min. Until about 30min, the adsorption sites are saturated, the curve tends to be balanced, the adsorption rate basically keeps unchanged, and the maximum adsorption rate is reached, so that the resin is proved to have faster adsorption kinetics, and the adsorption balance can be reached in 30 min.
Adsorption thermodynamics: solid-to-liquid ratio of 15.0g/L, 3M HNO3The Th (IV) concentration of the solution was 1 ppm. As the temperature increases, the adsorption rate of the CMPO @ XAD-7HP resin to Th (IV) shows an increasing trend, which indicates that the adsorption of Th (IV) by the adsorbent is an endothermic reaction. The temperature rise can obviously promote the forward progress of the reaction, and proves that the solid phase extraction resin CMPO @ XAD-7HP has better adsorption to Th (IV) within the temperature range of 25-55 ℃.
Claims (5)
1. A method for adsorbing Np (IV) and Pu (IV) is characterized in that modified CMPO @ XAD-7HP resin is adopted for extraction.
2. The modified CMPO @ XAD-7HP resin of claim 1, wherein the CMPO @ XAD-7HP resin is substantially impregnated with N-octylphenyl-N, N-diisobutylaminocarbonyl methyl phosphine oxide and tributyl phosphate.
3. The method for preparing a modified CMPO @ XAD-7HP resin according to claim 2, wherein the CMPO @ XAD-7HP resin is immersed in an ethanol solution of N-octylphenyl-N, N-diisobutylaminocarbonyl methyl phosphine oxide and tributyl phosphate to be sufficiently impregnated, followed by ethanol removal and drying to obtain the desired product.
4. The method for producing a resin according to claim 3, wherein XAD-7HP from which inorganic substances are sufficiently removed is immersed in ethanol in which N-octylphenyl-N, N-diisobutylaminocarbonyl methyl phosphine oxide and tributyl phosphate are dissolved at room temperature with sufficient shaking, followed by removal of ethanol, thorough washing with water and drying treatment.
5. The method for producing a resin according to claim 4, characterized in that: weighing 5g of inert matrix XAD-7HP with the particle size of 0.5-1mm, putting the inert matrix XAD-7HP into a container, adding 50mL of methanol solution, oscillating for 30 minutes, repeating for 4-5 times, then washing with 5% by mass of hydrochloric acid and 50mL of 0.5mol/L of sodium hydroxide respectively, repeating the steps for 4-5 times, then washing with ultrapure water to be neutral, vacuum-filtering, and vacuum-drying the filtered resin at 60 ℃ for 24 hours; weighing 5g of inert matrix XAD-7HP which is dried according to the steps, putting the inert matrix XAD-7HP into a container, simultaneously weighing 2g of extracting agent N-octylphenyl-N, N-diisobutylaminocarbonyl methyl phosphine oxide and 3.14g of tributyl phosphate, adding the extracting agent N-octylphenyl-N, N-diisobutylaminocarbonyl methyl phosphine oxide and the 3.14g of tributyl phosphate into 25mL of absolute ethyl alcohol serving as a diluent, adding the absolute ethyl alcohol into the container, oscillating at room temperature for 24h, carrying out vacuum infusion at the temperature of 60 ℃, then removing the absolute ethyl alcohol, then dipping for 10-12h, then washing for 5-6 times with ultrapure water, and carrying out vacuum drying to obtain CMPO @ XAD-7HP resin.
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| CN109174060A (en) * | 2018-09-26 | 2019-01-11 | 东华理工大学 | A method of chelating resin containing phosphonic acid base and separation and enrichment thorium under highly acidity |
| CN113667049A (en) * | 2021-09-09 | 2021-11-19 | 核工业北京化工冶金研究院 | Resin containing pyridine functional group and preparation method and application thereof |
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| CN109174060A (en) * | 2018-09-26 | 2019-01-11 | 东华理工大学 | A method of chelating resin containing phosphonic acid base and separation and enrichment thorium under highly acidity |
| CN113667049A (en) * | 2021-09-09 | 2021-11-19 | 核工业北京化工冶金研究院 | Resin containing pyridine functional group and preparation method and application thereof |
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