CN114231763A - Separation method for extracting terbium from gadolinium terbium mixed solution - Google Patents
Separation method for extracting terbium from gadolinium terbium mixed solution Download PDFInfo
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- 238000000926 separation method Methods 0.000 title claims abstract description 45
- 239000011259 mixed solution Substances 0.000 title claims abstract description 28
- 229910052771 Terbium Inorganic materials 0.000 title claims abstract description 20
- HQWUQSSKOBTIHZ-UHFFFAOYSA-N gadolinium terbium Chemical compound [Gd][Tb] HQWUQSSKOBTIHZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 73
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 239000008247 solid mixture Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- 239000002738 chelating agent Substances 0.000 claims description 22
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 claims description 17
- 238000002386 leaching Methods 0.000 claims description 13
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003729 cation exchange resin Substances 0.000 claims description 10
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000010828 elution Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 3
- -1 TbCl3 compound Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 206010028980 Neoplasm Diseases 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 210000004881 tumor cell Anatomy 0.000 description 2
- 108050001286 Somatostatin Receptor Proteins 0.000 description 1
- 102000011096 Somatostatin receptor Human genes 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005255 beta decay Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 231100000225 lethality Toxicity 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000009206 nuclear medicine Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/065—Nitric acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- 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
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- Chemical & Material Sciences (AREA)
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- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a separation method for extracting terbium from a gadolinium terbium mixed solution, which comprises the following steps: gd is added2O3And Tb2O3Respectively dissolving in inorganic acid solution, and then evaporating to dryness to obtain Gd/Tb solid mixture; then preparing Gd from inorganic acid solution3+/Tb3+Mixing the solution; separating the mixed solution to obtain a Tb compound; then purifying Tb3+A compound; evaporating and concentrating to obtain TbCl3Producing a product; the method realizes Gd/Tb separation by combining gradient elution and multi-stage chromatographic columns, obtains the target product TbCl3 compound, and has short separation time, high separation speed and high separation quantity.
Description
Technical Field
The invention relates to the technical field of medical radionuclides, in particular to a separation method for extracting terbium from a gadolinium terbium mixed solution.
Background
Tb-161 has important application value in the field of nuclear medicine. The Tb-161 labeled radioactive drug is directly combined with the surface of malignant tumor cells or internalized in the cells, and the low-energy Auger electrons and conversion electrons can enhance the lethality of beta rays to the tumor cells. In addition, low energy gamma radiation can be used for intraoperative scanning of somatostatin receptor positive tumors, and a hand-held probe can detect the gamma radiation, thereby guiding the surgeon to the tumor site to remove the tumor. Therefore, the Tb-161 labeled monoclonal antibody or polypeptide compound can be used for treating tumor diseases and can be used for gamma camera imaging.
There are two main production modes of Tb-161 nuclide, one is irradiation of Gd-160 by reactor, Gd-160 absorbs neutron and then generates Gd-161 (T)1/23.646min), followed by β -decay of Gd-161 to Tb-161; secondly, Tb-161 is prepared by an accelerator, and the related nuclear reaction is mainly160Gd(d，n)161Tb、160Gd(d，p)161Gd→161Tb. Therefore, whether Tb-161 is produced by reactor irradiation or accelerator, Tb-161 is obtained as a product of high nuclear purity for labeling reactions by Gd/Tb-161 separation. Gd/Tb belongs to lanthanide elements, and because lanthanide contraction causes ions with similar radiuses, Gd/Tb cannot be easily separated from each other by a common separation method.
Most of the existing separation methods are high-pressure ion chromatography, and the separation method has long separation time, slow separation speed and low separation amount, and is not suitable for separating a large amount of raw materials.
Disclosure of Invention
The invention aims to provide a separation method for extracting terbium from a gadolinium terbium mixed solution, which can solve the problems of long separation time, low separation speed, low separation amount and the like of Gd/Tb.
The embodiment of the invention is realized by the following technical scheme:
a separation method for extracting terbium from a gadolinium terbium mixed solution comprises the following steps:
s1, mixing Gd2O3And Tb2O3Respectively dissolving in inorganic acid solution, and then evaporating to dryness to obtain Gd/Tb solid mixture;
s2, dissolving the Gd/Tb solid mixture by using inorganic salt or inorganic acid solution to obtain Gd3+/Tb3+Mixing the solution;
s3, primary separation of Gd/Tb
Mixing Gd in S23+/Tb3+The mixed solution passes through a first chromatographic column, and Tb compound is washed out by different gradients of water and a chelating agent and collected;
s4 and purification Tb
Adding inorganic acid into Tb compound eluted from S3 to obtain ionic Tb3+A compound; then adjusting the acidity to 0.01-1M; then passing through a second chromatographic column, and performing gradient leaching by using an inorganic acid solution;
s5, evaporation and concentration
Tb is treated after leaching3+Evaporating and concentrating the solution, adding low-concentration inorganic acid for dissolving to obtain TbCl3And (5) producing the product.
The technical scheme of the embodiment of the invention at least has the following advantages and beneficial effects:
1. the method comprises the steps of performing primary separation on Gd/Tb by selecting a resin chromatographic column, and performing gradient elution by using a chelating agent and inorganic acids with different acidity values to realize separation of Gd/Tb and recovery of Gd; and after primary separation of Tb, adsorbing by using a resin chromatographic column and carrying out gradient elution by using inorganic acid to obtain a high-purity Tb compound.
2. The separation method achieves the aim of separating Gd/Tb, has simple separation process and short separation time, and can complete the separation within 9 hours to obtain a final product; and a large-volume separation device is not needed, the requirements on the chromatographic column and the leacheate are simple, the method can be applied to Gd/Tb separation related to reactor neutron irradiation or Tb-161 production by an accelerator, the application range is wide, and the production benefit is high.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following provides a specific description of the separation method for extracting terbium from gadolinium terbium mixed solution provided by the embodiment of the present invention.
A separation method for extracting terbium from a gadolinium terbium mixed solution comprises the following steps:
a) the mass ratio is 1: 102～1∶108Dissolving the mixture of Tb and Gd in a mineral acid solution with a high concentration, evaporating the solution to remove the mineral acid after the dissolution is finished, adding a mineral salt or the mineral acid solution to dissolve the Gd/Tb mixture to obtain Gd3+/Tb3+Mixing the solution, loading the solution into a first chromatographic column packed with a cation exchange resin or an extraction resin,
eluting with pure water to 0.15M chelating agent solution, eluting Tb compound from the first chromatographic column, and collecting the eluted Tb compound; secondly, increasing the concentration of a chelating agent, eluting Gd from the first chromatographic column, and collecting the Gd; then adding inorganic acid into the collected Tb compound solution to ensure that Tb is formed into Tb3+The ionic form exists in the solution, and then the acidity value is adjusted to be within the range of 0.01-1M;
b) connecting the outlet of the first chromatographic column with the inlet of a second chromatographic column filled with cation exchange material or extraction resin to obtain Tb3+The solution is connected into a second chromatographic column, and inorganic acid solution is used for gradient leaching, which comprises the following specific steps: firstly, leaching with low-concentration (0.001-0.5M) inorganic acid solution to remove the chelating agent; then leaching by 0.01-1M inorganic acid solution to remove a small amount of Gd3+(ii) a Finally, Tb is eluted by 0.5-4M inorganic acid solution3+Tb is added after washing3+Evaporating and concentrating the solution to remove inorganic acid, and adding low-concentration inorganic acid for dissolving to obtain TbCl3Producing a product;
it should be noted that: if the mass difference between Gd and Tb is large and Tb reaches milligram level, adding a first chromatographic column between the first chromatographic column and the second chromatographic column, wherein the column packing material is consistent with the first chromatographic column, and repeating the steps to obtain the high-purity TbCl3And (5) producing the product.
The invention can increase or decrease the column height or increase the separation stage number according to the mass of Gd/Tb to achieve the purpose of large-scale Gd/Tb separation.
The power device for providing power for eluting the chromatographic column can be a peristaltic pump, an HPLC pump, a vacuum pump and the like.
In the present invention, Gd2O3Is Gd after reactor irradiation2O3Or Gd after accelerator irradiation2O3Or Gd with a purity of more than 99.9%2O3Compounds, or enriched160Gd2O3Or naturalnatGd2O3One kind of (1).
In the present invention, Gd3+/Tb3+The flow rate of the mixed solution passing through the first chromatographic column is 0.1-3 mL/min.
In the invention, the inorganic salt is one or more of ammonium salt, potassium salt and sodium salt, and the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid and hydrofluoric acid.
In the present invention, the chelating agent comprises one or more of α -hydroxyisobutyrate, citric acid, citrate, butyric acid, butyrate, EDTA, DTPA.
In the invention, the filling agent in the first chromatographic column and the second chromatographic column is macroporous cation exchange resin or extraction resin.
In the present invention, the cation exchange resin is NH4 +The resin material in ion form is extracted resin which is a tree formed by loading organic small molecules on a solid phase matrixA lipid material.
Example 1
(ii) reacting Gd2O3And Tb2O3According to the mass ratio of 100: 1 in the ratio of 1, after the solution is dissolved, evaporating the solution to dryness to obtain a Gd/Tb solid mixture, and adding an ammonium chloride solution into the Gd/Tb solid mixture to dissolve the Gd/Tb solid mixture to obtain a Gd/Tb mixed solution;
secondly, enabling the Gd/Tb mixed solution to pass through a first chromatographic column filled with macroporous cation exchange resin, eluting with pure water to 0.15M alpha-Hydroxyisobutyrate (HIBA) chelating agent solution, eluting Tb compound from the first chromatographic column and collecting the Tb compound; secondly, the concentration of chelating agent Hydroxyisobutyrate (HIBA) is increased to 0.5M, and Gd is eluted from the first chromatographic column and collected;
thirdly, hydrochloric acid is added into the collected Tb compound solution to destroy Tb-HIBA structure and release ionic Tb3+Solution (containing small amount of Gd)3+) Then adjusting the acidity value to be 0.01M; finally Tb will be3+Solution (containing small amount of Gd)3+) Passing through a second chromatographic column packed with a cation exchange resin or an extraction resin and performing gradient elution with an inorganic acid solution: firstly, leaching with hydrochloric acid solution with the concentration of 0.001M to remove the chelating agent; then eluting with 0.01M hydrochloric acid solution to remove small amount of Gd3+(ii) a Finally, eluting TbCl by using 0.5M hydrochloric acid solution3After washing, TbCl is added3Evaporating and concentrating the solution to remove hydrochloric acid, and adding low-concentration hydrochloric acid to dissolve the solution to obtain TbCl3Producing a product;
fourthly, the steps are repeated, the total time is 8 hours and 16 minutes, and the TbCl with the purity of 99.9 percent is obtained3And (5) producing the product.
Example 2
(ii) reacting Gd2O3And Tb2O3According to the mass ratio of 500: 1 in the ratio of 1, after the solution is dissolved, evaporating the solution to dryness to obtain a Gd/Tb solid mixture, and adding a potassium chloride solution into the Gd/Tb solid mixture to dissolve the Gd/Tb solid mixture to obtain a Gd/Tb mixed solution;
secondly, enabling the Gd/Tb mixed solution to pass through a first chromatographic column filled with macroporous cation exchange resin, eluting with pure water to 0.15M alpha-Hydroxyisobutyrate (HIBA) chelating agent solution, eluting Tb compound from the first chromatographic column and collecting the Tb compound; secondly, increasing the concentration of chelating agent Hydroxyisobutyrate (HIBA) to 1M, eluting Gd from the first chromatographic column, and collecting;
thirdly, hydrochloric acid is added into the collected Tb compound solution to destroy Tb-HIBA structure and release ionic Tb3+Solution (containing small amount of Gd)3+) Then adjusting the acidity value to be 1M; finally Tb will be3+Solution (containing small amount of Gd)3+) Passing through a second chromatographic column packed with cation exchange resin and gradient elution with mineral acid solution: firstly, leaching with hydrochloric acid solution with the concentration of 0.5M to remove the chelating agent; then eluting with 1M hydrochloric acid solution to remove a small amount of Gd3+(ii) a Finally eluting TbCl by using 4M hydrochloric acid solution3After washing, TbCl is added3Evaporating and concentrating the solution to remove hydrochloric acid, and adding low-concentration hydrochloric acid to dissolve the solution to obtain TbCl3Producing a product;
fourthly, the steps are repeated, the total time is 8 hours and 35 minutes, and the TbCl with the purity of 99.8 percent is obtained3And (5) producing the product.
Example 3
(ii) reacting Gd2O3And Tb2O3According to the mass ratio of 1000: 1 in the ratio of 1, after the solution is dissolved, evaporating the solution to dryness to obtain a Gd/Tb solid mixture, and adding a sodium chloride solution into the Gd/Tb solid mixture to dissolve the Gd/Tb solid mixture to obtain a Gd/Tb mixed solution;
secondly, enabling the Gd/Tb mixed solution to pass through a first chromatographic column filled with macroporous cation exchange resin, eluting with pure water to 0.15M alpha-Hydroxyisobutyrate (HIBA) chelating agent solution, eluting Tb compound from the first chromatographic column and collecting the Tb compound; secondly, the concentration of chelating agent Hydroxyisobutyrate (HIBA) is increased to 0.3M, and Gd is eluted from the first chromatographic column and collected;
thirdly, hydrochloric acid is added into the collected Tb compound solution to destroy Tb-HIBA structure and release ionic Tb3+Solution (containing small amount of Gd)3+) Then, thenAdjusting the acidity value to 0.5M; finally Tb will be3+Solution (containing small amount of Gd)3+) Passing through a second chromatographic column packed with cation exchange resin and gradient elution with mineral acid solution: firstly, leaching with hydrochloric acid solution with the concentration of 0.1M to remove the chelating agent; then eluting with 0.5M hydrochloric acid solution to remove small amount of Gd3+(ii) a Finally eluting TbCl by using 2M hydrochloric acid solution3After washing, TbCl is added3Evaporating and concentrating the solution to remove hydrochloric acid, and adding low-concentration hydrochloric acid to dissolve the solution to obtain TbCl3Producing a product;
fourthly, the steps are repeated, the total time is 8 hours and 12 minutes, and the TbCl with the purity of 99.8 percent is obtained3And (5) producing the product.
Comparative example 1
This comparative example differs from example 3 in that: this comparative example was eluted in the first chromatography column with only 0.15M alpha-Hydroxyisobutyrate (HIBA) chelator solution, i.e. without a gradient elution with HIBA; finally obtaining TbCl3The purity of the product is as follows: 82 percent.
Comparative example 2
This comparative example differs from example 3 in that: this comparative example only eluted with 4M hydrochloric acid in the second column, i.e. no gradient elution with hydrochloric acid solution, resulting in TbCl3The purity of the product is as follows: 86 percent.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A separation method for extracting terbium from a gadolinium terbium mixed solution is characterized by comprising the following steps:
s1, mixing Gd2O3And Tb2O3Respectively dissolving in inorganic acid solution, and then evaporating to dryness to obtain Gd/Tb solid mixture;
s2, dissolving the Gd/Tb solid mixture by using inorganic salt or inorganic acid solution to obtain Gd3+/Tb3+Mixing the solution;
s3, primary separation of Gd/Tb
Mixing Gd in S23+/Tb3+The mixed solution passes through a first chromatographic column, and Tb compound is washed out by different gradients of water and a chelating agent and collected;
s4 and purification Tb
Adding inorganic acid into Tb compound eluted from S3 to obtain ionic Tb3+A compound; then adjusting the acidity to 0.01-1M; then passing through a second chromatographic column, and performing gradient leaching by using an inorganic acid solution;
s5, evaporation and concentration
Tb is treated after leaching3+Evaporating and concentrating the solution, adding low-concentration inorganic acid for dissolving to obtain TbCl3And (5) producing the product.
2. The separation method for extracting terbium from a gadolinium terbium mixed solution according to claim 1, further comprising the following steps between S3 and S4: s31, recovering the Gd compound in the first chromatographic column, i.e.: after collecting the Tb compound eluted in S3, the chelating agent concentration was increased, and the Gd compound was eluted with different gradients of water and chelating agent and collected.
3. The separation method for extracting terbium from a gadolinium terbium mixed solution according to claim 2, wherein the concentration of the chelating agent in S3 is less than 0.15M; the concentration of the chelating agent in S31 is more than 0.15M.
4. The separation method for extracting terbium from a gadolinium terbium mixed solution according to claim 1, wherein in S4, after passing through the second chromatographic column, it is eluted with a low concentration inorganic acid solution and then eluted with a high concentration inorganic acid.
5. The separation method for extracting terbium from a gadolinium terbium mixed solution according to claim 4, wherein when leaching with a low concentration inorganic acid solution, the inorganic acid solution is first leached with a concentration of 0.001-0.5M, and then leached with a concentration of 0.01-1M; when the high-concentration inorganic acid is used for leaching, the inorganic acid with the concentration of 0.5-4M is used for leaching.
6. The separation method for extracting terbium from a gadolinium terbium mixed solution according to claim 1, wherein said Gd is contained in S12O3And Tb2O3Has a mass ratio of 102～108∶1。
7. The separation method for extracting terbium from a gadolinium terbium mixed solution according to claim 1, wherein Gd in S12O3Is Gd after reactor irradiation2O3Or Gd after accelerator irradiation2O3Or Gd with a purity of more than 99.9%2O3Compounds, or enriched160Gd2O3Or naturalnatGd2O3One kind of (1).
8. The separation method for extracting terbium from a gadolinium terbium mixed solution according to claim 1, wherein said inorganic salt is one or more of ammonium salt, potassium salt and sodium salt, and said inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid and hydrofluoric acid.
9. The separation method for extracting terbium from a gadolinium terbium mixed solution according to claim 1, wherein said chelating agent comprises one or more of α -hydroxyisobutyrate, citric acid, citrate, butyric acid, butyrate, EDTA, DTPA.
10. The separation method for extracting terbium from a gadolinium terbium mixed solution according to claim 1, wherein the filling agent in said first chromatographic column and said second chromatographic column is macroporous cation exchange resin or extraction resin.
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