CN116808830A - Th/Ra generator containing natural thorium and production thereof 224 Method for Ra - Google Patents
Th/Ra generator containing natural thorium and production thereof 224 Method for Ra Download PDFInfo
- Publication number
- CN116808830A CN116808830A CN202310380062.9A CN202310380062A CN116808830A CN 116808830 A CN116808830 A CN 116808830A CN 202310380062 A CN202310380062 A CN 202310380062A CN 116808830 A CN116808830 A CN 116808830A
- Authority
- CN
- China
- Prior art keywords
- bottle
- resin column
- solution
- cationic resin
- generator
- 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.)
- Pending
Links
- 229910052776 Thorium Inorganic materials 0.000 title claims abstract description 46
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 112
- 229920005989 resin Polymers 0.000 claims abstract description 112
- 125000002091 cationic group Chemical group 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 52
- 239000011550 stock solution Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 238000000605 extraction Methods 0.000 claims abstract description 21
- 150000001768 cations Chemical class 0.000 claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 14
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000011049 filling Methods 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 89
- 230000002572 peristaltic effect Effects 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 9
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- -1 thorium ions Chemical class 0.000 description 5
- 238000011084 recovery Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 206010033128 Ovarian cancer Diseases 0.000 description 1
- 206010061535 Ovarian neoplasm Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 208000037819 metastatic cancer Diseases 0.000 description 1
- 208000011575 metastatic malignant neoplasm Diseases 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/50—Separation involving two or more processes covered by different groups selected from groups B01D59/02, B01D59/10, B01D59/20, B01D59/22, B01D59/28, B01D59/34, B01D59/36, B01D59/38, B01D59/44
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/22—Separation by extracting
- B01D59/24—Separation by extracting by solvent extraction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/28—Separation by chemical exchange
- B01D59/30—Separation by chemical exchange by ion exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F13/00—Compounds of radium
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention discloses a Th/Ra generator containing natural thorium and the production thereof 224 Ra method. The generator comprises a cation resin column and bottles I to VI; wherein the bottle I is filled with stock solution; filling deionized water in a bottle III; filling 4.0-6.0M nitric acid into the bottle IV; bottles II, V and VI are all empty; the bottle V is a specially-made collecting bottle, and the bottle mouth is provided with a resin extraction column for collecting 224 Ra (Ra). The method comprises the following steps: 1) By using a composition comprising 228 Concentrating natural thorium mixed solution of Th to obtain concentrated solution, and then regulating pH of the system to obtain filling stock solution of Th/Ra generator; 2) Passing the stock solution through a cation resin column to obtain a solution loaded on the cation resin column 224 Ra, and collecting the leaching solution of the stock solution for later use; 3) Eluting the cationic resin column with inorganic acid 224 Ra, collecting eluate with special collecting bottle 224 Ra (Ra). The invention can separate, purify and circularly produce 224 Ra to overcome 228 Th/ 224 The Ra generator is severely charged, avoiding the radioactivity risk caused by handling of natural thorium on the order of tons.
Description
Technical Field
The invention belongs to the field of medical radioisotope generator development, and relates to a natural thorium-containing Th/Ra generator and production thereof 224 Ra method.
Background
224 The half-life of Ra is 3.66 days, the average energy of alpha particles emitted by the Ra is 5.68MeV, and the Ra is an alternative 223 Potential medical isotopes for Ra treatment of various metastatic cancers, e.g 224 Ra-marked CaCO 3 Ovarian cancer (see, document Translational Oncology (2018) 11:259-267) and the like can be treated. At the same time, the method comprises the steps of, 224 daughter of Ra 212 Pb and 212 bi, also reported by a large number of literature, has proven to be a very valuable targeting alpha therapeutic nuclides, and therefore 224 Ra can be designed and filled 212 Pb/ 212 Direct feed to Bi generator.
At present, isotopes are not yet prepared 224 An effective method for Ra, the main source of which is from natural sources 232 Th(T 1/2 ＝1.405×10 10 y) decay to 228 Ra(T 1/2 =5.75y), and then separating to obtain a daughter 228 Ac(T 1/2 =6.15 h) before decaying to 228 Th(T 1/2 =1.91 y) before being separated again 224 Ra (Ra). Wherein due to 232 The half-life of Th is very long, resulting in the need for liquid/liquid extraction or precipitation steps to treat ton-scale natural thorium each time to produce micro-scale natural thorium 224 Ra, and can only meet several human injections. In addition, in the whole decay chain, the indirect parent 228 The Ra content is far higher than that of the product, and needs to be separated and removed in advance so as to enrich a large amount of Ra 228 Ac can be realized only after 228 Th/ 224 And (3) filling the Ra generator. The whole separation process is complex and tedious, and the production cost is extremely high.
Disclosure of Invention
The invention aims to provide a Th/Ra generator containing natural thorium and a production method thereof 224 Ra method. The invention can overcome 228 Th/ 224 The Ra generator is filled strictly to avoid the radioactivity risk caused by processing ton-level natural thorium, and is separated, purified and circularly produced 224 Ra。
The invention provides a natural thorium-containing Th/Ra generator production 224 A method of Ra comprising the steps of: 1) By using a composition comprising 228 Concentrating natural thorium mixed solution of Th to obtain concentrated solution, and then regulating pH of the system to obtain filling stock solution of Th/Ra generator;
2) The stock solution passes through a cation resin column to obtain the product loaded on the cation resin column 224 Ra, and collecting the leaching solution of the stock solution for later use;
3) Leaching the cationic resin column with an inorganic acid 224 Ra, collecting eluate with special collecting bottle 224 Ra；
The mouth of the special collecting bottle is provided with a resin extraction column.
In the invention, the bottleneck of the special collecting bottle is provided with a resin extraction column to purify and remove Th in the eluent.
In the above method, the method comprises 228 The natural thorium mixed solution of Th is selected from high-energy proton irradiation metal Th or ThO 2 Post-target solubilizate or enrichment 228 Ac/ 228 Mixed liquor of Th polluted by natural thorium;
the filling stock solution is filled in 228 Th (Th) 232 The mass specific activity of Th is more than 3.0KBq/g.
In the above method, if the system is in a turbid state after the concentration in step 1), the method further comprises the step of adding acid and water for dissolution;
the treatment of adding acid and water for dissolution is as follows: adding 0.2-2.0 mL of concentrated sulfuric acid and 1-2 drops of 40% hydrofluoric acid into the concentrated solution, heating to 60-80 ℃, preserving heat and dissolving for 20-80 minutes, then adding 4-20 mL of deionized water, and stirring at room temperature to completely dissolve and clarify the solution.
The volume ratio of the concentrated solution to the added concentrated sulfuric acid can be 0.25-40.0 mL:1.
in the present invention, the room temperature is common knowledge in the art, and generally means 10 to 30 ℃.
In the above method, the pH of the system is adjusted to 0.5-3.0 in step 1).
In the above method, the treatment of adjusting the pH of the system in step 1) is as follows: adding 0.3-0.5M ammonium sulfate solution, and then adopting concentrated ammonia water to adjust the pH;
the volume of the 0.3-0.5M ammonium sulfate solution and the content 228 Natural thorium mixed solution of Th 232 The mass ratio of Th is 30-50 mL/g.
In the above method, the flow rate of the stock solution passing through the cationic resin column in step 2) may be 0.5 to 5.0mL/min.
In the above method, in step 3), the inorganic acid is nitric acid, specifically 4.0-6.0M nitric acid;
the volume ratio of the inorganic acid to the cationic resin column can be 3-5: 1, which can be specifically 4:1;
the extraction resin column comprises a UTEVA resin column;
the cation resin column comprises AG50W-X8 (specifically, 100-300 meshes) cation resin;
the volume ratio of the extraction resin column to the cationic resin column can be 0.35-0.55 mL/mL.
In the above method, in the step 3), the cationic resin column is eluted with an inorganic acid 224 Eluting the Ra and the Ra by adopting deionized water, and adjusting the load mode of the cationic resin column to ensure the reset of the initial state of the generator;
the volume ratio of the deionized water to the cationic resin column can be 4-6: 1, which may be specifically 5:1.
In the method, after standing and balancing the leaching solution of the stock solution for 12-28 days, repeating the steps 2) -3) to circularly generate 224 Ra。
In the above method, the generating 224 The total period of the Ra cycle may be from 0.2 to 10 years.
The invention relates to a Th/Ra generator containing natural thorium, which comprises a cationic resin column, a bottle I, a bottle II, a bottle III, a bottle IV, a bottle V and a bottle VI;
a liquid inlet A and a liquid inlet B are formed in a liquid inlet pipeline of the cation resin column, a peristaltic pump is arranged on the liquid inlet pipeline, and one-way valves are respectively arranged on the liquid inlet pipeline between the liquid inlet A, the liquid inlet B and the cation resin column so as to control the material flow flowing into the cation resin column in one way; a liquid outlet C is arranged on a liquid outlet pipeline of the cation resin column;
the bottle I is filled with the stock solution and is positioned in a lead shielding area for placing the stock solution therein 224 Ra is supported on the cationic resin column;
the bottle III is filled with deionized water for leaching the cationic resin column by inorganic acid 224 Eluting the Ra and the Ra by adopting deionized water, and adjusting the load mode of the cationic resin column to ensure the reset of the initial state of the generator;
the bottle IV is filled with 4.0 to 6.0M nitric acid for leaching the cationic resin column 224 Ra；
The bottles II, V and VI are all empty; the bottle II is used for receiving the leaching solution of the stock solution to be used as a raw material again; the bottle V is a specially-made collecting bottle, the bottle mouth of the specially-made collecting bottle is provided with a resin extraction column for the liquid outlet C, and the bottle V is used for collecting 224 Ra (b); the bottle vi is for receiving deionized water rinse.
In the invention, the cationic resin column can be positioned in the protection area without shielding treatment.
In the Th/Ra generator containing natural thorium, the volume ratio of the extraction resin column to the cationic resin column is 0.35-0.55 mL/mL;
the extraction resin column comprises a UTEVA resin column;
the cationic resin column comprises AG50W-X8 (specifically, 100-300 meshes) cationic resin.
In the invention, the natural thorium-containing Th/Ra generator is used for production 224 A method of operating Ra comprising the steps of:
(1) The initial state of the Th/Ra generator containing natural thorium is as follows: peristaltic pumps and check valves are closed; all the liquid inlets and the liquid outlets are empty; bottle I is located in the lead shielding area; bottle III is filled with deionized water; the bottle IV is filled with 4.0 to 6.0M nitric acid; bottles II, V and VI are all empty;
(2) The liquid outlet C is connected with the bottle II, the liquid inlet A is immersed at the bottom of the bottle I, the peristaltic pump is opened, the valve A is opened, and the stock solution in the bottle I can pass through the cationic resin column in the protection zone and be collected into the bottle II;
the cationic resin column adopted in the generator protection zone can be AG50W-X8 (100-300 meshes) cationic resin, and the ratio of the volume of the raw liquid in the bottle I to the volume of the cationic resin column can be specifically as follows: 8.0-25 mL/mL;
the peristaltic pump is adopted to control the flow rate to be specifically 0.5-5.0 mL/min;
(3) When no liquid drops flow out of the liquid outlet C, the bottle VI is replaced, the valve A is closed, the empty bottle I is renamed as a bottle II to be moved out for standby, and the original bottle II is placed in a lead shielding area and renamed as a bottle I;
(4) Connecting the liquid inlet B with a bottle III, opening a valve B, and removing the bottle III after the solution with the volume of 4-6 times of that of the cationic resin column flows out;
(5) When the liquid outlet C is free from liquid drops again, the bottle V is replaced, the liquid inlet B is connected with the bottle IV, and after the solution which is 3-5 times of the volume of the cationic resin column flows out, the bottle IV is removed;
(6) When no liquid drops flow out of the liquid outlet C for the third time, the bottle VI is replaced again, the liquid inlet B is connected with the bottle III, and after the solution with the volume of 4-6 times of the column flows out, the bottle III is removed;
(7) When no liquid drops flow out from the liquid outlet C for the fourth time, the bottle VI is removed, the peristaltic pump and the check valves are closed, and the Th/Ra generator is restored to the initial state described in the step (1).
In the above method, after each use, the bottle v needs to be replaced with a new UTEVA resin, or a new special bottle cap of the collection bottle v needs to be directly replaced for later use.
The solution collected in the bottle V in the step (5) is a solution containing 4.0-6.0M nitric acid 224 An Ra product; the bottle VI collects an acidic waste solution containing a small amount of matrix Th.
In the above method, after the renamed bottle I is stationary and balanced for 12-28 days, but not limited to 12-28 days, the steps 2) to 7) in the above production method can be repeated for cyclic preparation 224 Ra product.
In the above method, according to each cycle of the Th/Ra generator 224 Whether the dosage of the Ra product meets the requirements of related researches and applications or not is determined to execute the cyclic production operation or not; the total cycle period may be, but is not limited to, 0.2 to 10 years in theory.
The invention has the following beneficial effects:
1. by using compositions containing relatively high specific activities 228 Natural thorium mixed liquid of Th, which can be but not limited to high-energy proton irradiation metal Th or ThO 2 The dissolved solution after target is concentrated and redissolved, and then is regulated into a weak acid ammonium sulfate system, and can be used as filling stock solution to overcome 228 Th/ 224 The Ra generator is filled strictly to avoid the radioactivity risk caused by the treatment of ton-level natural thorium;
2. loading target product by adopting cation resin column 224 Ra, after the ammonium sulfate system stock solution is directly connected, the stock solution can be collected and prepared for the next production period and is continuously recycled;
3. by specially-made means 224 Ra collecting bottle, bottle cap with UTEVA resin column, inorganic acid leaching supported on cationic resin column 224 Purifying and removing a small amount of impurity Th in the product during Ra;
4. rinsing 224 And before and after Ra, deionized water is adopted to rinse the generator, so that the load mode of the cationic resin column is adjusted, the reset of the initial state of the generator is ensured, the generator is directly used in the next cycle period, and no redundant operation is realized.
5. The Th/Ra generator with one-time filling of natural thorium with large matrix can be circularly used in a long period of several years, and a simple, efficient, economical and safe structure is correspondingly establishedThe process meets the requirements of separating and purifying isotopes in China 224 Ra, and is prepared repeatedly 224 Targets for Ra products.
Drawings
FIG. 1 is a schematic diagram of a Th/Ra generator containing natural thorium.
The individual labels in fig. 1 are as follows:
1-6 bottles I, II, III, IV, V and VI; 7 a cation resin column; 8UTEVA resin columns; 9 liquid inlet A;10 liquid inlet B;11 a liquid outlet C;12 one-way valve A;13 a one-way valve B; a peristaltic pump 14; 15 lead shielding areas; 16 guard regions.
FIG. 2 is a first preparation 224 Gamma energy spectrum of Ra crude product.
FIG. 3 is a cyclic preparation 224 Gamma energy spectrum of Ra product.
FIG. 4 is a cyclic preparation 224 Alpha energy spectrum of Ra product.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
As shown in FIG. 1, the Th/Ra generator of the present invention comprises a cationic resin column 7, a bottle I1, a bottle II 2, a bottle III 3, a bottle IV 4, a bottle V5 and a bottle VI 6. The bottle V5 is a specially-made collecting bottle, and the bottle mouth is provided with a resin extraction column (comprising a UTEVA resin column 8).
A liquid inlet A9 and a liquid inlet B10 are arranged on a liquid inlet pipeline of the cationic resin column 7, a peristaltic pump 14 is arranged on the liquid inlet pipeline, and a one-way valve A12 and a one-way valve B13 are respectively arranged on the liquid inlet pipeline between the liquid inlet A9, the liquid inlet B10 and the cationic resin column 7 so as to unidirectionally control the material flow flowing into the cationic resin column 7; a liquid outlet C11 is arranged on a liquid outlet pipeline of the cationic resin column 7; in use, the cationic resin column 7 is disposed within the guard zone 16;
the bottle I1 is filled with a stock solution in a lead shielding zone 15 for introducing the stock solution therein 224 Ra is supported on a cationic resin column 7; bottle III 3 contains deionized waterFor eluting said cationic resin column with an inorganic acid 224 Eluting the Ra and the Ra by adopting deionized water, and adjusting the load mode of the cationic resin column to ensure the reset of the initial state of the generator; bottle IV 4 contains 4.0-6.0M nitric acid, and bottle II 2, bottle V5 and bottle VI 6 are all empty; the bottle II 2 is used for receiving the leaching solution of the stock solution to be used as a raw material again; the bottle V5 is a specially-made collecting bottle, the bottle mouth is provided with a resin extraction column for the liquid outlet C, and the bottle V5 is used for collecting 224 Ra (b); bottle vi 6 is for receiving deionized water rinse.
Wherein Th-containing solution in bottle I1 (tip bottom bottle) is the filling stock solution of the generator, and the stock solution preparation process is:
will contain a higher specific activity 228 The natural thorium mixed raw material solution of Th is heated and concentrated to near dryness, 0.2-2.0 mL of concentrated sulfuric acid and 1-2 drops of 40% hydrofluoric acid are added, the temperature is kept between 60 and 80 ℃ for 20 to 80 minutes, then 4-20 mL of deionized water is added, and stirring is carried out at room temperature, so that the natural thorium mixed raw material solution is completely dissolved and clarified, and if residues are left, the natural thorium mixed raw material solution is filtered and removed. Then adding 0.3-0.5M ammonium sulfate solution, adopting concentrated ammonia water to adjust the acidity of the solution to pH value of 0.5-3.0, and transferring the solution into a bottle I1 of the generator;
adding the volume of 0.3-0.5M ammonium sulfate solution into the mixed raw materials 232 The mass ratio of Th can be: 30-50 mL/g;
when the natural thorium raw material is concentrated to near dryness, if the natural thorium raw material is still clear, the step of adding acid and water for dissolving in the step 1) can be omitted, and after only adding 0.3-0.5M ammonium sulfate solution, the acid is directly regulated to be 0.5-3.0 by using strong ammonia water.
In the invention, the Th/Ra generator is used for specific production 224 The Ra method comprises the following steps:
1) The initial state of the Th/Ra generator containing natural thorium is: peristaltic pumps and check valves are closed; all the liquid inlets and the liquid outlets are empty; bottle I1 is located in the lead shielding area; bottle III 3 is filled with deionized water; bottle IV 4 is filled with 4.0-6.0M nitric acid; bottle II 2, bottle V5 and bottle VI 6 are all empty;
2) The liquid outlet C11 is connected with a bottle II 2 (pointed bottom bottle), the liquid inlet A9 is immersed at the bottom of the bottle I1, the peristaltic pump 14 is opened, the one-way valve A12 is opened, and the stock solution in the bottle I1 can be collected to the bottle II 2 through the cationic resin column 7 in the protection zone 16;
the cationic resin column 7 adopted in the protection zone 16 can be specifically AG50W-X8 (100-300 meshes) cationic resin, and the ratio of the volume of the raw liquid in the bottle I to the volume of the cationic resin column can be as follows: 8-25 mL/mL;
a peristaltic pump is adopted to control the flow rate to be 0.5-5.0 mL/min;
3) When no liquid drops flow out of the liquid outlet C11, the bottle VI 6 is replaced, the one-way valve A12 is closed, the empty bottle I1 is renamed as a bottle II 2 to be removed for standby, and the original bottle II 2 is placed in a lead shielding area and renamed as a bottle I1;
4) Connecting a liquid inlet B10 with a bottle III 3, opening a one-way valve B13, and removing the bottle III after the solution which is 5 times the volume of the cationic resin column flows out;
5) When no liquid drops flow out of the liquid outlet C11 again, the bottle V5 is replaced, the liquid inlet B10 is connected with the bottle IV 4, and after the solution with the volume 4 times of the cationic resin column flows out, the bottle IV 4 is removed;
the inlet of the bottle V is specially customized, and comprises an extraction resin column, the adopted extraction resin can be UTEVA (100-300 meshes), and the ratio of the volume of the UTEVA resin to the volume of the cation resin column in the protection area can be as follows: 0.35-0.55 mL/mL;
after each use, the bottle V5 needs to be replaced and filled with new UTEVA resin or is directly replaced with a new bottle cap for standby;
6) When no liquid drops flow out of the liquid outlet C11 for the third time, the bottle VI 6 is replaced again, the liquid inlet B10 is connected with the bottle III 3, and after the solution with the volume of 5 times of column volume flows out, the bottle III 3 is removed;
7) When no liquid drops flow out from the liquid outlet C11 for the fourth time, removing the bottle VI 6, closing the peristaltic pump and each one-way valve, and recovering the Th/Ra generator to the initial state described in the step 1);
the solution in the bottle V5 obtained in the step 5) is a solution containing 4.0-6.0M nitric acid 224 An Ra product; the bottle VI 6 collects acid waste liquid containing a small amount of matrix Th;
the renamed bottle I1 is static balanced for 12 to 28After days, but not limited to 12-28 days, the steps 2) to 7) in the production method can be repeated, and the preparation can be circularly carried out in a long period of several years 224 Ra product.
Example 1
This example illustrates that a metallic thorium target raffinate cooled for 0.5-1.0 years after irradiation with high-energy protons is packed in the Th/Ra generator described above and isolated for the first time 224 Feasibility of Ra crude products.
The example adopts an accelerator HIRFL of the national academy of sciences of China, the modern physical institute (Lanzhou), the energy is 100MeV, the average flow intensity is 24-42 nA, after the proton beam is irradiated, most of metal thorium target residual liquid of Ac element is separated, the volume is about 200mL, and the metal thorium target residual liquid is analyzed by a high-purity germanium gamma detector, wherein the metal thorium target residual liquid mainly contains 228 Th and 232 decay daughter of Th. Meanwhile, according to experimental records of original target operation, the residual liquid can be determined to mainly contain about 3.5g of thorium ions. The others are hydrogen ions, ammonium ions, sulfate and nitrate ions, the molar concentration being about 4-15 times that of thorium ions.
The invention designs a Th/Ra generator containing large-matrix natural thorium, wherein Th-containing solution in a sharp-bottomed bottle I is filling stock solution of the generator, and the stock solution preparation process comprises the following steps:
the metal thorium target residual liquid cooled for 1.0 year after the high-energy proton irradiation is heated and concentrated to be nearly dry, 20mL of deionized water is directly added, and the mixture is stirred at room temperature to be completely dissolved and clarified; then, 120mL of a 0.4M ammonium sulfate solution was added, the acidity of the solution was adjusted to pH 2.0 with concentrated aqueous ammonia, and the solution was transferred to bottle I1 of the generator.
The invention utilizes the Th/Ra generator to specifically produce 224 The Ra method comprises the following steps:
1) The initial state of the Th/Ra generator containing natural thorium is as follows: peristaltic pumps and check valves are closed; all the liquid inlets and the liquid outlets are empty; the bottle I1 is filled with stock solution and is positioned in the lead shielding area; bottle III is filled with deionized water; bottle IV contains 5.0M nitric acid; bottles II, V and VI are all empty;
2) The liquid outlet C is connected with the sharp-bottomed bottle II, the liquid inlet A is immersed in the bottom of the sharp-bottomed bottle I, the peristaltic pump is opened, the valve A12 is opened, and the stock solution in the bottle I can pass through the cationic resin column in the protection area and be collected into the bottle II;
the cationic resin column adopted in the protection zone can be AG50W-X8 (100-300 meshes) cationic resin with the volume of 10mL;
a peristaltic pump is adopted to control the flow rate to be 2.5mL/min;
3) When no liquid drops flow out of the liquid outlet C, the bottle VI is replaced, the valve A is closed, the empty bottle I is renamed as a bottle II to be moved out for standby, and the original bottle II is placed in a lead shielding area and renamed as a bottle I;
4) Connecting the liquid inlet B with a bottle III, opening a valve B, and removing the bottle III after 50mL of solution flows out;
5) When the liquid outlet C is free from liquid drops again, the bottle V is replaced, the liquid inlet B is connected with the bottle IV, and after 40mL of solution flows out, the bottle IV is removed;
the inlet of the bottle V is specially customized, and comprises a resin extraction column, wherein the resin extraction column can be UTEVA (100-300 meshes), and the volume of the UTEVA resin is 4mL;
6) When no liquid drops flow out of the liquid outlet C for the third time, the bottle VI is replaced again, the liquid inlet B is connected with the bottle III, and after 50mL of solution flows out, the bottle III is removed;
7) When no liquid drops flow out from the liquid outlet C for the fourth time, the bottle VI is removed, the peristaltic pump and the check valves are closed, and the Th/Ra generator is restored to the initial state described in the step 1).
The procedure of this example yielded 40mL 224 Ra crude product solution with activity of 11kBq, recovery rate of more than 94.6%, radionuclides purity of more than 77.8%, and gamma energy spectrum referring to fig. 2. Due to the fact that the stock solution contains a large amount of raw materials generated in the irradiation process 228 Ra, leading to the crude product 228 The Ra content is about 15.4%, so that the crude product can be used as a preparation 212 Pb/ 212 Bi.
Example 2
This example illustrates the cyclic operation of the above described large matrix natural thorium-containing Th/Ra generator and the high purity obtained once every 10-28 days 224 Feasibility of Ra products.
The Th/Ra generator containing natural thorium is checked and confirmed to be in the initial state before each use, and after the solution in the renamed bottle I in the embodiment 1 of the invention is stationary balanced for 28 days, the steps 2) to 7) in the production method can be repeated;
bottle V in example 1 above was replaced with a fresh UTEVA resin after each use;
the example repeats steps 2) to 7) 4 times in a common cycle, and each repetition period is 21 to 28 days;
40mL of the product was obtained for each cycle 224 Ra product solution with activity of 8-13 KBq, recovery rate of more than 95.2% and radionuclides purity of more than 98.3%, and can be used for the related fields 224 Ra is studied, its gamma energy spectrum is shown in figure 3, and its alpha energy spectrum is shown in figure 4.
Claims (10)
1. Production of natural thorium-containing Th/Ra generator 224 A method of Ra comprising the steps of: 1) By using a composition comprising 228 Concentrating natural thorium mixed solution of Th to obtain concentrated solution, and then regulating pH of the system to obtain filling stock solution of Th/Ra generator;
2) The stock solution passes through a cation resin column to obtain the product loaded on the cation resin column 224 Ra, and collecting the leaching solution of the stock solution for later use;
3) Leaching the cationic resin column with an inorganic acid 224 Ra, collecting eluate with special collecting bottle 224 Ra；
The mouth of the special collecting bottle is provided with a resin extraction column.
2. The method according to claim 1, wherein said containing 228 The natural thorium mixed solution of Th is selected from high-energy proton irradiation metal Th or ThO 2 Post-target solubilizate or enrichment 228 Ac/ 228 Mixed liquor of Th polluted by natural thorium;
the filling stock solution is filled in 228 Th (Th) 232 The mass specific activity of Th is more than 3.0KBq/g.
3. The method according to claim 1 or 2, wherein the concentration in step 1) is followed by dissolution in acid and water if the system is in a cloudy state;
the treatment of adding acid and water for dissolution is as follows: adding 0.2-2.0 mL of concentrated sulfuric acid and 1-2 drops of 40% hydrofluoric acid into the concentrated solution, heating to 60-80 ℃, preserving heat and dissolving for 20-80 minutes, then adding 4-20 mL of deionized water, and stirring to completely dissolve and clarify the solution;
the volume ratio of the concentrated solution to the added concentrated sulfuric acid is 0.25-40.0 mL:1.
4. a method according to any one of claims 1 to 3, wherein in step 1) the pH of the system is adjusted to 0.5 to 3.0;
and/or, the treatment of adjusting the pH of the system in step 1) is as follows: adding 0.3-0.5M ammonium sulfate solution, and then adopting concentrated ammonia water to adjust the pH;
the volume of the 0.3-0.5M ammonium sulfate solution and the content 228 Natural thorium mixed solution of Th 232 The mass ratio of Th is 30-50 mL/g.
5. The method according to any one of claims 1 to 4, wherein the flow rate of the stock solution through the cationic resin column in step 2) is 0.5 to 5.0mL/min.
6. The method according to any one of claims 1 to 5, wherein in step 3), the inorganic acid is nitric acid;
the volume ratio of the inorganic acid to the cationic resin column is 3-5: 1, a step of;
the extraction resin column comprises a UTEVA resin column;
the cationic resin column comprises AG50W-X8 cationic resin;
the volume ratio of the extraction resin column to the cationic resin column is 0.35-0.55 mL/mL.
7. Root of Chinese characterThe method according to any one of claims 1 to 6, wherein the cationic resin column is eluted with an inorganic acid in step 3) 224 Eluting the front and the rear of Ra by adopting deionized water, and adjusting the load mode of the cationic resin column;
the volume ratio of the deionized water to the cationic resin column is 4-6: 1.
8. the method according to any one of claims 1 to 7, wherein after standing the stock solution in equilibrium for 12 to 28 days, repeating steps 2) -3) is cyclically effected 224 Ra；
The generation of 224 The total period of Ra cycle is 0.2-10 years.
9. A natural thorium-containing Th/Ra generator for use in the process of any one of claims 1 to 8 comprising a cationic resin column, bottle i, bottle ii, bottle iii, bottle iv, bottle v and bottle vi;
a liquid inlet A and a liquid inlet B are formed in a liquid inlet pipeline of the cation resin column, a peristaltic pump is arranged on the liquid inlet pipeline, and one-way valves are respectively arranged on the liquid inlet pipeline between the liquid inlet A, the liquid inlet B and the cation resin column so as to control the material flow flowing into the cation resin column in one way; a liquid outlet C is arranged on a liquid outlet pipeline of the cation resin column;
the bottle I is filled with the stock solution and is positioned in a lead shielding area for placing the stock solution therein 224 Ra is supported on the cationic resin column;
the bottle III is filled with deionized water for leaching the cationic resin column by inorganic acid 224 Eluting the Ra and the Ra by adopting deionized water, and adjusting the load mode of the cationic resin column to ensure the reset of the initial state of the generator;
the bottle IV is filled with 4.0 to 6.0M nitric acid for leaching the cationic resin column 224 Ra；
The bottles II, V and VI are all empty; the bottle II is used for receiving the leaching solution of the stock solution so as toAgain as a raw material; the bottle V is a specially-made collecting bottle, the bottle mouth of the specially-made collecting bottle is provided with a resin extraction column for the liquid outlet C, and the bottle V is used for collecting 224 Ra (b); the bottle vi is for receiving deionized water rinse.
10. The Th/Ra generator of claim 9 wherein the ratio of the extraction resin column to the cationic resin column volume is 0.35 to 0.55mL/mL;
the cationic resin column comprises AG50W-X8 cationic resin;
the extraction resin column comprises a UTEVA resin column.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310380062.9A CN116808830A (en) | 2023-04-11 | 2023-04-11 | Th/Ra generator containing natural thorium and production thereof 224 Method for Ra |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310380062.9A CN116808830A (en) | 2023-04-11 | 2023-04-11 | Th/Ra generator containing natural thorium and production thereof 224 Method for Ra |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116808830A true CN116808830A (en) | 2023-09-29 |
Family
ID=88117435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310380062.9A Pending CN116808830A (en) | 2023-04-11 | 2023-04-11 | Th/Ra generator containing natural thorium and production thereof 224 Method for Ra |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116808830A (en) |
-
2023
- 2023-04-11 CN CN202310380062.9A patent/CN116808830A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ali et al. | Production techniques of fission molybdenum-99 | |
| Lebedev et al. | Radiochemical separation of no-carrier-added 177Lu as produced via the 176Ybn, γ177Yb→ 177Lu process | |
| US5910971A (en) | Method and apparatus for the production and extraction of molybdenum-99 | |
| Dasgupta et al. | A new separation procedure for 67Cu from proton irradiated Zn | |
| CN111485123B (en) | Separation from large-amount and low-specific-activity Mo solution99mTc device and method | |
| Lee et al. | Development of fission 99Mo production process using HANARO | |
| Castillo et al. | Production of large quantities of 90Y by ion-exchange chromatography using an organic resin and a chelating agent | |
| Guseva | Radioisotope generators of short-lived α-emitting radionuclides promising for use in nuclear medicine | |
| CN113066598B (en) | Irradiation from high-energy proton beam 232 Separation and purification in spallation reaction caused by Th target 223 Method for Ra | |
| Rösch, Jörg Brockmann, Nikolai A. Lebedev, Syed M. Qaim | Production and radiochemical separation of the Auger electron emitter 140Nd | |
| Islami-Rad et al. | Reactor production and purification of 153 Sm radioisotope via nat Sm target irradiation | |
| Scott et al. | Isotope harvesting with hollow fiber supported liquid membrane (HFSLM) | |
| Shishkin et al. | Extraction generator of 223 Ra for nuclear medicine | |
| CN116808830A (en) | Th/Ra generator containing natural thorium and production thereof 224 Method for Ra | |
| Van Der Walt et al. | The isolation of 99Mo from fission material for use in the 99Mo/99mTc generator for medical use | |
| RU2439727C1 (en) | Method to produce radionuclide bismuth-212 | |
| Guseva et al. | Development of a tandem generator system 229 Th/225 Ac/213 Bi for repeated production of short-lived α-emitting radionuclides | |
| CN111068482B (en) | Extraction from dissolved irradiation uranium target tail gas131I device | |
| Boldyrev et al. | Possibility of Obtaining High-Activity 177 Lu in the IR-8 Research Reactor | |
| Dadachova et al. | Improved processes of molybdenum-99 production | |
| Fonseca et al. | GMP-Automated Purification of Copper-61 Produced in Cyclotron Liquid Targets: Methodological Aspects | |
| Cheng et al. | Study on the separation of molybdenum-99 and recycling of uranium to water boiler reactor | |
| RU2498434C1 (en) | Method to produce radionuclide bismuth-212 | |
| Unni et al. | Production and radiochemical separation of rhodium-105 for radiopharmaceutical applications | |
| Das et al. | Separation of carrier-free 199Au as a β-decay product of 199Pt |
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 |