Method and device for recovering enriched 176yb generated during preparation process of carrier-free 177lu

Abstract

A method and device for recovering enriched 176Yb generated during the preparation process of carrier-free 177Lu. The recovery method comprises: subjecting a waste liquid containing enriched 176Yb to acid removal and concentration, so as to obtain a solution to be precipitated; precipitating the solution to be precipitated, so as to obtain a precipitate containing 176Yb; and subjecting the precipitate containing 176Yb to high-temperature heating, so as to convert the precipitate containing 176Yb into ytterbium oxide. By subjecting the waste liquid to a pre-treatment by means of a column chromatography method, a phosphoric acid organic extractant having a relatively high content is removed from the liquid to be recovered, thereby lowering the level of difficulty of treating the waste liquid. The precipitate containing 176Yb is then obtained by using a precipitation method, and finally, by means of in-situ heating, evaporation and concentration, all of the precipitate is collected, thereby simplifying the process flow, improving the efficiency and effect of recovery and achieving an 176Yb recovery rate of 95%.

Description

A carrier-free 177 Enrichment during Lu preparation 176 Yb recovery method and device Technical Field

[0001] The present invention relates to the technical field of radiochemical research, and in particular to a method for 177 Enrichment during Lu preparation 176 Yb recovery method and device. Background Art

[0002] 177 Lu(T 1 / 2 =6.64 days), as a radionuclide with excellent nuclear decay properties, the approval of two radiopharmaceuticals "Lutathera" and "Pluvicto" by Novartis has triggered a global interest in nuclear medicine. 177 Lu's unprecedented attention. With more and more regions and more and more types 177 The approval of Lu radiopharmaceuticals has increased the use of 177 The demand for Lu nuclides will grow rapidly.

[0003] Currently, targeted radiotherapy 177 Lu nuclides are almost all carrier-free 177 Lu. Realize no carrier 177 The method for large-scale preparation of Lu is to use nuclear reactor irradiation enrichment 176 Yb target (≥99%), producing 176 Yb(n,γ) 177 Yb reaction, 177 Yb(T 1 / 2 =1.9h) is generated by decay 177 Lu. Because Yb and Lu are adjacent rare earth elements with very similar chemical properties, in order to avoid the 177 Lu produces coordination competition that reduces drug quality, and Yb / Lu radiochemical separation must be performed to obtain Yb with extremely low content. 177 Lu products. Currently, no carrier 177 The radiochemical separation method of Lu preparation is generally through solid phase extraction, and the separation and purification by multi-stage resin column is obtained to meet the requirements. 177 Lu products. The elution process of this method will produce a large amount of high-concentration acid solution, and the elution solution also contains expensive enrichment 176 Yb (market price is about RMB 150,000 to 200,000 per gram). Therefore, it is necessary to enrich the 176 Yb is recycled to reduce production costs.

[0004] No information on enrichment has been found in the existing public reports. 176 Introduction to Yb recovery methods and devices. During the recovery process, it is necessary to consider the large volume of waste liquid to be recovered and the difficulty of operation. It is very necessary to provide a recovery method and device that can recover a large amount of waste liquid with low operation difficulty.

[0005] In view of this, this patent application is filed.

[0006] Summary of the Invention

[0007] The present invention provides a method for 177 Enrichment during Lu preparation 176 Yb recovery method and device, used to solve the problem of simple recovery and enrichment from large volume of waste liquid 176 Yb's problem.

[0008] The first object of the present invention is to provide a carrier-free 177 Enrichment during Lu preparation 176 The Yb recovery method comprises the following steps:

[0009] (1) Enrichment 176 The Yb waste liquid is deacidified and concentrated to obtain a solution to be precipitated;

[0010] (2) The precipitated solution is subjected to a precipitation method to obtain 176 Yb precipitation;

[0011] (3) 176 Yb precipitate is heated at high temperature to 176 Yb precipitates and converts into ytterbium oxide.

[0012] In the embodiment of the present invention, firstly 176 The Yb waste liquid is deacidified and concentrated, which can change the volume and pH value of the liquid to be recovered, and can remove the high content of phosphoric acid organic extractants in the liquid to be recovered, thereby preventing the adverse effects of organic extractants on the recovery experiment in the subsequent process. At the same time, the content of organic phosphorus extractants in the waste liquid is greatly reduced, and the difficulty of waste liquid treatment is reduced. Then, the precipitation method is used to obtain the organic phosphorus extractants. 176 Yb precipitation, and finally after the precipitation reaction is completed, the precipitation is concentrated by in-situ heating evaporation, without using conventional centrifugation, filtration and other methods for solid-liquid separation to achieve the collection of all precipitates, simplifying the process, improving the recovery efficiency and recovery effect, 176 The recovery rate of Yb reached 95%.

[0013] The recovery method adopted in the embodiment of the present invention is particularly suitable for recovering a large amount of enriched 176The recovery of Yb waste liquid can achieve a large amount of recovery with a simple process and simple operation method. 176 Recovery of Yb waste liquid.

[0014] In an optional embodiment, in step (1), column chromatography is used for deacidification, the eluent used for column chromatography is HCl solution, and the concentration process adopts evaporation concentration.

[0015] In the embodiment of the present invention, the column chromatography method is used to remove acid, which is conducive to the recovery of the metallic element Yb in a high-acidity, large-volume solution.

[0016] In an optional embodiment, the concentration of the eluent HCl solution is 0.05-0.1 mol / L, thereby resolving Yb from the column. In an optional embodiment, the resin filled in the column chromatography is TODGA resin, and the resin is treated with 1.5-4 mol / L nitric acid solution.

[0017] In an optional embodiment, the pH value of the solution to be precipitated is 1-2, the reagent used for precipitation is oxalic acid or ammonium carbonate, and the concentration of the precipitation reagent is 0.5-2.5 mol / L.

[0018] In an optional embodiment, the heating temperature in step (3) is greater than or equal to 750°C.

[0019] The second object of the present invention is to provide a carrier-free 177 Enrichment during Lu preparation 176 The Yb recovery device includes a first waste liquid tank, pump A, an eluent tank, a chromatography column, a second waste liquid tank, an evaporation concentration tank, a precipitant tank, pump B, a reaction vessel, and a high-temperature heating furnace;

[0020] The outlet pipelines of the first waste liquid tank and the eluent tank are both connected to the inlet pipeline of the pump A, the outlet of the pump A is connected to the inlet of the chromatography column, the outlet of the chromatography column is connected to the second waste liquid tank, the outlet of the second waste liquid tank is connected to the evaporation concentration tank, the outlets of the evaporation concentration tank and the precipitant tank are both connected to pump B, the outlet of the pump B is connected to the reaction vessel, and the high-temperature heating furnace is located at the rear end of the reaction vessel.

[0021] In the embodiment of the present invention, first, column chromatography separation is performed by combining the first waste liquid tank, pump A, eluent tank, and chromatography column; then evaporation concentration is performed by combining the second waste liquid tank and evaporation concentration tank; then precipitation reaction is performed by combining the precipitant tank, pump B, and reaction container; finally, in-situ heating evaporation concentration is performed by using a high-temperature heating furnace to enrich the 176 The Yb element is converted into ytterbium oxide, and recyclable Yb2O3 powder is obtained.

[0022] In an optional embodiment, the system further comprises a first three-way valve, a second three-way valve and a third three-way valve, wherein the three ports of the first three-way valve are connected to the first waste liquid tank, the eluent tank and the pump A respectively;

[0023] The three ports of the second three-way valve are respectively connected to the chromatography column, the second waste liquid tank, and the evaporation concentration tank;

[0024] The three ports of the third three-way valve are connected to the evaporation concentration tank, the precipitant tank, and the pump B respectively.

[0025] In the embodiment of the present invention, remote control of the process flow is achieved by using a reasonable combination of two devices, a three-way valve and a pump, which can effectively reduce the radiation dose to personnel.

[0026] In an optional embodiment, a magnetic stirring heater is provided below the reaction vessel.

[0027] In an optional embodiment, the apparatus further comprises a fume hood, a video monitor, and a remote controller, wherein the fume hood is divided into two layers, the first waste liquid tank and the second waste liquid tank are arranged on the lower layer of the fume hood, and the pump A, the eluent tank, the chromatography column, the evaporation concentration tank, the precipitant tank, the pump B, the reaction vessel, and the high-temperature heating furnace are all located on the upper layer of the fume hood;

[0028] The video monitor is fixed on the top of the upper layer of the fume hood;

[0029] The remote controller is electrically connected to pump A, pump B and each valve.

[0030] Because the recovery process involves handling radioactive materials, it must be performed in a device with radiation shielding. However, performing these complex processes within a conventional shielded glove box is extremely difficult, and the manufacturing and maintenance costs are prohibitive, typically reaching hundreds of millions of yuan. The recovery device in the embodiments of the present invention is installed within a fume hood, eliminating the need for operation outside the hood. This allows for effective removal of radioactive aerosols and protects the work environment from radioactive contamination.

[0031] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0032] (1) The embodiment of the present invention provides a method for 177 Enrichment during Lu preparation 176The Yb recovery method pre-treats the wastewater using column chromatography to modify the volume and pH of the recovered liquid, removing the high concentration of organic phosphoric acid extractants. This prevents the organic extractants from adversely affecting subsequent recovery experiments, significantly reduces the content of organic phosphorus extractants in the wastewater, and eases wastewater treatment. This method is relatively simple, and the resin material in the chromatography column can be reused, making it highly operational, economical, and environmentally friendly.

[0033] Then, the precipitation method was used to obtain 176 Yb precipitation, and finally after the precipitation reaction is completed, the precipitation is concentrated by in-situ heating evaporation, without using conventional centrifugation, filtration and other methods for solid-liquid separation to achieve the collection of all precipitates, simplifying the process, improving the recovery efficiency and recovery effect, 176 The recovery rate of Yb reached 95%.

[0034] (2) The embodiment of the present invention provides a method for 177 Enrichment during Lu preparation 176 The Yb recovery device has a radiation shielding function and a simple overall structure that can be placed in a fume hood. In addition, the device can be remotely controlled, eliminating the need for personnel to be exposed to radiation for a long time and at close range. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the technical solutions of the exemplary embodiments of the present invention, the following briefly introduces the drawings required for use in the examples. It should be understood that the following drawings only illustrate certain embodiments of the present invention and should not be considered as limiting the scope. A person of ordinary skill in the art can also derive other relevant drawings based on these drawings without inventive effort. In the drawings:

[0036] FIG1 is a method for providing a carrier-free 177 Enrichment during Lu preparation 176 Schematic diagram of the structure of the Yb recovery device.

[0037] FIG2 is an XRD test diagram of the ytterbium oxide powder obtained in an embodiment of the present invention.

[0038] In the figure: 1-fume hood; 2-first waste liquid tank; 3-first three-way valve; 4-eluent tank; 5-pump A; 6-chromatographic column; 7-second three-way valve; 8-second waste liquid tank; 9-evaporation concentration tank; 10-third three-way valve; 11-precipitant tank; 12-pump B; 13-reaction vessel; 14-magnetic stirring heater; 15-muffle furnace; 16-camera monitor; 17-remote controller. DETAILED DESCRIPTION

[0039] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with examples and drawings. The exemplary embodiments of the present invention and their descriptions are only used to explain the present invention and are not intended to limit the present invention.

[0040] To make the objectives, technical solutions, and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the accompanying drawings of the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Generally, the components of the embodiments of the present application described and shown in the drawings herein can be arranged and designed in various different configurations.

[0041] It should be noted that similar reference numerals and letters represent similar items in the following figures. Therefore, once an item is defined in one figure, it does not need to be further defined or explained in subsequent figures. In the absence of conflict, the embodiments and features in the embodiments of this application can be combined with each other.

[0042] In the description of the embodiments of the present application, the terms "center", "up", "down", "left", "right", "vertical", "longitudinal", "lateral", "horizontal", "inside", "outside", "front", "back", "top", "bottom", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, or are the orientations or positional relationships in which the product of the application is conventionally placed when in use, or are the orientations or positional relationships conventionally understood by those skilled in the art. They are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present application.

[0043] In the description of the present invention, unless otherwise expressly specified or limited, the terms "disposed," "having," "installed," "connected," and "connected" should be understood in a broad sense. For example, they may refer to fixed, detachable, or integral connections; mechanical or electrical connections; direct or indirect connections through an intermediate medium; and internal communication between two components. Those skilled in the art will understand the specific meanings of the above terms in the present invention in specific contexts.

[0044] Example 1:

[0045] A carrier-free 177 Enrichment during Lu preparation 176Yb recovery device. The structure of the recovery device is shown in Figure 1, which mainly includes a fume hood 1; a first waste liquid tank 2; a first three-way valve 3; an eluent tank 4; a pump A 5; a chromatography column 6; a second three-way valve 7; a second waste liquid tank 8; an evaporation concentration tank 9; a pump B 12; a reaction vessel 13; a magnetic stirring heater 14; a muffle furnace 15; a video monitor 16; and a remote controller 17.

[0046] The device is installed inside a fume hood 1, eliminating the need for operation outside the hood. It effectively removes radioactive aerosols and protects the work environment from radioactive contamination. The fume hood 1 is divided into two layers. The fume hood glass window is made of two layers of plexiglass sandwiched between lead glass (5mm thick or greater). The door under the countertop is covered with a lead plate (5mm thick or greater).

[0047] The waste liquid to be recycled is collected in the first waste liquid tank 2. The volume of the first waste liquid tank 2 is more than 1 times the volume of the required treatment solution. It has a liquid inlet and a liquid outlet. The material is acid-corrosion-resistant materials such as PEEK, high borosilicate glass and polytetrafluoroethylene. The liquid outlet of the first waste liquid tank 2 is connected to one port of the first three-way valve 3. The other port of the first three-way valve 3 is connected to the eluent tank 4. The volume of the eluent tank 4 is more than 25 times the volume of the chromatography column 6 used. The eluent tank 4 has a liquid inlet and a liquid outlet. The material is high borosilicate glass; another port of the first three-way valve 3 is connected to the pump A 5; Pump A The liquid outlet of column 5 is connected to chromatography column 6, the liquid outlet of chromatography column 6 is connected to one port of second three-way valve 7, and the other two ports of second three-way valve 7 are connected to the liquid outlet pipes to second waste liquid tank B and evaporation concentration tank 9 respectively. The specifications of second waste liquid tank 8 are the same as those of first waste liquid tank 2. The volume of evaporation concentration tank 9 is 5-10L, and the tank is lined with non-metallic strong acid corrosion-resistant materials such as polytetrafluoroethylene or PEEK, and is equipped with a vapor collection tank. The liquid outlet of evaporation concentration tank 9 is connected to third three-way valve 10, and the other two ports of third three-way valve 10 are connected to pump B 12 and precipitant tank 11 respectively. The liquid outlet pipe of pump B 12 is connected to reaction vessel 13. Reaction vessel 13 has a volume of 100-250mL and is placed on a magnetic stirring heater 14. The rear end of magnetic stirring heater 14 is a high-temperature heating furnace, using a muffle furnace 15. All switches of pumps, valves, etc. are controlled by a remote controller 17. The experimental process is observed by a video monitor 16.

[0048] The first waste liquid tank 2 and the second waste liquid tank 8 are arranged on the lower level of the fume hood 1, and the pump A 5, the eluent tank 4, the chromatography column 6, the evaporation concentration tank 9, the precipitant tank 11, the pump B 12, the reaction vessel 13, and the high-temperature heating furnace are all located on the upper level of the fume hood 1; the video monitor 16 is fixed on the top of the upper level of the fume hood 1.

[0049] Example 2:

[0050] A carrier-free 177 Enrichment during Lu preparation176 The Yb recovery method is carried out using the following process:

[0051] The Yb-containing eluent produced during the Yb / Lu separation process was taken as the waste liquid to be recovered, with a volume of 10 L and a Yb content of 500 mg. The recovered liquid was stored in the first waste liquid tank A2. 5 L of 0.1 mol / L HCl solution was prepared as the eluent in the eluent tank 4. The size of the chromatography column 6 was 20×400 mm, filled with about 50 g of TODGA resin, and treated with 4 mol / L nitric acid solution.

[0052] S1: Preliminary concentration and deacidification of the waste liquid to be recovered: The waste liquid in the first waste liquid tank 2 is transferred to the chromatography column 6 via the first three-way valve 3 and pump A 5 through the remote controller 17. The effluent of the chromatography column 6 flows into the second waste liquid tank 8 through the second three-way valve 7. After the solution is loaded onto the column, the first three-way valve 3 is controlled to allow the 0.1 mol / L HCl solution in the eluent tank 4 to elute the chromatography column 6 through the first three-way valve 3 and pump A 5. The eluent of the chromatography column 6 flows into the evaporation concentration tank 9 through the second three-way valve 7. The total eluent volume is 1.5 L.

[0053] S2: Evaporation and concentration of the eluent: The evaporation and concentration is started by the remote controller 17. After evaporation to dryness, 0.25 L of 0.1 mol / L HCl solution is added through the eluent tank 4 to obtain 0.25 L of Yb-containing solution to be precipitated;

[0054] S3: Generating an ytterbium-containing precipitate: 0.1 L of the Yb-containing solution to be precipitated in the evaporation concentration tank 9 is transferred into the reaction vessel 13 via the third three-way valve 10 and pump B 12 via the remote controller 17. The reaction vessel is a quartz beaker (volume 0.25 L). After the solution transfer is completed, the third three-way valve 10 is controlled to allow the 1.2 mol / L oxalic acid solution in the precipitant tank 11 to be added to the quartz beaker via the third three-way valve 10 at a flow rate of 3 mL / min. Simultaneously, the magnetic stirring heater 14 is started and stirred at 800 rpm for 10 minutes. Subsequently, heating is continued to evaporate the water until it is nearly dry, and the heating is turned off and cooled to room temperature.

[0055] S4: Conversion to Ytterbium Oxide: The quartz beaker was transferred to a muffle furnace 15, heated to 800°C, kept at this temperature for 2 hours, cooled to room temperature, and taken out. The powder mass was weighed to be approximately 540 mg. The diffraction spectrum obtained by XRD analysis was shown in Figure 2. As shown in Figure 2, Yb2O3 was separated.

[0056] Calculation shows that the recovery rate of Yb is 95%.

[0057] The embodiment of the present invention provides a method for 177 Enrichment during Lu preparation 176Yb recovery device and method to achieve the recovery of Yb in radioactive environment 176 Yb waste liquid is deacidified, concentrated, transformed and extracted. The device can be remotely controlled, is compact, radiation shielded, has a simple structure, has a good solution volume reduction effect and can be placed in a conventional fume hood. The device design and layout can be based on a conventional fume hood to complete the above process, without the need for expensive shielding operation boxes and other facilities.

[0058] The above specific implementation methods further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above are only specific implementation methods of the present invention and are not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for carrier-free 177 Enrichment of Lu during preparation 176 Yb recovery method, It is characterized in that The following steps are involved: (1) Enrichment 176 The Yb waste liquid is deacidified and concentrated to obtain a solution to be precipitated; (2) The precipitate solution is subjected to a precipitation method to obtain 176 Yb precipitation; (3) 176 The Yb precipitate is heated at high temperature to 176 Yb precipitates and is converted into ytterbium oxide.

2. A method for use without a carrier according to claim 1. 177 Enrichment of Lu during preparation 176 Yb recovery method, It is characterized in that In the step (1), column chromatography is used for deacidification, the eluent used for column chromatography is HCl solution, and the concentration process adopts evaporation concentration.

3. A method for use without a carrier according to claim 2. 177 Enrichment of Lu during preparation 176 Yb recovery method, It is characterized in that The concentration of the eluent HCl solution is 0.05-0.1 mol / L.

4. A method for use without a carrier according to claim 2 177 Enrichment of Lu during preparation 176 Yb recovery method, It is characterized in that The resin filled in the column chromatography is TODGA resin, and the resin is treated with 1.5-4 mol / L nitric acid solution.

5. A method for use without a carrier according to claim 1. 177 Enrichment of Lu during preparation 176 Yb recovery method, It is characterized in that The pH value of the solution to be precipitated is 1-2, the reagent used for precipitation is oxalic acid or ammonium carbonate, and the concentration of the precipitation reagent is 0.5-2.5 mol / L.

6. A method for use without a carrier according to claim 1. 177 Enrichment of Lu during preparation 176 Yb recovery method, It is characterized in that The heating temperature in step (3) is greater than or equal to 750°C.

7. A method for realizing the carrier-free method as claimed in any one of claims 1 to 6 177 Enrichment of Lu during preparation 176 Yb recovery method and recovery device, It is characterized in that It includes a first waste liquid tank, a pump A, a washing liquid tank, a chromatography column, a second waste liquid tank, an evaporation concentration tank, a precipitant tank, a pump B, a reaction container, and a high-temperature heating furnace; The outlet pipelines of the first waste liquid tank and the eluent tank are both connected to the inlet pipeline of the pump A, the outlet of the pump A is connected to the inlet of the chromatography column, the outlet of the chromatography column is connected to the second waste liquid tank, the outlet of the second waste liquid tank is connected to the evaporation concentration tank, the outlets of the evaporation concentration tank and the precipitant tank are both connected to pump B, the outlet of the pump B is connected to the reaction container, and the high-temperature heating furnace is located at the rear end of the reaction container.

8. The method for use without a carrier according to claim 7. 177 Enrichment of Lu during preparation 176 Yb recovery device, It is characterized in that It also includes a first three-way valve, a second three-way valve and a third three-way valve, wherein the three ports of the first three-way valve are connected to the first waste liquid tank, the eluent tank and the pump A respectively; The three ports of the second three-way valve are respectively connected to the chromatography column, the second waste liquid tank, and the evaporation concentration tank; The three ports of the third three-way valve are connected to the evaporation concentration tank, the precipitant tank, and the pump B respectively.

9. The method for use without a carrier according to claim 7. 177 Enrichment of Lu during preparation 176 Yb recovery device, It is characterized in that A magnetic stirring heater is arranged below the reaction container.

10. The method for use without a carrier according to claim 8. 177 Enrichment of Lu during preparation 176 Yb recovery device, It is characterized in that It also includes a fume hood, a video monitor, and a remote controller. The fume hood is divided into two layers, the first waste liquid tank and the second waste liquid tank are arranged on the lower layer of the fume hood, and the pump A, the eluent tank, the chromatography column, the evaporation concentration tank, the precipitant tank, the pump B, the reaction container, and the high-temperature heating furnace are all located on the upper layer of the fume hood; The video monitor is fixed on the top of the upper layer of the fume hood; The remote controller is communicatively connected to pump A, pump B and each valve.

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