Device and method for rapidly separating actinide elements through four-column continuous color layer

Abstract

The invention relates to a device and a method for rapidly separating actinide elements through a four-column continuous color layer, belongs to the technical field of actinide element separation, and solves the technical problems of interference, complex process and low precision in actinide element separation. The device comprises a liquid storage tank unit, a color layer separation unit, a waste liquid collector, a product collection unit, a valve and a delivery pump. Liquid in the uppermost liquid storage tank unit flows into the color layer separation unit through a valve and a conveying pump; the liquid flowing out of the color layer separation unit is controlled by a valve to flow into a waste liquid collector or flow into a product collection unit. The method comprises the following steps: preparing a radioactive sample, a water-based washing solution, a water-based leacheate, a water-based desorption solution and a chromatography adsorption column before separation; adsorbing plutonium, uranium, americium and neptunium; washing is performed; leaching is conducted; and desorption: separating out radioactive solutions of plutonium, uranium, americium and neptunium. The method is used for separating and purifying the actinide elements.

Description

Technical Field

[0001] The invention belongs to the technical field of actinide separation, and in particular relates to a device and a method for rapidly separating actinide elements by four-column continuous chromatography. Background Art

[0002] Uranium and transuranium elements such as neptunium, plutonium, and americium are the main components of environmental alpha radioactive pollutants. In addition to uranium, which is a naturally occurring radioactive element, other toxic alpha radioactive pollutants mainly come from atmospheric test fallout, reactor nuclear accident leakage, and nuclear facility decommissioning. Because they have a very long half-life, they have the greatest long-term potential harm to the biosphere and human health. Therefore, the rapid analysis of actinides is of great significance in the fields of nuclear accident emergency monitoring, environmental radioactivity level assessment, and nuclear event identification.

[0003] The content of actinide elements in samples is usually at trace or ultra-trace levels. Environmental monitoring and analytical evaluation are mainly carried out by measuring the content of their main isotopes Pu-239, U-238, Am-241, Np-237 or lower abundance isotopes by mass spectrometer or alpha spectrometer. However, the accurate measurement of these isotopes is not only affected by the sample matrix, but also has serious measurement interference with each other. For example, the mass spectrometry measurement of Pu-239 will be interfered by the hydrogen ion complex of uranium-238 and the isotope interference of neptunium isotope Np-239. ; The mass spectrum of U-238 will be interfered by the isotope interference of plutonium isotope Pu-238 and the hydrogen ion complex interference of Np-237; the mass spectrum measurement of Am-241 will be interfered by the isotope interference of Pu-241, and in the α spectrum measurement, it will be interfered by the heavy peak (5.48MeV) of plutonium isotope Pu-238; Np-237 will be interfered by the hydrogen ion complex interference of uranium isotope U-236 in the mass spectrum measurement, and in the α spectrum measurement, it will be interfered by the heavy peak (4.78MeV) of plutonium isotope Pu-242. Therefore, the rapid and high decontamination separation and purification of plutonium, uranium, americium and neptunium, and the elimination of measurement interference between each other and the matrix are crucial for the high-precision test and analysis of their content and isotope abundance.

[0004] Extraction chromatography is a commonly used separation and purification method in actinide analysis. Literature reports use a single extraction chromatography column, constantly changing the elution reagent, and sequentially eluting and recovering single actinides such as uranium, plutonium, neptunium, and americium. Such as UTEVA extraction chromatography (Morgenstern et al., Single-column extraction chromatographic separation of U, Pu, Np and Am. Radiochimica Acta, 2002, 90 (2): 81-85) and DGA extraction chromatography (Groska et al., Determination of actinides in radioactive waste after separation on a single DGA resin column. Journal of radioanalytical and nuclear chemistry, 2016, 309: 1145-1158). These methods are limited by the selectivity of the complexation of different eluents with actinides and the influence of elution peak tailing, and the decontamination factor between actinides is not high. For example, the decontamination factor of the UTEVA method is in the range of 53 to 3000; in the DGA method, there is still 1-2% mutual contamination between actinide elements, and the temperature needs to be increased to improve decontamination. Due to multiple lengthy elutions and the use of high-temperature equipment, the separation process is more complicated, the separation and purification cycle is extended, and the technical requirements for rapid and high-precision testing and analysis of trace actinide isotopes cannot be met. Summary of the invention

[0005] In order to overcome the shortcomings of interference, complex process and low precision in separation of actinide elements, the present invention proposes a device and method for rapid separation of actinide elements by four-column continuous chromatography.

[0006] The technical solution adopted by the present invention to solve the technical problem is:

[0007] A device for rapid separation of actinide elements by four-column continuous chromatography, comprising a liquid storage tank unit, a chromatography separation unit, a waste liquid collector, a product collection unit, a valve, a delivery pump and a pipeline;

[0008] The above-mentioned liquid storage tank unit, chromatographic separation unit, waste liquid collector, valve and product collection unit are connected by pipelines;

[0009] The above-mentioned storage tank unit includes a storage tank for a radioactive solution containing actinide elements plutonium, uranium, americium and neptunium, a washing liquid storage tank, a first-stage eluent storage tank, a second-stage eluent storage tank, a third-stage eluent storage tank, a fourth-stage eluent storage tank, a first-stage desorption liquid storage tank, a second-stage desorption liquid storage tank, a third-stage desorption liquid storage tank and a fourth-stage desorption liquid storage tank;

[0010] The above-mentioned chromatography separation unit includes N263 or TEVA chromatography adsorption column, TBP or UTEVA chromatography adsorption column, DN chromatography adsorption column and TRU or RE chromatography adsorption column;

[0011] The above-mentioned product collection unit includes a plutonium product collector, a uranium product collector, an americium product collector, and a neptunium product collector;

[0012] The liquid outlets of the storage tank containing the radioactive solution of plutonium, uranium, americium and neptunium, the washing liquid storage tank, the first-stage eluent storage tank, the second-stage eluent storage tank, the third-stage eluent storage tank, the fourth-stage eluent storage tank, the first-stage desorption liquid storage tank, the second-stage desorption liquid storage tank, the third-stage desorption liquid storage tank and the fourth-stage desorption liquid storage tank are connected to the inlet of the delivery pump through a valve

[0013] The outlet of the delivery pump is respectively connected to the feed inlet of the N263 or TEVA chromatography adsorption column, the TBP or UTEVA chromatography adsorption column, the DN chromatography adsorption column, and the TRU or RE chromatography adsorption column;

[0014] The outlet of the N263 or TEVA chromatography adsorption column is connected to the waste liquid collector, the inlet of the TBP or UTEVA chromatography adsorption column and the plutonium product collector through valves;

[0015] The outlet of the TBP or UTEVA chromatography adsorption column is connected to the waste liquid collector, the inlet of the DN chromatography adsorption column and the uranium product collector respectively through valves;

[0016] The outlet of the DN chromatography adsorption column is connected to the waste liquid collector, the inlet of the TRU or RE chromatography adsorption column and the americium product collector through a valve;

[0017] The discharge port of the TRU or RE chromatography adsorption column is connected to the waste liquid collector and the neptunium product collector through a valve.

[0018] The above pipelines use silicone tubes; the valves are solenoid valves; and the delivery pumps are peristaltic pumps. In this way, the solenoid valves and peristaltic pumps can be controlled by a microcomputer to achieve automatic control of the separation process, reducing the impact of radioactive nuclides radiation and toxicity on the human body during separation. The peristaltic pump uses a hose to squeeze the liquid for separation, and controls the flow rate and velocity of the liquid through the rotation speed of the peristaltic pump.

[0019] The above-mentioned delivery pump has multiple inlets and outlets, and each liquid storage tank is connected to a different inlet of the delivery pump respectively. Each outlet of the delivery pump is connected to the feed port of the N263 or TEVA chromatography adsorption column, and is connected to the feed port of the TBP or UTEVA chromatography adsorption column, the DN chromatography adsorption column and the TRU or RE chromatography adsorption column through a valve respectively. In this way, after continuous loading, adsorption and washing, separation processes such as eluting impurities and desorbing and recovering product liquid can be carried out simultaneously without affecting each other.

[0020] A method for rapidly separating actinide elements by four-column continuous chromatography comprises the following steps:

[0021] Step 1: Preparation before separation

[0022] The radioactive sample containing actinide elements plutonium, uranium, americium and neptunium is first dissolved in acid, and then sodium nitrite is added to heat at 70 to 100 degrees and then cooled to form an aqueous radioactive sample containing plutonium, uranium, americium and neptunium;

[0023] Dissolving the acid in water respectively to form an aqueous washing solution, an aqueous eluent and an aqueous desorption solution;

[0024] N263 or TEVA, TBP or UTEVA, DN, TRU or RE resins are respectively loaded into chromatographic columns;

[0025] Step 2: Adsorption of plutonium, uranium, americium and neptunium

[0026] Separate and adsorb the aqueous radioactive sample containing plutonium, uranium, americium and neptunium prepared in step 1 by passing it through a N263 or TEVA chromatography adsorption column, a TBP or UTEVA chromatography adsorption column, a DN chromatography adsorption column and a TRU or RE chromatography adsorption column in sequence, and collect the effluent as waste liquid;

[0027] Plutonium is adsorbed on N263 or TEVA chromatographic adsorption column, uranium is adsorbed on TBP or UTEVA chromatographic adsorption column, americium is adsorbed on DN chromatographic adsorption column, and neptunium is adsorbed on TRU or RE chromatographic adsorption column.

[0028] Step 3: Washing

[0029] The washing liquid passes through N263 or TEVA chromatography adsorption column, TBP or UTEVA chromatography adsorption column, DN chromatography adsorption column and TRU or RE chromatography adsorption column in sequence to wash each chromatography column, and the effluent is collected as waste liquid;

[0030] Step 4: Rinse

[0031] The first-stage eluent is passed through an N263 or TEVA chromatography column to further decontaminate plutonium, and the effluent is collected as waste liquid;

[0032] The second-stage eluent is also passed through a TBP or UTEVA chromatography column to further decontaminate the uranium, and the effluent is collected as waste liquid;

[0033] The third-stage eluent is also passed through a DN chromatography adsorption column to further remove americium, and the effluent is collected as waste liquid;

[0034] The fourth-stage eluent is passed through the TRU or RE chromatography adsorption column to further decontaminate neptunium, and the effluent is collected as waste liquid;

[0035] Step 5: Desorption

[0036] The first-stage desorption liquid passes through the N263 or TEVA chromatography adsorption column; the effluent, i.e. the radioactive solution of plutonium, is collected in the plutonium product collector;

[0037] The second-stage desorption liquid passes through the TBP or UTEVA chromatography adsorption column at the same time; the effluent, i.e. the radioactive solution of uranium, is collected in the uranium product collector;

[0038] The third-stage desorption liquid passes through the DN chromatography adsorption column at the same time; the effluent liquid, i.e. the radioactive solution of americium, is collected in the americium product collector;

[0039] The fourth-stage desorption liquid passes through the TRU or RE chromatography adsorption column at the same time; the effluent, i.e. the radioactive solution of neptunium, is collected in the neptunium product collector.

[0040] The radioactive samples of plutonium, uranium, americium and neptunium mentioned above are complex matrix samples such as soil and rocks contaminated by nuclear accidents or environmental radioactivity.

[0041] The acid in step 1 is nitric acid and hydrochloric acid, hydrofluoric acid, oxalic acid or a combination of the above acids, and the concentration of the acid is 0.01 to 9.0 mol / L.

[0042] The acid for dissolving the radioactive sample is 3-5mol / L HNO3; the aqueous washing liquid is 3-5mol / L HNO3 solution; the first-stage eluent is 3-9mol / L HCl solution; the second-stage eluent is 4-6mol / L HCl solution; the third-stage eluent is 0.1-0.2mol / L HNO3 solution containing 0.01-0.1mol / L NaNO2; the fourth-stage eluent is 1-2mol / L HNO3 solution; the first-stage desorption liquid is 0.1-1.0mol / L HCl solution; the second-stage desorption liquid is 0.01-0.15mol / L HNO3 solution or 0.01mol / L HNO3-0.01mol / L H2C2O4 solution; the third-stage desorption liquid is 0.05-1.5mol / L HCl solution; the fourth-stage desorption liquid is 0.1mol / L HCl solution containing 0.1-0.4mol / L HF.

[0043] The plutonium is various long-lived plutonium isotopes including plutonium-239, the uranium is various long-lived uranium isotopes including uranium-238, the americium is various long-lived americium isotopes including americium-241, and the neptunium is various long-lived neptunium isotopes including neptunium-237.

[0044] The beneficial effects of the present invention are:

[0045] A method for rapid separation of actinide elements by four-column continuous chromatography can automatically obtain a measurement source of actinide elements of radiochemical analytical purity in a radioactive solution of trace plutonium, uranium, americium and neptunium rich in soil and rock complex matrix, and has the characteristics of simple and rapid process, high sample utilization rate and good separation effect.

[0046] A method for rapid separation of actinide elements by four-column continuous chromatography effectively utilizes the difference in the complexing and coordination ability of the actinide elements plutonium, uranium, americium and neptunium with the chromatographic stationary phase, so that they flow continuously in a feed solution and are adsorbed and retained in turn on the N263 or TEVA chromatographic column, TBP or UTEVA chromatographic column, DN chromatographic column and TRU or RE chromatographic column, and through their respective elution and desorption, plutonium, uranium, americium and neptunium are simultaneously separated and recovered with high selectivity.

[0047] A method for rapid separation of actinide elements by four-column continuous chromatography realizes the synchronous and efficient separation of actinide elements plutonium, uranium, americium and neptunium under automatic control conditions; the chemical recovery rate of plutonium is greater than 88%, the chemical recovery rate of uranium is greater than 96%, the recovery rate of americium is greater than 92%, the chemical recovery rate of neptunium is greater than 88%, and the decontamination factor between plutonium, uranium, americium and neptunium and the decontamination factor for major elements are better than 10 4 .

[0048] A device for rapid separation of actinide elements by four-column continuous chromatography, with clear separation unit functions, simple process and easy control. A streamlined automatic control separation process of simultaneous adsorption, elution and desorption of four-column continuous chromatography is constructed using simple separation solution and separation column. The entire separation process can be completed within 1 hour.

[0049] A device for rapid separation of actinide elements by four-column continuous chromatography. The entire separation process from the absorption of original radioactive liquid to the preparation of radioactive measurement sources of actinide elements plutonium, uranium, americium and neptunium is automatically controlled by a microcomputer program, which can significantly reduce the radiation dose of operators. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 It is a schematic diagram of the process and device of the separation method of actinide elements in an embodiment of the present invention.

[0051] Figure numerals: 1. a reservoir for a radioactive solution containing actinide elements plutonium, uranium, americium and neptunium, 2. a reservoir for a washing solution, 3. a reservoir for a first-stage eluent, 4. a reservoir for a first-stage desorption solution, 5. a reservoir for a second-stage eluent, 6. a reservoir for a second-stage desorption solution, 7. a reservoir for a third-stage eluent, 8. a reservoir for a third-stage desorption solution, 9. a reservoir for a fourth-stage eluent, 10. a reservoir for a fourth-stage desorption solution, 11. a plutonium product collector, 12. a uranium product collector, 13. americium product collector, 14. a neptunium product collector, 15. a waste liquid collector, 16. a N263 or TEVA chromatography adsorption column, 17. a TBP or UTEVA chromatography adsorption column, 18. a DN chromatography adsorption column, 19. a TRU or RE chromatography adsorption column, 20. a transfer pump, 21. a valve. DETAILED DESCRIPTION

[0052] The present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0053] like Figure 1 As shown, the separation device of the radioactive solution containing actinide elements plutonium, uranium, americium and neptunium of the present invention comprises a liquid storage tank unit, a chromatographic separation unit, a waste liquid collector 15, and a product collection unit. The above units and devices are connected by pipelines. Preferably, the pipeline adopts a silicone tube; and a corresponding valve 21 and a delivery pump 20 are configured in the pipeline. The valve 21 is a solenoid valve, and the delivery pump 20 is a peristaltic pump. In this way, the solenoid valve and the peristaltic pump can be controlled by a microcomputer to realize automatic control of the separation process, reduce the impact of radioactive nuclide radiation on the human body during separation, and reduce the labor intensity of personnel. The peristaltic pump uses a hose extrusion method to deliver the separation liquid, and the flow rate and flow velocity of the liquid are controlled by the rotation speed of the peristaltic pump.

[0054] The above-mentioned liquid storage tank unit comprises a liquid storage tank 1 for a radioactive solution containing actinide elements plutonium, uranium, americium and neptunium, a washing liquid storage tank 2, a first-stage eluent storage tank 3, a first-stage desorption liquid storage tank 4, a second-stage eluent storage tank 5, a second-stage desorption liquid storage tank 6, a third-stage eluent storage tank 7, a third-stage desorption liquid storage tank 8, a fourth-stage eluent storage tank 9 and a fourth-stage desorption liquid storage tank 10, each liquid storage tank is connected to a corresponding chromatographic adsorption column through a valve and a pump, and realizes different functions;

[0055] The above-mentioned chromatography separation unit includes N263 or TEVA chromatography adsorption column 16, TBP or UTEVA chromatography adsorption column 17, DN chromatography adsorption column 18, TRU or RE chromatography adsorption column 19.

[0056] The product collection unit includes a plutonium product collector 11, a uranium product collector 12, an americium product collector 13 and a neptunium product collector 14;

[0057] The connection relationship between the above-mentioned reservoirs and the chromatographic adsorption column is as follows: a reservoir 1 for a radioactive solution containing actinide elements plutonium, uranium, americium and neptunium, a washing liquid reservoir 2, a first-stage eluent reservoir 3, a first-stage desorption liquid reservoir 4, a second-stage eluent reservoir 5, a second-stage desorption liquid reservoir 6, a third-stage eluent reservoir 7, a third-stage desorption liquid reservoir 8, a fourth-stage eluent reservoir 9 and a fourth-stage desorption liquid reservoir 10 are arranged in parallel at the uppermost end, and the outlet of each reservoir is connected to the corresponding inlet of a delivery pump 20 through a valve 21; the corresponding outlet of the delivery pump 20 is connected to an N263 or TEVA chromatographic adsorption column 16, and is connected to a TBP or UTEVA chromatographic adsorption column 17, a DN chromatographic adsorption column 18 and a TRU or RE chromatographic adsorption column 19 through valves 21, respectively. The feed inlet of the attached column 19 is connected; the discharge port of the N263 or TEVA chromatography adsorption column 16 is connected to the waste liquid collector 15, the feed inlet of the TBP or UTEVA chromatography adsorption column 17 and the plutonium product collector 11 through a valve 21; the discharge port of the TBP or UTEVA chromatography adsorption column 17 is connected to the waste liquid collector 15, the feed inlet of the DN chromatography adsorption column 18 and the uranium product collector 12 through a valve 21; the discharge port of the DN chromatography adsorption column 18 is connected to the waste liquid collector 15, the feed inlet of the TRU or RE chromatography adsorption column 19 and the americium product collector 13 through a valve 21; the discharge port of the TRU or RE chromatography adsorption column 19 is connected to the waste liquid collector 15 and the neptunium product collector 14 through a valve 21.

[0058] The separation step of the present invention is:

[0059] Step 1: Preparation before separation

[0060] The radioactive samples such as soil and rock matrix contaminated with actinide elements plutonium, uranium, americium and neptunium are dissolved in acid to form an aqueous radioactive solution; the acid is dissolved in water to form an aqueous washing liquid, an aqueous eluent and an aqueous desorption liquid; the acid used is nitric acid and hydrochloric acid, hydrofluoric acid, oxalic acid or a combination of the above acids, and the concentration of the acid is 0.01 to 9.0 mol / L; N263 or TEVA, TBP or UTEVA, DN, TRU or RE resins are respectively loaded into chromatographic columns.

[0061] Among them, the N263 or TEVA chromatographic column is mainly used to separate Pu from U, Am, Np and constant elements (K, Ca, Mg, Al, Fe, Mn), etc.; the TBP or UTEVA chromatographic column is mainly used to further separate U from Pu, as well as separate it from Am, Np and constant elements (K, Ca, Mg, Al, Fe, Mn), etc.; the DN chromatographic column is mainly used to further separate Am from Pu and U, as well as separate it from Np and constant elements (K, Ca, Mg, Al, Fe, Mn), etc.; the TRU or RE chromatographic column is mainly used to further separate Np from Pu and U, as well as separate it from constant elements (K, Ca, Mg, Al, Fe, Mn), etc.

[0062] Step 2: using a peristaltic pump for delivery and a solenoid valve for selection, the radioactive solution containing plutonium, uranium, americium and neptunium is sequentially passed through the N263 or TEVA chromatography adsorption column 16, the TBP or UTEVA chromatography adsorption column 17, the DN chromatography adsorption column 18 and the TRU or RE chromatography adsorption column 19 for separation and adsorption, and the effluent is collected as waste liquid;

[0063] Plutonium, uranium, americium and neptunium are adsorbed on different chromatographic columns respectively; specifically, plutonium is adsorbed on N263 or TEVA chromatographic adsorption column 16, uranium is adsorbed on TBP or UTEVA chromatographic adsorption column 17, americium is adsorbed on DN chromatographic adsorption column 18, and neptunium is adsorbed on TRU or RE chromatographic adsorption column 19.

[0064] Step 3: Use a peristaltic pump to deliver and a solenoid valve to select, so that the washing liquid passes through the N263 or TEVA chromatography adsorption column 16, the TBP or UTEVA chromatography adsorption column 17, the DN chromatography adsorption column 18 and the TRU or RE chromatography adsorption column 19 in sequence for washing, adsorption and separation, and the effluent is collected as waste liquid;

[0065] Step 4: Use a peristaltic pump to deliver and an electromagnetic valve to select, so that the first-stage eluent passes through the N263 or TEVA chromatography adsorption column 16, the second-stage eluent passes through the TBP or UTEVA chromatography adsorption column 17, the third-stage eluent passes through the DN chromatography adsorption column 18, and the fourth-stage eluent passes through the TRU or RE chromatography adsorption column 19 for elution and separation, and the effluent is collected as waste liquid.

[0066] Step 5: Use a peristaltic pump to deliver and an electromagnetic valve to select, and at the same time pass the first-stage desorption liquid through an N263 or TEVA chromatography adsorption column 16, the second-stage desorption liquid through a TBP or UTEVA chromatography adsorption column 17, the third-stage desorption liquid through a DN chromatography adsorption column 18, and the fourth-stage desorption liquid through a TRU or RE chromatography adsorption column 19. The effluents are respectively a plutonium radioactive solution, a uranium radioactive solution, an americium radioactive solution, and a neptunium radioactive solution, which are collected in a plutonium product collector 11, a uranium product collector 12, an americium product collector 13, and a neptunium product collector 14; a radioactive measurement source can be prepared for test analysis.

[0067] In the above method, the plutonium is various long-lived plutonium isotopes including plutonium-239, the uranium is various long-lived uranium isotopes including uranium-238, the americium is various long-lived americium isotopes including americium-241, and the neptunium is various long-lived neptunium isotopes including neptunium-237.

[0068] The specific embodiments are as follows:

[0069] Embodiment 1

[0070] A radioactive sample containing plutonium, uranium, americium, and neptunium and matrix elements is dissolved in 10 mL of 3 mol / L HNO3, sodium nitrite is added, heated at 70 to 100 degrees, and cooled to form a solution containing plutonium, uranium, americium, and neptunium, and the solution is placed in a liquid storage tank 1.

[0071] The flow rate of the plutonium, uranium, americium and neptunium solution was controlled at 1 mL / min, and the plutonium, uranium, americium and neptunium solution was separated by N263 chromatographic adsorption column, TBP chromatographic adsorption column, DN chromatographic adsorption column 18 and TRU chromatographic adsorption column in sequence. N263 chromatography column, TBP chromatography adsorption column is The TBP chromatography column and the DN chromatography adsorption column 18 are DN chromatography column, TRU chromatography adsorption column is TRU chromatogram column, wherein the N263 chromatogram column realizes the separation of Pu from U, Am, Np and constant elements (K, Ca, Mg, Al, Fe, Mn), etc., the TBP chromatogram column realizes the further separation of U from Pu, as well as the separation of U from Am, Np and constant elements (K, Ca, Mg, Al, Fe, Mn), etc., the DN chromatogram column realizes the further separation of Am from Pu and U, as well as the separation of Am from Np and constant elements (K, Ca, Mg, Al, Fe, Mn), etc., the TRU chromatogram column realizes the further separation of Np from Pu and U, as well as the separation of Np from constant elements (K, Ca, Mg, Al, Fe, Mn), etc., and the effluent is collected in the waste liquid collector 15.

[0072] Use 30mL of 3mol / L HNO3 solution in the washing liquid reservoir 2, control the flow rate at 1.5mL / min, and wash through the N263 chromatography adsorption column, TBP chromatography adsorption column, DN chromatography adsorption column 18 and TRU chromatography adsorption column in sequence, and collect the effluent in the waste liquid collector 15.

[0073] Use 10mL 3mol / L HCl solution in the first-stage eluent reservoir 3, 10mL 4mol / L HCl solution in the second-stage eluent reservoir 5, 10mL 0.1mol / L HNO3-0.01mol / LNaNO2 solution in the third-stage eluent reservoir 7, and 10mL 1.5mol / L HNO3 solution in the fourth-stage eluent reservoir 9, control the flow rate to 1.5mL / min, and elute through the N263 chromatography adsorption column, TBP chromatography adsorption column, DN chromatography adsorption column 18 and TRU chromatography adsorption column respectively to further purify plutonium, uranium, americium and neptunium, and collect the effluent in the waste liquid collector 15.

[0074] 10mL 0.5mol / L HCl solution in the first-stage desorption liquid reservoir 4, 10mL 0.1mol / L HNO3 solution in the second-stage desorption liquid reservoir 6, 10mL 0.1mol / L HCl solution in the third-stage desorption liquid reservoir 8, and 10mL 0.1mol / L HCl-0.3mol / L HF solution in the fourth-stage desorption liquid reservoir 10 are used, and the flow rate is controlled at 1.5mL / min, and they pass through the N263 chromatographic adsorption column, TBP chromatographic adsorption column, DN chromatographic adsorption column 18 and TRU chromatographic adsorption column respectively. The effluent is collected in the plutonium product collector 11, the uranium product collector 12, the americium product collector 13 and the neptunium product collector 14, which are the radioactive measurement sources of plutonium, uranium, americium and neptunium.

[0075] The process recovery rates of plutonium, uranium, americium and neptunium are 88.7%, 96.3%, 92.6% and 89.4% respectively. The decontamination factors of plutonium, uranium, americium and neptunium are better than 10. 4 , the decontamination factor for constant elements is better than 10 4 The process takes less than 1 hour.

[0076] Embodiment 2

[0077] The N263 chromatographic adsorption column in Example 1 was replaced by a TEVA chromatographic adsorption column, the TBP chromatographic adsorption column was replaced by a UTEVA chromatographic adsorption column, and the 10 mL 0.1 mol / L HNO3 solution in the second-stage desorption liquid storage tank 6 was replaced by a 10 mL 0.01 mol / L HNO3-0.01 mol / L H2C2O4 solution. The separation process of Example 1 was repeated to obtain a radioactive measurement source of plutonium, a radioactive measurement source of uranium, a radioactive measurement source of americium, and a radioactive measurement source of neptunium. As shown in Table 1, the process recovery rates of plutonium, uranium, americium, and neptunium were 89.2%, 96.9%, 93.3%, and 88.6%, respectively, and the decontamination factor between plutonium, uranium, americium, and neptunium was better than 10. 4 , the decontamination factor for constant elements is better than 10 4 The process takes less than 1 hour.

[0078] Table 1 Analysis of the recovery rate and decontamination factor of plutonium, uranium, americium and neptunium

[0079]

[0080]

Claims

1. A device for rapid separation of actinide elements by four-column continuous chromatography, It is characterized in that It comprises a liquid storage tank unit, a chromatography separation unit, a waste liquid collector (15), a product collection unit, a valve (21), and a delivery pump (20); The liquid storage tank unit is located at the uppermost end. The liquid in the liquid storage tank unit flows into the chromatographic separation unit through a valve (21) and a delivery pump (20). The liquid flowing out of the chromatographic separation unit is controlled by the valve (21) to flow into a waste liquid collector (15) or into a product collection unit. The chromatographic separation unit is used for separation of actinide elements, and the chromatographic separation unit comprises four chromatographic adsorption columns connected in sequence, and the four chromatographic adsorption columns connected in sequence are, from top to bottom, N263 or TEVA chromatographic adsorption column (16), TBP or UTEVA chromatographic adsorption column (17), DN chromatographic adsorption column (18), and TRU or RE chromatographic adsorption column (19); The corresponding outlet of the delivery pump (20) is connected to the N263 or TEVA chromatography adsorption column (16), and is respectively connected to the feed inlet of the TBP or UTEVA chromatography adsorption column (17), the DN chromatography adsorption column (18) and the TRU or RE chromatography adsorption column (19) through the valve (21); The discharge port of the N263 or TEVA chromatography adsorption column (16) is connected to the waste liquid collector (15), the feed port of the TBP or UTEVA chromatography adsorption column (17) and the product collection unit through a valve (21); the discharge port of the TBP or UTEVA chromatography adsorption column (17) is connected to the waste liquid collector (15), the feed port of the DN chromatography adsorption column (18) and the product collection unit through a valve (21); the discharge port of the DN chromatography adsorption column (18) is connected to the waste liquid collector (15), the feed port of the TRU or RE chromatography adsorption column (19) and the product collection unit through a valve (21); the discharge port of the TRU or RE chromatography adsorption column (19) is connected to the waste liquid collector (15) and the product collection unit through a valve (21).

2. The device for rapid separation of actinide elements by four-column continuous chromatography according to claim 1, It is characterized in that The liquid storage tank unit comprises 10 liquid storage tanks, which are: a radioactive solution storage tank containing actinide elements plutonium, uranium, americium and neptunium (1), a washing liquid storage tank (2), a first-stage eluent storage tank (3), a first-stage desorption liquid storage tank (4), a second-stage eluent storage tank (5), a second-stage desorption liquid storage tank (6), a third-stage eluent storage tank (7), a third-stage desorption liquid storage tank (8), a fourth-stage eluent storage tank (9) and a fourth-stage desorption liquid storage tank (10); each liquid storage tank is connected to a corresponding chromatographic adsorption column via a valve (21) and a delivery pump (20); The actinide elements plutonium, uranium, americium and neptunium radioactive solution storage tank (1), the washing solution storage tank (2), the first-stage eluent storage tank (3) and the first-stage desorption solution storage tank (4) flow into the N263 or TEVA chromatography adsorption column (16) through the valve (21) and the delivery pump (20) respectively; The second-stage eluent storage tank (5) and the second-stage desorption liquid storage tank (6) flow into the TBP or UTEVA chromatography adsorption column (17) through the valve (21) and the delivery pump (20) respectively; The third-stage eluent storage tank (7) and the third-stage desorption liquid storage tank (8) flow into the DN chromatography adsorption column (18) through the valve (21) and the delivery pump (20) respectively; The fourth-stage eluent storage tank (9) and the fourth-stage desorption liquid storage tank (10) are respectively connected via valves (21), The delivery pump (20) flows into the TRU or RE chromatography adsorption column (19).

3. The device for rapid separation of actinide elements by four-column continuous chromatography according to claim 1, It is characterized in that The product collection unit comprises four product collectors, the four product collectors are: a plutonium product collector (11), a uranium product collector (12), an americium product collector (13) and a neptunium product collector (14); The discharge port of the N263 or TEVA chromatography adsorption column (16) is connected to the waste liquid collector (15), the feed port of the TBP or UTEVA chromatography adsorption column (17), and the plutonium product collector (11) through a valve (21); the discharge port of the TBP or UTEVA chromatography adsorption column (17) is connected to the waste liquid collector (15), the feed port of the DN chromatography adsorption column (18), and the uranium product collector (12) through a valve (21); the discharge port of the DN chromatography adsorption column (18) is connected to the waste liquid collector (15), the feed port of the TRU or RE chromatography adsorption column (19), and the americium product collector (13) through a valve (21); the discharge port of the TRU or RE chromatography adsorption column (19) is connected to the waste liquid collector (15) and the neptunium product collector (14) through a valve (21).

4. The device for rapid separation of actinide elements by four-column continuous chromatography according to claim 1, It is characterized in that It also includes microcomputers; The microcomputer is used to control a valve (21) and a delivery pump (20); the valve (21) is an electromagnetic valve, and the delivery pump (20) is a peristaltic pump.

5. A method for rapid separation of actinide elements by four-column continuous chromatography, using the device for rapid separation of actinide elements by four-column continuous chromatography according to any one of claims 1 to 4, It is characterized in that The following steps are involved: Step 1, preparation before separation: The radioactive sample containing actinide elements plutonium, uranium, americium and neptunium is first dissolved in acid, then sodium nitrite is added, heated to 70°C to 100°C, and cooled to room temperature to obtain an aqueous radioactive sample containing plutonium, uranium, americium and neptunium; Dissolving the acid in water respectively to obtain an aqueous washing liquid, an aqueous eluent and an aqueous desorption liquid; N263 or TEVA, TBP or UTEVA, DN, TRU or RE are loaded respectively to obtain the corresponding chromatographic adsorption columns; Step 2: Adsorption of plutonium, uranium, americium and neptunium: The aqueous radioactive sample containing plutonium, uranium, americium and neptunium prepared in step 1 is sequentially passed through an N263 or TEVA chromatographic adsorption column (16), a TBP or UTEVA chromatographic adsorption column (17), a DN chromatographic adsorption column (18) and a TRU or RE chromatographic adsorption column (19) for separation and adsorption, and the effluent is collected as waste liquid; Wherein, plutonium is adsorbed on a N263 or TEVA chromatographic adsorption column (16), uranium is adsorbed on a TBP or UTEVA chromatographic adsorption column (17), americium is adsorbed on a DN chromatographic adsorption column (18), and neptunium is adsorbed on a TRU or RE chromatographic adsorption column (19); Step 3, washing: The washing liquid passes through an N263 or TEVA chromatography adsorption column (16), a TBP or UTEVA chromatography adsorption column (17), a DN chromatography adsorption column (18) and a TRU or RE chromatography adsorption column (19) in sequence, and each chromatography adsorption column is washed, and the effluent is collected as waste liquid; Step 4: Rinse: The first-stage eluent passes through an N263 or TEVA chromatography adsorption column (16), and the effluent is collected as waste liquid; The second-stage eluent passes through a TBP or UTEVA chromatography adsorption column (17), and the effluent is collected as waste liquid; The third-stage eluent passes through the DN chromatography adsorption column (18), and the effluent is collected as waste liquid; The fourth-stage eluent passes through a TRU or RE chromatography adsorption column (19), and the effluent is collected as waste liquid; Step 5, desorption: The first-stage desorption liquid passes through a N263 or TEVA chromatography adsorption column (16); the effluent is collected in a plutonium product collector (11) to obtain a radioactive plutonium solution; The second-stage desorption liquid passes through a TBP or UTEVA chromatography adsorption column (17); the effluent is collected in a uranium product collector (12) to obtain a radioactive uranium solution; The third-stage desorption liquid passes through a DN chromatography adsorption column (18); the effluent is collected in an americium product collector (13) to obtain a radioactive americium solution; The fourth-stage desorption liquid passes through a TRU or RE chromatography adsorption column (19); the effluent is collected in a neptunium product collector (14) to obtain a radioactive neptunium solution.

6. The method for separating actinides according to claim 5, It is characterized in that The step 1, preparation before separation, further comprises: Dissolve the radioactive samples of soil and rock matrix contaminated with actinide elements plutonium, uranium, americium and neptunium in acid to form an aqueous radioactive solution; The acid is nitric acid and hydrochloric acid, or hydrofluoric acid, or oxalic acid, or a combination of nitric acid and hydrochloric acid, hydrofluoric acid, and oxalic acid, and the concentration of the acid is 0.01 mol / L to 9.0 mol / L; N263 or TEVA, TBP or UTEVA, DN, TRU or RE are loaded respectively to obtain N263 or TEVA chromatography adsorption column (16), TBP or UTEVA chromatography adsorption column (17), DN chromatography adsorption column (18), TRU or RE chromatography adsorption column (19).

7. The method for separating actinides according to claim 5, Features: Step 1, preparation before separation: Dissolve the radioactive sample containing plutonium, uranium, americium, neptunium and matrix elements in 10 mL 3 mol / L HNO 3 , adding sodium nitrite, heating at 70-100 degrees, cooling, obtaining a solution containing plutonium, uranium, americium and neptunium, and placing the solution in a storage tank (1) for a radioactive solution containing actinide elements plutonium, uranium, americium and neptunium; Step 2: Adsorption of plutonium, uranium, americium and neptunium: The flow rate of the plutonium, uranium, americium and neptunium solution is 1 mL / min, and the plutonium, uranium, americium and neptunium solution is separated by passing through an N263 chromatographic adsorption column, a TBP chromatographic adsorption column, a DN chromatographic adsorption column (18) and a TRU chromatographic adsorption column in sequence, wherein the N263 chromatographic adsorption column is TBP chromatography column is DN chromatography adsorption column (18) is TRU chromatography column is The effluent is collected in a waste liquid collector (15); Step 3, washing: 30 mL of 3 mol / L HNO3 solution in the washing liquid reservoir (2) is used at a flow rate of 1.5 mL / min to sequentially pass through the N263 chromatography adsorption column, the TBP chromatography adsorption column, the DN chromatography adsorption column (18) and the TRU chromatography adsorption column for washing, and the effluent is collected in the waste liquid collector (15); Step 4: Rinse: Use 10 mL of 3 mol / L HCl solution in the first eluent reservoir (3), 10 mL of 4 mol / L HCl solution in the second eluent reservoir (5), and 10 mL of 0.1 mol / L HNO in the third eluent reservoir (7). 3 -0.01mol / LNaNO 2 Solution, 10 mL 1.5 mol / L HNO in the fourth eluent reservoir (9) 3 The solution is eluted at a flow rate of 1.5 mL / min through a N263 chromatography column, a TBP chromatography column, a DN chromatography column (18) and a TRU chromatography column to further purify plutonium, uranium, americium and neptunium, and the effluent is collected in a waste liquid collector (15); Step 5, desorption: Use 10 mL of 0.5 mol / L HCl solution in the first-stage desorption liquid reservoir (4) and 10 mL of 0.1 mol / L HNO in the second-stage desorption liquid reservoir (6). 3 The solution, 10 mL of 0.1 mol / L HCl solution in the third-stage desorption liquid storage tank (8), and 10 mL of 0.1 mol / L HCl-0.3 mol / L HF solution in the fourth-stage desorption liquid storage tank (10) are all at a flow rate of 1.5 mL / min, and are simultaneously and respectively passed through an N263 chromatographic adsorption column, a TBP chromatographic adsorption column, a DN chromatographic adsorption column (18), and a TRU chromatographic adsorption column; the effluent is collected in a plutonium product collector (11), a uranium product collector (12), an americium product collector (13), and a neptunium product collector (14), thereby obtaining a radioactive measurement source of plutonium, a radioactive measurement source of uranium, a radioactive measurement source of americium, and a radioactive measurement source of neptunium.

8. The method for separating actinides according to claim 7, It is characterized in that Replace the N263 chromatography column with a TEVA chromatography column, and replace the TBP chromatography column with a UTEVA chromatography column; 10 mL 0.1 mol / L HNO in the second stage desorption liquid reservoir (6) 3 The solution was replaced with 10 mL 0.01 mol / L HNO 3 -0.01mol / LH 2 C 2 O 4 of solution.

9. The method for separating actinides according to claim 5, It is characterized in that The acid used to dissolve the radioactive sample is 3 mol / L to 5 mol / L HNO 3 ; The aqueous washing liquid is 3 mol / L to 5 mol / L HNO 3 The first eluent is 3mol / L to 9mol / L HCl solution; the second eluent is 4mol / L to 6mol / L HCl solution; the third eluent is 0.01mol / L to 0.1mol / L NaNO 2 0.1mol / L~0.2mol / L HNO 3 Solution; the fourth eluent is 1mol / L~2mol / L HNO 3 Solution; the first stage desorption liquid is 0.1mol / L~1.0mol / L HCl solution; the second stage desorption liquid is 0.01mol / L~0.15mol / L HNO 3 Solution or 0.01 mol / L HNO 3 -0.01mol / LH 2 C 2 O 4 solution; the third stage desorption liquid is 0.05mol / L~1.5mol / L HCl solution; the fourth stage desorption liquid is 0.1mol / L HCl solution containing 0.1mol / L~0.4mol / L HF.

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