CN115406995B - Device, method and application for nuclear fuel burnup analysis and fission product preparation - Google Patents
Device, method and application for nuclear fuel burnup analysis and fission product preparation Download PDFInfo
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Abstract
The application discloses a device, a method and application for nuclear fuel burnup analysis and fission product preparation, wherein the device comprises an ion chromatographic separation module, a combined interface module, a component collection module and a mass spectrum detection module. The nuclear fuel solution enters a chromatographic separation module through an automatic sampler of a chromatograph, and the effluent after the column flows into an ICP-MS detection module for burnup measurement through a one-to-two proportional valve, and flows into a component collection module for preparing a high-purity lanthanide fission product. The application realizes the integration of burnup analysis and fission product preparation, can carry out real-time on-line monitoring on the separation effect of uranium and fission products, obtains the nuclear fuel burnup value by measurement, and simultaneously automatically collects the separated high-purity components, thereby simplifying the flow.
Description
Technical Field
The application relates to the technical field of analytical chemistry, in particular to a device, a method and application for nuclear fuel burnup analysis and fission product preparation.
Background
Burnup is an indicative parameter for determining nuclear fuel irradiation level and energy release, and its determination is one of the important tasks of nuclear fuel characterization analysis. Burnup measurements require analysis of fissionable heavy elements such as uranium and plutonium and fission products representing the actual burnup consumption, also called burnup monitors. Researchers have summarized seven criteria for selecting burnup monitors, the most important of which is non-migration, and have demonstrated that lanthanoids are the major fission products that do not migrate relative to uranium and plutonium. Isotope dilution-thermal ionization mass spectrometry is a classical method of analyzing uranium and lanthanoids in nuclear fuel burnup measurements. However, the mutual interference of large amounts of isobaric elements limits the direct measurement of uranium and lanthanoid elements by mass spectrometry, thus requiring a sufficient separation of the elements before entering the mass spectrum.
The recycling of spent fuel has important economic and national defense values, and is the key point of research in various countries. After uranium, plutonium and lanthanide fission products are separated by adopting a high performance liquid chromatography technology, a part of the uranium, the plutonium and the lanthanide fission products flow into a component collection device for separation and purification of the uranium, the plutonium and the single fission products. Uranium and plutonium are important fuel resources in nuclear energy systems, and recycled uranium and plutonium can realize recycling of fuel. Secondly, many high purity nuclear fission products have extremely high application value, such as the lanthanide fission product Sm-152, which is the highest yielding lanthanide in the fission products, and its unique neutron absorption cross section and electrochemical properties are of great interest in the fields of reactor physics and dry aftertreatment. The lanthanide fission product Gd-153 can be used as a photon source of a two-photon absorption tester, and is particularly efficient for diagnosing and monitoring osteoporosis. Gd-153 also has magnetic properties for use as an intravenous radio contrast agent in nuclear magnetic resonance.
Different methods for separating uranium and lanthanides have been reported to date, including solvent extraction, precipitation and high performance liquid chromatography. Among these methods, high performance liquid chromatography enables rapid, efficient separation and extends the separation range from laboratory analysis to preparative purification. The high-efficiency chromatographic separation method can be used for carrying out rapid separation analysis on elements, and can avoid mutual interference among isobaric elements to a great extent.
When the existing high performance liquid chromatography is used for burnup measurement and analysis, most chromatographic columns are formed by connecting two chromatographic columns in series (such as two C18 reverse phase columns, C18 reverse phase column and cation exchange column), and the first C18 reverse phase column firstly separates uranium and plutonium in nuclear fuel dissolved solution, and then a second separation column separates lanthanide fission products. The method can complete the burnup analysis by the linkage of two chromatographic columns and three six-way valves, has complex control program, higher manufacturing cost of the analysis device and also increases the maintenance and operation cost of the instrument.
In addition, the existing nuclear fuel burnup analysis method generally adopts a process of separating first and then measuring: firstly, nuclear fuel core is dissolved, fission products to be detected are separated from a complex matrix by adopting chromatographic separation means, and then qualitative identification and quantitative measurement are carried out on samples obtained by separation through spectra, energy spectra and the like. If fission product separation fails, it can only be found afterwards. The nuclear fuel sample is precious, the radioactive experiment cost is very high, the separation effect cannot be monitored immediately, and huge waste of the sample and resources can be caused to influence the acquisition of key data. In addition, the existing method has the disadvantages of long separation and measurement process flow, multiple links, low efficiency, high personnel dosage and high sample pollution risk, and influences the accuracy of measurement results.
Disclosure of Invention
The application aims to provide a device, a method and application for nuclear fuel burnup analysis and fission product preparation, which realize integration of burnup analysis and fission product preparation, can monitor the separation effect of uranium and fission products on line in real time, measure and obtain nuclear fuel burnup values, and automatically collect high-purity components obtained by separation, thereby simplifying the flow.
The application is realized by the following technical scheme:
the device for nuclear fuel burnup analysis and fission product preparation comprises an ion chromatographic separation module, a combined interface module, a component collection module and a mass spectrum detection module;
the ion chromatographic separation module comprises a chromatographic column for separating each component in a sample, wherein the chromatographic column adopts cation exchange packing containing sulfonic groups and hydrophobic groups;
the component collection module comprises a component collector for realizing component collection;
the combined interface module comprises a proportional valve and a sample switching valve, the proportional valve is connected with the chromatographic column, the proportional valve is used for dividing effluent liquid after the column into two parts, the proportional valve comprises two outlets, one outlet is connected with the component collector, and the other outlet is connected with the sample switching valve;
the mass spectrum detection module comprises an inductively coupled plasma mass spectrometer, a peristaltic pump and an atomizer in the inductively coupled plasma mass spectrometer are respectively connected with two ports of a sample switching valve, and the inductively coupled plasma mass spectrometer is used for carrying out on-line monitoring on components of effluent after a column.
The chromatographic column of the application adopts cation exchange filler containing sulfonic acid groups and hydrophobic groups, so that the chromatographic column has cation exchange characteristics and hydrophobicity. Cation exchange characteristics are used for lanthanide fission product separation and hydrophobicity is used for uranium separation. Because the chromatographic column has the characteristics, the separation of components in a sample can be realized by using a single chromatographic column, and the serial connection of two chromatographic columns (such as two C18 reverse phase columns or C18 reverse phase columns and a cation exchange column) is not needed.
The mass spectrum detection module is composed of an inductively coupled plasma mass spectrometer (ICP-MS) with a sample injection system modified, a peristaltic pump of a conventional ICP-MS is directly connected with an atomizer, and the peristaltic pump is connected with a sample switching valve in the device, so that automatic switching between peristaltic pump sample injection and chromatographic sample injection can be realized through the sample switching valve.
The application can realize the on-line monitoring of effluent after the column by designing the component collection module and the mass spectrum detection module, and realizes the integration of fuel consumption analysis and fission product preparation by arranging the component collection module.
In conclusion, the device provided by the application realizes integration of burnup analysis and fission product preparation, can perform real-time on-line monitoring on the separation effect of uranium and fission products, measures to obtain the nuclear fuel burnup value, and simultaneously automatically collects the separated high-purity components, thereby simplifying the flow.
Further, the ion chromatographic separation module also comprises a protective column, a sample injection six-way valve and a quaternary gradient infusion pump;
the protective column is arranged at the front end of the chromatographic column;
the sample injection six-way valve comprises 6 ports, wherein one port is a chromatographic sample injection port for injecting samples, one port is connected with the protective column, and the sample injection six-way valve further comprises a quantitative ring communicated with the ports;
the quaternary gradient infusion pump is connected with one of the other four ports of the sample injection six-way valve, and is used for introducing a mobile phase into the chromatographic column.
Further, the 6 ports of the sample introduction six-way valve are respectively marked as 1# -6#, the sample introduction six-way valve comprises two states, and the state A: the adjacent ports 1# to 2#, 3# to 4#, 5# to 6# are communicated, and the adjacent ports 2# to 3#, 4# to 5#, 6# to 1# are disconnected; and B state: the adjacent ports 1# to 2#, 3# to 4#, 5# to 6# are disconnected, and the adjacent ports 2# to 3#, 4# to 5#, 6# to 1# are connected.
Further, the chromatographic column adopts 3 mobile phases for gradient elution, wherein the 3 mobile phases are mobile phase 1, mobile phase 2 and mobile phase 3 respectively, and the mobile phase 1 component is deionized water; the component of the mobile phase 2 is alpha-hydroxyisobutyric acid or 2-hydroxy-2-methylbutanoic acid, the pH range is 3.0-3.6, and the concentration range is 100-300 mM; the 3 component of the mobile phase is alpha-hydroxyisobutyric acid or 2-hydroxy-2-methylbutanoic acid, the pH range is 4.0-5.0, and the concentration range of the mobile phase is 30-400 mM.
Further, the gradient elution procedure of the chromatographic column is:
the following mobile phase elution columns were first maintained: 35-50% of mobile phase 1, 50-65% of mobile phase 2 and 0 of mobile phase 3; then adopting linear gradient change to increase and decrease the volume ratio of the mobile phase 1; gradually reducing the volume ratio of the mobile phase 2 to 0%; the volume ratio of the mobile phase 3 is gradually increased.
Further, the sample switching valve has 6 ports, respectively denoted as 1# -6#, and the sample switching valve includes two states, a state: the adjacent ports 1# to 2#, 3# to 4#, 5# to 6# are communicated, and the adjacent ports 2# to 3#, 4# to 5#, 6# to 1# are disconnected; and B state: the adjacent ports 1# to 2#, 3# to 4#, 5# to 6# are disconnected, and the adjacent ports 2# to 3#, 4# to 5#, 6# to 1# are connected.
Further, the device also comprises a waste liquid bottle for collecting waste liquid generated by the inductively coupled plasma mass spectrometer, the proportional valve and the sample switching valve, and sample waste liquid and mobile phase waste liquid generated at the front end of the chromatographic column.
The operation method based on the device comprises the following steps:
s1, preparation: all parts in the connecting device are adjusted to be in states of the sample injection six-way valve and the sample switching valve, so that the ion chromatographic separation module is in a chromatographic column pre-flushing mode, and the proportional valve is adjusted to enable 100% of post-column effluent in the proportional valve to enter the sample switching valve, so that the mobile phase is conveyed to the sample injection six-way valve and then sequentially passes through the chromatographic column, the proportional valve and the sample switching valve; the inductively coupled plasma mass spectrometer is in an instrument parameter adjusting mode, the peristaltic pump sends tuning liquid to the sample switching valve, and the tuning liquid flows to the atomizer through the sample switching valve to adjust instrument parameters;
s2, sample injection: switching the state of the sample injection six-way valve, wherein the setting states of the proportional valve and the sample switching valve are consistent with those of the step S1, and injecting the sample into the sample injection six-way valve, wherein the sample enters the quantitative ring through a chromatographic sample inlet;
s3, sample analysis and fission product preparation: switching states of a sample injection six-way valve and a sample switching valve to enable the ion chromatographic separation module to be in a working mode, and enabling a quaternary gradient infusion pump to convey a mobile phase to a quantitative ring, wherein a sample in the quantitative ring carried by the mobile phase enters a chromatographic column to perform component separation; the effluent liquid after the column carried by the mobile phase enters a proportional valve, and a flow path is divided into two parts after passing through the proportional valve: a part of post-column effluent enters a component collector through a proportional valve; and a part of effluent liquid after the column enters a sample switching valve through a proportional valve and then enters an atomizer through the sample switching valve to carry out mass spectrum real-time online analysis.
The application of the device is used for burnup analysis and fission product preparation of nuclear fuel solution samples.
When the device is applied to burnup analysis of nuclear fuel solution samples, the sample injection amount is 10-100 mu L; the flow rate of the mobile phase is 0.2-1 mL/min; when the sample is used for preparing fission products of nuclear fuel solution samples, the sample injection quantity is 101-500 mu L; the flow rate of the mobile phase is 1.1-10 mL/min.
Compared with the prior art, the application has the following advantages and beneficial effects:
1. the device of the application adds the sample switching valve between the mass spectrum detection module and the ion chromatographic separation module, can automatically switch the solution flow path, and realizes the automatic switching of two functions of the parameter adjustment of the mass spectrometer and the on-line analysis of the nuclear fuel solution sample.
2. The application can separate and measure uranium, plutonium and lanthanoid in the irradiated nuclear fuel solution on line to obtain a chromatographic outflow curve, concentration, isotope ratio and burnup value.
3. The nuclear fuel solution sample provided by the application can be directly sampled for analysis and preparation without adjusting the pH value and removing uranium and zirconium matrixes; typical actinides and lanthanides can be separated simultaneously using a single chromatographic column with one to two organic carboxylic acid solutions of different pH as mobile phases.
4. The application has high automation and small sample quantity, and greatly reduces the irradiated dose of operators.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application. In the drawings:
FIG. 1 is a schematic diagram of the structure of the device of the present application;
FIG. 2 is a graph of the simulated nuclear fuel solution sample chromatographic outflow of example 1;
FIG. 3 is a graph of the chromatographic effluent of sample 1 of nuclear fuel solution of example 2, wherein a is a schematic that does not show uranium or zirconium; b is a schematic diagram showing uranium and zirconium;
FIG. 4 is a graph of the chromatographic effluent of sample 2 of nuclear fuel solution of example 3, wherein a is a schematic that does not show uranium or zirconium; b is a schematic diagram showing uranium and zirconium.
In the drawings, the reference numerals and corresponding part names: the device comprises a 1-quaternary gradient infusion pump, a 2-sample injection six-way valve, a 3-protection column, a 4-chromatographic column, a 5-proportional valve, a 6-sample switching valve, a 7-peristaltic pump, an 8-component collector, a 9-waste liquid bottle, a 10-atomizer, an 11-fog chamber, a 12-plasma rectangular tube, a 13-RF coil, a 14-sample cone, a 15-ion optical system, a 16-quadrupole mass analyzer, a 17-electron multiplier, an 18-data acquisition and processing system, a 19-analysis chamber pump and a 20-molecular pump.
Detailed Description
The present application will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions and advantages of the present application more apparent, and the description thereof is merely illustrative of the present application and not intended to be limiting.
Examples:
as shown in fig. 1: the device for nuclear fuel burnup analysis and fission product preparation comprises an ion chromatographic separation module, a combined interface module, a component collection module and a mass spectrum detection module;
the ion chromatographic separation module comprises a chromatographic column 4 for separating each component in a sample, wherein the chromatographic column 4 adopts cation exchange packing containing sulfonic acid groups and hydrophobic groups; the system also comprises a protective column 3, a sample injection six-way valve 2 and a quaternary gradient infusion pump 1;
the protection column 3 is arranged at the front end of the chromatographic column 4;
the sample injection six-way valve 2 comprises 6 ports, wherein one port is a chromatographic sample injection port for injecting a sample, one port is connected with the protection column 3, and the sample injection six-way valve 2 further comprises a quantitative ring communicated with the ports;
specifically: the 6 ports of the sample introduction six-way valve 2 are respectively marked as 1# -6#, and the sample introduction six-way valve 2 comprises two states, namely a state: the adjacent ports 1# to 2#, 3# to 4#, 5# to 6# are communicated, and the adjacent ports 2# to 3#, 4# to 5#, 6# to 1# are disconnected; and B state: the adjacent ports 1# to 2#, 3# to 4#, 5# to 6# are disconnected, and the adjacent ports 2# to 3#, 4# to 5#, 6# to 1# are connected.
The No. 1 port of the sample injection six-way valve 2 is a chromatographic sample injection port, and a manual sample injection syringe or an automatic sample injection syringe can be used for injecting a nuclear fuel solution sample through the No. 1 port of the six-way valve; the 3# port is connected to the protection column 3, and the 5# port is connected to the waste liquid bottle 9.
The quaternary gradient infusion pump 1 is connected with a 3# port of the sample injection six-way valve 2, and the quaternary gradient infusion pump 1 is used for introducing a mobile phase into the chromatographic column 4. When the purpose of nuclear fuel burnup analysis is to be achieved, setting the flow speed range of the quaternary gradient infusion pump 1 to be 0.2-1 mL/min; when the preparation of the fission products in the nuclear fuel is aimed, the flow rate range of the quaternary gradient infusion pump 1 is set to be 1.1-10 mL/min.
The component collection module comprises a component collector 8 for effecting component collection; the component collector 8 has two modes of full automatic collection and full collection:
the full-automatic collection is to automatically collect the required components according to the component spectrum peaks of the mass spectrum real-time online analysis; total collection is the collection of the whole process solution in equal volumes, followed by screening of the desired components in combination with a chromatogram.
The combined interface module comprises a proportional valve 5 and a sample switching valve 6.
The sample switching valve 6 has 6 ports, respectively denoted as 1# -6#, and the sample switching valve 6 comprises two states, a state: the adjacent ports 1# to 2#, 3# to 4#, 5# to 6# are communicated, and the adjacent ports 2# to 3#, 4# to 5#, 6# to 1# are disconnected; and B state: the adjacent ports 1# to 2#, 3# to 4#, 5# to 6# are disconnected, and the adjacent ports 2# to 3#, 4# to 5#, 6# to 1# are connected.
The proportional valve 5 is a one-to-two proportional valve and is provided with 3 ports, namely 1# -3#, wherein the 1# port is an inlet end, and the 2# port and the 3# port are outlet ends; the 1# port of the proportional valve 5 is connected to the column 4, the 2# port of the proportional valve 5 is connected to the component collector 8, and the 3# port of the proportional valve 5 is connected to the #3 port of the sample switching valve 6. The volume ratio of the outlet solution of the 2# outlet end to the outlet end of the 3# outlet end of the proportional valve 5 can be adjusted according to the specification and the process purpose of the chromatographic column 4.
The sample switching valve 6 has a 1# port connected to the peristaltic pump 7, a 2# port connected to the atomizer 10, a 3# port connected to the 3# port of the proportional valve 5, a 4# port connected to the waste liquid bottle 9, and a 5# port connected to the 6# port. The sample switching valve 6 also has two states, and the on-off condition of the adjacent ports in the two states of A, B is completely consistent with that of the sample injection six-way valve of the ion chromatographic separation module.
The waste liquid bottle 9 is used for collecting waste liquid generated by the inductively coupled plasma mass spectrometer, the proportional valve 5 sample switching valve 6, the quaternary gradient infusion pump 1 and the sample injection six-way valve 2.
The mass spectrum detection module comprises an inductively coupled plasma mass spectrometer, a peristaltic pump 7 and an atomizer 10 in the inductively coupled plasma mass spectrometer are respectively connected with two ports of the sample switching valve 6, and the inductively coupled plasma mass spectrometer is used for carrying out on-line monitoring on components of post-column effluent.
The mass spectrum detection module of the embodiment is composed of an inductively coupled plasma mass spectrometer (ICP-MS) with a sample injection system modified, a peristaltic pump 7 of a conventional ICP-MS is directly connected with an atomizer 10, and the peristaltic pump 7 is connected with a 1# port of a sample switching valve 6 in the device, so that automatic switching between sample injection of the peristaltic pump 7 and chromatographic sample injection can be realized through the sample switching valve 6.
Specifically, an inductively coupled plasma mass spectrometer (ICP-MS) includes a peristaltic pump 7, an atomizer 10, a mist chamber 11, a plasma tube 12, an RF coil 13, a sample cone 14, an ion optical system 15, a quadrupole mass analyzer 16, and an electron multiplier 17. Also included are an analysis chamber pump 19, a molecular pump 20, and a data acquisition processing system 18 connected to an inductively coupled plasma mass spectrometer (ICP-MS). The connection relationship among the atomizer 10, the mist chamber 11, the plasma rectangular tube 12, the RF coil 13, the sample cone 14, the ion optical system 15, the quadrupole mass analyzer 16, and the electron multiplier 17 is the prior art.
The column 4 of this example employs the following 3 mobile phases: the component 1 of the mobile phase is deionized water; the component of the mobile phase 2 is alpha-hydroxyisobutyric acid (HIBA) or 2-hydroxy-2-methylbutanoic acid (HMBA), the pH range is 3.0-3.6, and the concentration range is 100-300 mM; the 3 component of the mobile phase is alpha-hydroxyisobutyric acid (HIBA) or 2-hydroxy-2-methylbutanoic acid (HMBA), the pH range is 4.0-5.0, and the concentration range of the mobile phase is 30-400 mM.
The gradient elution procedure was:
1) And starting the procedure for 7-9 min, and maintaining the following mobile phase leaching chromatographic column 4: the volume ratio of the mobile phase 1 is 35-50%, the volume ratio of the mobile phase 2 is 50-65%, and the volume ratio of the mobile phase 3 is 0.
2) Gradually increasing the volume ratio of the mobile phase 1 to 55-70% by adopting linear gradient change from the end of the step 1) to the starting of the program for 10-11 min, gradually decreasing the volume ratio of the mobile phase 2 to 20-40%, correspondingly increasing the volume ratio of the mobile phase 3, and enabling the separated uranium and plutonium components to flow out of the chromatographic column 4;
3) Gradually increasing the volume ratio of the mobile phase 1 to 60-80% by adopting linear gradient change from the end of the step 2) to the starting of the program for 20-25 min, and gradually decreasing the volume ratio of the mobile phase 2 to 0-20% correspondingly increasing the volume ratio of the mobile phase 3, wherein part of the separated heavy rare earth element component flows out of the chromatographic column 4;
4) And from the end of the step 3) to the starting of the program for 33-40 min, gradually reducing the volume ratio of the mobile phase 1 to 35-50% by adopting linear gradient change, gradually reducing the volume ratio of the mobile phase 2 to 0%, correspondingly increasing the volume ratio of the mobile phase 3, and enabling the separated light rare earth element component to flow out of the chromatographic column 4.
The specification of the chromatographic column 4 is phi 2-10 mm, the column temperature is 15-70 ℃, and the chromatographic column is replaced according to the analysis and preparation requirements.
The operation method of the device according to the embodiment is characterized by comprising the following steps:
s1, preparation: the sample injection six-way valve 2 is in the A state, the sample switching valve 6 is in the A state, and the outlet volume ratio of the 3# port of the proportional valve 5 is set to be 100%. The ion chromatographic separation module is in a chromatographic column pre-flushing mode, the quaternary gradient infusion pump 1 conveys a mobile phase to a 2# port of the sample injection six-way valve 2, flows into a quantitative ring between the 1# port and the 4# port through the 1# port, flows to the protective column 3 and the chromatographic column 4 through the 4# port and the 3# port in sequence, and then flows to a 3# port of the sample switching valve 6 through a 3# port of the proportional valve 5, and flows to the waste liquid bottle 9 from the 4# port of the sample switching valve 6. The mass spectrum detection module is in an instrument parameter adjustment mode, the peristaltic pump 7 sends tuning liquid to the No. 1 port of the sample switching valve 6, and then the tuning liquid flows to the atomizer 10 through the No. 2 port of the sample switching valve 6 to adjust instrument parameters.
S2, sample injection: the sample injection six-way valve 2 is switched to the B state, and the setting states of the sample switching valve 6 and the proportional valve 5 are consistent with the 1 st step and are kept unchanged. And a manual injection injector or an automatic injector is adopted to inject the nuclear fuel dissolution liquid sample into a 6# port of the injection six-way valve 2, the sample flows into a quantitative ring between the 1# port and the 4# port through the 1# port, and the redundant nuclear fuel dissolution liquid sample flows into the waste liquid bottle 9 through passages of the 4# port and the 5# port in sequence. At this time, the quaternary gradient infusion pump 1 conveys the mobile phase to the 2# port of the sample injection six-way valve 2, and directly flows to the protection column 3 and the chromatographic column 4 through the 3# port, and the subsequent flow path of the mobile phase is consistent with the step S1.
When the purpose of nuclear fuel burnup analysis is to be achieved, the sample injection amount is 10-100 mu L; when the preparation of the fission products in the nuclear fuel is aimed, the sample injection amount is 101-500 mu L;
s3, sample analysis and preparation: the sample introduction six-way valve 2 is switched to the A state, and the sample switching valve 6 is switched to the B state. The ion chromatographic separation module is in a working mode, the quaternary gradient infusion pump 1 conveys a mobile phase to a No. 2 port of the sample injection six-way valve 2, the mobile phase reaches a quantitative ring between the No. 1 port and the No. 4 port through the No. 1 port, and a nuclear fuel solution sample in the quantitative ring is carried by the mobile phase and sequentially passes through the No. 4 port and the No. 3 port to reach the guard column 3 and the chromatographic column 4. Because the retention time of each component in the sample in the chromatographic column 4 is different, the different components flow out of the chromatographic column 4 in sequence, so that uranium, plutonium and lanthanide fission products are separated, and the nuclear fuel solution sample is separated in the chromatographic column 4. The component carried by the mobile phase flows out of the chromatographic column 4 and then reaches the 1# port of the proportional valve 5, and the flow path is divided into two parts after passing through the proportional valve 5: most of the volume enters a component collector 8 through a No. 2 port of the proportional valve 5, the component collector 8 collects specific components according to component information monitored by mass spectrometry in real time, and unnecessary solution flows into a waste liquid bottle 9 at the rear end of the component collector 8; and a small part of volume enters the 3# port of the sample switching valve 6 through the 3# port of the proportional valve 5, and then enters the atomizer 10 through the 2# port of the sample switching valve 6, so that mass spectrum real-time online analysis is performed. At this time, the peristaltic pump 7 sends the waste liquid generated in the mass spectrum fog chamber to the 1# port of the sample switching valve 6, and then sequentially passes through the 6# port, the 5# port and the 4# port to be discharged to the waste liquid bottle 9.
In the embodiment, the nuclear fuel solution can be prepared by adopting the first step to the third step of Chinese patent 201110238418.2, and the solution is used as a sample to be analyzed.
The following are several specific examples:
example 1
Analysis and preparation of simulated nuclear fuel solution sample
A simulated nuclear fuel solution sample containing 0.1mg/L uranium and 14 lanthanoids each at a concentration of 0.1mg/L was prepared to verify the feasibility of the analysis method.
The device described in the embodiment is built, and the pipeline is connected. And analyzing the sample sequentially according to the three steps of process preparation, sample injection process, sample analysis and preparation process. The process parameters with optional ranges are set as follows:
(1) Column temperature: 22 ℃;
(2) Flow rate: 1mL/min;
(3) Sample injection amount: 25 μL;
(4) Mobile phase 1: deionized water;
(5) Mobile phase 2:300mm, HIBA solution at ph=3.0;
(6) Mobile phase 3:400mm, HIBA solution at ph=4.2;
(7) Chromatographic column diameter: phi 4.6mm;
(8) Outlet volume ratio of proportional valve 5: the outlet volume ratio of the 2# port was 70% and the outlet volume ratio of the 3# port was 30%.
The gradient elution program is shown in Table 1, and the chromatographic effluent graphs are shown in FIG. 2 and Table 2.
Table 1 gradient elution procedure for simulating nuclear fuel solution samples
As can be seen from the accompanying figures 2 and Table 2, the separation degree of uranium and lutetium is 3.8, the separation degree between adjacent lanthanoids is 2.2-7.6, and the separation degree is more than 1.5, namely, the baseline separation is achieved, which shows that the application can realize the effective separation of uranium and lanthanoids.
TABLE 2 degree of separation of uranium from lanthanoid elements
Example 2
Nuclear fuel solution sample 1:
the main matrix in the nuclear fuel solution sample 1 is uranium and zirconium, and the content of the uranium and zirconium is about 10 3 In the order of mg/L, the nuclear fuel burnup analysis is carried out after the dilution is 250 times.
The device described in the embodiment is built, and the pipeline is connected. And analyzing the sample sequentially according to the three steps of process preparation, sample injection process, sample analysis and preparation process. The process parameters with optional ranges are set as follows:
(1) Column temperature: 30 ℃;
(2) Flow rate: 0.8mL/min;
(3) Sample injection amount: 100. Mu.L;
(4) Mobile phase 1: deionized water;
(5) Mobile phase 2:200mm HIBA solution at ph=3.5;
(6) Mobile phase 3:400mm, HIBA solution at ph=4.2;
(7) Chromatographic column diameter: phi 4.6mm;
(8) Outlet volume ratio of proportional valve 5: the outlet volume ratio of the 2# port is 50%, and the outlet volume ratio of the 3# port is 50%.
The gradient elution procedure is shown in Table 3, the chromatographic effluent graph is shown in FIG. 3, and the baseline separation of the components is shown in FIG. 3. And (3) giving out the content and isotope ratio of uranium and neodymium through online analysis of a mass spectrum detection module, and obtaining the nuclear fuel burnup value according to a burnup calculation formula.
TABLE 3 gradient elution procedure for Nuclear Fuel solution sample 1
Example 3
Nuclear fuel solution sample 2:
the main matrix in the nuclear fuel solution sample 2 is uranium, and the uranium content is about 10 3 On the order of mg/L, the fission product preparation is carried out after dilution by 10 times.
The device described in the embodiment is built, and the pipeline is connected. And analyzing the sample sequentially according to the three steps of process preparation, sample injection process, sample analysis and preparation process. The process parameters with optional ranges are set as follows:
(1) Column temperature: 40 ℃;
(2) Flow rate: 3mL/min;
(3) Sample injection amount: 500. Mu.L;
(4) Mobile phase 1: deionized water;
(5) Mobile phase 2:100mm, ph=3.5 HMBA solution;
(6) Mobile phase 3:50mm, ph=5.0 HMBA solution;
(7) Chromatographic column diameter: phi 10mm;
(8) Outlet volume ratio of proportional valve 5: the outlet volume ratio of the 2# port is 90%, and the outlet volume ratio of the 3# port is 10%.
The gradient elution procedure is shown in Table 4, and the chromatographic effluent graph is shown in FIG. 4, and it is seen from FIG. 4 that baseline separation of the components is achieved. The components of uranium and 7 lanthanide fission products are obtained through a component collector, and the purity is more than 99.9%.
Table 4 gradient elution procedure for nuclear fuel solution sample 2
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the application, and is not meant to limit the scope of the application, but to limit the application to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the application are intended to be included within the scope of the application.
Claims (8)
1. The device for nuclear fuel burnup analysis and fission product preparation is characterized by comprising an ion chromatographic separation module, a combined interface module, a component collection module and a mass spectrum detection module;
the ion chromatographic separation module comprises a chromatographic column (4) for separating components in a sample, wherein the chromatographic column (4) adopts cation exchange packing containing sulfonic acid groups and hydrophobic groups;
the component collection module comprises a component collector (8) for effecting component collection;
the combined interface module comprises a proportional valve (5) and a sample switching valve (6), the proportional valve (5) is connected with the chromatographic column (4), the proportional valve (5) is used for dividing post-column effluent into two parts, the proportional valve (5) comprises two outlets, one outlet is connected with the component collector (8), and the other outlet is connected with the sample switching valve (6);
the mass spectrum detection module comprises an inductively coupled plasma mass spectrometer, a peristaltic pump (7) and an atomizer (10) in the inductively coupled plasma mass spectrometer are respectively connected with two ports of a sample switching valve (6), and the inductively coupled plasma mass spectrometer is used for carrying out on-line monitoring on components of post-column effluent;
the chromatographic column (4) adopts 3 mobile phases for gradient elution, wherein the 3 mobile phases are respectively mobile phase 1, mobile phase 2 and mobile phase 3, and the mobile phase 1 is composed of deionized water; the component of the mobile phase 2 is alpha-hydroxyisobutyric acid or 2-hydroxy-2-methylbutyric acid, the pH range is 3.0-3.6, and the concentration range is 100-300 mM; the component 3 of the mobile phase is alpha-hydroxyisobutyric acid or 2-hydroxy-2-methylbutyric acid, the pH range is 4.0-5.0, and the concentration range of the mobile phase is 30-400 mM;
the gradient elution procedure of the chromatographic column (4) is:
the following mobile phase elution columns were first maintained: 35-50% of mobile phase 1, 50-65% of mobile phase 2 and 0 of mobile phase 3; then adopting linear gradient change to increase and decrease the volume ratio of the mobile phase 1; gradually reducing the volume ratio of the mobile phase 2 to 0%; the volume ratio of the mobile phase 3 is gradually increased.
2. The device for nuclear fuel burnup analysis and fission product preparation according to claim 1, characterized in that said ion chromatographic separation module further comprises a guard column (3), a sample injection six-way valve (2) and a quaternary gradient infusion pump (1);
the protection column (3) is arranged at the front end of the chromatographic column (4);
the sample injection six-way valve (2) comprises 6 ports, wherein one port is a chromatographic sample injection port for injecting samples, one port is connected with the protection column (3), and the sample injection six-way valve (2) further comprises a quantitative ring communicated with the ports;
the quaternary gradient infusion pump (1) is connected with one of the other four ports of the sample injection six-way valve (2), and the quaternary gradient infusion pump (1) is used for introducing a mobile phase into the chromatographic column (4).
3. The device for nuclear fuel burnup analysis and fission product preparation according to claim 2, wherein the 6 ports of the sample introduction six-way valve (2) are respectively marked as 1# -6#, and the sample introduction six-way valve (2) comprises two states, namely a state: the adjacent ports 1# to 2#, 3# to 4#, 5# to 6# are communicated, and the adjacent ports 2# to 3#, 4# to 5#, 6# to 1# are disconnected; and B state: the adjacent ports 1# to 2#, 3# to 4#, 5# to 6# are disconnected, and the adjacent ports 2# to 3#, 4# to 5#, 6# to 1# are connected.
4. The device for nuclear fuel burnup analysis and fission product preparation according to claim 1, characterized in that said sample switching valve (6) has 6 ports, respectively denoted 1# -6#, the sample switching valve (6) comprises two states, a state: the adjacent ports 1# to 2#, 3# to 4#, 5# to 6# are communicated, and the adjacent ports 2# to 3#, 4# to 5#, 6# to 1# are disconnected; and B state: the adjacent ports 1# to 2#, 3# to 4#, 5# to 6# are disconnected, and the adjacent ports 2# to 3#, 4# to 5#, 6# to 1# are connected.
5. The device for nuclear fuel burnup analysis and fission product preparation according to any of claims 1 to 4, characterized by further comprising a waste liquid bottle (9), said waste liquid bottle (9) being used for collecting waste liquid generated by inductively coupled plasma mass spectrometer, proportional valve (5) and sample switching valve (6), and sample waste liquid and mobile phase waste liquid generated at the front end of chromatographic column (4).
6. A method of operation based on the device of claim 2, comprising the steps of:
s1, preparation: the method comprises the steps of connecting all parts in a device, adjusting states of a sample injection six-way valve (2) and a sample switching valve (6), enabling an ion chromatographic separation module to be in a chromatographic column pre-flushing mode, adjusting a proportional valve (5), enabling post-column effluent in the proportional valve (5) to enter the sample switching valve (6) by 100%, enabling a mobile phase to sequentially pass through the chromatographic column (4), the proportional valve (5) and the sample switching valve (6) after being conveyed to the sample injection six-way valve (2); the inductively coupled plasma mass spectrometer is in an instrument parameter adjusting mode, a peristaltic pump (7) sends tuning liquid to a sample switching valve (6), and then the tuning liquid flows to an atomizer (10) through the sample switching valve (6) to adjust instrument parameters;
s2, sample injection: switching the state of the sample injection six-way valve (2), wherein the setting states of the proportional valve (5) and the sample switching valve (6) are consistent with those of the step S1, injecting the sample into the sample injection six-way valve (2), and enabling the sample to enter the quantitative ring through a chromatographic sample inlet;
s3, sample analysis and fission product preparation: switching states of a sample injection six-way valve (2) and a sample switching valve (6) to enable the ion chromatographic separation module to be in a working mode, conveying a mobile phase to a quantitative ring by a quaternary gradient infusion pump (1), and enabling a sample in the quantitative ring carried by the mobile phase to enter a chromatographic column (4) for component separation; the effluent liquid after the column carried by the mobile phase enters a proportional valve (5), and the flow path is divided into two parts after passing through the proportional valve (5): a part of post-column effluent enters a component collector (8) through a proportional valve (5); and a part of effluent liquid after the column enters a sample switching valve (6) through a proportional valve (5), and then enters an atomizer (10) through the sample switching valve (6) to carry out mass spectrum real-time online analysis.
7. Use of the device according to any one of claims 1-5 for burnup analysis and fission product preparation of nuclear fuel solution samples.
8. The application of claim 7, wherein the sample injection amount is 10-100 μl when used for burnup analysis of nuclear fuel solution samples; the flow rate of the mobile phase is 0.2-1 mL/min; when the sample is used for preparing fission products of nuclear fuel solution samples, the sample injection amount is 101-500 mu L; the flow rate of the mobile phase is 1.1-10 mL/min.
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