Method and application of calibrating hydrogen isotope gas sensitivity

Abstract

The present invention provides a method and application for calibrating hydrogen isotope gas sensitivity. The provided method comprises: (1) detecting a gas to be tested based on mass spectrometry-chromatography to determine the sample components and content contained in the gas to be tested, which is counted as a first detection result; (2) using the hydrogen isotope gas percentage in the gas to be tested obtained from the first detection result to determine the positive calibration sensitivity; (3) based on the positive calibration sensitivity, using a high-resolution mass spectrometer to measure the sample components and content contained in the gas to be tested, which is counted as a second detection result; (4) using the hydrogen isotope gas percentage in the gas to be tested obtained from the second detection result to determine the recalibration sensitivity. The provided method can calibrate hydrogen isotope sensitivity without using national standard substances, thereby ensuring the accuracy of hydrogen isotope abundance determination.

Description

Technical Field

[0001] The present invention relates to the field of hydrogen isotope gas detection, and in particular to a method for calibrating the sensitivity of hydrogen isotope gas and its application. Background Art

[0002] Hydrogen isotope mass spectrometry utilizes a mass spectrometer to achieve charge / mass ratio separation and isotope abundance determination of components in a mixture of hydrogen, deuterium, and tritium. When using a high-resolution gas phase mass spectrometer to measure hydrogen isotope gas content, it is necessary to calibrate the mass spectrometer's sensitivity to each gas. This metric plays a crucial role in determining the accuracy of the test results. Currently, the sensitivity of the components being tested is calibrated using national standard materials with a purity of ≥99.999%. However, due to the high cost and rarity of some hydrogen isotope gases, and the lack of national standard materials with a purity of ≥99.999%, determining the sensitivity of some hydrogen isotope gases is difficult.

[0003] The determination methods of hydrogen isotope gas sensitivity need further improvement. Summary of the Invention

[0004] The present invention aims to address, at least to some extent, at least one of the technical problems existing in the prior art. It establishes a method for calibrating the sensitivity of hydrogen isotope gases in a mass spectrometer. This method significantly reduces the cost of mass spectrometer sensitivity calibration and addresses the difficulty of calibrating sensitivity due to the lack of standard materials for hydrogen isotope gases. While calibrating hydrogen isotope sensitivity without using national standard materials, it also ensures the accuracy of hydrogen isotope abundance measurements.

[0005] Specifically, the present invention provides the following technical solutions:

[0006] The first aspect of the present invention provides a method for calibrating the sensitivity of hydrogen isotope gas, comprising: (1) detecting a gas to be tested based on mass spectrometry-chromatography to determine the sample components and content contained in the gas to be tested, which is counted as a first detection result; (2) using the percentage of hydrogen isotope gas in the gas to be tested obtained from the first detection result to determine the positive calibration sensitivity; (3) based on the positive calibration sensitivity, using a mass spectrometer to measure the sample components and content contained in the gas to be tested, which is counted as a second detection result; (4) using the percentage of hydrogen isotope gas in the gas to be tested obtained from the second detection result to determine the recalibration sensitivity.

[0007] The present invention establishes a method for calibrating the gas sensitivity of hydrogen isotopes measured by a high-resolution gas mass spectrometer, which can calibrate the hydrogen isotope sensitivity without using national standard substances while ensuring the accuracy of hydrogen isotope abundance measurement.

[0008] According to an embodiment of the present invention, the above-mentioned method for calibrating hydrogen isotope gas sensitivity may further include the following technical features:

[0009] According to an embodiment of the present invention, the abundance of hydrogen isotopes in the gas to be measured is an arbitrary value. According to a preferred embodiment of the present invention, the abundance of hydrogen isotopes in the gas to be measured is above 90%.

[0010] According to an embodiment of the present invention, the gas to be measured includes at least one of hydrogen, deuterium and / or tritium, and the abundance of hydrogen, deuterium and tritium is arbitrary. According to a preferred embodiment of the present invention, the total abundance of hydrogen, deuterium and tritium is above 90%.

[0011] According to an embodiment of the present invention, the range value of the positive standard sensitivity in step (2) is [0, 100].

[0012] According to an embodiment of the present invention, the mass spectrometer in step (3) is a high-resolution mass spectrometer.

[0013] According to an embodiment of the present invention, the range value of the re-marking sensitivity in step (4) is [0, 100].

[0014] In a second aspect, the present invention provides an application of the method for calibrating hydrogen isotope gas sensitivity in the field of detecting hydrogen isotope content. The present invention provides a method for detecting the hydrogen isotope content in a test gas, comprising: calibrating the hydrogen isotope gas sensitivity based on the method described in the first aspect of the present invention; and, based on the hydrogen isotope gas sensitivity calibration result, detecting the test gas using a mass spectrometer to determine the hydrogen isotope content in the test gas.

[0015] The beneficial effects achieved by the present invention are:

[0016] 1) The present invention provides a method for calibrating the sensitivity of hydrogen isotopes in a high-resolution gas mass spectrometer. The method has the characteristics of low purity requirements and can be used to complete calibration when the purity and abundance of the calibrated gas are ≥90%.

[0017] 2) It has a wide range of applications. This method can be applied to the mass spectrometer detection sensitivity calibration of hydrogen isotope gases such as hydrogen isotopes and light helium, for which no national standard substances exist.

[0018] 3) The method has the characteristics of high detection accuracy. It uses multiple detection means and multiple calibrations such as positive calibration, reverse calculation, and double calibration, and fully considers the influence of impure substances on sensitivity calibration.

[0019] 4) It has the characteristics of low cost and strong economy. The sensitivity calibration method avoids the stringent requirements of expensive and pure hydrogen isotope gas.

[0020] Additional aspects and advantages of the present invention will be set forth in part in the description which follows and, in part, will be obvious from the description which follows, or may be learned by practice of the present invention. DETAILED DESCRIPTION

[0021] The first aspect of the present invention provides a method for calibrating the sensitivity of hydrogen isotope gas, comprising: (1) detecting a gas to be tested based on mass spectrometry-chromatography to determine the sample components and content contained in the gas to be tested, which is counted as a first detection result; (2) using the percentage of hydrogen isotope gas in the gas to be tested obtained from the first detection result to determine the positive calibration sensitivity; (3) based on the positive calibration sensitivity, using a mass spectrometer to measure the sample components and content contained in the gas to be tested, which is counted as a second detection result; (4) using the percentage of hydrogen isotope gas in the gas to be tested obtained from the second detection result to determine the recalibration sensitivity.

[0022] The present invention establishes a method for calibrating the gas sensitivity of hydrogen isotopes measured by a high-resolution gas mass spectrometer, which can calibrate the hydrogen isotope sensitivity without using national standard substances while ensuring the accuracy of hydrogen isotope abundance measurement.

[0023] According to a specific embodiment of the present invention, the abundance of hydrogen isotopes in the gas to be measured is above 90%.

[0024] According to a specific embodiment of the present invention, the gas to be measured includes a gas whose isotope abundance needs to be measured, and the total abundance of the gas is above 90%.

[0025] According to a specific embodiment of the present invention, the range of the positive standard sensitivity in step (2) is [0, 100]. The sensitivity mentioned herein is calculated based on the instrument's analysis of the hydrogen isotope gas in the gas to be measured.

[0026] According to a specific embodiment of the present invention, the mass spectrometer in step (3) is a high-resolution mass spectrometer.

[0027] According to a specific embodiment of the present invention, the range of the re-calibration sensitivity in step (4) is [0,100]. The re-calibration sensitivity is obtained based on the instrument's calculation of the hydrogen isotope gas in the gas to be measured. The re-calibration sensitivity can be used to determine the content of hydrogen isotopes in the gas to be measured. For example, the following formula can be used for calculation: Qt can be obtained by calculating the leak rate and peak time detected by the instrument, S t This can be obtained by dividing the instrument-determined corrected signal by the contribution factor. The S0 result is then multiplied by the pressure drop factor to obtain the time-corrected signal. This time-corrected signal is then divided by the recalibrated sensitivity to obtain the gas partial pressure. Combined with the gas partial pressure results, the hydrogen isotope content can be determined.

[0028] Qt =leak rate*peak time

[0029] S t =Correction signal / contribution factor

[0030] S0=S t e -Qt

[0031] Time correction signal = S0 * voltage drop factor

[0032] Voltage division = time correction signal / recalibration sensitivity

[0033] To this end, in a second aspect of the present invention, a method for detecting hydrogen isotope content is provided, comprising: calibrating the hydrogen isotope gas sensitivity based on the method described in the first aspect of the present invention; and based on the hydrogen isotope gas sensitivity calibration result, detecting the gas to be measured using a mass spectrometer to determine the hydrogen isotope content in the gas to be measured.

[0034] Below, the scheme of the present invention will be explained in conjunction with embodiment.It will be understood by those skilled in the art that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention.In the embodiment, if specific technology or conditions are not indicated, the technology or conditions described in the literature in this area or the product instructions are used.The reagents or instruments used are not indicated by the manufacturer, and are all conventional products that can be obtained by commercial purchase.

[0035] Example 1

[0036] The mass spectrometer-chromatograph used in Example 1 is a single-analyzer mass spectrometer-Agilent chromatograph, and the high-resolution mass spectrometer used is an Evolution 2 double-focusing analyzer mass spectrometer.

[0037] 1) 3 For example, the He sample was detected by mass spectrometry-chromatography. 3 The abundance of He is detected to determine that the purity and abundance of the calibration component to be measured in the sample are ≥90%, and the abundance of the calibration component to be measured is obtained.

[0038] 2) 3 The abundance of He is taken as the purity (considered as the pure substance of this abundance) and brought into the high-resolution mass spectrometry sensitivity calibration to calibrate the 3 He sensitivity.

[0039] 3) Write the sensitivity of the positive standard into the mass spectrometer, and then perform mass spectrometry analysis on the sample to be calibrated to obtain the type and content of each component.

[0040] 4) Bring the detected components and their corresponding contents into the high-resolution mass spectrometry sensitivity calibration and re-calibrate 3And sensitivity.

[0041] 5) Write the re-calibrated sensitivity into the mass spectrometer and re-test the types and contents of each component of the sample to be calibrated.

[0042] The results are as follows:

[0043] Serial number Theoretical helium content (%) Helium detection content (%) Relative error (%) 1 95.12 95.31 0.19 2 96.78 96.53 0.25 3 95.89 95.95 0.06 4 96.76 96.59 -0.17 5 97.35 97.25 -0.10

[0044] Example 2

[0045] In the research process of Example 2, it was found that if the sensitivity calibrated by step 2 alone was 34.9, but the sensitivity calibrated by step 4 was 34.1, the sensitivity could be improved by the method provided by the present invention.

[0046] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. A method for calibrating hydrogen isotope gas sensitivity, characterized in that: include: (1) Detecting the gas to be tested based on mass spectrometry-chromatography to determine the sample components and content contained in the gas to be tested, which is counted as a first detection result; (2) Using the hydrogen isotope gas percentage in the gas to be tested obtained from the first detection result, the hydrogen isotope gas percentage is brought into the high-resolution mass spectrometry sensitivity calibration as the purity to determine the positive standard sensitivity; (3) Based on the positive standard sensitivity, using a high-resolution mass spectrometer to measure the sample components and content contained in the gas to be tested, and calculating it as a second detection result; (4) Using the hydrogen isotope gas percentage in the gas to be measured obtained from the second detection result, the hydrogen isotope gas percentage is brought into the high-resolution mass spectrometry sensitivity calibration to determine the recalibration sensitivity; the abundance of the hydrogen isotope in the gas to be measured is above 90%.

2. The method according to claim 1, characterized in that The gas to be measured includes at least one of protium, deuterium and / or tritium.

3. The method according to claim 1, characterized in that The range of the positive standard sensitivity in step (2) is [0,100].

4. The method according to claim 1, wherein The range of the re-calibration sensitivity in step (4) is [0,100].

5. Application of the method for calibrating hydrogen isotope gas sensitivity according to any one of claims 1 to 4 in the field of detecting hydrogen isotope content.

6. The use according to claim 5, characterized in that Methods for detecting hydrogen isotope content include: Calibrate hydrogen isotope gas sensitivity based on the method according to any one of claims 1 to 4, Based on the hydrogen isotope gas sensitivity calibration result, the gas to be tested is detected using a mass spectrometer to determine the content of hydrogen isotopes in the gas to be tested.