CN-122016956-A - Portable electrochemical hydrogen meter, calibration method, measurement method and software system

CN122016956ACN 122016956 ACN122016956 ACN 122016956ACN-122016956-A

Abstract

The application discloses a portable electrochemical hydrogen meter, a calibration method, a measurement method and a software system. The portable electrochemical hydrogen meter comprises a standard hydrogen partial pressure generating module, an electrochemical sensing module, a flow path switching module and a control and operation module. The standard hydrogen partial pressure generating module is used for outputting at least two hydrogen partial pressures, the flow path switching module is connected with the flow cell, and the control and operation module is in communication connection with the standard hydrogen partial pressure generating module, the electrochemical sensing module and the flow path switching module. In the calibration state, the control and operation module establishes the corresponding relation between the dissolved hydrogen concentration and the electric signal according to at least two hydrogen partial pressures and corresponding current signals, and in the measurement state, the portable electrochemical hydrogen meter outputs the dissolved hydrogen concentration value of the measured liquid based on the corresponding relation and the real-time temperature signals. The device is portable, and can immediately give out legal and effective dissolved hydrogen concentration on the nuclear power site.

Inventors

WANG SHAOJIAN
LIANG YAXUN
KONG YONGHONG
DING JIAPENG
XU WEIMIN
LIU WUSHUANG
LI HAITAO

Assignees

中广核工程有限公司

Dates

Publication Date: 20260512
Application Date: 20260227

Claims (17)

1. A portable electrochemical hydrogen meter, comprising: the standard hydrogen partial pressure generating module is used for outputting at least two hydrogen partial pressures; The electrochemical sensing module comprises a flow cell, an electrochemical hydrogen sensor and a temperature sensor, wherein the hydrogen sensitive electrode and the temperature sensitive element are connected with the flow cell; a flow path switching module connected with the flow cell and used for communicating the flow cell with the standard hydrogen partial pressure generating module or communicating the flow cell with the tested liquid; The control and operation module is in communication connection with the standard hydrogen partial pressure generation module, the electrochemical sensing module and the flow path switching module; The portable electrochemical hydrogen meter is configured to have a calibration state and a measurement state, in the calibration state, the control and operation module establishes a corresponding relation between dissolved hydrogen concentration and an electric signal according to the at least two hydrogen partial pressures and corresponding current signals, and in the measurement state, the portable electrochemical hydrogen meter outputs a dissolved hydrogen concentration value of the measured liquid based on the corresponding relation and a real-time temperature signal.
2. The portable electrochemical hydrogen meter of claim 1, wherein the portable electrochemical hydrogen meter comprises, The standard hydrogen partial pressure generating module comprises a replaceable hydrogen storage unit, a pressure reducing valve and an electric regulating valve, wherein the hydrogen storage unit, the pressure reducing valve and the electric regulating valve are all communicated with the flow cell.
3. The portable electrochemical hydrogen meter of claim 2, wherein the portable electrochemical hydrogen meter comprises, The hydrogen storage unit comprises at least one of a high-pressure pure hydrogen cylinder, a metal hydride hydrogen storage device or an in-situ water electrolysis hydrogen production device, the hydrogen volume fraction of the hydrogen storage unit is more than or equal to 99 percent, and/or, The pressure of the hydrogen storage unit ranges from 0 to 15mpa.a.
4. The portable electrochemical hydrogen meter of claim 2, wherein the portable electrochemical hydrogen meter comprises, The pressure reducing valve and the electrically operated regulator valve are configured to be cooperatively adjustable to maintain a pressure of 0.1mpa.a to 1.0mpa.a within the flow-through cell and to provide at least three discrete hydrogen partial pressure points.
5. The portable electrochemical hydrogen meter of claim 1, wherein the portable electrochemical hydrogen meter comprises, And a standard calibration curve is arranged in the control and operation module, and is a linear fitting equation between the hydrogen pressure and the dissolved hydrogen concentration reference value.
6. The portable electrochemical hydrogen meter of claim 5, wherein the portable electrochemical hydrogen meter comprises, And a linear fitting equation C=k.P+b of the standard calibration curve, wherein C is a dissolved hydrogen concentration reference value, P is a hydrogen pressure value, and k and b are constant terms.
7. The portable electrochemical hydrogen meter of claim 5, wherein the portable electrochemical hydrogen meter comprises, The calculation formula of the goodness of fit R 2 is as follows: Wherein, the The sum of squares of the residual errors is used for representing the sum of squares of errors between the predicted value and the true value of the model and reflecting the variation which is not captured by the model; Is the sum of squares of the residuals, representing the sum of squares of the differences of the true values from their mean, reflecting the total variation of the dependent variable.
8. A calibration method for a portable electrochemical hydrogen meter according to any one of claims 1 to 7, comprising the steps of: s101, enabling the portable electrochemical hydrogen meter to be in a calibration state, and communicating the flow cell with the standard hydrogen partial pressure generation module; s103, setting a measuring range of the concentration of the dissolved hydrogen through the control and operation module, and automatically determining a corresponding hydrogen pressure calibration range based on the measuring range; S105, the control and operation module controls the standard hydrogen partial pressure generation module to sequentially establish 2 to 10 different target hydrogen pressure points P in the flow cell within the hydrogen pressure calibration range; s107, under each target hydrogen pressure point, measuring a corresponding current signal i through the electrochemical hydrogen sensor, and measuring the current temperature T through the temperature sensor; S109, for each target hydrogen pressure point P, the control and operation module calculates the target hydrogen pressure point P and the current temperature T to obtain a theoretical reference value C _ref of the dissolved hydrogen concentration according to Henry' S law, so as to generate a set of calibration data (C _ref , i), wherein C _ref is a theoretical concentration true value, and i is an actual measurement current; S111, performing linear fitting by using the calibration data (C _ref , i) to generate a new calibration curve, and replacing the original built-in calibration curve in the control and operation module by the new calibration curve; And S113, after calibration is completed, switching the portable electrochemical hydrogen meter to a measurement mode, and communicating the flow cell with the measured liquid.
9. The method according to claim 8, wherein the step S103 includes: when the measurement range of the dissolved hydrogen concentration is set to 0 to 5ppm, the automatically selected hydrogen partial pressure calibration interval is 0 to 5bar.
10. The method according to claim 8, wherein the step S105 includes: the number of target hydrogen pressure points established is 3 to 5.
11. The method according to claim 8, wherein the step S109 includes: the temperature signal is used for correcting the henry's law constant in real time, and the corrected temperature range is 10-50 ℃.
12. The calibration method according to claim 8, characterized in that in the step S109, the henry' S law is: ; Wherein, the Is the mole fraction of volatile solute B (i.e., dissolved gas) in solution; Is the pressure of the gas above the liquid surface at equilibrium; is a constant whose value depends on the temperature, pressure and nature of the solute and solvent.
13. The method according to claim 8, wherein the step S111 includes: And when the linear fitting goodness R2 is more than or equal to 0.999, executing the replacement operation, otherwise, displaying the calibration failure and prompting checking.
14. A measurement method for a portable electrochemical hydrogen meter according to any one of claims 1 to 7, comprising: S201, switching the flow cell to be communicated with the tested liquid; S203, measuring a current signal i and a real-time temperature generated by the liquid to be measured through the electrochemical sensing module; s205, the control and operation module calls a new calibration curve generated by the calibration method according to any one of claims 8 to 13, processes the current signal i, compensates in combination with the real-time temperature, and finally calculates and outputs a corrected dissolved hydrogen concentration value.
15. A computer readable storage medium, in which a processor executable program is stored, which when executed by a processor is adapted to carry out the calibration method according to any one of claims 8 to 13.
16. A computer program product comprising a computer program or computer instructions, characterized in that the computer program or the computer instructions are stored in a computer readable storage medium, from which the computer program or the computer instructions are read by a processor of a computer device, which processor executes the computer program or the computer instructions, so that the computer device performs the calibration method according to any one of claims 8 to 13.
17. A software system for the portable electrochemical hydrogen meter of any one of claims 1 to 7, integrated within the control and operational module, the software system comprising: a pressure control unit for precisely outputting at least two hydrogen partial pressures during the calibration phase; the signal processing unit is used for synchronously collecting current and temperature signals; a calibration calculation unit for performing multi-point linear fitting and generating a new correspondence between concentration and current; and the measurement compensation unit is used for dynamically correcting the corresponding relation based on the real-time temperature in the measurement stage so as to eliminate the system drift error.

Description

Portable electrochemical hydrogen meter, calibration method, measurement method and software system Technical Field The application relates to the technical field of dissolved hydrogen concentration measurement, in particular to a portable electrochemical hydrogen meter, a calibration method, a measurement method and a software system. Background In the running process of the pressurized water reactor nuclear power unit, the primary loop coolant simultaneously bears the dual tasks of heat conduction and neutron moderation, and the water chemical state of the primary loop coolant directly influences the integrity of a fuel cladding, the stress corrosion resistance of a structural material and the migration behavior of a radioactive source. The concentration of dissolved hydrogen is used as a key oxidation-reduction regulation index and needs to be maintained in a technical specification limit interval through continuous or intermittent monitoring so as to prevent stainless steel and nickel-based alloy stress corrosion cracking caused by the rise of dissolved oxygen and inhibit the activation and deposition of radioactive isotopes. In view of the narrow space inside the nuclear island, high radiation dose rate and scattered equipment arrangement, stringent requirements higher than those of conventional industrial scenes are put forward on the miniaturization, light weight and on-site rapid deployment capability of the hydrogen meter. Although the existing hydrogen analyzer has the response advantage of an electrochemical sensing principle, the existing hydrogen analyzer generally depends on an external device and manual calibration in a field calibration link, so that the whole hydrogen analyzer has large carrying weight and long preparation time, and is difficult to maintain the integrity of a magnitude transmission chain in strong radiation, high temperature and high humidity environments. In addition, the external gas circuit is complex, the manual operation of the valve is frequent, and the risk of on-site leakage and personnel exposure is further amplified. Disclosure of Invention The application mainly aims to provide a portable electrochemical hydrogen meter, a calibration method, a measurement method and a software system, which are portable and can immediately give out legal and effective dissolved hydrogen concentration on a nuclear power site. To achieve the above object, some embodiments of the present application provide a portable electrochemical hydrogen meter, comprising: the standard hydrogen partial pressure generating module is used for outputting at least two hydrogen partial pressures; the electrochemical sensing module comprises a flow cell, an electrochemical hydrogen sensor and a temperature sensor, and the hydrogen sensitive electrode and the temperature sensitive element are connected with the flow cell; the flow path switching module is connected with the flow cell and is used for communicating the flow cell with the standard hydrogen partial pressure generating module or communicating the flow cell with the tested liquid; the control and operation module is in communication connection with the standard hydrogen partial pressure generation module, the electrochemical sensing module and the flow path switching module; The portable electrochemical hydrogen meter is configured to have a calibration state and a measurement state, wherein in the calibration state, the control and operation module establishes a corresponding relation between dissolved hydrogen concentration and an electric signal according to at least two hydrogen partial pressures and corresponding current signals thereof, and in the measurement state, the portable electrochemical hydrogen meter outputs a dissolved hydrogen concentration value of the measured liquid based on the corresponding relation and a real-time temperature signal. In some embodiments, the standard hydrogen partial pressure generating module comprises a replaceable hydrogen storage unit, a pressure reducing valve and an electrically operated regulating valve, all of which are in communication with the flow cell. In some embodiments, the hydrogen storage unit comprises at least one of a high pressure pure hydrogen cylinder, a metal hydride hydrogen storage device or an in situ electrolyzed water hydrogen generator, the hydrogen volume fraction of the hydrogen storage unit is greater than or equal to 99%, and/or, The pressure of the hydrogen storage unit ranges from 0 to 15mpa.a. In some embodiments, the pressure reducing valve and the electrically operated regulating valve are configured to be cooperatively adjustable to maintain a pressure of 0.1mpa.a to 1.0mpa.a within the flow-through cell and to provide at least three discrete hydrogen partial pressure points. In some embodiments, the control and calculation module has a standard calibration curve built into it that is a linear fit equation between the hydrogen pressure and the dissolved hydrogen