JP4514737B2 - pH electrode - Google Patents

Description

  The present invention relates to water quality measurement in high-temperature and high-pressure water environments such as chemical plants, boilers, thermal power plants and nuclear power plants, and more particularly to a technique for measuring with a simple pH sensor.

Conventionally, the method of measuring pH in high-temperature and high-pressure water has been measured and evaluated with an electrode using a zirconia diaphragm as a solid electrolyte as described in Patent Document 1. However, the solid electrolyte has a defect that it operates as an electrolyte only in a high temperature range of 200 ° C. or higher, and measurement at 200 ° C. or lower is impossible. Moreover, the pH glass electrode using the glass diaphragm prescribed | regulated to JIS and generally used is prescribed | regulated only from room temperature to 80 degreeC, and cannot be measured.
Japanese Laid-Open Patent Publication No. 1-165902

  This electrode can be measured in a temperature range of 80 ° C. to 200 ° C. and a high-temperature and high-pressure water environment up to 300 ° C., which cannot be measured with a conventional glass electrode or zirconia diaphragm electrode.

  Measurements can be made in a wide temperature range from room temperature to 300 ° C. by the potential difference from the external and internal reference electrodes installed in the same environment. To briefly explain the principle, the pH electrode and the reference electrode serving as the reference electrode are installed in a predetermined solution, and each is connected to a potentiometer. If the type of solution, that is, the measurement atmosphere is changed, a potential corresponding to the hydrogen ion concentration on the surface of the pH electrode is generated.

  In an aqueous solution containing hydrogen, it is appropriate to use a conventional classic platinum / hydrogen electrode as a pH electrode. May adversely affect the environment, and is often not suitable for practical use. When compared with a conventional platinum / hydrogen electrode that always requires a hydrogen partial pressure, this pH electrode does not require hydrogen in the measurement system because hydrogen is occluded in the alloy by cathodic electrolytic hydrogen charging.

  A palladium electrode using pure palladium as an electrode (two-phase hydride region of (α + β)) can measure pH in a temperature range up to about 200 ° C. by cathodic electrolytic hydrogen charging.

  However, in the temperature range higher than 200 ° C., the range of the stable two-phase region becomes smaller, the diffusion loss of hydrogen into an unsaturated solution of hydrogen becomes very fast and requires frequent hydrogen charging. In addition, the pure palladium electrode may be mechanically destroyed by repeated α-β changes with a volume change of approximately 10% due to the temperature cycle.

  In order to achieve the above object, the present invention employs a palladium-silver (80 wt% palladium-20 wt% silver) alloy for the electrode element used in the pH electrode sensor.

  Since palladium-silver alloy has a higher hydrogen retention capacity in a high-temperature water environment than pure palladium, it can be used in a higher-temperature environment. By making an alloy of silver and palladium that reduces the α-β miscibility gap at room temperature, it is possible to avoid changes in α-β accompanied by volume changes. This alloy has characteristics such as higher hydrogen permeability than pure palladium.

[Action]
In the present invention, pH measurement is performed in a high-temperature and high-pressure water environment over a temperature range from room temperature to 300 ° C. using a palladium-silver alloy as a hydride electrode.

  Thermodynamic consideration-The potential of a palladium-silver alloy hydride electrode in an aqueous solution is expressed by the following equation (1).

In order to understand the potential formation of Equation 1, it is necessary to analyze the thermodynamic characteristics of the palladium hydride system. Here, H ⁺ represents a hydrogen ion, and e represents an electron. The phase diagram of the Pd—H system shown in Non-Patent Document 1 is shown in FIG.
FA Lewis, The Palladium-Hydrogen System, Academic Press, London (1967)

Each isotherm at a temperature of 310 ° C or lower is between the equilibrium between α (solid solution of hydrogen in palladium) and β (Pd _x H and x are given near the boundary between α + β and β regions). Show the plateau about what to do. By definition, the activity of Pd _X H is constant, and the hydrogen activity of the lattice in the α + β region is given by the following formula 2.

は格子の水素の標準部分モル・ギブスエネルギー、Rは気体定数，Tは絶対温度である。これらの量は温度（定圧で）だけの関数であるため、格子の水素活量はTにより与えられた値に固定される。 Where μ ⁰ _PdxH , μ ⁰ _Pd is the Gibbs energy per mole of Pd _x H and Pd,

Is the standard partial molar Gibbs energy of hydrogen in the lattice, R is the gas constant, and T is the absolute temperature. Since these quantities are functions only of temperature (at constant pressure), the hydrogen activity of the lattice is fixed at the value given by T.

  Here, if the palladium hydride electrode is in an equilibrium state, the chemical potential of hydrogen in the lattice is considered to be equal to the chemical potential of hydrogen in the solution. That is, the equilibrium is expressed by the equation (4).

Lattice hydrogen activity lna _{H, α + β} is given by equation 5

Here, p _βα is an appropriate hydrogen partial pressure that is isothermal with the plateau region. The potential E _Pd-H of the palladium hydride electrode is given by

に従い数５を置換すれば、次式のように示される。 And

If the equation 5 is replaced according to the following equation, the following equation is obtained.

_Equation 8 is an equation for a hydrogen electrode with a hydrogen partial pressure equal to P _βα (on the definition of electrochemistry, the first half of the equation is 0). This pH electrode performs measurement based on the principle of such electrochemical equilibrium.

  According to the present invention, since the electrode structure is simple and a small pH sensor can be provided, the application range of the pH measurement method in a high-temperature and high-pressure water environment can be greatly expanded.

  By using a palladium-silver alloy, the use of a pH electrode used for pH measurement at a high temperature was realized.

  Embodiments of the present invention will be described below with reference to FIGS.

  FIG. 2 shows a configuration of a pH measuring device in high-temperature and high-pressure water to which the present invention is applied. The type of the measurement environment solution 5 in the measurement vessel 6 that can withstand a high temperature and high pressure water environment such as stainless steel or titanium, that is, a change in the measurement atmosphere is measured as pH. A potential measuring device 3 having a high input impedance is connected between a pH electrode 1 and a reference electrode 2 placed in a solution environment to be measured by a shielded lead wire 4, and the potential difference is measured. The potential of the pH electrode 1 measured with respect to the reference electrode 2 is converted into a hydrogen electrode potential reference, and the change is corrected to the measured value by the pH temperature, and is expressed as the pH at that temperature. The reference electrode 2 can be an electrochemical reference electrode such as an internal verification electrode or an external verification electrode, and there is no particular limitation. The PH electrode 1, the reference electrode 2, and the lead wire 4 are insulated from the measurement container 6.

FIG. 3 shows a hydrogen storage method and circuit diagram in a palladium-silver alloy. Occlusion of hydrogen into the palladium-silver alloy 11 is performed by a cathodic electrolytic hydrogen charging method. The hydrogen occlusion in the palladium-silver alloy 11 and the measurement of the occlusion rate are carried out with respect to the platinum electrode 12 using the palladium-silver alloy 11 as a cathode in a hydrogen charging electrolyte solution 14 such as a 1N hydrochloric acid solution in a measuring vessel 13. Then, charging is performed by performing electrolysis for 1 to 180 minutes from the power source 16 for electrolytic charging at a constant current value of 100 to 200 mA / cm ² . The current value at this time is measured by the ammeter 15. Water is electrolyzed by applying a voltage of 1.23 V or more, and oxygen is generated on the anode side and hydrogen is generated on the cathode side. Cathodic electrolytic hydrogen charging is a circuit in which a palladium-silver alloy 11 is used as a cathode and a platinum electrode 12 is used as an anode, thereby generating hydrogen on the palladium-silver alloy 11 side and storing hydrogen from the surface of the palladium-silver alloy 11. . Further, the amount of hydrogen in the palladium-silver alloy 11 is based on the fact that the resistance value of the alloy changes depending on the amount of hydrogen occluded in the palladium alloy. It can obtain | require by comparing the silver alloy 18 and resistance value. The resistance value of each alloy is measured by the bridge method. A current is applied to the bridge circuit formed by the palladium-silver alloy 11 and the comparative palladium-silver alloy 18 by the constant current applying device 19, and the resistance value is calculated from the voltage value measured by the precision voltage measuring device 20.

  FIG. 4 is an example of data obtained by measuring the amount of hydrogen with a hydrogen analyzer. The amount of hydrogen occluded in the palladium-silver alloy was analyzed twice using the method shown in FIG. 3 while changing the hydrogen charging time. The vertical axis represents the hydrogen storage amount (%), and the horizontal axis represents the hydrogen charge time (minutes). The hydrogen occlusion amount of the palladium-silver alloy with a hydrogen charge time of 0 is 0.001%, which is the detection limit of the measuring apparatus, and it can be seen that there is almost no hydrogen in the palladium-silver alloy. A palladium-silver alloy that has been charged with hydrogen for 5 minutes has a hydrogen storage amount of 0.1 to 0.2%, and a hydrogen charge time of 120 minutes is 0.3 to 0.4%. It can be seen that the hydrogen is occluded.

  FIG. 5 is a production example diagram of a pH electrode. The electrode holder portion 24 is made of stainless steel and has a thickness calculated for strength to withstand the use of high temperature and pressure, and a connection portion to a pressure vessel or the like. The electrode and the lead wire 21 are fixed to the electrode holder portion 24 by tightening a cap 22 that fixes the electrode. Considering the use at high temperature, the electrode holder portion 24 has a cooling jacket 23 so that cooling can be performed. By flowing a cooling medium such as water and air through the cooling portion, the pressure at the time of use in a high temperature and high pressure environment It becomes possible to suppress deterioration of the pressure seal from the container and the insulating material of the lead wire 21 and the electrode. The electrode is designed to be installed at a fixed location by the electrode guide 25. Also, a porous ceramic cover to protect the electrode from the influence of the flow velocity on the electrode surface when impurities adhere to the electrode surface from the test solution environment, poisoning due to ion species, etc., and the flow of the test solution. 26. The ceramic cover 26 is made of ceramics and does not affect the measurement itself. A pH electrode for measurement is installed inside the ceramic cover 26.

FIG. 6 shows measurement data of pH in an environment of 200 ° C. using this pH electrode. The vertical axis represents the potential converted to the hydrogen electrode potential reference, and the horizontal axis represents the pH at that temperature. No. 1 and no. The plot of 2 is data in a 0.05 mol sodium sulfate (Na ₂ SO ₄ ) solution (pH value at 200 ° C. by theoretical calculation: 7.3). The data of 3 is the result of pH measurement in 0.045 mol sodium sulfate (Na ₂ SO ₄ ) +0.005 mol sulfuric acid (H ₂ SO ₄ ) solution (pH value at 200 ° C. by theoretical calculation: 4.65). The dotted line represents the theoretical calculated value of pH at that temperature. In the test, a static autoclave made of SUS316 having an internal volume of 400 ml was heated from the outside by a heater, and the temperature was controlled by a K-sheath thermocouple installed inside to adjust the test temperature to ± 1 ° C. The test solution was degassed with oxygen, carbon dioxide, etc. by nitrogen gas ventilation for 1 hour. The pressure is the saturated vapor pressure at that temperature. A pressure balanced external reference electrode (silver / silver chloride, 0.1N potassium chloride electrolyte) is used as a reference electrode. The test results using this electrode show that solutions with different pHs of the test solution approximate the theoretical calculation values in the solution, and that reproducible data can be obtained under the same conditions.

FIG. 7 shows pH measurement data in an environment of 250 ° C. using this electrode. The vertical axis represents the potential converted to the hydrogen electrode potential reference, and the horizontal axis represents the pH at that temperature. No. 1-3 plot 0.05mol of sodium sulfate _(Na 2 SO ₄₎ solution (pH value of 250 ° C. by theoretical calculations: 7.66) is the data in, No. The plot of 4 is the result of pH measurement in 0.045 mol sodium sulfate (Na ₂ SO ₄ ) +0.005 mol sulfuric acid (H ₂ SO ₄ ) solution (pH value at 250 ° C. by theoretical calculation: 5.31). The dotted line represents the theoretical calculated value of pH at that temperature. In the test, a static autoclave made of SUS316 having an internal volume of 400 ml was heated from the outside by a heater, and the temperature was controlled by a K-sheath thermocouple installed inside to adjust the test temperature to ± 1 ° C. The test solution was degassed with oxygen, carbon dioxide, etc. by nitrogen gas ventilation for 1 hour. A pressure balanced external reference electrode (silver / silver chloride, 0.1N potassium chloride electrolyte) is used as a reference electrode. The test results using this electrode show that solutions with different pHs of the test solution approximate the theoretical calculation values in the solution, and that reproducible data can be obtained under the same conditions.

FIG. 8 is an example of data actually measured using the present pH electrode under the following use conditions. The vertical axis represents the pH value, and the horizontal axis represents the measurement time. The test conditions for this test were a test temperature of 300 ° C., a test pressure of 8.5 MPa (saturated vapor pressure), 0.05 mol of sodium sulfate (Na ₂ SO ₄ ) solution. In a test in a stationary autoclave made of SUS316 having an internal volume of 400 ml, it is heated from the outside by a heater. The temperature was adjusted with an accuracy of ± 1 ° C. of the test temperature by a K-sheath thermocouple installed inside. A pressure balanced external reference electrode (silver / silver chloride, 0.1N potassium chloride electrolyte) is used as a reference electrode for pH measurement. The potential between the pH electrode and the reference electrode was measured with a potential measuring device having a high input impedance. By performing a correction calculation based on the temperature based on the measurement data, the potential was converted to a hydrogen electrode standard, and the pH at that temperature was determined. It shows that stable pH data can be obtained in tests up to 100 hours.

  It should be noted that the present invention should not be construed as being limited to the above-described embodiments, and it goes without saying that modifications and improvements can be made as appropriate without departing from the spirit of the present invention. For example, the detailed structure of the pH electrode, the type of solution, and gas can be selected as necessary.

It is a correlation diagram of hydrogen and palladium, and is an explanatory diagram showing the stability of a palladium-silver alloy hydride electrode. It is explanatory drawing which showed the basic apparatus structure in the case of implementing this invention. It is explanatory drawing of the hydrogen charge by the cathode electrolysis to a palladium-silver alloy. It is a data example of the resistance change at the time of hydrogen charge to a palladium-silver alloy. It is explanatory drawing which showed the manufacture example of the electrode. This is an example of reproducible data obtained by measuring pH at 200 ° C. and approximating a theoretical value. This is an example of reproducible data obtained by measuring the pH at 250 ° C. and approximating the theoretical value. It is a data example in which pH measurement at 300 ° C. is performed and stable measurement is performed.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 pH electrode 2 Reference electrode 3 Potential measuring device 4 Lead wire 5 Liquid of measurement environment 6 Measuring container 11 Palladium-silver alloy 12 Platinum counter electrode 13 Measuring container 14 Electrolytic solution for hydrogen charging 15 Ammeter 16 Power source for electrolytic charging 17 Lead wire 18 Palladium-silver alloy for comparison 19 Constant current applying device 20 Precision voltage measuring device 21 Lead wire 22 Cap for fixing electrode 23 Cooling jacket 24 Electrode holder portion 25 Electrode guide 26 Ceramic cover

Claims (10)

In an apparatus having a cathode made of a palladium-silver alloy and an anode, an electric current is supplied to the anode in an electrolytic solution, and the palladium-silver alloy is made to absorb hydrogen by occluding hydrogen. Manufactured as a chemical,
By storing hydrogen, a palladium-silver alloy pH measurement sensor electrode that operates as a pH measurement sensor electrode for a predetermined time by the stored hydrogen without supplying hydrogen to the measurement system from the outside during pH measurement. .
In an apparatus in which a palladium-silver alloy is connected to a cathode and platinum is used as an anode, a predetermined current is supplied to the platinum in an electrolytic solution, and the palladium-silver alloy is made to store hydrogen by occluding hydrogen. Manufactured by hydriding silver alloy,
By storing hydrogen, a palladium-silver alloy pH measurement sensor electrode that operates as a pH measurement sensor electrode for a predetermined time by the stored hydrogen without supplying hydrogen to the measurement system from the outside during pH measurement. .
The hydrogen-containing palladium-silver alloy pH measurement sensor according to claim 1, wherein the electrode for hydrogen-containing palladium-silver alloy pH measurement sensor has a hydrogen storage amount of at least 0.1% or more. Sensor electrode.
In an apparatus in which a palladium-silver alloy is connected to a cathode and platinum is used as an anode, a predetermined current is supplied to the platinum in an electrolytic solution, and hydrogen is occluded in the palladium-silver alloy. -A palladium-silver alloy pH measurement sensor that operates as a pH measurement sensor electrode for a predetermined time by occluded hydrogen without hydriding the silver electrode and supplying hydrogen to the measurement system from the outside during pH measurement. Of manufacturing an electrode.
5. The palladium-silver alloy pH measurement sensor containing hydrogen according to claim 4, wherein the electrode for hydrogen-containing palladium-silver alloy pH measurement sensor has a hydrogen storage amount of at least 0.1% or more. A method of manufacturing an electrode.
A palladium-silver alloy pH measurement sensor electrode containing hydrogen, an electrode support portion that supports the pH measurement electrode, a lead wire connected to the electrode support portion, and an anode,
The palladium-silver alloy pH measurement sensor electrode containing hydrogen supplies a predetermined current to the anode in an electrolytic solution, and occluding the palladium-silver alloy by hydride by storing hydrogen in the palladium-silver alloy. Manufactured,
A pH measurement sensor electrode device that operates as a pH measurement sensor electrode for a predetermined period of time by storing hydrogen, without supplying hydrogen from the outside to the measurement system during pH measurement.
The electrode device for a pH measurement sensor according to claim 6, wherein the anode is made of platinum.
The electrode device for a pH measurement sensor according to claim 6 or 7, wherein the electrode for a palladium-silver alloy pH measurement sensor containing hydrogen has a hydrogen storage amount of at least 0.1% or more.
A measurement device for a pH measurement sensor, wherein the electrode device for a pH measurement sensor according to claim 6 is connected to a potential measurement device.
  The measurement device for a pH measurement sensor according to claim 9, wherein the electrode for a palladium-silver alloy pH measurement sensor containing hydrogen has a hydrogen occlusion amount of at least 0.1% or more.

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