CN114324536B - Hydrogen probe device is decided to metal melt - Google Patents

Abstract

A metal melt hydrogen determination probe device, including an upper insulating connector, a lower insulating connector, a stainless steel tube and a conductive protective cover; the interior of the upper insulating connector, the lower insulating connector, the stainless steel tube and the conductive protective cover is from top to bottom There are stainless steel rods and proton conductors in turn; the proton conductor is a blind-end tube, the lower part of which is a hemispherical head, the top of the hemispherical head is connected to the cylindrical side wall to form an integrated structure, and the inner wall of the cylindrical side wall is fixed with High-temperature cement board; the high-temperature cement board separates the proton conductor into an upper space and a lower space; the upper surface of the high-temperature cement board is coated with a porous electrode coating; the outer surface and inner surface of the proton conductor are respectively coated with an outer porous electrode coating and an inner Porous Electrode Coating. The device of the present invention is easy to assemble and disassemble, and when the sensor reaches the service life, only the probe can be replaced without replacing the main part of the sensor, which can save a lot of cost.

Description

A metal melt hydrogen determination probe device

technical field

The invention relates to the technical field of sensors in the metallurgical industry, in particular to a metal melt hydrogen determination probe device.

Background technique

Hydrogen measurement by proton conductor sensing is a new method of hydrogen measurement. This method can accurately, rapidly and real-time measure hydrogen in metal melts and gases, and realize online intelligent monitoring. It is a promising hydrogen measurement method. method. When the sensing material used in the sensor is an ideal pure proton conductor, its galvanic battery reaction is shown in formula (1):

H ₂ (reference pole) = H ₂ (metal pole) (1);

The electromotive force generated by the primary battery under ideal conditions is shown in formula (2):

The hydrogen content in the metal melt is shown in formula (3):

为金属熔体的氢分压，单位atm，

为参比侧的氢分压，单位atm。In the above formulas, R is the gas constant 8.314J/(mol K); T is the temperature, unit K; F is the Faraday constant 96485C/mol; E is the electromotive force, unit V; k is the alloy coefficient; S is the metal melt Hydrogen content in hydrogen, unit ml/100g;

is the hydrogen partial pressure of the metal melt, in atm,

is the partial pressure of hydrogen on the reference side, in atm.

When the proton conductor is pure proton conduction, by controlling the hydrogen partial pressure of the reference electrode, the hydrogen content in the metal melt of the electrode to be measured is calculated by using the electromotive force generated by the primary battery.

EP0544281 TYK company's device for measuring hydrogen content in molten metal below 1000 ℃, using proton conductors such as SrCe _0.95 Yb _0.05 O _3-x , CaZr _0.9 In _0.1 O _3-x , BaCe _0.95 Y _0.05 O _3-x as hydrogen sensors Materials, metal wires such as Pt and Ni are used as electrode leads, and ceramic binders are used to bond parts such as proton conductors, mullite tubes, and gas chambers to ensure their connection; the patent application with publication number CN105319253 has announced a A sensor and measurement method for measuring hydrogen content in molten metal, using CaZr _0.9 In _0.1 O _3-x proton conductors as hydrogen sensitive materials, platinum, gold, silver, nickel chromium and other metal wires as electrode leads, and insulating ceramic binders , the proton conductor and the through pipe are bonded together to ensure their connection; patent US 2005/0252789 discloses a hydrogen sensing device and method, using SrCe _0.95 Yb _0.05 O _3-δ , CaZr _0.9 In _0.1 O _3-δ As a hydrogen sensitive material, α-Ti/β-Ti, α-Zr/β-Zr, β-Zr/δ-Zr, α-Hf/δ-Hf are used as solid reference electrodes, and internal filling materials and glass sealants The device is sealed as a whole, but the patent only involves the probe part, and the support and electrode lead connection part required by the sensor are not disclosed.

In the current hydrogen measuring device, the proton conductor sensing hydrogen measuring probes are all integrated. When the sensor has a problem, it is difficult to check and maintain, and when the sensor reaches the end of its service life, it must be replaced as a whole. These problems increase the sensor’s cost of use; therefore, a split sensor probe that is easy to disassemble, repair and replace is required.

Contents of the invention

In order to solve the above problems, the present invention provides a metal melt hydrogen determination probe device, based on the proton conductor concentration cell hydrogen measurement method, using solid metal hydride as a reference electrode, the proton conductor probe outputs the electromotive force of the concentration cell, and the metal hydride Together with the inner porous electrode as the positive electrode; the outer porous electrode and the protective cover as the negative electrode, it is easy to assemble and disassemble. When the sensor reaches the end of its service life, only the probe needs to be replaced without replacing the main part of the sensor.

The metal melt hydrogen determination probe device of the present invention includes an upper insulating connector 4, a lower insulating connector 8, a stainless steel tube 6 and a conductive protective cover 7; the upper insulating connector 4 is an integral body composed of a top plate, a side wall and a hollow tube structure, wherein the top plate is provided with a through hole, an electrode hole and a galvanic hole; the top of the hollow tube is connected to the bottom of the top plate, the upper part of the side wall is sleeved outside the side of the top plate, and an internal thread is provided in the side wall, and the hollow tube is connected to the middle through The holes are coaxial, and the inner diameter of the hollow tube is larger than the inner diameter of the through hole; the electrode hole and the galvanic hole are located between the outer wall of the hollow tube and the inner wall of the side wall; the lower insulating connector 8 is cylindrical, and the outer wall is provided with external threads ; The stainless steel pipe 6 is cylindrical, and the upper and lower parts of the outer wall are respectively provided with an upper external thread and a lower external thread; The air hole 14; the upper insulating connector 4 and the upper external thread of the stainless steel pipe 6 are connected by thread sealing, and the lower external thread of the stainless steel pipe 6 is connected with the conductive protective cover 7 and the lower insulating connector 8 by thread sealing at the same time; the upper insulating connector 4 , the lower insulating connector 8, the stainless steel pipe 6 and the conductive protective cover 7 are provided with a stainless steel rod 2 and a proton conductor 15 from top to bottom; The top of the head is connected to the cylindrical side wall to form an integrated structure, and a high-temperature cement board 11 is fixed on the inner wall of the cylindrical side wall; the high-temperature cement board 11 divides the proton conductor 15 into an upper space and a lower space, and the lower space is used to place The reference electrode 13; the upper surface of the high-temperature cement board 11 is coated with a porous electrode coating; the outer and inner surfaces of the proton conductor 15 are coated with an outer porous electrode coating 12 and an inner porous electrode coating 10, respectively.

In the above device, the stainless steel rod 2 is composed of a rod body and a single-stage pagoda joint on its upper part to form an integrated structure; the stainless steel rod 2 passes through the through hole and the hollow tube on the top plate of the upper insulating connector 4; the bottom end of the stainless steel rod 2 is connected to the high temperature The porous electrode coating of the cement board 11 is connected; the spring 3 is placed on the single-stage pagoda joint, and the top of the spring 3 is pressed and connected with the bottom surface of the top plate of the upper connector 4 .

In the above-mentioned device, the upper part of the outer surface of the cylindrical side wall of the proton conductor 15 is bonded and fixed with the inner wall of the lower insulating connector 8 by a high-temperature adhesive 9; 11 is sealed in the lower space of the proton conductor 15; the reference electrode 13 is metal hydride CaH _x or YH _x ; the proton conductor 15, the high temperature cement plate 11 and the reference electrode 13 constitute the probe part.

In the above device, the hemispherical head of the proton conductor 15 is opposite to the air hole 14 , and the hemispherical head of the proton conductor 15 is tightly connected to the bottom plate of the conductive protective cover 7 .

In the above-mentioned device, a thermocouple 5 is installed in the couple hole of the upper insulating connector 4, the bottom end of the thermocouple 5 is located in the upper space of the proton conductor 15, and there is a gap between the bottom end of the thermocouple 5 and the high-temperature cement plate 11; Couple 5 is a double-hole corundum tube, and the inner double holes are the positive and negative poles of the K-type thermocouple wire respectively. There is a slot on the lower side wall, and the bottom ends of the positive and negative poles of the thermocouple wire located at the slot are connected by welding. The wires connected to the top of the positive and negative poles are connected to the external temperature measuring device.

In the above device, a stainless steel electrode 1 is arranged in the electrode hole of the upper insulating connector 4; the stainless steel electrode 1 is an inverted T-shaped structure, the vertical bar part of the stainless steel electrode 1 passes through the electrode hole, and the horizontal bar part of the stainless steel electrode 1 is connected to the stainless steel tube 6 top compression connection.

In the above device, the conductive protective cover 7 is made of graphite.

In the above device, the material of the upper insulating connector 4 is polytetrafluoroethylene.

In the above device, the material of the lower insulating connector 8 is ceramic; the ceramic is macor ceramic.

In the above device, each porous electrode is coated with a porous Pt electrode.

In the above device, the high temperature cement board 11 is made of Aremco 503 high temperature cement.

The using method of the metal melt hydrogen determination probe device of the present invention is:

(1) Immerse the metal melt hydrogen determination probe device in the metal melt. At this time, the hydrogen in the metal melt diffuses through the vent hole 14, and establishes a hydrogen concentration difference with the reference electrode 13; between the inner and outer sides of the proton conductor 15 generate electromotive force;

(2) With the porous electrode coating 10 and the stainless steel rod 2 as the positive pole, the outer porous electrode coating 11, the conductive protective cover 7, the stainless steel tube 6 and the stainless steel electrode 1 are used as the negative pole; measure the voltage between the two poles by a voltmeter; Even 5 measures the temperature in the stainless steel pipe 6;

(3) When the temperature and voltage values are in a steady state, the measured voltage value is brought into formulas (2) and (3) to calculate the hydrogen content in the metal melt.

In the above method, the voltage value in a steady state means that the voltage value is measured every second, and when the standard deviation of the voltage value for 10 consecutive seconds is ≤0.3mV, it is a steady state.

In the above method, the stable state of the voltage value is 2-4 minutes after the start of the measurement, and the stable state of the temperature is 1-1.5 minutes after the start of the measurement; that is, when the voltage value is in a stable state, the temperature is also in a stable state.

In the above method, the metal melt is aluminum melt, magnesium melt, zinc melt, nickel melt, copper melt, iron melt or steel melt.

The invention adopts metal hydride, porous electrode inside the proton conductor, and stainless steel rod as the positive electrode; the porous electrode outside the proton conductor and stainless steel pipe are used as the negative electrode; the proton conductor is connected with other components through threads, which is easy to disassemble; the hydrogen-sensitive material is a lattice defect Type high-temperature proton conductor, using the electromotive force of the concentration cell of the proton conductor and Schwart's law to measure hydrogen; the two electrodes are stainless steel, and no thermoelectric potential will be generated in the temperature change area.

The device of the present invention is easy to assemble and disassemble, and when the sensor reaches the service life, only the probe can be replaced without replacing the main part of the sensor, which can save a lot of cost.

Description of drawings

Fig. 1 is the structural representation of the metal melt hydrogen determination probe device of the present invention;

Fig. 2 is the structural representation of each part in Fig. 1;

In the figure, 1. Stainless steel electrode, 2. Stainless steel rod, 3. Spring, 4. Upper insulating connector, 5. Thermocouple, 6. Stainless steel tube, 7. Conductive protective cover, 8. Lower insulating connector, 9. High temperature Binder, 10. Inner porous electrode coating, 11. High temperature cement board, 12. Outer porous electrode coating, 13. Reference electrode, 14. Air vent, 15. Proton conductor;

Fig. 3 is the time-temperature/voltage curve chart that records in the embodiment of the present invention 1;

Fig. 4 is the time-temperature/voltage curve chart that records in the embodiment of the present invention 2;

Fig. 5 is the time-temperature/voltage graph that records in the embodiment of the present invention 3;

Fig. 6 is the time-temperature/voltage graph measured in the embodiment of the present invention 4;

Fig. 7 is the time-temperature/voltage graph measured in the embodiment of the present invention 5;

Fig. 8 is the time-temperature/voltage graph measured in embodiment 6 of the present invention;

Fig. 9 is a graph of time-temperature/voltage measured in Example 7 of the present invention.

Detailed ways

The following are the preferred embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

In the embodiment of the present invention, the material of the conductive protective cover 7 is graphite; the material of the upper insulating connector 4 is polytetrafluoroethylene; the material of the lower insulating connector 8 is ceramic; the ceramic is macor ceramic; each porous electrode coating is a porous Pt electrode; the high temperature cement board 11 is made of Aremco 503 high temperature cement.

In the embodiment of the present invention, the diameter of the ventilation holes 14 is 1-3 mm, and the number of ventilation holes is 1-20.

In the embodiment of the present invention, the height of the conductive protective cover 7 is 5-50 mm greater than the height of the proton conductor 15 .

In the embodiment of the present invention, the outer walls of the stainless steel pipe 6 and the conductive protective cover 7 are sprayed with a metal melt corrosion-resistant coating to protect the metal melt from corrosion.

In the embodiment of the present invention, the thermocouple 5 is covered with a high temperature resistant insulating sleeve to prevent the thermocouple 5 from contacting the inner porous electrode coating 10 .

The high temperature binder in the embodiment of the present invention is Aremco 503 high temperature cement.

The steps for replacing the probe device of the metal melt hydrogen determination probe device of the present invention are as follows: the metal melt hydrogen determination probe device is inverted, that is, the conductive protective cover 7 is located at the top, and the stainless steel rod 2 is located at the bottom; The protective cover and the probe part are also removed; the conductive protective cover 7 and the probe part are rotated and separated;

为参比电极的氢分压所参考的文献为L.N.Yannopoulos,R.K.Edwards,P.G.Wahlbeck,The Thermodynamics of the Yttrium-Hydrogen System[J],The Journal of Physical Chemistry,1965,69(8):2510-2515.和R.W.Curtis,P.Chiotti,Thermodynamic properties of calcium hydride[J],1963,67,5,1061–1065.。In the embodiment of the present invention

The referenced literature for the hydrogen partial pressure of the reference electrode is LNYannopoulos, RK Edwards, PG Wahlbeck, The Thermodynamics of the Yttrium-Hydrogen System [J], The Journal of Physical Chemistry, 1965,69 (8): 2510-2515. and RW Curtis , P. Chiotti, Thermodynamic properties of calcium hydride [J], 1963, 67, 5, 1061–1065.

The reference electrode in the embodiment of the present invention is YH _x +YH _2-δ .

Example 1

The structure of the metal melt hydrogen determination probe device is shown in Figure 1, including an upper insulating connector 4, a lower insulating connector 8, a stainless steel tube 6 and a conductive protective cover 7;

The structure of each part is shown in Figure 2;

The upper insulating connector 4 is an integrated structure composed of a top plate, a side wall and a hollow tube, wherein the top plate is provided with a through hole, an electrode hole and a galvanic couple hole; the top of the hollow tube is connected with the bottom surface of the top plate, and the upper part of the side wall is sleeved on Outside the side of the top plate, the side wall is provided with internal threads, the hollow tube is coaxial with the through hole, and the inner diameter of the hollow tube is larger than the inner diameter of the through hole; the electrode hole and the galvanic hole are located between the outer wall of the hollow tube and the inner wall of the side wall ;

The lower insulating connector 8 is cylindrical, and the outer wall is provided with external threads;

The stainless steel pipe 6 is cylindrical, and the upper and lower parts of the outer wall are respectively provided with an upper external thread and a lower external thread;

The conductive protective cover 7 is barrel-shaped, and the upper part of the inner wall surface of the side wall is provided with an internal thread, and the bottom plate is provided with a ventilation hole 14;

The upper insulating connecting piece 4 is connected with the upper external thread of the stainless steel pipe 6 through thread sealing, and the lower external thread of the stainless steel pipe 6 is connected with the conductive protective cover 7 and the lower insulating connecting piece 8 through thread sealing at the same time;

Stainless steel rods 2 and proton conductors 15 are sequentially arranged inside the upper insulating connector 4, the lower insulating connector 8, the stainless steel tube 6 and the conductive protective cover 7 from top to bottom;

The proton conductor 15 is a blind-end tube, and its lower part is a hemispherical head. The top of the hemispherical head is connected to a cylindrical side wall to form an integrated structure. A high-temperature cement board 11 is fixed on the inner wall of the cylindrical side wall; the high-temperature cement board 11 The proton conductor 15 is divided into an upper space and a lower space, and the lower space is used to place the reference electrode 13; the upper surface of the high temperature cement board 11 is coated with a porous electrode coating; the outer surface and the inner surface of the proton conductor 15 are respectively coated with Outer porous electrode coating 12 and inner porous electrode coating 10;

The stainless steel rod 2 is composed of the rod body and the single-stage pagoda joint on the upper part to form an integrated structure; the stainless steel rod 2 passes through the through hole and the hollow tube on the top plate of the upper insulating connector 4; the bottom end of the stainless steel rod 2 and the high temperature cement plate 11 The porous electrode coating is connected; the spring 3 is placed on the single-stage pagoda joint, and the top of the spring 3 is pressed and connected with the bottom surface of the top plate of the upper connector 4;

The upper part of the outer surface of the cylindrical side wall of the proton conductor 15 is bonded and fixed to the inner wall of the lower insulating connector 8 by a high-temperature adhesive 9; The lower space of the conductor 15; the reference electrode 13 is a metal hydride CaH _x or YH _x ; the proton conductor 15, the high temperature cement plate 11 and the reference electrode 13 constitute the probe part;

The hemispherical head of the proton conductor 15 is opposite to the air hole 14, and the hemispherical head of the proton conductor 15 is tightly connected to the bottom plate of the conductive protective cover 7;

A thermocouple 5 is installed in the couple hole of the upper insulating connector 4, the bottom end of the thermocouple 5 is located in the upper space of the proton conductor 15, and there is a gap between the bottom end of the thermocouple 5 and the high-temperature cement board 11; Hole corundum tube, the inner double holes are the positive and negative poles of the K-type thermocouple wire respectively, the lower side wall is provided with a slot, the bottom end of the positive and negative poles of the thermocouple wire located at the slot is connected by welding, the top of the positive and negative poles The connecting wire is connected with the external temperature measuring device;

A stainless steel electrode 1 is set in the electrode hole of the upper insulating connector 4; the stainless steel electrode 1 is an inverted T-shaped structure, the vertical rod part of the stainless steel electrode 1 passes through the electrode hole, and the horizontal rod part of the stainless steel electrode 1 is pressed against the top of the stainless steel tube 6 connect;

The method of use is:

Immerse the metal melt hydrogen determination probe device into the metal melt, at this time, the hydrogen in the metal melt diffuses through the vent hole 14, and establishes a hydrogen concentration difference with the reference electrode 13; an electromotive force is generated between the inner and outer sides of the proton conductor 15;

The inner porous electrode coating 10 and the stainless steel rod 2 are used as the positive pole, and the outer porous electrode coating 11, the conductive protective cover 7, the stainless steel tube 6 and the stainless steel electrode 1 are used as the negative pole; the voltage between the two poles is measured by a voltmeter; measured by a thermocouple 5 The temperature in the stainless steel pipe 6;

When the temperature and the voltage value are all in a steady state, the measured voltage value is brought into formula (3) to calculate the hydrogen content in the metal melt;

The voltage value in a stable state refers to measuring the voltage value every second. When the standard deviation of the voltage value for 10 consecutive seconds is less than or equal to 0.3mV, it is a stable state.

The stable state of the voltage value is 2 to 4 minutes after the start of the measurement, and the stable state of the temperature is 1 to 1.5 minutes after the start of the measurement; that is, when the voltage value is in a stable state, the temperature is also in a stable state;

取纯铝的合金的系数k为1.0057，则

含氢量

The metal melt is pure aluminum melt; the measured time-temperature/voltage curve is shown in Figure 3; E=213.6×10 ^-3 V and T=988K in the steady state, then there is

Taking the coefficient k of the alloy of pure aluminum as 1.0057, then

Hydrogen content

Example 2

The structure of the metal melt hydrogen determination probe device is the same as in Embodiment 1;

Using method is the same as embodiment 1, and difference is:

取ZL108铝合金的系数k为0.543，则

The metal melt is a ZL108 aluminum alloy melt; the measured time-temperature/voltage curve is shown in Figure 4; E=267.2×10 ^-3 V and T=955K in the steady state, then there is

Taking the coefficient k of ZL108 aluminum alloy as 0.543, then

Hydrogen content according to the calculation

Example 3

The structure of the metal melt hydrogen determination probe device is the same as in Embodiment 1;

Using method is the same as embodiment 1, and difference is:

取A356铝合金的系数k为0.8309，则

The metal melt is A356 aluminum alloy melt; the measured time-temperature/voltage curve is shown in Figure 5; E=196.1×10 ^-3 V and T=986K in the steady state, then there is

Taking the coefficient k of A356 aluminum alloy as 0.8309, then

Hydrogen content according to the calculation

Example 4

The structure of the metal melt hydrogen determination probe device is the same as in Embodiment 1;

Using method is the same as embodiment 1, and difference is:

取纯镁的系数k为36.423，则

The metal melt is pure magnesium melt; the measured time-temperature/voltage curve is shown in Figure 6; E=216.0×10 ^-3 V and T=1021K in the steady state, then there is

Taking the coefficient k of pure magnesium as 36.423, then

Hydrogen content according to the calculation

Example 5

The structure of the metal melt hydrogen determination probe device is the same as in Embodiment 1;

Using method is the same as embodiment 1, and difference is:

取AZ91E镁合金的系数k为33.920，则

The metal melt is an AZ91E magnesium alloy melt; the measured time-temperature/voltage curve is shown in Figure 7; the steady state E=220.5×10 ^-3 V, T=1025K, then

Taking the coefficient k of AZ91E magnesium alloy as 33.920, then

Hydrogen content according to the calculation

Example 6

The structure of the metal melt hydrogen determination probe device is the same as in Embodiment 1;

Using method is the same as embodiment 1, and difference is:

取ZL101铝合金的系数k为0.762，则

The metal melt is ZL101 aluminum alloy melt; the measured time-temperature/voltage curve is shown in Figure 8; E=97.6×10 ^-3 V and T=973K in the steady state, then there is

Taking the coefficient k of ZL101 aluminum alloy as 0.762, then

Hydrogen content according to the calculation

Example 7

The structure of the metal melt hydrogen determination probe device is the same as in Embodiment 1;

Using method is the same as embodiment 1, and difference is:

取ZM5镁合金的系数k为32.461，则

The metal melt is a ZM5 magnesium alloy melt; the measured time-temperature/voltage curve is shown in Figure 9; E=122.7×10 ^-3 V and T=1019K in the steady state, then there is

Taking the coefficient k of ZM5 magnesium alloy as 32.461, then

Hydrogen content according to the calculation

Claims (9)

1. A metal melt hydrogen determination probe device is characterized in that it includes an upper insulating connector, a lower insulating connector, a stainless steel tube and a conductive protective cover; the upper insulating connector is an integral body composed of a top plate, a side wall and a hollow tube structure, wherein the top plate is provided with a through hole, an electrode hole and a galvanic hole; the top of the hollow tube is connected to the bottom of the top plate, the upper part of the side wall is sleeved outside the side of the top plate, and an internal thread is provided in the side wall, and the hollow tube is connected to the middle through The holes are coaxial, and the inner diameter of the hollow tube is larger than the inner diameter of the through hole; the electrode hole and the galvanic hole are located between the outer wall of the hollow tube and the inner wall of the side wall; the lower insulating connector is cylindrical, and an external thread is provided on the outer wall; The stainless steel tube is cylindrical, and the upper and lower parts of the outer wall are respectively provided with upper and lower external threads; the conductive protective cover is in the shape of a barrel, and the upper part of the inner wall of the side wall is provided with internal threads, and the bottom plate is provided with ventilation holes; The insulating connecting piece is connected with the upper external thread of the stainless steel pipe through thread sealing, and the lower external thread of the stainless steel pipe is connected with the conductive protective cover and the lower insulating connecting piece through thread sealing at the same time; the upper insulating connecting piece, the lower insulating connecting piece, the stainless steel pipe and the conductive The interior of the protective cover is provided with stainless steel rods and proton conductors in turn from top to bottom; the proton conductor is a blind-end tube, the lower part of which is a hemispherical head, and the top of the hemispherical head is connected to the cylindrical side wall to form an integrated structure. A high-temperature cement board is fixed on the inner wall of the shaped side wall; the high-temperature cement board divides the proton conductor into an upper space and a lower space, and the lower space is used to place a reference electrode; the upper surface of the high-temperature cement board is coated with a porous electrode coating; The outer surface and the inner surface of the conductor are respectively coated with an outer porous electrode coating and an inner porous electrode coating; The stainless steel rod is composed of a rod body and a single-stage pagoda joint on its upper part to form an integrated structure; the stainless steel rod passes through the through hole and the hollow tube on the top plate of the upper insulating connector; the bottom end of the stainless steel rod and the porous electrode of the high temperature cement board Coating connection; a spring is placed on the single-stage pagoda joint, and the top of the spring is pressed and connected with the bottom surface of the top plate of the upper connector. 2. A metal melt hydrogen determination probe device according to claim 1, characterized in that the upper part of the outer surface of the cylindrical side wall of the proton conductor is bonded to the inner wall of the lower insulating connector by a high-temperature adhesive connected and fixed; the reference electrode is set in the proton conductor, and is sealed in the lower space of the proton conductor by a high-temperature cement board; the reference electrode is a metal hydride CaH _x or YH _x ; the proton conductor, the high-temperature cement board and the reference electrode constitute the probe part. 3. A metal melt hydrogen determination probe device according to claim 1, characterized in that the hemispherical head of the proton conductor is opposite to the air hole, and the hemispherical head of the proton conductor and the bottom plate of the conductive protective cover Compression connection between. 4. A metal melt hydrogen determination probe device according to claim 1, characterized in that a thermocouple is installed in the galvanic couple hole of the upper insulating connector, and the bottom end of the thermocouple is located in the upper space of the proton conductor , there is a gap between the bottom end of the thermocouple and the high-temperature cement board; the thermocouple is a double-hole corundum tube, and the inner double holes are the positive and negative poles of the K-type thermocouple wire, and there is a slot on the lower side wall, which is located at the slot The positive and negative bottom ends of the thermocouple wires are connected by welding, and the wires connected to the top of the positive and negative electrodes are connected to the external temperature measuring device. 5. A metal melt hydrogen determination probe device according to claim 1, characterized in that a stainless steel electrode is arranged in the electrode hole of the upper insulating connector; the stainless steel electrode is an inverted T-shaped structure, and the vertical position of the stainless steel electrode is The rod part passes through the electrode hole, and the cross rod part of the stainless steel electrode is pressed and connected with the top of the stainless steel tube. 6. A metal melt hydrogen determination probe device according to claim 1, characterized in that the material of the conductive protective cover is graphite. 7. A metal melt hydrogen determination probe device according to claim 1, characterized in that the material of the upper insulating connector is polytetrafluoroethylene. 8. A metal melt hydrogen determination probe device according to claim 1, characterized in that the material of the lower insulating connector is ceramic; the ceramic is macor ceramic. 9. A method for using a metal melt hydrogen determination probe device according to claim 1, characterized in that the following steps are performed: (1) Immerse the metal melt hydrogen determination probe device into the metal melt. At this time, the hydrogen in the metal melt diffuses through the vent hole, and establishes a hydrogen concentration difference with the reference electrode; an electromotive force is generated between the inner and outer sides of the proton conductor; (2) The inner porous electrode coating and stainless steel rod are used as positive electrodes, and the outer porous electrode coating, conductive protective cover, stainless steel tube and stainless steel electrode are used as negative electrodes; the voltage between the two electrodes is measured by a voltmeter; the temperature inside the stainless steel tube is measured by a thermocouple ; (3) When the temperature and voltage values are in a stable state, the hydrogen content in the metal melt is calculated by the measured voltage value.

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