阅读说明：本技术 一种高温电解直接制备干燥纯氢的装置 (Device for directly preparing dry pure hydrogen by high-temperature electrolysis ) 是由 王建强 杜贤龙 洪春峰 高娜 严慧娟 吕欣婷 马亚飞 魏高泰 肖国萍 于 2021-01-14 设计创作，主要内容包括：本发明涉及一种高温电解直接制备干燥纯氢的装置,水蒸气发生器连接在纯水箱和质子传导型SOEC电解槽之间以将来自于纯水箱的水蒸发为水蒸气并向质子传导型SOEC电解槽提供水蒸气,质子传导型SOEC电解槽由多个电解单元串联组成,每个电解单元包括位于质子传导型高温固体电解质的相对两侧的氧侧通道和氢侧通道,水蒸气进入氧侧通道电解后失去电子产生氧气,电解出的氢离子通过质子传导型高温固体电解质进入氢侧通道获得电子直接得到干燥的氢气,储氢装置和质子传导型SOEC电解槽的氢侧通道连接以接收存储氢气。该高温电解直接制备干燥纯氢的装置,具有氢气纯度高、露点低、开机时间短、产氢效率高、工艺简单、更安全可靠等优点。(The invention relates to a device for directly preparing dry pure hydrogen by high-temperature electrolysis, wherein a water vapor generator is connected between a pure water tank and a proton conduction type SOEC electrolytic cell to evaporate water from the pure water tank into water vapor and provide the water vapor for the proton conduction type SOEC electrolytic cell, the proton conduction type SOEC electrolytic cell is formed by connecting a plurality of electrolytic units in series, each electrolytic unit comprises an oxygen side channel and a hydrogen side channel which are positioned on two opposite sides of a proton conduction type high-temperature solid electrolyte, the water vapor enters the oxygen side channel to be electrolyzed and then loses electrons to generate oxygen, the electrolyzed hydrogen ions enter the hydrogen side channel through the proton conduction type high-temperature solid electrolyte to obtain electrons to directly obtain dry hydrogen, and a hydrogen storage device is connected with the hydrogen side channel of the proton conduction type SOEC electrolytic cell to receive and store the hydrogen. The device for directly preparing dry pure hydrogen by high-temperature electrolysis has the advantages of high hydrogen purity, low dew point, short startup time, high hydrogen production efficiency, simple process, safety, reliability and the like.)

1. The device for directly preparing dry pure hydrogen by high-temperature electrolysis is characterized by comprising a pure water tank (1), a water vapor generator (3), a proton conduction type SOEC electrolytic cell (5) and a hydrogen storage device (13), wherein the water vapor generator (3) is connected between the pure water tank (1) and the proton conduction type SOEC electrolytic cell (5) to evaporate water from the pure water tank (1) into water vapor and provide the water vapor for the proton conduction type SOEC electrolytic cell (5), the proton conduction type SOEC electrolytic cell (5) is formed by connecting a plurality of electrolytic units in series, each electrolytic unit comprises an oxygen side channel and a hydrogen side channel which are positioned at two opposite sides of a proton conduction type high-temperature solid electrolyte, the water vapor enters the oxygen side channel to be electrolyzed and then loses electrons to generate oxygen, the electrolyzed hydrogen ions enter the hydrogen side channel through the proton conduction type high-temperature solid electrolyte to obtain electrons to directly obtain dry hydrogen, the hydrogen storage device (13) is connected with the hydrogen side channel of the proton conduction type SOEC electrolytic cell (5) to receive and store hydrogen gas.

2. The arrangement as claimed in claim 1, characterized in that the proton-conducting SOEC cell (5) has a non-noble metal oxygen electrode next to the proton-conducting high-temperature solid electrolyte in the oxygen-side channel and a nickel-based hydrogen electrode next to the proton-conducting high-temperature solid electrolyte in the hydrogen-side channel.

3. The apparatus according to claim 1, characterized in that the apparatus further comprises a gas cooling module (6), the gas cooling module (6) having an oxygen cooling channel communicating with the oxygen side channel of the proton conducting SOEC cell (5) to cool the oxygen gas and a hydrogen cooling channel communicating with the hydrogen side channel of the proton conducting SOEC cell (5) to cool the hydrogen gas.

4. The apparatus according to claim 3, characterized in that it further comprises a moisture separator (7) communicating with the oxygen cooling channel of the gas cooling module (6) for removing moisture from the oxygen.

5. The apparatus according to claim 3, further comprising a pressurizing device (10) connected between the gas cooling module (6) and the hydrogen storage device (13), wherein the pressurizing device (10) is communicated with the hydrogen cooling passage of the gas cooling module (6) to pressurize the hydrogen gas and then charge the hydrogen storage device (13).

6. The apparatus according to claim 5, characterized in that the apparatus further comprises a purification device (8) connected between the gas cooling module (6) and the pressurizing device (10), the purification device (8) being in communication with the hydrogen cooling channel of the gas cooling module (6) to increase the purity of the hydrogen gas.

7. The apparatus according to claim 1, characterized in that it further comprises a gas preheating assembly (4) connected between the water vapor generator (3) and the proton conducting SOEC cell (5), the gas preheating assembly (4) having a water vapor heating channel communicating with the water vapor generator (3) to superheat the water vapor entering the proton conducting SOEC cell (5).

8. The apparatus according to claim 7, characterized in that it further comprises a control valve (12) connected between the hydrogen storage means (13) and the gas preheating assembly (4), the gas preheating assembly (4) having a hydrogen heating channel communicating with the hydrogen storage means (13) to heat hydrogen entering the proton conducting SOEC cell (5) as a shielding gas.

9. The apparatus according to claim 1, further comprising a heating furnace (9) and a direct current power supply (11), wherein the proton conducting SOEC cell (5) is located inside the heating furnace (9) to ensure the operating temperature of the proton conducting SOEC cell (5) by the heating furnace (9), and the direct current power supply (11) is connected to the proton conducting SOEC cell (5) through positive and negative electrode connections to supply the direct current power supply to the proton conducting SOEC cell (5).

10. The device according to claim 1, characterized in that it further comprises a water pump (2) connected between the pure water tank (1) and the water vapor generator (3).

Technical Field

The invention relates to electrolytic hydrogen production, in particular to a device for directly preparing dry pure hydrogen by high-temperature electrolysis.

Background

The existing water electrolysis hydrogen production technology mainly comprises three types, namely alkaline water electrolysis hydrogen production (AEC), pure water electrolysis hydrogen Production (PEMEC) and high-temperature solid oxide water electrolysis hydrogen production (SOEC). The alkaline water electrolysis hydrogen production and PEM water electrolysis hydrogen production technology is developed more mature, but the electrolysis efficiency is not high; the technology for producing hydrogen by electrolyzing water by using high-temperature solid oxide has high electrolysis efficiency and is a good development direction.

The common high-temperature solid oxide electrolysis water hydrogen production electrolytic cell takes oxygen ion conduction type YSZ as an electrolyte, as shown in FIG. 3, the high temperature of 600 ℃ to 1000 ℃ is required, which causes the problems of weak sealing of the electrolytic cell, electrode deactivation, difficulty in manufacturing equipment, high manufacturing cost and the like. In addition, in order to ensure that the hydrogen-side electrode is not oxidized, the oxygen ion conduction type SOEC electrolytic cell must mix water vapor and a certain amount of hydrogen gas to enter the hydrogen side of the electrolytic cell during electrolysis, which requires a large amount of protective hydrogen gas on one hand, and causes mixing of unreacted water vapor and hydrogen gas on the other hand, thereby reducing the purity of hydrogen gas.

Disclosure of Invention

In order to solve the problem of oxygen ion conduction type SOEC in the prior art, the invention provides a device for directly preparing dry pure hydrogen by high-temperature electrolysis.

The device for directly preparing dry pure hydrogen by high-temperature electrolysis comprises a pure water tank, a water vapor generator, a proton conduction type SOEC electrolytic cell and a hydrogen storage device, the water vapor generator is connected between the pure water tank and the proton conduction type SOEC electrolytic cell to evaporate water from the pure water tank into water vapor and provide the water vapor for the proton conduction type SOEC electrolytic cell, the proton conduction type SOEC electrolytic cell is formed by connecting a plurality of electrolytic units in series, each electrolytic unit comprises an oxygen side channel and a hydrogen side channel which are positioned on two opposite sides of a proton conduction type high-temperature solid electrolyte, the water vapor enters the oxygen side channel to be electrolyzed and then loses electrons to generate oxygen, the electrolyzed hydrogen ions enter the hydrogen side channel through the proton conduction type high-temperature solid electrolyte to obtain electrons to directly obtain dry hydrogen, and the hydrogen storage device is connected with the hydrogen side channel of the proton conduction type SOEC electrolytic cell to receive and store the hydrogen.

Preferably, the proton conducting SOEC cell has a non-noble metal oxygen electrode in the oxygen-side channel next to the proton conducting high temperature solid electrolyte and a nickel-based hydrogen electrode in the hydrogen-side channel next to the proton conducting high temperature solid electrolyte.

Preferably, the apparatus further comprises a gas cooling assembly having an oxygen cooling channel in communication with the oxygen side channel of the proton conducting SOEC electrolytic cell to cool the oxygen gas and a hydrogen cooling channel in communication with the hydrogen side channel of the proton conducting SOEC electrolytic cell to cool the hydrogen gas.

Preferably, the apparatus further comprises a gas-water separator in communication with the oxygen cooling passage of the gas cooling module to remove moisture from the oxygen.

Preferably, the device also comprises a pressurizing device connected between the gas cooling assembly and the hydrogen storage device, and the pressurizing device is communicated with the hydrogen cooling channel of the gas cooling assembly so as to pressurize the hydrogen and then charge the hydrogen into the hydrogen storage device.

Preferably, the apparatus further comprises a purification device connected between the gas cooling module and the pressurization device, the purification device being in communication with the hydrogen cooling channel of the gas cooling module to increase the purity of the hydrogen gas.

Preferably, the apparatus further comprises a gas preheating assembly connected between the water vapor generator and the proton conducting SOEC cell, the gas preheating assembly having a water vapor heating passage in communication with the water vapor generator to superheat water vapor entering the proton conducting SOEC cell.

Preferably, the apparatus further comprises a control valve connected between the hydrogen storage device and the gas preheating assembly, the gas preheating assembly having a hydrogen heating passage in communication with the hydrogen storage device to heat hydrogen entering the proton conducting SOEC cell as shielding gas.

Preferably, the apparatus further comprises a heating furnace and a direct current power supply, the proton conduction type SOEC electrolytic cell is positioned inside the heating furnace to ensure the working temperature of the proton conduction type SOEC electrolytic cell through the heating furnace, and the direct current power supply is connected with the proton conduction type SOEC electrolytic cell through positive and negative electrode connections to supply the direct current power supply to the proton conduction type SOEC electrolytic cell.

Preferably, the apparatus further comprises a water pump connected between the pure water tank and the water vapor generator.

According to the device for directly preparing the dry pure hydrogen by high-temperature electrolysis, the dry pure hydrogen is directly prepared by electrolyzing water vapor at high temperature through the proton conduction type SOEC electrolytic cell. Compared with the prior oxygen ion conduction type SOEC, the device for directly preparing the dry pure hydrogen by high-temperature electrolysis has the advantages that the working temperature is reduced to 400-700 ℃, so that the manufacturing difficulty and the cost of hydrogen production equipment are reduced, and the startup stability time is shortened; meanwhile, the purity of hydrogen is improved, protective hydrogen does not need to be continuously introduced after the startup is stable, and the use of gas purification equipment is reduced to a certain extent. Compared with the conventional AEC and PEMEC devices, the device for directly preparing dry pure hydrogen by high-temperature electrolysis has high hydrogen production efficiency; compared with the existing oxygen ion conduction type SOEC, the hydrogen gas has the advantages of high hydrogen purity, low dew point, short startup time, simple process, higher safety and reliability and the like.

Drawings

FIG. 1 is a schematic diagram showing the overall structure of an apparatus for directly producing dry pure hydrogen by high-temperature electrolysis according to a preferred embodiment of the present invention;

FIG. 2 is a schematic diagram of the operating principle of the proton-conducting SOEC cell of FIG. 1;

FIG. 3 is a schematic representation of the operating principle of a prior art oxygen ion conducting SOEC cell.

Detailed Description

The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

As shown in fig. 1, the apparatus for directly preparing dry pure hydrogen by high-temperature electrolysis according to a preferred embodiment of the present invention comprises a pure water tank 1, a water pump 2, a water vapor generator 3, a gas preheating assembly 4, a proton conduction SOEC electrolytic cell 5, a gas cooling assembly 6, a gas-water separator 7, a purification apparatus 8, a heating furnace 9, a pressurization apparatus 10, a direct current power supply 11, a control valve 12, and a hydrogen storage apparatus 13.

The pure water tank 1 is connected with the water pump 2, the treated deionized water is stored in the pure water tank 1, and the internal equipment is provided with a liquid level detection device to detect the residual water amount.

The rear end of the water pump 2 is connected with the water vapor generator 3, and the water pump 2 has water flow control and detection functions and can stably and uninterruptedly convey water into the water vapor generator 3.

The outlet end of the water vapor generator 3 is connected with the gas preheating assembly 4, and the water vapor generator 3 can evaporate water from the water pump 2 into saturated water vapor which is conveyed to the gas preheating assembly 4. The water vapor generator 3 should have an outlet temperature detection and be able to completely evaporate the incoming water to saturated water vapor.

Besides being connected with the water vapor generator 3, the gas preheating assembly 4 is also connected with a hydrogen storage device 13 through a control valve 12 at the inlet end and connected with the proton conduction SOEC electrolytic cell 5 at the outlet end. The gas preheater module 4 has at least two gas heating paths, one for superheating the water vapor from the water vapor generator 3 and one for heating the hydrogen gas from the hydrogen storage device 13.

The proton conducting SOEC electrolytic cell 5 is a core device. The proton-conducting SOEC cell 5 comprises multiple groups of electrolytic cells, and the electrolyte material is proton-conducting high-temperature solid electrolyte, such as cubic perovskite BaCeO3-BaZrO₃Material system (BCZY) or Y and Yb co-doped BaCeO3-BaZrO₃Has good proton conductivity at 400-700 ℃. As shown in fig. 2, the proton-conducting SOEC electrolytic cell 5 is composed of a plurality of electrolytic cells connected in series,each electrolysis unit comprises an oxygen side channel and a hydrogen side channel which are positioned on two opposite sides of the proton-conducting high-temperature solid electrolyte, wherein the oxygen side channel is provided with a non-noble metal oxygen electrode on the side close to the electrolyte, and the hydrogen side channel is provided with a nickel-based hydrogen electrode on the side close to the electrolyte. When the device works, water vapor enters the oxygen side channel, and loses electrons after electrolysis to generate oxygen and leave a small amount of water; the hydrogen ions obtained by electrolysis enter a hydrogen side channel through a proton conduction type high-temperature solid electrolyte to obtain electrons so as to obtain hydrogen.

The gas cooling module 6 is located at the outlet of the proton conducting SOEC cell 5, in which there are an oxygen cooling channel and a hydrogen cooling channel. The gas cooling module 6 can be used in combination with the gas preheating module 4, i.e. the heat in the gas cooling module 6 is used to heat the water vapor or hydrogen in the gas preheating module 4 by means of heat exchange equipment, and then cooled to room temperature; the gas may also be cooled directly to room temperature.

The gas-water separator 7 is connected with the outlet of the oxygen cooling channel of the gas cooling assembly 6 and mainly used for separating residual water in the oxygen.

The purification device 8 is connected to the outlet of the hydrogen cooling channel of the gas cooling module 6, and is used for further purifying the hydrogen generated by electrolysis and improving the purity of the hydrogen. The purification method can adopt molecular sieve purification, membrane purification, pressure swing purification and the like according to actual conditions, and can also be used in occasions with low requirements on hydrogen purity without installation.

Inside the heating furnace 9 is placed a proton conducting SOEC cell 5. The inner side of the heating furnace 9 is provided with a heat preservation layer and a heating resistance wire, which not only ensures that the temperature in the furnace is not lost, but also ensures that the proton conduction type SOEC electrolytic tank 5 can be heated to work at the required temperature.

The pressurizing device 10 is connected between the hydrogen storage device 13 and the purification device 8, and can be pressurized by a plurality of groups of pressurizing pumps or a multi-stage compressor, so that the hydrogen from the purification device 8 is pressurized and then charged into the hydrogen storage device 13.

The direct current power supply 11 is connected with the proton conduction type SOEC electrolytic cell 5 through positive and negative electrode wiring to provide a direct current power supply. The direct current power supply can stabilize voltage or stabilize current output.

The control valve 12 is connected between the hydrogen storage device 13 and the proton conducting SOEC electrolytic cell 5, and the amount of entry of the protective hydrogen gas can be adjusted by controlling the opening degree of the valve. It should be understood that the oxygen ion conducting SOEC must ensure continuous supply of protective hydrogen, and the proton conducting SOEC can completely close the valve after stable operation, and is protected by self-generated hydrogen.

The hydrogen storage device 13 is arranged at the outlet end of the pressurizing device 10, and the hydrogen storage mode can adopt a high-pressure gas cylinder for storing hydrogen, metal for storing hydrogen and the like and can be selected according to actual requirements.

The operation scheme of the device for directly preparing dry pure hydrogen by high-temperature electrolysis according to the embodiment comprises the following steps: after the equipment is installed and leakage detection is finished, water in the pure water tank 1 enters the water vapor generator 3 through the water pump 2 to start generating water vapor, the gas preheating component 4 and the heating furnace 9 start heating and warming, and nitrogen and water vapor respectively enter a hydrogen side channel and an oxygen side channel of the proton conduction type SOEC electrolytic cell 5 after being overheated and warmed in the gas preheating component 4. After the temperature is raised to the working temperature, the introduction of the nitrogen is stopped, and the control valve 12 is opened to enable the hydrogen in the hydrogen storage device 13 to pass through the gas preheating assembly 4 and then enter the hydrogen side of the proton conduction type SOEC electrolytic cell 5 to activate the hydrogen electrode. After a period of activation, the direct current power supply 11 is turned on to start electrifying, at this time, the oxygen side of the electrolytic cell starts to generate oxygen, the hydrogen side starts to generate hydrogen, and after stabilization, the control valve 12 is closed and hydrogen is not introduced. The generated oxygen is condensed by the gas cooling component 6, and then water is separated from the oxygen by the gas-water separator 7; the generated hydrogen passes through the gas cooling assembly 6 and enters the purification device 8 for further treatment, and then enters the hydrogen storage device 13 through the pressurization device 10.

It should be understood that the purpose of introducing nitrogen and water vapor is to preheat the interior of the proton conducting SOEC electrolytic cell 5. If hydrogen is directly introduced without introducing nitrogen into the hydrogen-side channel, the hydrogen and oxygen in the air easily react with each other, and explosion occurs. If water vapor is introduced only into the oxygen-side passages, the heat distribution of the inner seal of the proton-conducting SOEC electrolyzer 5 becomes uneven, and gas leakage inside the electrolyzer tends to occur.

Example 1

The proton conducting SOEC cell 5 requires a working temperature of 500 ℃ and an activation time of 1 hour.

After the equipment is installed and leakage detection is finished, water in the pure water tank 1 enters the water vapor generator 3 through the water pump 2 to start generating water vapor, the gas preheating assembly 4 is gradually heated to 200 ℃, the heating furnace 9 is gradually heated to 500 ℃, and nitrogen and water vapor are respectively introduced into the hydrogen side channel and the oxygen side channel of the proton conduction type SOEC electrolytic cell 5 after being subjected to overheating heating in the gas preheating assembly 4. And stopping introducing the nitrogen after the temperature does not fluctuate obviously, and opening the control valve 12 to ensure that the hydrogen in the hydrogen storage device 13 enters the hydrogen side of the proton conduction type SOEC electrolytic cell 5 to activate the hydrogen electrode after passing through the gas preheating component 4. After 1h of activation, the direct current power supply 11 is turned on to start electrifying, the oxygen side of the electrolytic cell starts to generate oxygen, the hydrogen side starts to generate hydrogen, the direct current voltage and the direct current are observed to be stable after a period of time, and at the moment, the control valve 12 is closed to stop introducing hydrogen. The generated oxygen is condensed by the gas cooling component 6, and water is separated from the oxygen by the gas-water separator 7; the generated hydrogen passes through the gas cooling assembly 6 and enters the purification device 8 for further treatment, and then enters the hydrogen storage device 13 through the pressurization device 10. And then the operation is stable. If the computer is stopped under a certain condition, the computer is restarted according to the steps.

The above embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and various changes may be made in the above embodiments of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.