Tubular hydrogen and ammonia co-production device system and method based on proton-conductor electrolyzer

Abstract

The application discloses a tubular hydrogen-ammonia co-production device system and method based on a proton conductor electrolytic cell, and belongs to the technical field of power system energy storage; the system comprises a valve system, a circulating gas system, a circulating water system, an air separation nitrogen production system and a gas-liquid separation system; the application realizes the switching of hydrogen-ammonia co-production mode, single hydrogen production mode and single ammonia production mode through linkage between the valves, can realize single hydrogen production, single ammonia production or hydrogen-ammonia co-production, and can realize production mode conversion through simple control, adapt to production arrangement and improve utilization rate; in addition, the application utilizes the characteristics that the proton conductive electrolytic cell has a low requirement on raw material gas supply stability, and in combination with the nested structure integrated with the tubular proton conductor electrolytic cell and two layers of sealing materials, the green electricity hydrogen production and ammonia synthesis are deeply coupled to form the tubular hydrogen-ammonia co-production device based on the proton conductor electrolytic cell, the investment and system complexity are reduced, the unit product power consumption is reduced, and the power consumption is reduced.

Description

Technical Field

[0001] This invention belongs to the field of solid oxide electrolyzer technology, specifically relating to a tubular hydrogen-ammonia co-production device system and method based on a proton conductor electrolyzer. Background Technology

[0002] In recent years, the global energy supply and demand pattern, trade pattern, pace of transformation, and pricing system have all undergone profound adjustments. The high dependence on imported crude oil and natural gas means that ensuring energy security and supply remains under considerable pressure.

[0003] Hydrogen energy has become an important direction for the global green and low-carbon energy transition and a key technological route. In 2023, hydrogen production reached 35 million tons, of which 99% was produced from fossil fuels and industrial byproducts, while the proportion of hydrogen produced from renewable energy was less than 1%. According to relevant estimates, hydrogen consumption is expected to reach 120 million tons or more by 2060, of which green hydrogen will account for 100 million tons.

[0004] Hydrogen production from renewable energy sources, such as wind and solar power, drives water electrolysis to produce green hydrogen. This includes proton exchange membrane electrolyzers, alkaline water electrolyzers, and solid oxide electrolyzers. Using green hydrogen as a feedstock to produce green ammonia can solve the problems of hydrogen storage and transportation and promote hydrogen consumption, making it a crucial part of building a hydrogen-based energy society. Currently, wind-solar-hydrogen-ammonia storage projects primarily involve generating green electricity from wind and solar power, which is then used to produce green hydrogen through electrolyzers. This green hydrogen is then stored in a hydrogen storage unit to provide a stable hydrogen source for downstream chemical ammonia synthesis plants. The entire system has high requirements for the stability of both hydrogen and wind / solar power, and its composition is complex.

[0005] Currently, there are few reports on systems and methods for simultaneously producing hydrogen, ammonia, and heat in a single device. Patent title: A System and Method for the Joint Preparation of Green Hydrogen and Green Ammonia, application number: CN202311504174.7. This application describes a system where, when the oxygen carrier reaction chamber is heated to a first reaction temperature, the oxygen carrier generates intermediate oxygen products and oxygen gas. The nitrogen carrier reaction chamber is heated by the heated oxygen carrier reaction chamber to a second reaction temperature, where the nitrogen carrier and nitrogen gas react to generate intermediate nitrogen products. When the oxygen carrier reaction chamber is de-heated and gradually cooled to a third reaction temperature, the intermediate oxygen products react with water to generate oxygen carrier and hydrogen gas. The nitrogen carrier reaction chamber is then heated by the de-heated oxygen carrier reaction chamber to a fourth reaction temperature, where the intermediate nitrogen products and hydrogen gas react to generate nitrogen carrier and ammonia gas. This application, by designing the above system, uses water and nitrogen gas as raw materials and utilizes high-temperature heat energy provided by renewable energy sources to simultaneously produce hydrogen and ammonia gas without generating byproducts. However, this reaction system has numerous components and is complex overall, and the reaction mode cannot be controlled. Summary of the Invention

[0006] The purpose of this invention is to address the problem of numerous and complex components in existing systems that simultaneously achieve hydrogen, ammonia, and heat co-production. This invention proposes a tubular hydrogen-ammonia co-production system and method based on a proton conductor electrolyzer. This invention achieves switching between hydrogen-ammonia co-production mode, hydrogen-only mode, and ammonia-only mode through the linkage of various valves, enabling separate hydrogen production, separate ammonia production, or hydrogen-ammonia co-production. Production mode switching can be achieved through simple control, adapting to production schedules and improving utilization. Furthermore, this solution utilizes the characteristic of proton conduction electrolyzers having relatively low requirements for the stability of feed gas supply. Combined with a tubular proton conductor electrolyzer and an embedded structure integrating two layers of sealing material, this deeply couples green electricity hydrogen production and synthetic ammonia into a tubular hydrogen-ammonia co-production device based on a proton conductor electrolyzer, reducing investment and system complexity, decreasing unit product power consumption, and lowering overall power consumption.

[0007] On one hand, the present invention provides a tubular hydrogen-ammonia co-production device system based on a proton conductor electrolyzer, comprising: inner and outer nested tubular proton conductor electrolyzers, namely a first tubular proton conductor electrolyzer and a second tubular proton conductor electrolyzer, wherein the second tubular proton conductor electrolyzer is further nested with two layers of sealing material, and the tubular hydrogen-ammonia co-production device is divided into a first cavity, a second cavity, a third cavity and a fourth cavity;

[0008] Valve systems are used to control the switching between different modes and the output of different products;

[0009] A renewable energy power supply system is used to provide electricity to drive the electrolysis reaction in a proton conductor electrolyzer;

[0010] The circulating gas system, including a nitrogen circulating system and a hydrogen circulating system, is used to recycle unreacted nitrogen or hydrogen back to the tubular proton conductor electrolyzer for further reaction; the nitrogen circulating system includes an ammonia gas-liquid separator and a circulating gas pump;

[0011] The circulating water system, wherein the fourth chamber is a cooling circulating water layer, is used to maintain a constant temperature of the device;

[0012] An air separation nitrogen generation system, including an air separation nitrogen generation unit and a compressor, is responsible for generating nitrogen gas.

[0013] The steam system, including steam production equipment and compressor, is responsible for generating steam for high-temperature electrolysis.

[0014] Preferably, the valve system includes a first gate, a second gate, a third gate, and a fourth gate, and the switching between hydrogen-ammonia co-production mode, hydrogen production mode alone, and ammonia production mode alone is achieved by controlling the valve system.

[0015] Preferably, the hydrogen-ammonia co-production mode connects the anode and cathode of the tubular proton conductor electrolyzer to a renewable energy power supply system. High-pressure steam enters the anode through the first chamber, where an oxidation reaction occurs to generate oxygen and protons. The oxygen is discharged through the first chamber, while the protons pass through the electrolyte membrane to the cathode, where a reduction reaction occurs to generate hydrogen. Part of the hydrogen is transported through the second chamber to a hydrogen drying tower via the first valve, while the other part is transferred to the second tubular proton conductor electrolyzer to provide a proton source. Nitrogen is generated by an air separation nitrogen generator and enters the third chamber. In the second chamber, some of the hydrogen undergoes an oxidation reaction at the anode of the second tubular proton conductor electrolyzer to generate protons. The protons pass through the electrolyte membrane of the second tubular proton conductor electrolyzer to the cathode, where they react with nitrogen and electrons to generate a mixed gas. The ammonia is then separated by an ammonia gas-liquid separator and discharged through the third chamber via the second valve. The remaining mixed gas is pumped back into the third chamber for further reaction.

[0016] As a preferred option, the fourth gate is in the closed state under the hydrogen-ammonia co-production mode.

[0017] Preferably, in the standalone hydrogen production mode, the anode and cathode of the tubular proton conductor electrolyzer are connected to the renewable energy power supply system, respectively. The air separation nitrogen production system and nitrogen circulation system are shut down. The polarity of the current applied to the second tubular proton conductor electrolyzer is reversed and the fourth gate is opened. At the same time, a portion of the high-pressure steam flows to the first chamber, while another portion of the high-pressure steam flows to the third chamber through the fourth valve. An oxidation reaction occurs at the anode to generate oxygen and protons. The oxygen is discharged from the first and third chambers through the second valve. The protons pass through the electrolyte membrane to the cathode, where a reduction reaction occurs to generate hydrogen. The hydrogen is then transported to the hydrogen drying tower through the first valve and discharged.

[0018] Preferably, in the ammonia-only production mode, the anode and cathode of the tubular proton conductor electrolyzer are connected to a renewable energy power supply system, respectively. The outlet of the first valve is connected to a hydrogen pump. High-pressure steam flows into the first chamber, where an oxidation reaction occurs at the anode to generate oxygen and protons. The oxygen is discharged through the first chamber, while the protons pass through the electrolyte membrane to the cathode, where a reduction reaction occurs to generate hydrogen. The hydrogen is then transported from the second chamber to the hydrogen pump for recycling via the first valve. Simultaneously, the fourth valve is closed, and nitrogen is released through... <s>anode< / s> The third chamber enters the second tubular proton conductor electrolyzer. In the second chamber, some of the hydrogen gas undergoes an oxidation reaction at the anode of the second tubular proton conductor electrolyzer to generate protons. The protons pass through the electrolyte membrane of the second tubular proton conductor electrolyzer to reach the cathode. The protons react with nitrogen and electrons to generate a mixed gas. The ammonia gas is separated by an ammonia gas-liquid separator and discharged from the third chamber through the second valve. The remaining mixed gas enters the third chamber again through a circulating gas pump for further reaction.

[0019] Preferably, the fourth cavity is a cooling circulating water layer.

[0020] As a preferred option, the third valve is opened as needed to output hot water.

[0021] A tubular method for co-production of hydrogen and ammonia based on a proton conductor electrolyzer, applicable to the system, includes the following steps:

[0022] S1. Power from a renewable energy power supply system is used as support, and high-pressure steam and / or nitrogen are used as raw material inputs for the tubular proton conductor electrolyzer.

[0023] S2 controls or adjusts the input of S1, and selects the working mode of producing hydrogen alone, producing ammonia alone, or producing hydrogen and ammonia together as needed;

[0024] S3. Electrolysis and ammonia synthesis reactions are carried out through a tubular proton conductor electrolytic cell to generate hydrogen and ammonia.

[0025] S4. Collect the generated hydrogen, ammonia, and nitrogen using the circulating gas system and air separation nitrogen production system.

[0026] As a preferred option, the working mode for hydrogen-ammonia co-production in S2 includes the following steps:

[0027] Step 1: High-pressure steam is introduced into the anode of the first tubular proton conductor electrolytic cell, where an oxidation reaction occurs to generate oxygen and protons;

[0028] Step 2: Protons are transported through the electrolyte membrane to the cathode of the first tubular proton conductor electrolyzer, where a reduction reaction occurs to generate hydrogen gas;

[0029] Step 3: Hydrogen gas is diffused through the second chamber to the anode of the second electrolytic cell, where it undergoes an oxidation reaction to generate protons;

[0030] Step 4: Protons are transported to the cathode via the electrolyte in the second electrolyzer;

[0031] Step 5: Nitrogen gas is introduced into the cathode of the second tubular proton conductor electrolytic cell, where a reduction reaction occurs to generate nitrogen ions;

[0032] Step Six: At the cathode of the second tubular proton conductor electrolyzer, protons react with nitrogen ions and electrons to generate ammonia gas;

[0033] Step 7: Control the output of hydrogen, ammonia, and nitrogen through the valve system.

[0034] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0035] 1. This solution achieves switching between hydrogen-ammonia co-production mode, hydrogen-only production mode, and ammonia-only production mode through the linkage between various valves, enabling separate hydrogen production, separate ammonia production, or hydrogen-ammonia co-production. Traditional chemical methods for ammonia synthesis are difficult to start and stop, making flexible start-up and shutdown impossible. This invention achieves production mode switching through simple control, adapting to production schedules, improving utilization, and facilitating large-scale promotion and application.

[0036] 2. This solution improves the tolerance of ammonia synthesis to the volatility of renewable energy: Unlike traditional green hydrogen ammonia synthesis methods, which use electricity to produce hydrogen in an electrolyzer and then feed it into a chemical synthesis tower to catalytically generate ammonia, with hydrogen production and ammonia production being separate processes, the chemical process requires high stability of the hydrogen source. This invention deeply couples green electricity hydrogen production and ammonia synthesis into a single system. The hydrogen production rate determines the ammonia production rate, avoiding the high hydrogen stability requirements of traditional chemical synthesis.

[0037] 3. This scheme deeply couples green electricity hydrogen production and ammonia synthesis into a tubular hydrogen-ammonia co-production unit based on a proton conductor electrolyzer, reducing investment and system complexity. Traditional methods of producing hydrogen through water electrolysis followed by chemical ammonia synthesis require a high degree of stability in the supply of green hydrogen. Furthermore, traditional chemical ammonia synthesis involves the reaction of hydrogen and nitrogen under specific temperature, pressure, atmosphere, and catalyst conditions to produce ammonia, requiring a constant ratio of each component. Significant variations in the hydrogen supply necessitate adjustments to the reaction conditions; otherwise, product quality and yield will be affected, potentially leading to safety risks. However, in practice, adjusting reaction conditions in large-scale chemical synthesis towers is difficult and time-consuming, necessitating the installation of numerous hydrogen storage tanks as a buffer. This invention employs a completely different technical approach. The proton conduction electrolyzer has lower requirements for the stability of the feed gas supply, an inherent characteristic of this technology. Supplying feed gas initiates ammonia synthesis, and stopping the feed gas supply stops ammonia production without causing harmful effects on the system.

[0038] 4. This solution uses a tubular hydrogen-ammonia co-production unit based on a proton conductor electrolyzer to deeply couple green electricity hydrogen production and ammonia synthesis, which greatly reduces the project's footprint. As mentioned earlier, this system reduces the project's footprint compared to the complex system structure of traditional water electrolysis for hydrogen production and ammonia synthesis.

[0039] 5. This solution utilizes a tubular hydrogen-ammonia co-production device based on a proton conductor electrolyzer, avoiding heat loss in individual sections and improving system energy utilization efficiency. In traditional water electrolysis for hydrogen production and ammonia synthesis, hydrogen production and ammonia production are separate processes, and the heat from ammonia synthesis cannot be used for hydrogen production, resulting in energy waste. This invention uses the heat from the hydrogen production section to supply ammonia production, achieving multiple energy utilization and higher efficiency.

[0040] 6. This scheme deeply couples water electrolysis for hydrogen production and ammonia synthesis, reducing the power consumption per unit product by 50%, which helps to lower costs. The 50% reduction is relative to using two separate units: one for water electrolysis to produce hydrogen and the other for ammonia electrolysis. If hydrogen production and ammonia production are separated into two parts, the heat required to maintain the normal operation of the unit is doubled. By combining them into one unit, the same amount of heat can be supplied to both reactions simultaneously, reducing heat consumption by half, and thus reducing the power consumption for maintaining the heat by half. Attached Figure Description

[0041] Figure 1 This is a schematic diagram of the device of the present invention;

[0042] Figure 2 This is a three-dimensional schematic diagram of the device of the present invention;

[0043] Figure 3 This is a schematic diagram illustrating the working principle of the system of the present invention.

[0044] The following are explanations of the reference numerals in the attached figures:

[0045] 1. First cavity; 2. Second cavity; 3. Third cavity; 4. Fourth cavity. Detailed Implementation

[0046] Example 1: As Figure 1 - Figure 3 As shown, the tubular hydrogen-ammonia co-production unit system based on a proton conductor electrolyzer (PCEC) uses a PCEC as the main body. A first layer of PCEC is nested within a second layer of PCEC, which are respectively the first and second tubular PCECs. Two layers of sealing material are nested within the second layer of PCEC, thus forming the nested tubular proton conductor electrolyzers of the hydrogen-ammonia co-production unit. Figure 1 As shown, the tubular hydrogen-ammonia co-production unit is divided into a first chamber 1, a second chamber 2, a third chamber 3, and a fourth chamber 4; this unit is combined with a renewable energy power supply system, a steam supply system, a valve system, a circulating gas system, a circulating water system, an air separation nitrogen production system, and a gas-liquid separation system to form a hydrogen-ammonia co-production system;

[0047] Specifically, the system includes a steam supply system, consisting of a water source, steam production equipment, and a compressor; a valve system for controlling the switching of different modes and the output of different products; a renewable energy power supply system to provide electricity to drive the proton conductor electrolyzer for electrolysis; and a circulating gas system, including a nitrogen circulation system and a hydrogen circulation system, for circulating unreacted nitrogen or hydrogen back to the tubular proton conductor electrolyzer for further reaction; the nitrogen circulation system includes an ammonia gas-liquid separator and a circulating gas pump; such as... Figure 1As shown, the circulating water system includes a fourth chamber 4, which is a cooling circulating water layer used to maintain a constant temperature in the device; a gas-liquid separation system, used to separate ammonia and nitrogen; and an air separation nitrogen generation system, including an air separation nitrogen generation unit, a compressor, an ammonia-liquid separator, and a circulating gas pump, which is responsible for generating hydrogen.

[0048] The valve system includes a first gate, a second gate, a third gate, and a fourth gate. By controlling the valve system, the switching between hydrogen-ammonia co-production mode, hydrogen-only production mode, and ammonia-only production mode can be achieved.

[0049] It should be noted that the hydrogen-ammonia cogeneration mode is achieved by connecting the anode and cathode of the tubular proton conductor electrolyzer to the renewable energy power supply system respectively. High-pressure steam enters the first chamber 1 through the anode, where an oxidation reaction occurs to generate oxygen and protons. The oxygen is discharged through the first chamber 1, as shown in reaction formula (1).

[0050] (1)

[0051] Protons pass through the electrolyte membrane to the cathode, where a reduction reaction occurs to generate hydrogen gas, as shown in reaction (2).

[0052] (2)

[0053] One part of the hydrogen gas is transported from the second chamber 2 to the hydrogen drying tower through the first valve and discharged, while the other part of the hydrogen gas is transferred to the second tubular proton conductor electrolyzer to provide a proton source; nitrogen gas enters the second tubular proton conductor electrolyzer through the cathode, and some of the hydrogen gas in the second chamber 2 undergoes an oxidation reaction at the anode of the second tubular proton conductor electrolyzer to generate protons, as shown in reaction (3).

[0054] (3)

[0055] Protons pass through the electrolyte membrane of the second tubular proton conductor electrolyzer to reach the cathode. The protons react with nitrogen and electrons to generate a mixed gas. The ammonia gas is separated by the ammonia gas-liquid separator and discharged through the second valve in the third chamber 3. The reaction formula is shown in formula (4).

[0056] (4)

[0057] The remaining mixed gas enters the third chamber 3 via a circulating gas pump for further reaction. In the hydrogen-ammonia co-production mode, the fourth gate is closed.

[0058] The proton conductor electrolyzer operates at temperatures between 450-650℃. Using two layers of electrolyzers allows for efficient heat utilization. However, ammonia is unstable within this temperature range and decomposes into nitrogen and hydrogen. Therefore, a fourth chamber (4) with an insulated water layer is incorporated, with a maximum temperature of 100℃. This design creates a temperature gradient of 550-100℃ within the third chamber (3). The high-temperature region near the second electrolyzer layer facilitates ammonia electrolysis, while the low-temperature region near the insulated water layer helps maintain ammonia stability and prevent decomposition. Simultaneously, the proton conductor electrolyzer avoids heat loss in isolated areas, improving system energy efficiency and making energy use more efficient. In traditional water electrolysis for hydrogen production and ammonia synthesis, hydrogen production and ammonia production are separate processes, and the heat from ammonia synthesis cannot be used for hydrogen production, resulting in energy waste. This invention uses the heat from the hydrogen production portion to supply ammonia production, achieving multiple energy utilization, reducing unit power consumption, and increasing efficiency.

[0059] Regarding the reduction in unit power consumption, power consumption is reduced by 50%. This 50% is relative to two separate units: one for hydrogen production by electrolyzing water in a proton conductor electrolyzer and the other for ammonia production by electrolysis in a proton conductor electrolyzer. If hydrogen production and ammonia production are separated into two parts, the heat required to maintain the normal operation of the unit is doubled. When combined into one unit, the same amount of heat can be supplied to both reactions simultaneously. With the heat consumption reduced by half, the power consumption to maintain the heat is also reduced by half.

[0060] In the standalone hydrogen production mode, the anode and cathode of the tubular proton conductor electrolyzer are connected to the renewable energy power supply system, respectively. The air separation nitrogen production system and nitrogen circulation system are shut down. The polarity of the current applied to the second tubular proton conductor electrolyzer is reversed and the fourth gate is opened. At the same time, a portion of the high-pressure steam flows to the first chamber 1, while another portion of the high-pressure steam flows to the third chamber 3 through the fourth valve. An oxidation reaction occurs at the anode to generate oxygen and protons. The oxygen is discharged from the first chamber 1 and the third chamber 3 through the second valve. The protons pass through the electrolyte membrane to the cathode, where a reduction reaction occurs to generate hydrogen. All the hydrogen is generated in the second chamber 2 and is then transported to the hydrogen drying tower through the first valve before being discharged.

[0061] In the standalone ammonia production mode, the anode and cathode of the tubular proton conductor electrolyzer are connected to the renewable energy power supply system, respectively. The outlet of the first valve is connected to the hydrogen pump. High-pressure steam flows to the first chamber 1, where an oxidation reaction occurs at the anode to generate oxygen and protons. The oxygen is discharged through the first chamber 1, and the protons pass through the electrolyte membrane to the cathode, where a reduction reaction occurs to generate hydrogen. The hydrogen is then transported to the hydrogen pump for recycling through the second chamber 2 via the first valve. At the same time, the fourth valve is closed, and nitrogen enters the second tubular proton conductor electrolyzer through the cathode. In the second chamber 2, some of the hydrogen undergoes an oxidation reaction at the anode to generate protons. The protons pass through the electrolyte membrane of the second tubular proton conductor electrolyzer to the cathode, where they react with nitrogen and electrons to generate a mixed gas. The ammonia is separated by an ammonia gas-liquid separator and discharged through the third chamber 3 via the second valve. The remaining mixed gas enters the third chamber 3 again via a circulating gas pump for further reaction.

[0062] In the combined hydrogen and ammonia production mode, the hydrogen production mode alone, and the ammonia production mode alone, the third valve opens as needed to output hot water.

[0063] This solution achieves switching between hydrogen-ammonia co-production, hydrogen-only production, and ammonia-only production modes through the linkage of various valves, enabling separate hydrogen production, separate ammonia production, or hydrogen-ammonia co-production. Traditional chemical methods for ammonia synthesis are difficult to start and stop, making flexible start-up and shutdown impossible. This invention enables production mode switching through simple control, adapting to production schedules, improving utilization, and facilitating large-scale application.

[0064] This application also provides a tubular method for co-producing hydrogen and ammonia based on a proton conductor electrolyzer, comprising the following steps:

[0065] S1. Power from a renewable energy power supply system is used as support, and high-pressure steam and / or nitrogen are used as raw material inputs for the tubular proton conductor electrolyzer.

[0066] S2 controls or adjusts the input of S1, selecting the operating mode for hydrogen production alone, ammonia production alone, or combined hydrogen and ammonia production as needed; the combined hydrogen and ammonia production operating mode includes the following steps:

[0067] Step 1: High-pressure steam is introduced into the anode of the first tubular proton conductor electrolytic cell, where an oxidation reaction occurs to generate oxygen and protons;

[0068] Step 2: Protons are transported through the electrolyte membrane to the cathode of the first tubular proton conductor electrolyzer, where a reduction reaction occurs to generate hydrogen gas;

[0069] Step 3: Hydrogen gas is diffused through the second chamber to the anode of the second electrolytic cell, where it undergoes an oxidation reaction to generate protons;

[0070] Step 4: Protons are transported to the cathode via the electrolyte in the second electrolyzer;

[0071] Step 5: Nitrogen gas is introduced into the cathode of the second tubular proton conductor electrolytic cell, where a reduction reaction occurs to generate nitrogen ions;

[0072] Step Six: At the cathode of the second tubular proton conductor electrolyzer, protons react with nitrogen ions and electrons to generate ammonia gas;

[0073] Step 7: Control the output of hydrogen, ammonia, and nitrogen through the valve system.

[0074] S3. Electrolysis and ammonia synthesis reactions are carried out through a tubular proton conductor electrolytic cell to generate hydrogen and ammonia.

[0075] S4. Collect the generated hydrogen, ammonia, and nitrogen using a circulating gas system, an air separation nitrogen production system, and a gas-liquid separation system.

[0076] Traditional methods for producing hydrogen through water electrolysis, followed by ammonia synthesis, require a high degree of stability in the supply of green hydrogen. Furthermore, in these methods, hydrogen is produced via an electrolyzer and then fed into a chemical synthesis tower for catalytic ammonia production. Hydrogen and ammonia production are separate processes, making the chemical process highly dependent on the stability of the hydrogen source. Simultaneously, traditional ammonia synthesis involves the reaction of hydrogen and nitrogen under specific temperature, pressure, atmosphere, and catalyst conditions, requiring a constant ratio of components. Significant fluctuations in the hydrogen supply necessitate adjustments to the reaction conditions; otherwise, product quality and yield will be affected, potentially leading to safety risks. However, in practice, adjusting reaction conditions in large-scale chemical synthesis towers is difficult and time-consuming, necessitating the installation of numerous hydrogen storage tanks as a buffer.

[0077] This application employs a completely different technical approach. The proton conduction electrolyzer has relatively low requirements for the stability of the feed gas supply, an inherent characteristic of this technology. Supplying feed gas initiates ammonia synthesis, and stopping the feed gas supply ceases ammonia production without causing any harmful effects on the system. Furthermore, this scheme utilizes a tubular hydrogen-ammonia co-production unit based on a proton conductor electrolyzer, deeply coupling green electricity hydrogen production and ammonia synthesis, significantly reducing the project's footprint. As mentioned earlier, this system reduces the project's land area compared to the complex system structure of traditional water electrolysis for hydrogen production and ammonia synthesis.

[0078] Example 2: Producing 20,000 Nm per hour 3 Taking a hydrogen and 5-ton liquid ammonia project as an example (excluding power substation and hydrogen / ammonia storage), the estimated land area for this application compared to traditional methods is shown in Table 1:

[0079]

[0080] The invention occupies an area of ​​55.65m². 2 (Bloom Energy 600Nm) 3 / h solid oxide electrolytic cell area) × 33 = 2.8 mu

[0081] Traditional alkaline electrolytic cell + chemical ammonia synthesis occupies 120m² 2 (1000Nm) 3 (Land area of ​​alkaline electrolytic cell) × 20 + 800m 2 (A 5-ton / hour chemical synthesis tower occupies 4.8 acres)

[0082] The power consumption of this invention is equal to the power consumption of hydrogen production via solid oxide electrolysis (3.7 kWh / Nm³). 3 ×20000Nm 3 / h+ Ammonia production in a solid oxide electrolyzer consumes 3kWh / Nm 3 ×13130Nm 3 / h=113390kWh=113.39MWh.

[0083] The combined power consumption of a traditional alkaline electrolyzer and chemical ammonia synthesis equals the power consumption of an alkaline electrolyzer for hydrogen production (5 kWh / Nm³). 3 ×20000Nm 3 / h+ Chemical ammonia synthesis power consumption 2kWh / Nm 3 ×13130Nm 3 / h+ The electricity required to maintain the temperature of chemical ammonia synthesis at 500℃ is 5389kWh=131649kWh=131.65MWh.

[0084] It can be seen that this scheme, through the design of a tubular hydrogen-ammonia co-production unit based on a proton conductor electrolyzer, deeply couples green electricity hydrogen production and ammonia synthesis, greatly reducing the project's footprint. Compared with the complex system structure of traditional water electrolysis for hydrogen production and ammonia synthesis, this system can reduce the project's footprint.

Claims

1. A tubular hydrogen-ammonia co-production unit system based on a proton conductor electrolyzer, characterized in that, include: The inner and outer nested tubular proton conductor electrolyzers are respectively the first tubular proton conductor electrolyzer and the second tubular proton conductor electrolyzer. The second tubular proton conductor electrolyzer is further nested with two layers of sealing material. The tubular hydrogen-ammonia co-production device is divided into the first chamber (1), the second chamber (2), the third chamber (3) and the fourth chamber (4). Valve systems are used to control the switching between different modes and the output of different products; A renewable energy power supply system is used to provide electricity to drive the electrolysis reaction in a proton conductor electrolyzer; The circulating gas system, including a nitrogen circulating system and a hydrogen circulating system, is used to recycle unreacted nitrogen or hydrogen back to the tubular proton conductor electrolyzer for further reaction; the nitrogen circulating system includes an ammonia gas-liquid separator and a circulating gas pump; The circulating water system, wherein the fourth cavity (4) is a cooling circulating water layer, is used to maintain a constant temperature of the device; An air separation nitrogen generation system, including an air separation nitrogen generation unit and a compressor, is responsible for generating nitrogen gas. The steam system, including steam production equipment and compressor, is responsible for generating steam for high-temperature electrolysis; The valve system includes a first gate, a second gate, a third gate, and a fourth gate. By controlling the valve system, the switching between hydrogen-ammonia co-production mode, hydrogen-only production mode, and ammonia-only production mode can be achieved.

2. The tubular hydrogen-ammonia co-production unit system based on a proton conductor electrolyzer according to claim 1, characterized in that, The hydrogen-ammonia co-production mode connects the anode and cathode of the tubular proton conductor electrolyzer to the renewable energy power supply system. High-pressure steam enters the anode through the first chamber (1), where an oxidation reaction occurs to generate oxygen and protons. The oxygen is discharged through the first chamber (1), and the protons pass through the electrolyte membrane to the cathode, where a reduction reaction occurs to generate hydrogen. Part of the hydrogen is transported to the hydrogen drying tower through the first valve in the second chamber (2), and the other part is transferred to the second tubular proton conductor electrolyzer to provide a proton source. Nitrogen is generated by the air separation nitrogen generator and enters the third chamber (3). Part of the hydrogen in the second chamber (2) undergoes an oxidation reaction at the anode of the second tubular proton conductor electrolyzer to generate protons. The protons pass through the electrolyte membrane of the second tubular proton conductor electrolyzer to the cathode. The protons react with nitrogen and electrons to generate a mixed gas, which is then separated by an ammonia gas-liquid separator. The ammonia is discharged through the second valve in the third chamber (3), and the remaining mixed gas enters the third chamber (3) again through a circulating gas pump for further reaction.

3. The tubular hydrogen-ammonia co-production unit system based on a proton conductor electrolyzer according to claim 2, characterized in that, In the hydrogen-ammonia co-production mode, the fourth gate is in the closed state.

4. The tubular hydrogen-ammonia co-production unit system based on a proton conductor electrolyzer according to claim 1, characterized in that, In the standalone hydrogen production mode, the anode and cathode of the tubular proton conductor electrolyzer are connected to the renewable energy power supply system, respectively. The air separation nitrogen production system and nitrogen circulation system are shut down. The polarity of the current applied to the second tubular proton conductor electrolyzer is reversed and the fourth gate is opened. At the same time, a part of the high-pressure steam flows to the first chamber (1) and another part of the high-pressure steam flows to the third chamber (3) through the fourth valve. Oxidation reaction occurs at the anode to generate oxygen and protons. Oxygen is discharged from the first chamber (1) and the third chamber (3) through the second valve. Protons reach the cathode through the electrolyte membrane and undergo reduction reaction at the cathode to generate hydrogen. Hydrogen is transported to the hydrogen drying tower through the first valve and then discharged.

5. The tubular hydrogen-ammonia co-production unit system based on a proton conductor electrolyzer according to claim 1, characterized in that, In the ammonia production mode, the anode and cathode of the tubular proton conductor electrolyzer are connected to the renewable energy power supply system respectively. The outlet of the first valve is connected to the hydrogen pump. High-pressure steam flows to the first chamber (1). Oxidation reaction occurs at the anode to generate oxygen and protons. Oxygen is discharged through the first chamber (1). Protons pass through the electrolyte membrane to the cathode and undergo reduction reaction to generate hydrogen. Hydrogen is transported from the second chamber (2) to the hydrogen pump for recycling through the first valve. At the same time, the fourth valve is closed. Nitrogen enters the second tubular proton conductor electrolyzer through the anode third chamber (3). Part of the hydrogen in the second chamber (2) undergoes oxidation reaction at the anode of the second tubular proton conductor electrolyzer to generate protons. The protons pass through the electrolyte membrane of the second tubular proton conductor electrolyzer to the cathode. The protons react with nitrogen and electrons to generate a mixed gas. Ammonia is separated by an ammonia gas-liquid separator and discharged from the third chamber (3) through the second valve. The remaining mixed gas enters the third chamber (3) again through the circulating gas pump for further reaction.

6. The tubular hydrogen-ammonia co-production unit system based on a proton conductor electrolyzer according to claim 1, characterized in that, The fourth cavity (4) is a cooling circulating water layer.

7. The tubular hydrogen-ammonia co-production unit system based on a proton conductor electrolyzer according to claim 1, characterized in that, The third valve opens as needed to output hot water.

8. A tubular hydrogen-ammonia co-production method based on a proton conductor electrolyzer, applicable to the system described in any one of claims 1-7, characterized in that, Includes the following steps: S1. Power from a renewable energy power supply system is used as support, and high-pressure steam and / or nitrogen are used as raw material inputs for the tubular proton conductor electrolyzer. S2 controls or adjusts the input of S1, and selects the working mode of producing hydrogen alone, producing ammonia alone, or producing hydrogen and ammonia together as needed; S3. Electrolysis and ammonia synthesis reactions are carried out through a tubular proton conductor electrolytic cell to generate hydrogen and ammonia. S4. Collect the generated hydrogen, ammonia, and nitrogen using the circulating gas system and air separation nitrogen production system.

9. The tubular hydrogen-ammonia co-production method based on a proton conductor electrolyzer according to claim 8, characterized in that, The working mode of hydrogen-ammonia co-production in S2 includes the following steps: Step 1: High-pressure steam is introduced into the anode of the first tubular proton conductor electrolytic cell, where an oxidation reaction occurs to generate oxygen and protons; Step 2: Protons are transported through the electrolyte membrane to the cathode of the first tubular proton conductor electrolyzer, where a reduction reaction occurs to generate hydrogen gas; Step 3: Hydrogen gas is diffused through the second chamber (2) to the anode of the second electrolytic cell, where it undergoes an oxidation reaction to generate protons; Step 4: Protons are transported to the cathode via the electrolyte in the second electrolyzer; Step 5: Nitrogen gas is introduced into the cathode of the second tubular proton conductor electrolytic cell, where a reduction reaction occurs to generate nitrogen ions; Step Six: At the cathode of the second tubular proton conductor electrolyzer, protons react with nitrogen ions and electrons to generate ammonia gas; Step 7: Control the output of hydrogen, ammonia, and nitrogen through the valve system.

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