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

Abstract

The invention 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. Comprising a valve system, a circulating gas system, a circulating water system, an air separation nitrogen generation system and a gas-liquid separation system, switching of a hydrogen-ammonia co-production mode, an independent hydrogen production mode and an independent ammonia production mode is achieved through linkage of all the valves, independent hydrogen production, independent ammonia production or hydrogen-ammonia co-production can be achieved, production mode switching can be achieved through simple control, production arrangement is adapted, and the utilization rate is increased; in addition, according to the scheme, the characteristic that the proton conduction electrolytic cell has low requirement on feed gas supply stability is utilized, and the tubular proton conductor electrolytic cell and a nested structure integrated by two layers of sealing materials are combined, so that 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; investment and system complexity are reduced, power consumption of unit products is reduced, and power consumption is reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field of solid oxide electrolyzers, and in particular relates to a tubular hydrogen-ammonia cogeneration device system and method based on a proton conductor electrolyzer. Background Art

[0002] In recent years, the global energy supply and demand structure, trade structure, transformation rhythm, and price system have all faced profound adjustments. With a high degree of external dependence on crude oil and natural gas, energy security and supply are still under great pressure.

[0003] Under the dual requirements of "energy security" and "dual carbon goals", hydrogen energy has become an important direction for the green and low-carbon transformation of global energy, and an important technical route for achieving "energy security" and "dual carbon goals". In 2023, the hydrogen production will be 35 million tons, of which 99% will be hydrogen produced from fossil energy and industrial by-product hydrogen, and the proportion of hydrogen produced from renewable energy will be less than 1%. According to relevant estimates, it is expected that hydrogen consumption will reach 120 million tons or more in 2060, of which green hydrogen will account for 100 million tons.

[0004] Renewable energy hydrogen production uses wind and solar power and other renewable energy power generation to drive water electrolysis hydrogen production equipment to produce green hydrogen, including proton exchange membrane electrolyzer hydrogen production, alkaline water hydrogen production, solid oxide electrolyzer hydrogen production, etc. Using green hydrogen as raw material to produce green ammonia can not only solve the problem of hydrogen storage and transportation but also promote hydrogen consumption. It is an important part of building a hydrogen-based energy society. At present, wind and solar power hydrogen storage ammonia projects are basically wind and solar power to produce green electricity. Green electricity is used to produce green hydrogen through electrolyzers. Green hydrogen is passed through hydrogen storage devices to provide a stable hydrogen source for the chemical synthesis ammonia device in the rear. The entire system has high requirements for the stability of hydrogen and wind and solar power, and the system composition is complex.

[0005] At present, there are few reports on the device system and method for achieving the co-production of hydrogen, ammonia and heat with a set of devices. Patent name: A system and method for the joint preparation of green hydrogen and green ammonia, application number: CN202311504174.7, this application When the oxygen carrier reaction chamber is heated to the first reaction temperature, the oxygen carrier generates intermediate oxygen products and oxygen, and the nitrogen carrier reaction chamber is heated by the heated oxygen carrier reaction chamber to the second reaction temperature, and the nitrogen carrier reacts with nitrogen to generate intermediate nitrogen products; when the oxygen carrier reaction chamber is no longer heated and gradually cools down to the third reaction temperature, the intermediate oxygen product reacts with water to generate oxygen carrier and hydrogen, and the nitrogen carrier reaction chamber is heated by the no longer heated oxygen carrier reaction chamber to the fourth reaction temperature, and the intermediate nitrogen product reacts with hydrogen to generate nitrogen carrier and ammonia. This application designs the above system, uses water and nitrogen as raw materials, and uses the high-temperature heat energy provided by renewable energy to simultaneously prepare hydrogen and ammonia without generating by-products. However, this reaction system has many components and is complex as a whole, and it is also impossible to regulate the reaction mode. Summary of the invention

[0006] The purpose of the present invention is to address the problem that the existing devices for simultaneously achieving the cogeneration of hydrogen, ammonia and heat have many system components and are complex as a whole. The present invention proposes a tubular hydrogen-ammonia cogeneration device system and method based on a proton conductor electrolyzer. The present invention realizes the switching of the hydrogen-ammonia cogeneration mode, the single hydrogen production mode and the single ammonia production mode through the linkage between various valves, and can achieve single hydrogen production, single ammonia production or hydrogen-ammonia cogeneration. The production mode conversion can be achieved through simple control, which adapts to production arrangements and improves utilization rate. In addition, this scheme utilizes the characteristic of proton conduction electrolyzers that the stability of raw gas supply is not high, and combines the tubular proton conductor electrolyzer and the nested structure integrated with two layers of sealing materials. By deeply coupling green electricity hydrogen production and synthetic ammonia into a tubular hydrogen-ammonia cogeneration device based on a proton conductor electrolyzer, the investment and system complexity are reduced, and the power consumption per unit product is reduced.

[0007] On the one hand, the present invention provides a tubular hydrogen-ammonia cogeneration device system based on a proton conductor electrolyzer, comprising: a tubular proton conductor electrolyzer nested inside and outside, respectively a first tubular proton conductor electrolyzer and a second tubular proton conductor electrolyzer, two layers of sealing material are further nested outside the second tubular proton conductor electrolyzer, and the tubular hydrogen-ammonia cogeneration device is divided into a first cavity, a second cavity, a third cavity and a fourth cavity; Valve system, used to control the switching of different modes and the output of different products; A renewable energy power supply system for providing power to drive a proton conductor electrolyzer to perform an electrolysis reaction; A circulating gas system, including a nitrogen circulating system and a hydrogen circulating system, for circulating the incompletely reacted 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; Circulating water system, the fourth cavity is a cooling circulating water layer, which is used to maintain a constant temperature of the device; The air separation nitrogen production system, including the air separation nitrogen production device and the compressor, is responsible for producing nitrogen.

[0008] The steam system, including the steam production unit and the compressor, is responsible for generating steam for high-temperature electrolysis.

[0009] Preferably, the valve system includes a first gate, a second gate, a third gate and a fourth gate, and switching among a hydrogen-ammonia co-production mode, a hydrogen production mode alone and an ammonia production mode alone is achieved by controlling the valve system.

[0010] Preferably, the hydrogen-ammonia cogeneration mode is that the anode and cathode of the tubular proton conductor electrolyzer are respectively connected to the renewable energy power supply system, high-pressure steam enters the anode through the first cavity, an oxidation reaction occurs at the anode to generate oxygen and protons, the oxygen is discharged through the first cavity, the protons reach the cathode through the electrolyte membrane, and a reduction reaction occurs at the cathode to generate hydrogen, wherein a part of the hydrogen is transported from the second cavity through the first valve to the hydrogen drying tower for discharge, and the other part of the hydrogen is transferred to the second tubular proton conductor electrolyzer to provide a proton source; nitrogen is generated by the air separation nitrogen production device and enters the third cavity, part of the hydrogen in the second cavity 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 and separate ammonia through an ammonia gas-liquid separator, the ammonia is discharged from the third cavity through the second valve, and the remaining mixed gas enters the third cavity through the circulating air pump to react again.

[0011] Preferably, the fourth gate is in a closed state in the hydrogen-ammonia cogeneration mode.

[0012] Preferably, in the single hydrogen production mode, the anode and cathode of the tubular proton conductor electrolyzer are respectively connected to the renewable energy power supply system, the air separation nitrogen production system and the nitrogen circulation system are closed, the positive and negative current applied to the second tubular proton conductor electrolyzer is reversed and the fourth gate is opened, while a part of the high-pressure steam flows to the first cavity, the other part of the high-pressure steam flows to the third cavity through the fourth valve, an oxidation reaction occurs at the anode to generate oxygen and protons, the oxygen is discharged from the first cavity and the third cavity through the second valve, the protons reach the cathode through the electrolyte membrane, a reduction reaction occurs at the cathode to generate hydrogen, the hydrogen is transported to the hydrogen drying tower through the first valve and then discharged.

[0013] Preferably, in the single ammonia production mode, the anode and cathode of the tubular proton conductor electrolyzer are respectively connected to the renewable energy power supply system, the outlet of the first valve is connected to the hydrogen pump, and the high-pressure steam flows to the first cavity, an oxidation reaction occurs at the anode to generate oxygen and protons, the oxygen is discharged through the first cavity, the protons pass through the electrolyte membrane to the cathode, and a reduction reaction occurs at the cathode to generate hydrogen, wherein the hydrogen is transported from the second cavity to the hydrogen pump through the first valve for recycling, and the fourth valve is closed at the same time, and nitrogen enters the second tubular proton conductor electrolyzer through the third cavity of the anode, part of the hydrogen in the second cavity undergoes an oxidation reaction at the anode of the second tubular proton conductor electrolyzer to generate protons, and 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, and the ammonia is separated by the ammonia gas-liquid separator and discharged from the third cavity through the second valve, and the remaining mixed gas enters the third cavity through the circulating gas pump to react again.

[0014] Preferably, the fourth cavity is a cooling circulating water layer.

[0015] Preferably, the third valve is opened to output hot water as needed.

[0016] A tubular hydrogen-ammonia cogeneration method based on a proton conductor electrolyzer is applicable to a system, comprising 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 input for a tubular proton conductor electrolyzer; S2, control or adjust the input of S1, and select the working mode of single hydrogen production, single ammonia production or hydrogen-ammonia co-production according to the needs; S3, performing electrolysis reaction and ammonia synthesis reaction in a tubular proton conductor electrolyzer to generate hydrogen and ammonia; S4. Use the circulating gas system and air separation nitrogen production system to collect the generated hydrogen, ammonia and nitrogen.

[0017] Preferably, in S2, the working mode of hydrogen-ammonia cogeneration includes the following steps: Step 1: High-pressure steam is input into the anode of the first tubular proton conductor electrolyzer, and an oxidation reaction occurs at the anode to generate oxygen and protons; Step 2: transporting protons to the cathode of the first tubular proton conductor electrolyzer through the electrolyte membrane, causing a reduction reaction to generate hydrogen; Step 3: Diffusing hydrogen through the second cavity to the anode of the second electrolytic cell, causing an oxidation reaction to generate protons; Step 4: transporting protons to the cathode through the second electrolyzer electrolyte; Step 5: nitrogen is introduced into the cathode of the second tubular proton conductor electrolyzer, where a reduction reaction occurs to generate nitrogen ions; Step 6: At the cathode of the second tubular proton conductor electrolyzer, the protons react with the nitrogen ions and the electrons to generate ammonia gas; Step 7: Control the output of hydrogen, ammonia and nitrogen through the valve system.

[0018] Compared with the prior art, the present invention has the following beneficial effects: 1. This solution realizes the switching of hydrogen-ammonia co-production mode, single hydrogen production mode and single ammonia production mode through the linkage between various valves, and can realize single hydrogen production, single ammonia production or hydrogen-ammonia co-production. The traditional chemical method of synthetic ammonia is difficult to start and stop, and it is impossible to realize flexible start and stop. The present invention can realize the conversion of production mode through simple control, adapt to production arrangements, improve utilization rate, and is conducive to large-scale promotion and utilization.

[0019] 2. This solution improves the tolerance of synthetic ammonia to the volatility of renewable energy: Unlike the traditional green hydrogen ammonia synthesis method, the traditional method uses electricity to produce hydrogen through an electrolyzer and then inputs it into a chemical synthesis tower for catalytic production of ammonia. The hydrogen production and ammonia production are separate parts, and the chemical part has high requirements for the stability of the hydrogen source. The present invention deeply couples green electricity hydrogen production and synthetic ammonia, integrating them into a system. The hydrogen output determines the ammonia output, avoiding the high stability requirements of hydrogen for traditional chemical synthesis.

[0020] 3. This scheme reduces investment and system complexity by deeply coupling green electricity hydrogen production and synthetic ammonia into a tubular hydrogen-ammonia co-production device based on a proton conductor electrolyzer. The traditional method of electrolyzing water to produce hydrogen and then synthesizing ammonia through chemical industry has high requirements for the stability of green hydrogen supply. At the same time, the traditional chemical synthesis ammonia method makes hydrogen and nitrogen react to generate ammonia under a certain temperature, pressure, atmosphere and catalyst, requiring the proportion of each component to remain constant. If the hydrogen supply changes greatly, the reaction conditions need to be adjusted, otherwise it will affect the product quality and yield and even cause safety risks. However, in actual operation, it is difficult and time-consuming to adjust the reaction conditions of large chemical synthesis towers, so a large number of hydrogen storage tanks need to be set up as buffers. The present invention adopts a completely different technical route. The proton conduction electrolyzer does not require high stability relative to the raw gas supply. This is an inherent feature of this technology. When the raw gas is supplied, ammonia synthesis begins. Stopping the supply of raw gas will not have a harmful effect on the system while stopping the production of ammonia.

[0021] 4. This scheme deeply couples green electricity hydrogen production and synthetic ammonia through the design of a tubular hydrogen-ammonia cogeneration device based on a proton conductor electrolyzer, greatly reducing the size of the project. As mentioned earlier, this system can reduce the project's footprint compared to the complex system structure of traditional water electrolysis to produce hydrogen and then synthesize ammonia.

[0022] 5. This solution avoids heat loss in a single part by designing a tubular hydrogen-ammonia cogeneration device based on a proton conductor electrolyzer, improves the energy utilization efficiency of the system, and makes energy use more efficient. In the traditional electrolysis of water to produce hydrogen and ammonia, hydrogen production and ammonia production are separated into different parts, and the heat of ammonia synthesis cannot be supplied to hydrogen production, resulting in energy waste. In the present invention, the heat of the hydrogen production part is supplied to ammonia production, and energy is used in multiple ways, which is more efficient.

[0023] 6. This scheme deeply couples the production of hydrogen by water electrolysis and the synthesis of ammonia, which reduces the power consumption per unit product by 50%, which is beneficial to reducing costs. The 50% is relative to the use of two sets of devices, namely, the use of proton conductor electrolyzers to first electrolyze water to produce hydrogen and the use of proton conductor electrolyzers to electrolyze ammonia. If the hydrogen production and ammonia production are divided into two parts, the heat required to maintain the normal operation of the device is doubled. After being combined into one set of devices, the same heat can be supplied to two reactions at the same time, and the heat consumption is reduced by half, and the power consumption for maintaining the heat is reduced by half. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a schematic diagram of the device of the present invention; Figure 2 It is a three-dimensional schematic diagram of the device of the present invention; Figure 3 It is a schematic diagram of the working principle of the system of the present invention.

[0025] Wherein, the accompanying drawings are described as follows: 1. The first cavity; 2. The second cavity; 3. The third cavity; 4. The fourth cavity. DETAILED DESCRIPTION

[0026] Example 1: Figure 1 - Figure 3 As shown in the figure, the tubular hydrogen-ammonia cogeneration device system based on the proton conductor electrolyzer is based on the tubular proton conductor electrolyzer (PCEC) as the main body, the second layer of PCEC is nested outside the first layer of PCEC, which are the first tubular proton conductor electrolyzer and the second tubular proton conductor electrolyzer respectively, and two layers of sealing materials are nested outside the second layer of PCEC, thereby forming a tubular proton conductor electrolyzer nested inside and outside the hydrogen-ammonia cogeneration device, as shown in the figure. Figure 1 As shown, the tubular hydrogen-ammonia cogeneration device is divided into a first cavity 1, a second cavity 2, a third cavity 3 and a fourth cavity 4; the device is combined with a renewable energy power supply system, a water vapor 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 cogeneration system; Specifically, the water vapor supply system is composed of a water source, a steam production device, and a compressor; a valve system is used to control the switching of different modes and the output of different products; a renewable energy power supply system is used to provide power to drive the proton conductor electrolyzer to perform electrolysis; a circulating gas system includes a nitrogen circulation system and a hydrogen circulation system, which is used to circulate the incompletely reacted 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; Figure 1 As shown, the circulating water system, the fourth cavity 4 is a cooling circulating water layer, which is used to maintain a constant temperature of the device; the gas-liquid separation system is used to separate ammonia and nitrogen; the air separation nitrogen production system, including an air separation nitrogen production device, a compressor, an ammonia gas-liquid separator and a circulating air pump, is responsible for producing hydrogen.

[0027] The valve system includes a first gate, a second gate, a third gate and a fourth gate. The switching among the hydrogen-ammonia co-production mode, the hydrogen production mode alone and the ammonia production mode alone is realized by controlling the valve system.

[0028] It should be noted that the hydrogen-ammonia cogeneration mode is to connect the anode and cathode of the tubular proton conductor electrolyzer to the renewable energy power supply system respectively, and the high-pressure steam enters the first cavity 1 through the anode, and an oxidation reaction occurs at the anode to generate oxygen and protons, and the oxygen is discharged through the first cavity 1, as shown in reaction formula (1); (1) The protons pass through the electrolyte membrane to the cathode, where they undergo a reduction reaction to generate hydrogen, as shown in reaction equation (2); (2) Part of the hydrogen is transported from the second chamber 2 to the hydrogen drying tower through the first valve for discharge, and the other part of the hydrogen is transferred to the second tubular proton conductor electrolyzer to provide a proton source; nitrogen enters the second tubular proton conductor electrolyzer through the cathode, and 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, as shown in reaction formula (3); (3) Protons pass through the electrolyte membrane of the second tubular proton conductor electrolyzer to reach the cathode, and the protons react with nitrogen and electrons to generate a mixed gas, which is separated by the ammonia gas-liquid separator and discharged from the third chamber 3 through the second valve. The reaction equation is shown in equation (4); (4) The remaining mixed gas enters the third chamber 3 through the circulating gas pump for further reaction. In the hydrogen-ammonia cogeneration mode, the fourth gate is in a closed state.

[0029] The operating temperature of the proton conductor electrolyzer is 450-650°C. The two-layer electrolyzer can achieve efficient use of heat, but ammonia is unstable in this temperature range and will decompose into nitrogen and hydrogen. Therefore, a fourth cavity 4 is provided with an insulating water layer, and the temperature of this layer is up to 100°C. The advantage of this is that a temperature gradient of 550-100°C is formed in the third cavity 3, which is conducive to electrolytic ammonia production in the high-temperature area near the second electrolyzer layer, and is conducive to the stability of ammonia without decomposition in the low-temperature area near the insulating water layer. At the same time, the proton conductor electrolyzer can avoid the loss of heat in a single part, improve the energy utilization efficiency of the system, and make energy use more efficient. In the traditional electrolysis of water to produce hydrogen and ammonia, hydrogen production and ammonia production are divided into different parts, and the heat of synthetic ammonia cannot be supplied to hydrogen production, resulting in energy waste. The heat of the hydrogen production part of the present invention is supplied to ammonia production, and energy is used in multiple ways, reducing unit power consumption and being more efficient.

[0030] As for reducing unit power consumption, power consumption is reduced by 50%, among which 50% is relative to the two sets of equipment that use proton conductor electrolyzer to electrolyze water to produce hydrogen and proton conductor electrolyzer to electrolyze ammonia. If hydrogen production and ammonia production are divided into two parts, the heat required to maintain the normal operation of the device is doubled. After being combined into one set of equipment, the same heat can be supplied to two reactions at the same time, and the heat consumption is reduced by half, so the power consumption for maintaining heat is reduced by half.

[0031] In the single hydrogen production mode, the anode and cathode of the tubular proton conductor electrolyzer are respectively connected to the renewable energy power supply system, the air separation nitrogen production system and the nitrogen circulation system are closed, the positive and negative current applied to the second tubular proton conductor electrolyzer is reversed and the fourth gate is opened. While part of the high-pressure steam flows to the first cavity 1, the other part of the high-pressure steam flows to the third cavity 3 through the fourth valve. An oxidation reaction occurs at the anode to generate oxygen and protons. The oxygen is discharged from the first cavity 1 and the third cavity 3 through the second valve. The protons reach the cathode through the electrolyte membrane, and a reduction reaction occurs at the cathode to generate hydrogen. All the hydrogen is produced in the second cavity 2 and is transported to the hydrogen drying tower through the first valve and then discharged.

[0032] In the single ammonia production mode, the anode and cathode of the tubular proton conductor electrolyzer are respectively connected to the renewable energy power supply system, the outlet of the first valve is connected to the hydrogen pump, and the high-pressure steam flows to the first cavity 1, an oxidation reaction occurs at the anode to generate oxygen and protons, the oxygen is discharged through the first cavity 1, the protons pass through the electrolyte membrane to reach the cathode, and a reduction reaction occurs at the cathode to generate hydrogen, wherein the hydrogen is transported from the second cavity 2 to the hydrogen pump through the first valve for recycling, and the fourth valve is closed at the same time, and nitrogen enters the second tubular proton conductor electrolyzer through the cathode, part of the hydrogen in the second cavity 2 undergoes an oxidation reaction at the anode of the second tubular proton conductor electrolyzer to generate protons, and the protons pass through the electrolyte membrane of the second tubular proton conductor electrolyzer to the cathode, and the protons react with nitrogen and electrons to generate a mixed gas, and the ammonia is separated by the ammonia gas-liquid separator and discharged from the third cavity 3 through the second valve, and the remaining mixed gas enters the third cavity 3 through the circulating gas pump to react again.

[0033] In the hydrogen-ammonia co-production mode, the hydrogen production mode and the ammonia production mode, the third valve is opened to output hot water as needed.

[0034] This solution realizes the switching of hydrogen-ammonia co-production mode, single hydrogen production mode and single ammonia production mode through the linkage between various valves, and can realize single hydrogen production, single ammonia production or hydrogen-ammonia co-production. The traditional chemical method of synthesizing ammonia is difficult to start and stop, and it is impossible to realize flexible start and stop. The present invention can realize the conversion of production mode through simple control, adapt to production arrangements, improve utilization rate, and is conducive to large-scale promotion and utilization.

[0035] The present application also provides a tubular hydrogen-ammonia cogeneration method based on a proton conductor electrolyzer, comprising 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 input for a tubular proton conductor electrolyzer; S2, control or adjust the input of S1, and select the working mode of single hydrogen production, single ammonia production or hydrogen-ammonia co-production according to the needs; the hydrogen-ammonia co-production working mode includes the following steps: Step 1: High-pressure steam is input into the anode of the first tubular proton conductor electrolyzer, and an oxidation reaction occurs at the anode to generate oxygen and protons; Step 2: transporting protons to the cathode of the first tubular proton conductor electrolyzer through the electrolyte membrane, causing a reduction reaction to generate hydrogen; Step 3: Diffusing hydrogen through the second cavity to the anode of the second electrolytic cell, causing an oxidation reaction to generate protons; Step 4: transporting protons to the cathode through the second electrolyzer electrolyte; Step 5: nitrogen is introduced into the cathode of the second tubular proton conductor electrolyzer, where a reduction reaction occurs to generate nitrogen ions; Step 6: At the cathode of the second tubular proton conductor electrolyzer, the protons react with the nitrogen ions and the electrons to generate ammonia gas; Step 7: Control the output of hydrogen, ammonia and nitrogen through the valve system.

[0036] S3, performing electrolysis reaction and ammonia synthesis reaction in a tubular proton conductor electrolyzer to generate hydrogen and ammonia; S4. Use the circulating gas system, air separation nitrogen production system and gas-liquid separation system to collect the generated hydrogen, ammonia and nitrogen.

[0037] The traditional method of electrolyzing water to produce hydrogen and then synthesizing ammonia through chemical industry has high requirements for the stability of green hydrogen supply. Furthermore, the traditional method uses electricity to produce hydrogen through an electrolyzer and then inputs it into a chemical synthesis tower for catalytic production of ammonia. Hydrogen production and ammonia production are separate parts, and the chemical part has high requirements for the stability of the hydrogen source. At the same time, the traditional chemical synthesis ammonia method makes hydrogen and nitrogen react to produce ammonia under a certain temperature, pressure, atmosphere and catalyst, requiring the proportion of each component to remain constant. If the hydrogen supply changes greatly, the reaction conditions need to be adjusted, otherwise it will affect the product quality and yield and even cause safety risks; however, in actual operation, it is difficult and time-consuming to adjust the reaction conditions of large chemical synthesis towers, so a large number of hydrogen storage tanks need to be set up as a buffer.

[0038] This application adopts a completely different technical route. The proton conduction electrolyzer does not require high stability in the supply of raw gas, which is an inherent feature of this technology. When the raw gas is supplied, ammonia synthesis begins. Stopping the supply of raw gas will not have a harmful effect on the system while stopping the production of ammonia. In addition, this scheme deeply couples green electricity hydrogen production and synthetic ammonia through the design of a tubular hydrogen-ammonia cogeneration device based on a proton conductor electrolyzer, greatly reducing the size of the project. As mentioned above, this system can reduce the project area compared to the complex system structure of traditional water electrolysis to produce hydrogen and then synthesize ammonia.

[0039] Example 2: Producing 20,000 Nm per hour 3 Taking the hydrogen and 5 tons of liquid ammonia project as an example (excluding the substation and hydrogen and ammonia storage parts), the land area required for this application and the traditional method is estimated as shown in Table 1: The present invention Traditional alkaline electrolyzer + chemical synthesis ammonia (heat provided by electricity) Area size (mu) 2.8 4.8 Power consumption (MWh / h) 113.39 131.65 The invention occupies an area of ​​55.65m 2 (Bloom Energy 600Nm 3 / h solid oxide electrolyzer occupies 2.8 acres Traditional alkaline electrolyzer + chemical synthesis ammonia area = 120m 2 (1000Nm 3 Alkaline electrolytic cell area) × 20 + 800m 2 (5 tons / hour chemical synthesis tower occupies 4.8 acres); The power consumption of the present invention = the power consumption of hydrogen production by electrolysis in solid oxide electrolyzer 3.7kWh / Nm 3 ×20000Nm 3 / h+Power consumption of solid oxide electrolyzer for ammonia production 3kWh / Nm 3 ×13130Nm 3 / h=113390kWh=113.39MWh.

[0040] Traditional alkaline electrolyzer + chemical synthesis ammonia power consumption = alkaline electrolyzer electrolysis hydrogen production power consumption 5kWh / Nm 3 ×20000Nm 3 / h+Chemical synthesis ammonia power consumption 2kWh / Nm 3 ×13130Nm 3 / h+chemical synthetic ammonia heat to maintain 500℃ power consumption 5389kWh=131649kWh=131.65MWh.

[0041] It can be seen from this that this scheme deeply couples green electricity hydrogen production and synthetic ammonia through the designed tubular hydrogen-ammonia cogeneration device based on proton conductor electrolyzer, which greatly reduces the size of the project. Compared with the complex system structure of traditional water electrolysis to produce hydrogen and then synthesize ammonia, this system can reduce the project's footprint.

Claims

1. A tubular hydrogen-ammonia cogeneration device system based on a proton conductor electrolyzer, characterized in that: include: The tubular proton conductor electrolyzers are nested inside and outside, and are respectively a first tubular proton conductor electrolyzer and a second tubular proton conductor electrolyzer, wherein two layers of sealing material are further nested outside the second tubular proton conductor electrolyzer, and the tubular hydrogen-ammonia cogeneration device is divided into a first cavity (1), a second cavity (2), a third cavity (3) and a fourth cavity (4); Valve system, used to control the switching of different modes and the output of different products; A renewable energy power supply system for providing power to drive a proton conductor electrolyzer to perform an electrolysis reaction; A circulating gas system, including a nitrogen circulating system and a hydrogen circulating system, for circulating the incompletely reacted 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; Circulating water system, the fourth cavity (4) is a cooling circulating water layer, used to maintain a constant temperature of the device; The air separation nitrogen production system, including the air separation nitrogen production device and the compressor, is responsible for producing nitrogen.

2. The steam system, including the steam production device and the compressor, is responsible for generating steam for high-temperature electrolysis.

3. The tubular hydrogen-ammonia cogeneration device system based on a proton conductor electrolyzer according to claim 1 is characterized in that: The valve system comprises a first gate, a second gate, a third gate and a fourth gate, and the switching among a hydrogen-ammonia co-production mode, a hydrogen production mode alone and an ammonia production mode alone is achieved by controlling the valve system.

4. The tubular hydrogen-ammonia cogeneration device system based on a proton conductor electrolyzer according to claim 2 is characterized in that: The hydrogen-ammonia cogeneration mode is that the anode and cathode of the tubular proton conductor electrolyzer are respectively connected to the renewable energy power supply system, high-pressure steam enters the anode through the first chamber (1), an oxidation reaction occurs at the anode to generate oxygen and protons, the oxygen is discharged through the first chamber (1), the protons pass through the electrolyte membrane to reach the cathode, a reduction reaction occurs at the cathode to generate hydrogen, part of the hydrogen is transported from the second chamber (2) to the hydrogen drying tower through the first valve and discharged, and the other part of the hydrogen is transferred to the second tubular proton conductor electrolyzer to provide a proton source; nitrogen is generated by the air separation nitrogen production device 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 reach the cathode, the protons react with nitrogen and electrons to generate a mixed gas, and ammonia is separated through the ammonia gas-liquid separator, the ammonia is discharged from the third chamber (3) through the second valve, and the remaining mixed gas enters the third chamber (3) through the circulating air pump to react again.

5. The tubular hydrogen-ammonia cogeneration device system based on a proton conductor electrolyzer according to claim 3 is characterized in that: In the hydrogen-ammonia cogeneration mode, the fourth gate is in the closed state.

6. The tubular hydrogen-ammonia cogeneration device system based on a proton conductor electrolyzer according to claim 2 is characterized in that: In the single hydrogen production mode, the anode and cathode of the tubular proton conductor electrolyzer are respectively connected to the renewable energy power supply system, the air separation nitrogen production system and the nitrogen circulation system are closed, the positive and negative current applied to the second tubular proton conductor electrolyzer is reversed and the fourth gate is opened, a part of the high-pressure steam flows to the first chamber (1) while another part 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 reach the cathode, a reduction reaction occurs at the cathode to generate hydrogen, and the hydrogen is transported to the hydrogen drying tower through the first valve and then discharged.

7. The tubular hydrogen-ammonia cogeneration device system based on a proton conductor electrolyzer according to claim 2 is characterized in that: In the single ammonia production mode, the anode and cathode of the tubular proton conductor electrolyzer are respectively connected to the renewable energy power supply system, the outlet of the first valve is connected to the hydrogen pump, and the high-pressure steam flows to the first chamber (1), an oxidation reaction occurs at the anode to generate oxygen and protons, the oxygen is discharged through the first chamber (1), the protons pass through the electrolyte membrane to reach the cathode, and a reduction reaction occurs at the cathode to generate hydrogen, wherein the hydrogen is transported from the second chamber (2) to the hydrogen pump through the first valve for recycling, and the fourth valve is closed at the same time, and nitrogen enters the second tubular proton conductor electrolyzer through the anode 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 reach the cathode, the protons react with nitrogen and electrons to generate a mixed gas, and the ammonia is separated by the ammonia gas-liquid separator and discharged from the third chamber (3) through the second valve, and the remaining mixed gas enters the third chamber (3) through the circulating gas pump to react again.

8. The tubular hydrogen-ammonia cogeneration device system based on a proton conductor electrolyzer according to claim 1 is characterized in that: The fourth cavity (4) is a cooling circulating water layer.

9. The tubular hydrogen-ammonia cogeneration device system based on a proton conductor electrolyzer according to claim 2, characterized in that: The third valve is opened to output hot water as needed.

10. A tubular hydrogen-ammonia cogeneration method based on a proton conductor electrolyzer, applicable to a system as claimed in any one of claims 1 to 8, characterized in that: The steps include: 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 input for a tubular proton conductor electrolyzer; S2, control or adjust the input of S1, and select the working mode of single hydrogen production, single ammonia production or hydrogen-ammonia co-production according to the needs; S3, performing electrolysis reaction and ammonia synthesis reaction in a tubular proton conductor electrolyzer to generate hydrogen and ammonia; S4. Use the circulating gas system and air separation nitrogen production system to collect the generated hydrogen, ammonia and nitrogen.

11. The tubular hydrogen-ammonia cogeneration method based on a proton conductor electrolyzer according to claim 9, characterized in that: In S2, the operation mode of hydrogen-ammonia cogeneration includes the following steps: Step 1: High-pressure steam is input into the anode of the first tubular proton conductor electrolyzer, and an oxidation reaction occurs at the anode to generate oxygen and protons; Step 2: transporting protons to the cathode of the first tubular proton conductor electrolyzer through the electrolyte membrane, causing a reduction reaction to generate hydrogen; Step 3: Diffusing the hydrogen through the second chamber (2) to the anode of the second electrolytic cell to undergo an oxidation reaction to generate protons; Step 4: transporting protons to the cathode through the second electrolyzer electrolyte; Step 5: nitrogen is introduced into the cathode of the second tubular proton conductor electrolyzer, where a reduction reaction occurs to generate nitrogen ions; Step 6: At the cathode of the second tubular proton conductor electrolyzer, the protons react with the nitrogen ions and the electrons to generate ammonia gas; Step 7: Control the output of hydrogen, ammonia and nitrogen through the valve system.

Images