A device and method for cogeneration of electricity, hydrogen, ammonia and heat using biomass gas as raw material

Abstract

The present invention provides an electric hydrogen ammonia heat cogeneration device and method using biomass gas as raw material, the device includes an oxygen supply chamber, a fuel cell layer, a methane reforming hydrogen production chamber, an electrolyzer layer, a synthetic ammonia chamber and a cooling water chamber; the electric hydrogen ammonia heat cogeneration device using biomass gas as raw material adopts a multi-layer sleeve structure, and the oxygen supply chamber, the fuel cell layer, the methane reforming hydrogen production chamber, the electrolyzer layer, the synthetic ammonia chamber and the cooling water chamber are sequentially arranged from the inside to the outside. The present invention proposes an electric hydrogen ammonia heat cogeneration device and method using biomass gas as raw material, using biomass gas as raw material, integrating power generation, hydrogen production, synthetic ammonia and heat supply in the same device, and coordinating with auxiliary facilities to form an electric hydrogen ammonia heat cogeneration system, and providing a cogeneration method of the electric hydrogen ammonia heat cogeneration system. The invention has high integration, is conducive to reducing investment, has low equipment complexity, is convenient for operation and maintenance, and is conducive to large-scale promotion and efficient production.

Description

Technical Field

[0001] The present invention belongs to the technical field of biomass resource utilization, and in particular relates to an electricity-hydrogen-ammonia-heat cogeneration device and method using biomass gas as raw material. Background Art

[0002] Rural areas have abundant biomass resources, such as crop straw, livestock and poultry manure, and forestry waste. Biomass resources can be converted into biomass gas through anaerobic fermentation and other technologies, and its main components include methane and carbon dioxide. The relatively scattered nature of rural areas makes the use of biomass gas locally a feasible energy solution. Using biomass gas as a raw material to produce heat, electricity, hydrogen, and ammonia has important practical significance and broad development prospects, and can meet various distributed energy needs in rural areas.

[0003] At present, using biomass gas as raw material, the basic methods are to use internal combustion engines to burn or drive turbines to generate electricity, direct combustion to provide heat, steam reforming to produce hydrogen, and the hydrogen obtained from steam reforming to produce ammonia through chemical synthesis methods. This type of technical route has a low degree of integration, large equipment investment, complex construction, and inconvenient operation and maintenance. Summary of the invention

[0004] In view of the defects of the prior art, the present invention provides an electricity, hydrogen, ammonia and heat cogeneration device and method using biomass gas as raw material, which can effectively solve the above problems.

[0005] The technical solution adopted by the present invention is as follows:

[0006] The present invention provides an electric hydrogen ammonia heat cogeneration device using biomass gas as raw material, comprising an oxygen supply chamber, a fuel cell layer, a methane reforming hydrogen production chamber, an electrolyzer layer, a synthetic ammonia chamber and a cooling water chamber;

[0007] The electricity-hydrogen-ammonia-heat cogeneration device using biomass gas as raw material adopts a multi-layer sleeve structure, and the oxygen supply chamber, the fuel cell layer, the methane reforming hydrogen production chamber, the electrolyzer layer, the synthetic ammonia chamber and the cooling water chamber are arranged in sequence from the inside to the outside.

[0008] Preferably, the fuel cell layer comprises a fuel cell layer anode, a fuel cell layer cathode and a fuel cell electrolyte layer; the electrolyzer layer comprises an electrolyzer layer positive electrode, an electrolyzer layer negative electrode and an electrolyzer electrolyte layer;

[0009] The oxygen supply chamber is located in the innermost central area; an annular fuel cell layer cathode is arranged outside the oxygen supply chamber, and the fuel cell layer cathode also forms the cavity wall of the oxygen supply chamber; an annular fuel cell layer anode is arranged outside the fuel cell layer cathode, and a dense fuel cell electrolyte layer is filled between the fuel cell layer anode and the fuel cell layer cathode, thereby forming the fuel cell layer outside the oxygen supply chamber;

[0010] The outer portion of the anode of the fuel cell layer is provided with an annular positive electrode of the electrolyzer layer, and the methane reforming hydrogen production chamber is formed between the anode of the fuel cell layer and the positive electrode of the electrolyzer layer. Therefore, the anode of the fuel cell layer and the positive electrode of the electrolyzer layer serve as the inner wall and the outer wall of the chamber of the methane reforming hydrogen production chamber respectively.

[0011] The outer portion of the electrolytic cell layer positive electrode is provided with the annular electrolytic cell layer negative electrode, and the dense electrolytic cell electrolyte layer is filled between the electrolytic cell layer positive electrode and the electrolytic cell layer negative electrode, thereby forming the arrangement structure of the electrolytic cell layer;

[0012] The outer portion of the negative electrode of the electrolytic cell layer is provided with an annular outer wall of the synthetic ammonia chamber, and the synthetic ammonia chamber is formed between the negative electrode of the electrolytic cell layer and the outer wall of the synthetic ammonia chamber. Therefore, the negative electrode of the electrolytic cell layer also serves as the inner wall of the synthetic ammonia chamber.

[0013] The annular cooling water chamber is arranged outside the outer wall of the synthetic ammonia chamber.

[0014] Preferably, the fuel cell layer cathode, the fuel cell layer anode, the electrolyzer layer positive electrode and the electrolyzer layer negative electrode are all made of porous materials.

[0015] Preferably, the outer wall of the synthetic ammonia chamber is a sealing layer, isolating the synthetic ammonia chamber from the cooling water chamber.

[0016] Preferably, the input port of the oxygen supply chamber is connected to an oxygen supply system for delivering oxygen to the oxygen supply chamber;

[0017] The input port of the methane reforming hydrogen production chamber is connected to the biomass gas supply system and the water vapor supply system respectively, and is used to transport biomass gas and water vapor to the methane reforming hydrogen production chamber, and the biomass gas and water vapor react in the methane reforming hydrogen production chamber to generate hydrogen;

[0018] The fuel cell layer is used to make the hydrogen generated by the methane reforming hydrogen production chamber react at the anode of the fuel cell layer to become protons. The protons pass through the fuel cell electrolyte layer to reach the cathode of the fuel cell layer and combine with the oxygen in the oxygen supply chamber to generate water. In this process, the fuel cell layer performs a power generation reaction and releases electrical energy.

[0019] The input port of the synthetic ammonia chamber is connected to a nitrogen supply system for delivering nitrogen to the synthetic ammonia chamber;

[0020] The electrolytic cell layer is used to make the hydrogen generated by the methane reforming hydrogen production chamber react at the positive electrode of the electrolytic cell layer to generate protons, and the protons reach the negative electrode of the electrolytic cell layer after passing through the electrolytic cell electrolyte layer, and react with the nitrogen in the ammonia synthesis chamber to synthesize ammonia; the ammonia synthesis reaction of the electrolytic cell layer consumes electrical energy, and the electrical energy is stored in the energy storage system by the electrical energy generated by the fuel cell layer and then released and supplied stably;

[0021] The cooling water chamber is used to circulate cooling water to absorb the heat released during the power generation reaction of the fuel cell layer and the ammonia synthesis reaction through the electrolyzer layer, thereby providing high-quality thermal energy.

[0022] Preferably, the biomass gas supply system comprises: a raw gas processing system for filtering the raw gas;

[0023] The nitrogen supply system and the oxygen supply system are arranged in combination, and include: a filter for filtering air, and an air separation nitrogen production unit for producing nitrogen from the air filtered by the filter, wherein the nitrogen outlet of the air separation nitrogen production unit is compressed by a compressor and then transmitted to the input port of the synthetic ammonia chamber; the oxygen outlet of the air separation nitrogen production unit is compressed by a compressor and then transmitted to the oxygen supply chamber;

[0024] The water vapor supply system includes: a water source system, a steam generator and a compressor; a branch is led from the hot water output from the cooling water chamber to the water source system, the water source system transports hot water to the steam generator, and after being processed by the steam generator, water vapor is generated, which is compressed by the compressor and transmitted to the methane reforming hydrogen production chamber.

[0025] Preferably, it also includes a circulating gas system and a gas separation and purification system;

[0026] A portion of the hydrogen output from the methane reforming hydrogen production chamber is processed by the gas separation and purification system and then output externally, and the other portion is refluxed to the methane reforming hydrogen production chamber through the circulating gas system to improve the purity of the hydrogen;

[0027] After the ammonia synthesized in the synthetic ammonia chamber is processed by the gas separation and purification system, a part of it is output to the outside, and the other part is processed by the compressor and then flows back into the synthetic ammonia chamber to improve the purity of ammonia.

[0028] The present invention also provides a method for a power-hydrogen-ammonia-heat cogeneration device using biomass gas as a raw material, comprising the following steps:

[0029] Step 1, methane reforming to produce hydrogen:

[0030] transporting biomass gas and water vapor to a methane reforming hydrogen production chamber, where the biomass gas and water vapor react in the methane reforming hydrogen production chamber to generate hydrogen;

[0031] Step 2: Since the inner wall and outer wall of the chamber for hydrogen production by methane reforming are respectively the anode of the fuel cell layer and the positive electrode of the electrolyzer layer, and both the anode of the fuel cell layer and the positive electrode of the electrolyzer layer are porous materials, the hydrogen generated by the chamber for hydrogen production by methane reforming is directly in full contact with the anode of the fuel cell layer and the positive electrode of the electrolyzer layer, and steps 3 and 4 are performed simultaneously;

[0032] Step 3, fuel cell layer power generation reaction:

[0033] The hydrogen generated by the methane reforming hydrogen production chamber is directly in contact with the anode of the fuel cell layer at the same time. Therefore, the hydrogen reacts at the anode of the fuel cell layer to become protons. The protons pass through the fuel cell electrolyte layer and reach the cathode of the fuel cell layer, and combine with the oxygen in the oxygen supply chamber to generate water, thereby performing a power generation reaction in the fuel cell layer and releasing electrical energy. The released electrical energy is stored in the storage system.

[0034] Step 4, synthesizing ammonia through the electrolytic cell layer:

[0035] The hydrogen generated by the methane reforming hydrogen production chamber is in direct contact with the positive electrode of the electrolytic cell layer at the same time. Therefore, the hydrogen reacts at the positive electrode of the electrolytic cell layer to generate protons. The protons pass through the electrolytic cell electrolyte layer and reach the negative electrode of the electrolytic cell layer, and react with the nitrogen in the ammonia synthesis chamber to synthesize ammonia.

[0036] The ammonia synthesis reaction of the electrolytic cell layer consumes electric energy, and the electric energy generated by the power generation reaction of the fuel cell layer is stored in the energy storage system and then released and supplied stably;

[0037] Step 5, heat generation process of cooling water chamber:

[0038] The cooling water chamber circulates cooling water to absorb the heat released during the power generation reaction of the fuel cell layer and the ammonia synthesis reaction through the electrolyzer layer, thereby providing high-quality thermal energy.

[0039] The invention provides an electric hydrogen ammonia heat cogeneration device and method using biomass gas as raw material, which has the following advantages:

[0040] The present invention proposes an electric hydrogen ammonia heat cogeneration device and method using biomass gas as raw material. Using biomass gas as raw material, power generation, hydrogen production, ammonia synthesis and heat supply are integrated in the same device, and auxiliary facilities are used to form an electric hydrogen ammonia heat cogeneration system, and a cogeneration method of the electric hydrogen ammonia heat cogeneration system is provided. The invention has high integration, is conducive to reducing investment, has low equipment complexity, and is convenient for operation and maintenance, which is conducive to large-scale promotion and efficient production. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 The schematic diagram of a power-hydrogen-ammonia-heat cogeneration device using biomass gas as raw material provided by the present invention;

[0042] Figure 2 A three-dimensional diagram of an electric hydrogen ammonia heat cogeneration device using biomass gas as raw material provided by the present invention;

[0043] Figure 3 A block diagram of an electricity, hydrogen, ammonia and heat cogeneration device using biomass gas as raw material provided by the present invention.

[0044] in:

[0045] 1. Oxygen supply chamber; 2. Fuel cell layer; 2-1. Fuel cell layer anode; 2-2. Fuel cell layer cathode; 2-3. Fuel cell electrolyte layer; 3. Methane reforming hydrogen production chamber; 4. Electrolyzer layer; 4-1. Electrolyzer layer positive electrode; 4-2. Electrolyzer layer negative electrode; 4-3. Electrolyzer electrolyte layer; 5. Ammonia synthesis chamber; 5-1. Outer wall of ammonia synthesis chamber; 6. Cooling water chamber. DETAILED DESCRIPTION

[0046] In order to make the technical problems, technical solutions and beneficial effects solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0047] The present invention proposes an electric hydrogen ammonia heat cogeneration device and method using biomass gas as raw material. Using biomass gas as raw material, power generation, hydrogen production, ammonia synthesis and heat supply are integrated in the same device, and auxiliary facilities are used to form an electric hydrogen ammonia heat cogeneration system, and a cogeneration method of the electric hydrogen ammonia heat cogeneration system is provided. The invention has high integration, is conducive to reducing investment, has low equipment complexity, and is convenient for operation and maintenance, which is conducive to large-scale promotion and efficient production.

[0048] Combination Figure 1 to Figure 3 The present invention provides an electric hydrogen ammonia heat cogeneration device using biomass gas as raw material, comprising an oxygen supply chamber 1, a fuel cell layer 2, a methane reforming hydrogen production chamber 3, an electrolyzer layer 4, a synthetic ammonia chamber 5 and a cooling water chamber 6;

[0049] The electricity, hydrogen, ammonia and heat cogeneration device using biomass gas as raw material adopts a multi-layer sleeve structure, and the oxygen supply chamber 1, the fuel cell layer 2, the methane reforming hydrogen production chamber 3, the electrolyzer layer 4, the synthetic ammonia chamber 5 and the cooling water chamber 6 are arranged in sequence from the inside to the outside.

[0050] Its detailed structure is:

[0051] The fuel cell layer 2 includes a fuel cell layer anode 2-1, a fuel cell layer cathode 2-2 and a fuel cell electrolyte layer 2-3; the electrolyzer layer 4 includes an electrolyzer layer positive electrode 4-1, an electrolyzer layer negative electrode 4-2 and an electrolyzer electrolyte layer 4-3; the fuel cell layer cathode 2-2, the fuel cell layer anode 2-1, the electrolyzer layer positive electrode 4-1 and the electrolyzer layer negative electrode 4-2 are all porous materials.

[0052] The oxygen supply chamber 1 is located in the innermost central area; an annular fuel cell layer cathode 2-2 is arranged outside the oxygen supply chamber 1, and the fuel cell layer cathode 2-2 also forms the cavity wall of the oxygen supply chamber 1; an annular fuel cell layer anode 2-1 is arranged outside the fuel cell layer cathode 2-2, and a dense fuel cell electrolyte layer 2-3 is filled between the fuel cell layer anode 2-1 and the fuel cell layer cathode 2-2, thereby forming the fuel cell layer 2 arranged outside the oxygen supply chamber 1;

[0053] The outer portion of the fuel cell layer anode 2-1 is provided with an annular electrolyzer layer positive electrode 4-1, and the methane reforming hydrogen production chamber 3 is formed between the fuel cell layer anode 2-1 and the electrolyzer layer positive electrode 4-1. Therefore, the fuel cell layer anode 2-1 and the electrolyzer layer positive electrode 4-1 respectively serve as the inner wall and outer wall of the methane reforming hydrogen production chamber 3;

[0054] The outer portion of the electrolytic cell layer positive electrode 4-1 is provided with the annular electrolytic cell layer negative electrode 4-2, and the dense electrolytic cell electrolyte layer 4-3 is filled between the electrolytic cell layer positive electrode 4-1 and the electrolytic cell layer negative electrode 4-2, thereby forming the arrangement structure of the electrolytic cell layer;

[0055] The outer portion of the electrolytic cell layer negative electrode 4-2 is provided with an annular synthetic ammonia chamber outer wall 5-1, and the synthetic ammonia chamber 5 is formed between the electrolytic cell layer negative electrode 4-2 and the synthetic ammonia chamber outer wall 5-1, so that the electrolytic cell layer negative electrode 4-2 also serves as the inner wall of the synthetic ammonia chamber 5;

[0056] The outer wall 5-1 of the synthetic ammonia chamber is provided with the annular cooling water chamber 6. In the present invention, the outer wall 5-1 of the synthetic ammonia chamber is a sealing layer, which isolates the synthetic ammonia chamber 5 and the cooling water chamber 6.

[0057] Furthermore, the following auxiliary equipment is also included:

[0058] The input port of the oxygen supply chamber 1 is connected to the oxygen supply system for delivering oxygen to the oxygen supply chamber 1;

[0059] The input port of the methane reforming hydrogen production chamber 3 is connected to the biomass gas supply system and the water vapor supply system respectively, and is used to transport biomass gas and water vapor to the methane reforming hydrogen production chamber 3, and the biomass gas and water vapor react in the methane reforming hydrogen production chamber 3 to generate hydrogen;

[0060] The fuel cell layer 2 is used to make the hydrogen generated by the methane reforming hydrogen production chamber 3 react at the fuel cell layer anode 2-1 to become protons. The protons pass through the fuel cell electrolyte layer 2-3 and reach the fuel cell layer cathode 2-2, and combine with the oxygen in the oxygen supply chamber 1 to generate water. In this process, the fuel cell layer 2 performs a power generation reaction and releases electrical energy.

[0061] The input port of the synthetic ammonia chamber 5 is connected to a nitrogen supply system for delivering nitrogen to the synthetic ammonia chamber 5;

[0062] The electrolytic cell layer 4 is used to make the hydrogen generated by the methane reforming hydrogen production chamber 3 react at the electrolytic cell layer positive electrode 4-1 to generate protons, and the protons reach the electrolytic cell layer negative electrode 4-2 after passing through the electrolytic cell electrolyte layer 4-3, and react with the nitrogen in the ammonia synthesis chamber 5 to synthesize ammonia; the ammonia synthesis reaction of the electrolytic cell layer consumes electrical energy, and the electrical energy is stored in the energy storage system by the electrical energy generated by the fuel cell layer and then released and supplied stably;

[0063] The cooling water chamber 6 is used to circulate cooling water and absorb the heat released during the power generation reaction of the fuel cell layer and the ammonia synthesis reaction through the electrolyzer layer, thereby providing high-quality thermal energy. The cooling water chamber 6 is specifically a liquid cooling water layer that can produce hot water for heating. The square design is conducive to modular combination on demand.

[0064] In practical applications, each auxiliary device can be implemented in the following ways:

[0065] The biomass gas supply system comprises: a raw gas processing system for filtering the raw gas, the raw gas processing system can filter impurities such as particulate matter, hydrogen sulfide and organic and inorganic liquids in the biomass gas;

[0066] The nitrogen supply system and the oxygen supply system are arranged in combination, and include: a filter for filtering air, an air separation nitrogen production unit for producing nitrogen from the air filtered by the filter, the nitrogen outlet of the air separation nitrogen production unit is compressed by a compressor and then transmitted to the input port of the synthetic ammonia chamber 5; the oxygen outlet of the air separation nitrogen production unit is compressed by a compressor and then transmitted to the oxygen supply chamber 1. Therefore, nitrogen and oxygen are simultaneously produced through the air supply processing system.

[0067] The water vapor supply system includes: a water source system, a steam generator and a compressor; a branch is led from the hot water output from the cooling water chamber 6 to the water source system, the water source system delivers hot water to the steam generator, and after being processed by the steam generator, water vapor is generated, which is compressed by the compressor and then transmitted to the methane reforming hydrogen production chamber 3. The water vapor supply system provides steam required for the reaction, and the steam can be used for the methane reforming reaction.

[0068] It also includes a circulating gas system and a gas separation and purification system;

[0069] A portion of the hydrogen output from the methane reforming hydrogen production chamber 3 is processed by the gas separation and purification system and then output externally, and the other portion is refluxed to the methane reforming hydrogen production chamber 3 through the circulating gas system to improve the purity of the hydrogen;

[0070] After the ammonia synthesized in the synthetic ammonia chamber 5 is processed by the gas separation and purification system, a part of it is output to the outside, and the other part is processed by the compressor and then flows back into the synthetic ammonia chamber 5 to improve the purity of ammonia.

[0071] The present invention also provides a method for a power-hydrogen-ammonia-heat cogeneration device using biomass gas as a raw material, comprising the following steps:

[0072] Step 1, methane reforming to produce hydrogen:

[0073] transporting biomass gas and water vapor to the methane reforming hydrogen production chamber 3, where the biomass gas and water vapor react in the methane reforming hydrogen production chamber 3 to generate hydrogen;

[0074] Step 2: Since the inner wall and outer wall of the chamber 3 for hydrogen production by methane reforming are respectively the anode 2-1 of the fuel cell layer and the positive electrode 4-1 of the electrolyzer layer, and both the anode 2-1 of the fuel cell layer and the positive electrode 4-1 of the electrolyzer layer are porous materials, the hydrogen generated by the chamber 3 for hydrogen production by methane reforming is directly in full contact with the anode 2-1 of the fuel cell layer and the positive electrode 4-1 of the electrolyzer layer, and steps 3 and 4 are performed simultaneously;

[0075] Step 3, fuel cell layer power generation reaction:

[0076] The hydrogen generated by the methane reforming hydrogen production chamber 3 is directly in contact with the fuel cell layer anode 2-1 at the same time. Therefore, the hydrogen reacts at the fuel cell layer anode 2-1 to become protons. The protons pass through the fuel cell electrolyte layer 2-3 and reach the fuel cell layer cathode 2-2, and combine with the oxygen in the oxygen supply chamber 1 to generate water, thereby performing a fuel cell layer power generation reaction and releasing electrical energy. The released electrical energy is stored in the storage system.

[0077] Step 4, synthesizing ammonia through the electrolytic cell layer:

[0078] The hydrogen generated by the methane reforming hydrogen production chamber 3 is directly in contact with the electrolytic cell layer positive electrode 4-1 at the same time. Therefore, the hydrogen reacts at the electrolytic cell layer positive electrode 4-1 to generate protons. The protons pass through the electrolytic cell electrolyte layer 4-3 and reach the electrolytic cell layer negative electrode 4-2, and react with the nitrogen in the ammonia synthesis chamber 5 to synthesize ammonia.

[0079] The ammonia synthesis reaction of the electrolytic cell layer consumes electric energy, and the electric energy generated by the power generation reaction of the fuel cell layer is stored in the energy storage system and then released and supplied stably;

[0080] Step 5, heat generation process of cooling water chamber 6:

[0081] The cooling water chamber 6 circulates cooling water to absorb the heat released during the power generation reaction of the fuel cell layer and the ammonia synthesis reaction through the electrolyzer layer, thereby providing high-quality thermal energy.

[0082] A specific embodiment is described below:

[0083] The multi-layer shell-and-tube device combines the raw gas processing system, air supply system, steam supply system, heat circulation system, gas circulation system, energy storage system, and gas separation and purification system to form an electricity, hydrogen, ammonia and heat cogeneration system.

[0084] The raw gas treatment system can filter impurities such as particulate matter, hydrogen sulfide, and organic and inorganic liquids present in the biomass gas. The air supply system is used to generate oxygen and nitrogen required for the oxygen supply chamber 1 and the synthetic ammonia chamber 5. The water vapor generation system is used to provide steam required for the reaction, and the steam can be used for methane reforming reaction and proton source. The energy storage system is used to collect the electrical energy generated by the fuel cell layer, which can be returned to the electrolyzer layer for synthetic ammonia, or it can be exported to the outside. The circulating gas system is used for hydrogen circulation, which can improve the purity of hydrogen or output hydrogen. The heat circulation system can keep the temperature of this co-production device in a suitable range. Given that the operating temperature of this type of device is 500-750 degrees Celsius, this layer can generate high-quality heat for heating. The gas separation system is mainly used to separate gases of different components in each chamber to obtain the target product.

[0085] The implementation process is:

[0086] The present invention uses biomass gas as raw material, and its main component is methane CH4. After the raw gas passes through the gas treatment system to remove impurities and harmful substances, it enters the methane reforming hydrogen production chamber 3, where it reacts with water vapor to generate hydrogen H2 and carbon monoxide CO, and carbon monoxide continues to react with water vapor to generate hydrogen H2 and carbon dioxide CO2. The hydrogen can be purified by the gas separation system and then output. In addition, the hydrogen can be transferred to the fuel cell layer 2, reacting at the anode 2-1 of the fuel cell layer to become protons, and the protons reach the cathode 2-2 of the fuel cell layer after passing through the dense fuel cell electrolyte layer 2-3, and combine with oxygen to generate water and release electrical energy. The oxygen comes from the air supply system. Hydrogen can also reach the electrolytic cell layer 4, reacting at the positive electrode 4-1 of the electrolytic cell layer to generate protons, and the protons pass through the dense electrolytic cell electrolyte layer 4-3 to reach the negative electrode 4-2 of the electrolytic cell layer, and react with nitrogen to generate ammonia NH3. The reaction of producing ammonia consumes electrical energy, which is stably released after being stored in the energy storage system by the electrical energy generated by the fuel cell layer. The energy storage system plays the role of electrical energy allocation. The outermost layer is the cooling water chamber 6. The power generation reaction of the fuel cell layer and the ammonia synthesis reaction through the electrolyzer layer both release heat. The outermost layer is the heat circulation system, which can maintain the temperature of the device at a suitable level and provide high-quality thermal energy.

[0087] The present invention provides an electric hydrogen ammonia heat cogeneration device and method using biomass gas as raw material, which has the following innovations:

[0088] (1)Technological innovation 1:

[0089] In the existing technology, power generation, hydrogen production, ammonia synthesis and heat supply using biomass gas as raw material can only be produced separately, which requires the coordination of 4 sets of equipment systems, which is technically complex, requires large investment and has high maintenance costs.

[0090] The present invention is based on a proton conductor reaction cell, which deeply couples a fuel cell and an electrolyzer into a set of devices in the form of a sleeve. Based on this device, hydrogen can be produced by biomass gas reforming reaction, hydrogen can generate electricity in the fuel cell layer, and the generated electricity can be output to do work or to supply electricity to the electrolyzer layer to synthesize ammonia. Since the operating temperature range of the proton conductor reaction cell is 500-750℃, the thermal cycle system of the device can provide a large amount of high-quality waste heat.

[0091] In summary, the present invention highly integrates the originally complex four independent systems into one system, achieving the simultaneous production of electricity, hydrogen, ammonia and heat by one device.

[0092] (2)Technological innovation 2:

[0093] The present invention places the fuel cell layer at the innermost center, the middle layer is the electrolyzer layer, and the outermost layer is the circulating water layer. The advantage of this design is that the heat released by the power generation reaction of the fuel cell layer at the innermost center can provide reaction heat for the electrolyzer layer to synthesize ammonia, thereby reducing power consumption and increasing ammonia yield. Secondly, since the optimal temperature for synthesizing ammonia is lower than the operating temperature of the fuel cell, the outermost circulating water layer can reduce the temperature of the electrolyzer layer without affecting the operating temperature of the core fuel cell layer, thereby increasing ammonia yield.

[0094] (3)Technological innovation three:

[0095] The design of the outermost square circulating water layer allows the device to be assembled at will according to power requirements, greatly improving the power density per unit volume, reducing floor space, and achieving modular customization to meet various application scenarios.

[0096] (4)Technological innovation 4:

[0097] The present invention realizes efficient heat utilization design and reduces the power consumption of synthetic ammonia. Traditional ammonia synthesis requires hydrogen and nitrogen to be combined and sent into a chemical synthesis tower to synthesize ammonia under high temperature and catalyst. This method requires a large amount of heat supplement from hydrogen production to ammonia synthesis. The present invention directly uses the fuel cell reaction heat to synthesize ammonia in the electrolytic cell layer, reducing the energy consumption per unit of ammonia production.

[0098] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be considered as the scope of protection of the present invention.

Claims

1. An electricity, hydrogen, ammonia and heat cogeneration device using biomass gas as raw material, characterized in that: It includes an oxygen supply chamber, a fuel cell layer, a methane reforming hydrogen production chamber, an electrolyzer layer, a synthetic ammonia chamber and a cooling water chamber; The electricity-hydrogen-ammonia-heat cogeneration device using biomass gas as raw material adopts a multi-layer sleeve structure, and the oxygen supply chamber, the fuel cell layer, the methane reforming hydrogen production chamber, the electrolyzer layer, the synthetic ammonia chamber and the cooling water chamber are sequentially arranged from the inside to the outside; The fuel cell layer comprises a fuel cell layer anode, a fuel cell layer cathode and a fuel cell electrolyte layer; the electrolyzer layer comprises an electrolyzer layer positive electrode, an electrolyzer layer negative electrode and an electrolyzer electrolyte layer; The oxygen supply chamber is located in the innermost central area; an annular fuel cell layer cathode is arranged outside the oxygen supply chamber, and the fuel cell layer cathode also forms the cavity wall of the oxygen supply chamber; an annular fuel cell layer anode is arranged outside the fuel cell layer cathode, and a dense fuel cell electrolyte layer is filled between the fuel cell layer anode and the fuel cell layer cathode, thereby forming the fuel cell layer outside the oxygen supply chamber; The outer portion of the anode of the fuel cell layer is provided with an annular positive electrode of the electrolyzer layer, and the methane reforming hydrogen production chamber is formed between the anode of the fuel cell layer and the positive electrode of the electrolyzer layer. Therefore, the anode of the fuel cell layer and the positive electrode of the electrolyzer layer serve as the inner wall and the outer wall of the chamber of the methane reforming hydrogen production chamber respectively. The outer portion of the electrolytic cell layer positive electrode is provided with the annular electrolytic cell layer negative electrode, and the dense electrolytic cell electrolyte layer is filled between the electrolytic cell layer positive electrode and the electrolytic cell layer negative electrode, thereby forming the arrangement structure of the electrolytic cell layer; The outer portion of the negative electrode of the electrolytic cell layer is provided with an annular outer wall of the synthetic ammonia chamber, and the synthetic ammonia chamber is formed between the negative electrode of the electrolytic cell layer and the outer wall of the synthetic ammonia chamber. Therefore, the negative electrode of the electrolytic cell layer also serves as the inner wall of the synthetic ammonia chamber. The annular cooling water chamber is arranged outside the outer wall of the synthetic ammonia chamber.

2. The electric hydrogen ammonia heat cogeneration device using biomass gas as raw material according to claim 1, characterized in that: The fuel cell layer cathode, the fuel cell layer anode, the electrolyzer layer positive electrode and the electrolyzer layer negative electrode are all made of porous materials.

3. The electric hydrogen ammonia heat cogeneration device using biomass gas as raw material according to claim 1, characterized in that: The outer wall of the synthetic ammonia chamber is a sealing layer, which isolates the synthetic ammonia chamber from the cooling water chamber.

4. The electric hydrogen ammonia heat cogeneration device using biomass gas as raw material according to claim 1, characterized in that: The input port of the oxygen supply chamber is in communication with an oxygen supply system for delivering oxygen to the oxygen supply chamber; The input port of the methane reforming hydrogen production chamber is connected to the biomass gas supply system and the water vapor supply system respectively, and is used to transport biomass gas and water vapor to the methane reforming hydrogen production chamber, and the biomass gas and water vapor react in the methane reforming hydrogen production chamber to generate hydrogen; The fuel cell layer is used to make the hydrogen generated by the methane reforming hydrogen production chamber react at the anode of the fuel cell layer to become protons. The protons pass through the fuel cell electrolyte layer to reach the cathode of the fuel cell layer and combine with the oxygen in the oxygen supply chamber to generate water. In this process, the fuel cell layer performs a power generation reaction and releases electrical energy. The input port of the synthetic ammonia chamber is connected to a nitrogen supply system for delivering nitrogen to the synthetic ammonia chamber; The electrolytic cell layer is used to make the hydrogen generated by the methane reforming hydrogen production chamber react at the positive electrode of the electrolytic cell layer to generate protons, and the protons reach the negative electrode of the electrolytic cell layer after passing through the electrolytic cell electrolyte layer, and react with the nitrogen in the ammonia synthesis chamber to synthesize ammonia; the ammonia synthesis reaction of the electrolytic cell layer consumes electrical energy, and the electrical energy is stored in the energy storage system by the electrical energy generated by the fuel cell layer and then released and supplied stably; The cooling water chamber is used to circulate cooling water to absorb the heat released during the power generation reaction of the fuel cell layer and the ammonia synthesis reaction through the electrolyzer layer, thereby providing high-quality thermal energy.

5. The electric hydrogen ammonia heat cogeneration device using biomass gas as raw material according to claim 4, characterized in that: The biomass gas supply system comprises: a raw gas processing system for filtering the raw gas; The nitrogen supply system and the oxygen supply system are arranged in combination, and include: a filter for filtering air, and an air separation nitrogen production unit for producing nitrogen from the air filtered by the filter, wherein the nitrogen outlet of the air separation nitrogen production unit is compressed by a compressor and then transmitted to the input port of the synthetic ammonia chamber; the oxygen outlet of the air separation nitrogen production unit is compressed by a compressor and then transmitted to the oxygen supply chamber; The water vapor supply system includes: a water source system, a steam generator and a compressor; a branch is led from the hot water output from the cooling water chamber to the water source system, the water source system transports hot water to the steam generator, and after being processed by the steam generator, water vapor is generated, which is compressed by the compressor and transmitted to the methane reforming hydrogen production chamber.

6. The electric hydrogen ammonia heat cogeneration device using biomass gas as raw material according to claim 4, characterized in that: It also includes a circulating gas system and a gas separation and purification system; A portion of the hydrogen output from the methane reforming hydrogen production chamber is processed by the gas separation and purification system and then output externally, and the other portion is refluxed to the methane reforming hydrogen production chamber through the circulating gas system to improve the purity of the hydrogen; After the ammonia synthesized in the synthetic ammonia chamber is processed by the gas separation and purification system, a part of it is output to the outside, and the other part is processed by the compressor and then flows back into the synthetic ammonia chamber to improve the purity of ammonia.

7. A method for a combined electricity, hydrogen, ammonia and heat production device using biomass gas as raw material according to any one of claims 1 to 6, characterized in that: The following steps are involved: Step 1, methane reforming to produce hydrogen: transporting biomass gas and water vapor to a methane reforming hydrogen production chamber, where the biomass gas and water vapor react in the methane reforming hydrogen production chamber to generate hydrogen; Step 2: Since the inner wall and outer wall of the chamber for hydrogen production by methane reforming are respectively the anode of the fuel cell layer and the positive electrode of the electrolyzer layer, and both the anode of the fuel cell layer and the positive electrode of the electrolyzer layer are porous materials, the hydrogen generated by the chamber for hydrogen production by methane reforming is directly in full contact with the anode of the fuel cell layer and the positive electrode of the electrolyzer layer, and steps 3 and 4 are performed simultaneously; Step 3, fuel cell layer power generation reaction: The hydrogen generated by the methane reforming hydrogen production chamber is directly in contact with the anode of the fuel cell layer at the same time. Therefore, the hydrogen reacts at the anode of the fuel cell layer to become protons. The protons pass through the fuel cell electrolyte layer and reach the cathode of the fuel cell layer, and combine with the oxygen in the oxygen supply chamber to generate water, thereby performing a power generation reaction in the fuel cell layer and releasing electrical energy. The released electrical energy is stored in the storage system. Step 4, synthesizing ammonia through the electrolytic cell layer: The hydrogen generated by the methane reforming hydrogen production chamber is in direct contact with the positive electrode of the electrolytic cell layer at the same time. Therefore, the hydrogen reacts at the positive electrode of the electrolytic cell layer to generate protons. The protons pass through the electrolytic cell electrolyte layer and reach the negative electrode of the electrolytic cell layer, and react with the nitrogen in the ammonia synthesis chamber to synthesize ammonia. The ammonia synthesis reaction of the electrolytic cell layer consumes electric energy, and the electric energy generated by the power generation reaction of the fuel cell layer is stored in the energy storage system and then released and supplied stably; Step 5, heat generation process of cooling water chamber: The cooling water chamber circulates cooling water to absorb the heat released during the power generation reaction of the fuel cell layer and the ammonia synthesis reaction through the electrolyzer layer, thereby providing high-quality thermal energy.

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