System and method for co-producing green methanol, ammonia and carbon-based fertilizer by renewable energy sources

Abstract

The invention relates to the technical field of green chemical engineering, in particular to a system and a method for co-producing green methanol, ammonia and carbon-based fertilizer by renewable energy sources, which comprises an electrolyzed water device, an air separation device, a gasification furnace, a methanol synthesis device, an ammonia synthesis device, a pyrolysis device and an ammoniation device, an oxygen outlet of the water electrolysis device and / or an oxygen outlet of the air separation device are / is communicated with the gasification furnace and the pyrolysis device; a nitrogen outlet of the air separation device and a hydrogen outlet of the electrolyzed water device are communicated with the ammonia synthesis device; a gasified gas outlet of the gasification furnace and a hydrogen outlet of the water electrolysis device are communicated with the methanol synthesis device; a gas-phase product outlet of the pyrolysis device is communicated with the gasification furnace, a residue outlet of the gasification furnace is communicated with the pyrolysis device, and a pyrolytic carbon outlet of the pyrolysis device and an ammonia outlet of the ammonia synthesis device are both communicated with the ammoniation device. According to the system, the adaptability of biomass raw materials and the quality of gasified gas are improved to the maximum extent, and all-component green utilization of biomass resources is achieved.

Description

Technical Field

[0001] The present invention relates to the field of green chemical technology, and in particular to a system and method for co-producing green methanol, ammonia and carbon-based fertilizer with renewable energy. Background Art

[0002] As global awareness of sustainable development and environmental protection increases, vigorously developing renewable energy represented by wind, solar and biomass energy and building a green and low-carbon energy system have become the only way to achieve energy transformation and respond to climate change. As one of the world's largest energy producers and consumers, China's wind and solar power generation installed capacity are among the highest in the world, demonstrating remarkable achievements in the field of renewable energy. However, in actual applications, due to the intermittent and unstable nature of wind, solar and other renewable energy power generation, the problem of wind and solar abandonment has become increasingly prominent, seriously restricting the efficient use of renewable energy.

[0003] In order to solve the above problems, green methanol and ammonia, as new low-carbon energy carriers, have shown great application potential and market prospects in the field of energy and chemical industry. These two green energy sources can not only effectively alleviate the excessive dependence on fossil energy, but also significantly reduce carbon emissions and promote the transformation and upgrading of energy structure. The production process of green methanol and ammonia can rely on renewable energy electricity, through water electrolysis to produce hydrogen, air separation and subsequent chemical synthesis. Among them, the synthesis of green methanol requires that the carbon source used must all come from biomass or carbon dioxide in the air, which not only helps to achieve carbon recycling, but also effectively reduces greenhouse gas emissions.

[0004] Biomass gasification, as a technical means of efficiently utilizing biomass resources, is of great significance for the production of green methanol and hydrogen. my country has abundant biomass resources, including straw, livestock and poultry manure, forestry residues, and domestic waste, which provide a solid foundation for the development of biomass gasification technology. However, different types of biomass raw materials exhibit different characteristics during the gasification process. For example, livestock and poultry manure usually contains high moisture, ash, and pollutant elements, which have an adverse effect on the gasification process and the quality of the gasification products.

[0005] In the existing biomass gasification technology for preparing green methanol and ammonia, some patents have proposed solutions. For example, patent CN 118620663 discloses a method and system for co-producing green methanol and green ammonia by coupling green hydrogen with biomass gasification. The method achieves the co-production of green methanol and green ammonia by gasifying biomass raw materials with oxygen obtained from a water electrolysis hydrogen production device and an air separation device. However, the patent does not clearly specify the specific type of biomass raw materials, and the gasification agent component is limited to oxygen, which may cause the internal temperature of the gasification device to be too high, affecting the gasification efficiency and product quality.

[0006] In addition, patents CN 116496141 and CN 118105904 respectively proposed a green methanol preparation process and system, in which the gasifying agent is a mixture of flue gas and oxygen, and is composed of carbon dioxide and oxygen. These two methods optimize the gasification process to a certain extent and improve the product quality. However, these patents do not consider the utilization of biomass gasification residues, resulting in waste of resources and potential environmental pollution.

[0007] In summary, although the existing biomass gasification technology for preparing green methanol and ammonia has made some progress, there are still many problems and challenges, especially in the selection of biomass raw materials, optimization of gasification agent components, and utilization of gasification residues. Therefore, it is necessary to develop a more efficient and environmentally friendly method and system for preparing green methanol and ammonia by biomass gasification to achieve efficient utilization of biomass resources and green development.

[0008] In view of this, the present invention is proposed. Summary of the invention

[0009] The purpose of the present invention is to provide a system and method for co-producing green methanol, ammonia and carbon-based fertilizer using renewable energy, which can realize green utilization of all components of biomass resources.

[0010] In a first aspect, the present invention provides a system for co-producing green methanol, ammonia and carbon-based fertilizer using renewable energy, including a water electrolysis device, an air separation device, a gasifier, a methanol synthesis device, an ammonia synthesis device, a pyrolysis device and an ammonia device.

[0011] The gasifier has a first biomass inlet, a gaseous product inlet, an oxygen inlet, a gasification gas outlet and a residue outlet;

[0012] The pyrolysis device has a second biomass inlet, an oxygen inlet, a residue inlet, a gas phase product outlet and a pyrolysis char outlet;

[0013] The oxygen outlet of the water electrolysis device and / or the oxygen outlet of the air separation device are in communication with the gasifier and the pyrolysis device;

[0014] The nitrogen outlet of the air separation device and the hydrogen outlet of the water electrolysis device are connected to the ammonia synthesis device;

[0015] The gasification gas outlet of the gasifier and the hydrogen outlet of the water electrolysis device are connected to the methanol synthesis device;

[0016] The gas phase product outlet of the pyrolysis device is connected to the gasifier, the residue outlet of the gasifier is connected to the pyrolysis device, and the pyrolysis char outlet of the pyrolysis device and the ammonia outlet of the synthetic ammonia device are both connected to the ammonia device.

[0017] The present invention fully utilizes the resource characteristics of different types of renewable energy by integrating a water electrolysis device, an air separation device, a gasifier, a methanol synthesis device, a synthetic ammonia device, a pyrolysis device, and an ammonia device, so that biomass resources can be greenly utilized in all components, thereby improving the utilization efficiency of resources. In addition, the present invention can convert biomass resources into high value-added products such as methanol, ammonia, and carbon-based fertilizers by reasonably configuring the connections and inputs and outputs between the various devices, thereby maximizing the output benefits and improving the economic benefits.

[0018] As a preferred embodiment of the present technical solution, it also includes a wind power generation device, a solar power generation device and / or a biomass power generation device, and the wind power generation device, the solar power generation device and / or the biomass power generation device provide the electricity required in the renewable energy co-production of green methanol, ammonia and carbon-based fertilizer system.

[0019] As a preferred embodiment of the present technical solution, the gasifier is a fluidized bed gasifier or an entrained flow gasifier, wherein, when the gasifier is a fluidized bed gasifier, in the fluidized bed gasifier, the biomass particles and the gasifying agent (such as oxygen) are fully contacted in a fluidized state, thereby increasing the reaction area, thereby increasing the gasification intensity, and due to the good gas-solid contact, the biomass can be more fully converted into gasified gas, thereby improving the gasification efficiency. When the gasifier is an entrained flow gasifier, the single furnace capacity of the entrained flow gasifier is usually large, which can meet the needs of large-scale production. It quickly converts biomass into gasified gas through gas-solid reaction at high temperature, and has the characteristics of high efficiency.

[0020] In a second aspect, the present invention further discloses a method for co-producing green methanol, ammonia and carbon-based fertilizer using the above-mentioned renewable energy co-production system, comprising the following steps:

[0021] S1. Water from outside enters the water electrolysis device to undergo electrochemical reaction to obtain hydrogen and oxygen;

[0022] S2, the air from outside enters the air separation unit to obtain oxygen and nitrogen;

[0023] S3, the first biomass raw material and the oxygen obtained in step S1 and step S2 enter the gasifier for gasification reaction to obtain gasification gas and residue;

[0024] S4, the second biomass raw material, the oxygen obtained in step S1 and / or step S2, and the residue produced in step S3 are put into a pyrolysis device for pyrolysis to obtain a gas phase product and pyrolysis char, wherein the gas phase product is sent to a gasifier as a gasifying agent component;

[0025] S5, the hydrogen obtained in step S1 and the nitrogen obtained in step S2 enter the synthetic ammonia unit to obtain ammonia, and the gasification gas obtained in step S3 and the hydrogen obtained in step S1 enter the methanol synthesis unit to obtain methanol;

[0026] S6. The pyrolytic char obtained in step S4 and the ammonia obtained in step S5 enter an ammoniation device to obtain charcoal-based fertilizer.

[0027] As a preferred embodiment of the present technical solution, the first biomass raw material is agricultural and forestry waste, and the second biomass raw material is livestock and poultry manure.

[0028] As a preferred embodiment of the present technical solution, the volatile matter content of the agricultural and forestry waste is 60-80%, such as crop straw, forestry residues and energy plants. The gasifier of the present invention only processes biomass with a high volatile matter content, which can effectively avoid the direct addition of biomass with a high ash content into the gasifier, resulting in energy being wasted by heating ash, and at the same time avoid the release of components that are detrimental to the quality of synthesis gas at high temperatures; the ash content of the livestock and poultry manure is 35%-50%, such as cow dung. For biomass with a high ash content, the present invention preferentially uses pyrolysis carbonization to achieve component separation, and then transports the gaseous products produced by pyrolysis to the gasifier. The gaseous products can not only adjust the volume concentration of oxygen in the gasifying agent, but also enable the gasifier to operate stably at a higher temperature, and the volume concentration of carbon monoxide in the gasification gas is higher.

[0029] As a preferred embodiment of the present technical solution, in the gasifier, the gasification temperature is 800-1500° C., the volume concentration of oxygen in the gasifying agent is 16%-50%, and the volume concentration of carbon monoxide in the gasification gas is greater than 45%.

[0030] As a preferred embodiment of the present technical solution, during the pyrolysis, the temperature is controlled to be 350-500°C, and the pyrolysis temperature is much lower than the temperature of the gasifier, which effectively avoids the release of pollutants. In addition, part of the heat required for pyrolysis in the present invention comes from the sensible heat of the high-temperature gasification residue, and the other part of the heat can be released by introducing a small amount of oxygen to make the charcoal in the solid phase burn and release heat. Moreover, the carbon dioxide generated by the combustion of charcoal enters the gasifier with the gas phase product (as a gasifying agent component) to participate in the reaction, thereby improving the carbon conversion rate of the entire system.

[0031] As a preferred embodiment of the present technical solution, in the ammoniaation device, the mass ratio of pyrolytic carbon to ammonia is (4-20):1, wherein the pyrolytic carbon includes mixed gasification residue.

[0032] As a preferred embodiment of the present technical solution, the carbon-based fertilizer has a nitrogen content greater than 10%, and can be used as a biochar-based nitrogen fertilizer with good slow-release properties.

[0033] The renewable energy co-production system of green methanol, ammonia and carbon-based fertilizer of the present invention has at least the following features:

[0034] Beneficial effects:

[0035] 1. The renewable energy co-production system of green methanol, ammonia and carbon-based fertilizer of the present invention comprises a water electrolysis device, an air separation device, a gasifier, a methanol synthesis device, an ammonia synthesis device, a pyrolysis device and an ammonia production device, wherein the water electrolysis device decomposes water into hydrogen and oxygen by an electrochemical method, the air separation device separates oxygen and nitrogen in the air, the gasifier uses oxygen produced by the water electrolysis device and / or the air separation device as one of the gasifying agent components, and converts the first biomass into gasification gas and residue with hydrogen and carbon monoxide as main components, the methanol synthesis device uses the gasification gas and hydrogen produced by the water electrolysis device to synthesize green methanol, and the remaining hydrogen and nitrogen are used to synthesize ammonia, and the pyrolysis device is used in the water electrolysis device and / or the air separation device. Under the supply of a small amount of oxygen prepared by the device, the second biomass and the residue produced by the gasifier can be pyrolyzed at low temperature into gas products and pyrolytic carbon. The gas products produced by pyrolysis include water vapor, carbon dioxide and organic matter. Among them, water vapor and carbon dioxide can be used as gasifying agent components together with oxygen to control the volume concentration of oxygen in the gasifying agent within an appropriate range to avoid over-temperature slagging in the gasifier. The organic matter is a high-quality gasification raw material, and most of the available carbon in the second biomass can be introduced into the gasifier to be converted into gasification gas. In addition, the setting of the pyrolysis device also effectively utilizes the waste heat of the gasification residue, plays the role of a slag cooler, and recycles the gasification residue. Finally, the pyrolytic carbon produced by the pyrolysis can be ammoniated to obtain nitrogen-containing carbon-based fertilizer. The system makes full use of the resource characteristics of different types of renewable energy, maximizes the output benefits through reasonable configuration, and realizes the green utilization of all components of biomass resources;

[0036] 2. The gasifier and pyrolysis device in the renewable energy co-production system of green methanol, ammonia and carbon-based fertilizer of the present invention are respectively used to process different biomass raw materials. For biomass with high ash content, by introducing its pyrolysis product into the gasifier, not only can the oxygen concentration in the gasifier be controlled to avoid the over-temperature slagging problem of pure oxygen gasification, but also no other flue gas or water vapor source is required, simplifying the gasification process of the gasifier; in addition, the temperature of the gasifier is mainly limited by the ash content of the biomass entering the furnace. After the ash is separated by pyrolysis and the generated organic matter is transported to the gasifier, the gasifier can stably operate at a higher temperature, which is beneficial to the reforming reaction and tar cracking, and obtains high-quality gasification gas;

[0037] 3. The oxygen in the renewable energy co-production system of green methanol, ammonia and carbon-based fertilizer of the present invention is provided by a water electrolysis device and / or an air separation device. On the one hand, oxygen can be used as a component of the gasification agent, avoiding the problem of low syngas content in the gasification gas and the need to separate nitrogen caused by air as a gasification agent. On the other hand, oxygen can also be used to provide a weak oxygen atmosphere for the pyrolysis device, so that the first biomass gasification residue and the second biomass pyrolysis heat release to achieve energy self-supply. In addition, the weak oxygen atmosphere is also conducive to activating the pyrolysis product pyrolysis carbon, so that it has better ammonia adsorption capacity;

[0038] 4. In the renewable energy co-production system of green methanol, ammonia and carbon-based fertilizer of the present invention, the gasifier provides hydrogen and carbon monoxide for methanol synthesis. Since hydrogen can be derived from the water electrolysis device, the key is carbon monoxide. On the one hand, the carbon element in both the first biomass and the second biomass is transferred to the gasification gas to the maximum extent through the exchange between the gasification furnace residue and the gas phase product of the pyrolysis device. On the other hand, the solid phase in the gasifier has a high carbon content and strong reducing properties at high temperatures. Carbon dioxide is converted into carbon monoxide through the gasification reaction of carbon. Therefore, the volume concentration of carbon monoxide in the gasification gas can be significantly increased through the above technical ideas. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0040] Figure 1 This is a schematic diagram of the structure of the renewable energy co-production system of green methanol, ammonia and carbon-based fertilizer of the present invention;

[0041] Figure 2 The present invention is a schematic flow chart of the method for co-producing green methanol, ammonia and carbon-based fertilizer using renewable energy. Description of the drawings:

[0043] 1: Water electrolysis unit; 2: Air separation unit; 3: Gasification furnace; 4: Methanol synthesis unit; 5: Ammonia synthesis unit; 6: Pyrolysis unit; 7: Ammonia unit. DETAILED DESCRIPTION

[0044] It should be noted that the following detailed descriptions are illustrative and are intended to provide further explanation of the present application. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present application belongs.

[0045] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. As used herein, unless the context clearly indicates otherwise, the singular form also includes the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this description, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0046] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0047] Example 1

[0048] like Figure 1As shown, this embodiment provides a renewable energy co-production system of green methanol, ammonia, and carbon-based fertilizer, including a water electrolysis device 1, an air separation device 2, a gasifier 3, a methanol synthesis device 4, a synthetic ammonia device 5, a pyrolysis device 6, and an ammonia device 7, wherein the water electrolysis device 1 has a water inlet, an oxygen outlet, and a hydrogen outlet, the air separation device 2 has an air inlet, an oxygen outlet, and a nitrogen outlet, the gasifier 3 has a first biomass inlet, a gaseous product inlet, an oxygen inlet, a gasification gas outlet, and a residue outlet; the pyrolysis device 6 has a second biomass inlet, an oxygen inlet, a residue inlet, a gaseous product outlet, and a pyrolysis carbon outlet; the oxygen outlet and / or air outlet of the water electrolysis device 1 The oxygen outlet of the separation device 2 is connected to the gasifier 3 and the pyrolysis device 6, and the two oxygen production methods cooperate with each other to ensure the oxygen supply; the nitrogen outlet of the air separation device 2 and the hydrogen outlet of the water electrolysis device 1 are connected to the ammonia synthesis device 5, that is, the ammonia synthesis device 5 can synthesize ammonia using the nitrogen generated by the air separation device 2 and the hydrogen generated by the water electrolysis device 1, wherein the volume ratio of the hydrogen and nitrogen used is about 3:1; the gasification gas outlet of the gasifier 3 and the hydrogen outlet of the water electrolysis device 1 are connected to the methanol synthesis device 4, and the gasifier 3 uses the oxygen produced by the water electrolysis device 1 and / or the air separation device 2 as one of the gasifying agent components to convert the first biomass into a methanol synthesis device composed of hydrogen and one The methanol synthesis device 4 uses the gasification gas and the hydrogen produced by the water electrolysis device 1 to synthesize green methanol, wherein the main components of the gasification gas are hydrogen and carbon monoxide. The gasification gas and hydrogen are prepared into synthesis gas for synthesizing green methanol, and the volume ratio of hydrogen to carbon monoxide in the synthesis gas is about 2:1; the gas phase product outlet of the pyrolysis device 6 is connected to the gasifier 3, the residue outlet of the gasifier 3 is connected to the pyrolysis device 6, the pyrolysis char outlet of the pyrolysis device 6 and the ammonia outlet of the ammonia synthesis device 5 are both connected to the ammonia device 7, and the pyrolysis device 6 can be supplied with a small amount of oxygen produced by the water electrolysis device 1 and / or the air separation device 2. The second biomass and the residue produced by the gasifier 3 are pyrolyzed at low temperature into gas products and pyrolytic charcoal. The gas products produced by the pyrolysis include water vapor, carbon dioxide and organic matter. Among them, water vapor and carbon dioxide can be used as gasifying agent components together with oxygen to control the volume concentration of oxygen in the gasifying agent within an appropriate range to avoid over-temperature slagging in the gasifier 3. The organic matter is a high-quality gasification raw material, and most of the available carbon in the second biomass can be introduced into the gasifier 3 to be converted into gasification gas. In addition, the setting of the pyrolysis device 6 also effectively utilizes the waste heat of the gasification residue and recycles the gasification residue. Finally, the pyrolysis product pyrolytic charcoal can be subjected to ammoniation to obtain nitrogen-containing carbon-based fertilizer.

[0049] Therefore, this system makes full use of the resource characteristics of different types of renewable energy, maximizes the adaptability of biomass raw materials and the quality of gasification gas, and organically combines the pyrolytic carbon produced by pyrolysis with synthetic ammonia to produce biochar-based nitrogen fertilizer, realizing the green utilization of all components of biomass resources.

[0050] On the basis of the above technical scheme, it is further preferred that the renewable energy co-production system of green methanol, ammonia and charcoal-based fertilizer of the present invention also includes a wind power generation device, a solar power generation device and / or a biomass power generation device, wherein the wind power generation device, the solar power generation device and / or the biomass power generation device provide the electric energy required by the renewable energy co-production system of green methanol, ammonia and charcoal-based fertilizer.

[0051] In this embodiment, the gasifier 3 used is a fluidized bed gasifier or an entrained flow gasifier, wherein the gasifying agent of the fluidized bed gasifier or the entrained flow gasifier is composed of gas phase products generated by pyrolysis of the second biomass and oxygen.

[0052] In this embodiment, the water electrolysis device 1, air separation device 2, methanol synthesis device 4, ammonia synthesis device 5, pyrolysis device 6 and ammoniaization device 7 used can all refer to the existing technology and will not be described in detail here.

[0053] Example 2

[0054] like Figure 2 As shown, this embodiment discloses a method for co-producing green methanol, ammonia, and carbon-based fertilizer using the above-mentioned renewable energy co-production system, comprising the following steps:

[0055] S1, water from outside enters the water electrolysis device 1 to undergo electrochemical reaction to obtain hydrogen and oxygen;

[0056] S2, the air from outside enters the air separation device 2 to obtain oxygen and nitrogen;

[0057] S3, the first biomass raw material and the oxygen obtained in step S1 and / or step S2 enter the gasifier 3, and a gasification reaction is carried out under the conditions of a gasification temperature of 800-1500°C and a volume concentration of oxygen in the gasifying agent of 16%-50%, to obtain gasified gas and residue, wherein the volume concentration of carbon monoxide in the gasified gas is greater than 45%, wherein the first biomass raw material is conventional agricultural and forestry waste, such as crop straw, forestry residues and energy plants, etc., and its volatile matter content is 60-80%, which is suitable for direct gasification in the furnace;

[0058] S4, the second biomass raw material, a small amount of oxygen obtained in step S1 and / or step S2, and the residue produced in step S3 enter the pyrolysis device 6 and are pyrolyzed at 350-500°C to obtain gas phase products and pyrolysis charcoal, wherein the gas phase products are sent to the gasifier 3 as a gasifying agent component, the second biomass raw material is livestock and poultry manure with an ash content of 35%-50%, such as cow dung. Since the second biomass raw material has a high ash content, if it is directly added to the gasifier 3, a considerable part of the energy will be wasted for heating the ash, and some components that are unfavorable to the quality of the synthesis gas (hydrogen and carbon monoxide) will be released at high temperature. At the same time, the ash wrapped in coke will also lead to a low carbon conversion rate. The pyrolysis temperature is much lower than the temperature of the gasifier 3, which effectively avoids the release of pollutants;

[0059] S5, the hydrogen obtained in step S1 and the nitrogen obtained in step S2 enter the synthetic ammonia device 5 to obtain ammonia, wherein the volume ratio of the hydrogen and nitrogen used is about 3:1;

[0060] The gasification gas obtained in step S3 and the hydrogen obtained in step S1 enter the methanol synthesis device 4 to obtain methanol, wherein the main components of the gasification gas are hydrogen and carbon monoxide, and the gasification gas and hydrogen are mixed into synthesis gas for synthesizing green methanol, and the volume ratio of hydrogen to carbon monoxide in the synthesis gas is about 2:1;

[0061] S6. The pyrolytic char obtained in step S4 and the ammonia obtained in step S5 enter the ammoniation device 7, and the mass ratio of the pyrolytic char to the ammonia is controlled to be (4-20):1, and the mass of the pyrolytic char includes the mixed gasification residue to obtain a charcoal-based fertilizer. The pyrolytic char prepared by the pyrolysis device 6 has developed pores and abundant surface functional groups, which can more fully adsorb ammonia. Therefore, the nitrogen content of the charcoal-based fertilizer obtained after the ammoniation treatment is greater than 10%, and it can be used as a biochar-based nitrogen fertilizer with good slow-release performance.

[0062] Example 3

[0063] This embodiment specifically provides a system and method for co-producing green methanol, ammonia, and carbon-based fertilizer with renewable energy, such as Figure 1-2 As shown, the system includes a water electrolysis device 1, an air separation device 2, a gasifier 3, a methanol synthesis device 4, an ammonia synthesis device 5, a pyrolysis device 6, and an ammoniaization device 7.

[0064] The water electrolysis device 1 decomposes water into hydrogen and oxygen by an electrochemical method, producing 6.7 tons of hydrogen and 53.6 tons of oxygen per hour.

[0065] Air separation unit 2 separates oxygen and nitrogen from the air, producing 23 tons of nitrogen and 7 tons of oxygen per hour.

[0066] Gasifier 3 uses corn stalks as raw material (its volatile content is 68%), with an hourly feed rate of 25 tons; it uses a circulating fluidized bed gasifier, the gasification temperature is 950°C, and the fluidizing air (also the gasifying agent) flow rate is 23200Nm 3 / h, where the volume concentration of oxygen is 20%, and the oxygen comes from the water electrolysis device 1 and the air separation device 2; the gas production of the gasifier 3 is about 28000Nm 3 / h, the volume concentration of the main components is: carbon monoxide 45.2%, hydrogen 25.3%.

[0067] The methanol synthesis device 4 uses the gasification gas produced by the gasifier 3 plus about 1.7 tons / hour of hydrogen as the synthesis gas raw material (the hydrogen comes from the water electrolysis device 1, and the volume ratio of hydrogen and carbon monoxide in the final synthesis gas is 2.1:1), and synthesizes about 12 tons of methanol per hour.

[0068] The ammonia synthesis unit 5 uses 23 tons / hour of nitrogen and 5 tons / hour of hydrogen as raw materials (the volume ratio of hydrogen to nitrogen is 3:1), and synthesizes about 26 tons of ammonia per hour.

[0069] The pyrolysis device 6 uses dry cow dung as raw material (with an ash content of 41%), with an hourly feed rate of 30 tons, and mixes and heats it with about 2 tons / hour of high-temperature residue (950°C) from the gasifier 3, and adds about 400 kg / hour of oxygen, so that the char in the solid phase burns and releases heat, and the temperature of the pyrolysis device reaches 400°C. The output of the pyrolysis device 6 includes a flow rate of about 45,000 m 3 / h of gaseous products (400°C) and 14 tons / hour of pyrolytic carbon, wherein the gaseous products are used as fluidizing air (also a gasifying agent) in a circulating fluidized bed gasifier, so that the oxygen volume concentration is maintained at 20%.

[0070] The ammoniation device 7 performs ammoniation treatment according to the mass ratio of pyrolytic carbon to ammonia of 10:1, that is, 14 tons of pyrolytic carbon and 1.4 tons of ammonia per hour, to obtain 15.4 tons of biochar-based nitrogen fertilizer with a nitrogen content of about 10%.

[0071] In the renewable energy co-production system of green methanol, ammonia and carbon-based fertilizer in this embodiment, all equipment uses wind energy, solar energy and biomass energy for power generation.

[0072] Research shows that this embodiment can process 25 tons of corn stalks and 30 tons of dry cow dung per hour, producing 12 tons of green methanol, 24.6 tons of ammonia and 15.4 tons of carbon-based fertilizer; the remaining approximately 53 tons of oxygen can be provided to the biomass power generation device.

[0073] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A renewable energy co-production system of green methanol, ammonia and carbon-based fertilizer, characterized in that: The invention comprises a water electrolysis device (1), an air separation device (2), a gasification furnace (3), a methanol synthesis device (4), an ammonia synthesis device (5), a pyrolysis device (6) and an ammoniaization device (7), The gasifier (3) has a first biomass inlet, a gaseous product inlet, an oxygen inlet, a gasification gas outlet and a residue outlet; The pyrolysis device (6) has a second biomass inlet, an oxygen inlet, a residue inlet, a gas phase product outlet and a pyrolysis charcoal outlet; The oxygen outlet of the water electrolysis device (1) and / or the oxygen outlet of the air separation device (2) are in communication with the gasification furnace (3) and the pyrolysis device (6); The nitrogen outlet of the air separation device (2) and the hydrogen outlet of the water electrolysis device (1) are connected to the ammonia synthesis device (5); The gasification gas outlet of the gasifier (3) and the hydrogen outlet of the water electrolysis device (1) are in communication with the methanol synthesis device (4); The gas phase product outlet of the pyrolysis device (6) is connected to the gasifier (3), the residue outlet of the gasifier (3) is connected to the pyrolysis device (6), and the pyrolysis char outlet of the pyrolysis device (6) and the ammonia outlet of the synthetic ammonia device (5) are both connected to the ammonia device (7).

2. The renewable energy co-production system of green methanol, ammonia and carbon-based fertilizer according to claim 1 is characterized in that: It also includes a wind power generation device, a solar power generation device and / or a biomass power generation device, which provides the electricity required by the renewable energy co-production system of green methanol, ammonia and carbon-based fertilizer.

3. The renewable energy co-production system of green methanol, ammonia and carbon-based fertilizer according to claim 1 is characterized in that: The gasifier (3) is a fluidized bed gasifier or an entrained flow gasifier.

4. A method for co-producing green methanol, ammonia and carbon-based fertilizer using the renewable energy co-production green methanol, ammonia and carbon-based fertilizer system according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1, water from outside enters the water electrolysis device (1) to undergo electrochemical reaction to obtain hydrogen and oxygen; S2, the air from outside enters the air separation device (2) to obtain oxygen and nitrogen; S3, the first biomass raw material and the oxygen obtained in step S1 and step S2 enter the gasifier (3) for gasification reaction to obtain gasification gas and residue; S4, the second biomass raw material, the oxygen obtained in step S1 and / or step S2, and the residue produced in step S3 are introduced into a pyrolysis device (6) for pyrolysis to obtain a gas phase product and pyrolysis char, wherein the gas phase product is introduced into a gasifier (3) as a gasifying agent component; S5. The hydrogen obtained in step S1 and the nitrogen obtained in step S2 enter into an ammonia synthesis device (5) to obtain ammonia, and the gasification gas obtained in step S3 and the hydrogen obtained in step S1 enter into a methanol synthesis device (4) to obtain methanol; S6. The pyrolytic char obtained in step S4 and the ammonia obtained in step S5 enter an ammoniaizing device (7) to obtain a charcoal-based fertilizer.

5. The method for co-producing green methanol, ammonia and carbon-based fertilizer according to claim 4, characterized in that: The first biomass raw material is agricultural and forestry waste, and the second biomass raw material is livestock and poultry manure.

6. The method for co-producing green methanol, ammonia and carbon-based fertilizer according to claim 5, characterized in that: The ash content of the livestock and poultry manure is 35%-50%.

7. The method for co-producing green methanol, ammonia and carbon-based fertilizer according to claim 4, characterized in that: In the gasifier (3), the gasification temperature is 800-1500° C., the volume concentration of oxygen in the gasifying agent is 16%-50%, and the volume concentration of carbon monoxide in the gasification gas is greater than 45%.

8. The method for co-producing green methanol, ammonia and carbon-based fertilizer according to claim 4, characterized in that: During the pyrolysis, the temperature is controlled at 350-500°C.

9. The method for co-producing green methanol, ammonia and carbon-based fertilizer according to claim 4, characterized in that: In the ammoniation device (7), the mass ratio of pyrolytic carbon to ammonia is (4-20):

1.

10. The method for co-producing green methanol, ammonia and carbon-based fertilizer according to claim 4, characterized in that: The nitrogen content of the carbon-based fertilizer is greater than 10%.

Images