Hydrogen and carbon monoxide mixed storage system and operation method and application thereof

Abstract

The invention belongs to the technical field of methanol synthesis, and provides a hydrogen and carbon monoxide mixed storage system and an operation method and application thereof. The mixed storage system comprises a hydrogen preparation device, a hydrogen control device, a hydrogen compression device, a carbon monoxide preparation device, a carbon monoxide control device, a carbon monoxide compression device, a mixed storage tank and a discharging pipeline. The mixing storage tank is used for co-storage of carbon monoxide and hydrogen. The hydrogen and carbon monoxide mixed storage system is suitable for mixing and storage of two or more gases of green hydrogen prepared by electrolysis of new energy and carbon monoxide prepared by conversion of carbon dioxide or synthesis gas prepared by biomass, compared with traditional methanol prepared by synthesis gas, a synthesis gas conversion system is omitted, and when an external hydrogen source or green hydrogen is introduced, the production cost is reduced. The premixing link of traditional coal-to-methanol is reduced, the carbon-hydrogen ratio of the mixed gas can be adjusted by directly using green hydrogen, the technological process is simplified, and the energy consumption and the methanol synthesis cost are reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of synthetic methanol, and in particular to a hydrogen and carbon monoxide mixed storage system, an operation method and an application thereof. Background Art

[0002] Sustainably produced renewable methanol has become an effective way to achieve decarbonization in the chemical and transportation industries. Ultra-low carbon, carbon-neutral, and net-zero emissions renewable methanol can be produced from a variety of sources. For example, renewable methanol produced from biomass such as forestry and agricultural waste and byproducts, biogas, sewage, municipal solid waste, and black liquor from the pulp and paper industry is often referred to as biomethanol; renewable methanol obtained from carbon monoxide and green hydrogen produced from renewable electricity is often referred to as "green methanol."

[0003] Hydrogen is stable at room temperature, but when conditions change, its properties become more reactive, further increasing its activity and making it prone to explosion when exposed to a fire source. Carbon monoxide has a melting point of -205°C and a boiling point of -191.5°C. It is insoluble in water and difficult to liquefy or solidify. In traditional coal-to-methanol production, coal gasification produces crude syngas, which contains carbon monoxide (CO), hydrogen (H2), and a small amount of carbon dioxide (CO2). This crude syngas undergoes dust removal and desulfurization to remove impurities such as sulfides. A shift reaction adjusts the syngas (H2 and CO) to an appropriate hydrogen-to-carbon ratio. High-pressure water scrubbing removes carbon dioxide (CO2). Further purification occurs through oil and carbon filters. Finally, the syngas (H2 and CO) enters the synthesis tower as a mixture for methanol production, eliminating the need for separate tank storage and mixing of H2 and CO. With the rapid development and application of green hydrogen production from renewable energy sources, the production of "green methanol" using green hydrogen and carbon monoxide or biomass to produce syngas has gradually become the primary method for methanol production. In "green methanol," different storage environments are set up based on the properties and sources of hydrogen and carbon monoxide, and a mixed hydrogen and carbon monoxide storage system has been developed. This system is suitable for mixing and storing two or more gases, such as green hydrogen produced by renewable energy electrolysis, carbon dioxide conversion to carbon monoxide, or biomass synthesis gas. Compared with traditional synthesis gas to methanol, this system reduces the synthesis gas conversion system and can directly use green hydrogen to adjust the carbon-hydrogen ratio of the mixture, simplifying the process and reducing energy consumption and the cost of synthesizing methanol. Regarding gaseous hydrogen storage, it is generally carried out in accordance with the requirements of the "GB4962-1985 Technical Regulations for the Safety of Hydrogen Use," but this method of hydrogen storage has problems such as poor safety, large floor space requirements, and high requirements for storage tank materials. Improper hydrogen storage methods can also easily lead to hydrogen leakage, combustion, or explosion, which may cause serious harm and damage to personnel, the environment, and equipment.

[0004] Therefore, storing hydrogen and carbon monoxide together and improving their storage safety and economy will facilitate the subsequent methanol synthesis process and have good prospects. Summary of the Invention

[0005] The purpose of the present invention is to provide a hydrogen and carbon monoxide mixed storage system and its operation method and application in response to the deficiencies of the existing technology.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a mixed storage system of hydrogen and carbon monoxide, comprising the following devices: a hydrogen production device, a hydrogen control device, a hydrogen compression device, a carbon monoxide production device, a carbon monoxide control device, a carbon monoxide compression device, a mixed storage tank, and a discharge pipe;

[0008] The mixed storage tank is used for the co-storage of carbon monoxide and hydrogen.

[0009] Preferably, the hydrogen comes from a hydrogen preparation device and is transported to a hydrogen control device through a pipeline; the carbon monoxide comes from a carbon monoxide preparation device and is transported to a carbon monoxide control device through a pipeline.

[0010] Preferably, the hydrogen control device is used to regulate the hydrogen supply rate of the hydrogen production device; the carbon monoxide control device is used to regulate the carbon monoxide supply rate of the carbon monoxide production device.

[0011] Preferably, the mixing storage tank comprises a stirring device; the hydrogen entering the mixing storage tank through the hydrogen control device and the hydrogen compression device and the carbon monoxide entering the mixing storage tank through the carbon monoxide control device and the carbon monoxide compression device are uniformly mixed under the action of the stirring device.

[0012] The present invention also provides an operating method of the hydrogen and carbon monoxide mixed storage system, comprising the following steps:

[0013] Hydrogen is output from the hydrogen preparation device and transported to the mixed storage tank via the hydrogen control device and the hydrogen compression device; carbon monoxide is output from the carbon monoxide preparation device and transported to the mixed storage tank via the carbon monoxide control device and the carbon monoxide compression device; the hydrogen and carbon monoxide in the mixed storage tank are output via the discharge pipe.

[0014] Preferably, the temperature of the mixing storage tank is 0-150° C., and the pressure of the mixing storage tank is 0-80 MPa.

[0015] Preferably, the volume proportion of hydrogen in the mixed storage tank is 0-60%.

[0016] The present invention also provides application of the hydrogen and carbon monoxide mixed storage system in methanol synthesis.

[0017] Preferably, the mixing storage tank is connected to the synthetic methanol system via a discharge pipe.

[0018] The beneficial effects of the present invention include the following:

[0019] 1) The present invention provides a mixed storage system for hydrogen and carbon monoxide, wherein hydrogen and carbon monoxide are respectively derived from a hydrogen preparation device and a carbon monoxide preparation device. The rate at which the raw gas enters the mixed storage tank is effectively controlled by a hydrogen control device and a carbon monoxide control device to ensure that the proportion of the mixed gas can be directly used for subsequent methanol synthesis; the hydrogen compression device and the carbon monoxide compression device can pressurize the hydrogen and carbon monoxide into the mixed storage tank, and the hydrogen and carbon monoxide are quickly mixed in the mixed storage tank by a stirring device to achieve the purpose of long-term uniform mixing and storage of hydrogen and carbon monoxide. After sufficient mixing, the hydrogen and carbon monoxide are transported to the synthetic methanol system through a discharge pipe; compared with static mixers such as multi-stage Venturi premixing devices, spiral blade static mixers, and microchannel multi-stage mixers currently used for gas mixing, the stirred mixing storage tank of the present invention can quickly achieve uniform mixing of gases.

[0020] 2) The present invention adopts the idea of raw gas preparation and mixed storage of hydrogen and carbon monoxide gases, realizing an integrated system of raw material production, gas mixed storage and gas utilization, greatly reducing the synthesis cost of methanol and improving the situation of separate storage and transportation of raw gas; the hydrogen and carbon monoxide mixed storage system of the present invention is suitable for mixing and storing two or more gases of green hydrogen produced by new energy electrolysis and carbon dioxide conversion to carbon monoxide or biomass synthesis gas. Compared with traditional synthesis gas to methanol, it reduces the synthesis gas conversion system. When introducing an external hydrogen source or green hydrogen, it reduces the pre-mixing link of traditional coal-to-methanol. Green hydrogen can be directly used to adjust the carbon-hydrogen ratio of the mixed gas, simplifying the process flow, reducing energy consumption and the cost of synthesizing methanol; at the same time, because of the presence of carbon monoxide in the mixed gas tank, it prevents hydrogen deflagration and ensures the safety of the process, and also reduces the requirements for the tank body and avoids the occurrence of hydrogen embrittlement. Under the premise of ensuring high-quality methanol synthesis, the present invention reduces process requirements and costs and facilitates large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Schematic diagram of a hydrogen and carbon monoxide mixed storage system according to the present invention. DETAILED DESCRIPTION

[0022] The present invention provides a mixed storage system of hydrogen and carbon monoxide, comprising the following devices: a hydrogen production device, a hydrogen control device, a hydrogen compression device, a carbon monoxide production device, a carbon monoxide control device, a carbon monoxide compression device, a mixed storage tank, and a discharge pipe;

[0023] The mixed storage tank is used for the co-storage of carbon monoxide and hydrogen.

[0024] The schematic diagram of the mixed storage system of hydrogen and carbon monoxide of the present invention is as follows Figure 1 shown.

[0025] In the present invention, the hydrogen comes from the hydrogen preparation device and is transported to the hydrogen control device through a pipeline; the carbon monoxide comes from the carbon monoxide preparation device and is transported to the carbon monoxide control device through a pipeline.

[0026] In the present invention, the hydrogen preparation device preferably uses electricity provided by a renewable energy power generation device to prepare hydrogen, and the hydrogen production process in the hydrogen preparation device preferably includes alkaline water electrolysis to produce hydrogen, proton exchange membrane water electrolysis to produce hydrogen, or solid oxide water electrolysis to produce hydrogen.

[0027] In the present invention, the hydrogen control device is used to regulate the hydrogen supply rate of the hydrogen production device; the carbon monoxide control device is used to regulate the carbon monoxide supply rate of the carbon monoxide production device.

[0028] In the present invention, the volume ratio of hydrogen and carbon monoxide in the mixed storage tank is controlled within a preset range by the hydrogen control device and the carbon monoxide control device to ensure subsequent joint storage.

[0029] In the present invention, the mixing storage tank preferably includes a stirring device; the hydrogen entering the mixing storage tank through the hydrogen control device and the hydrogen compression device and the carbon monoxide entering the mixing storage tank through the carbon monoxide control device and the carbon monoxide compression device are uniformly mixed under the action of the stirring device.

[0030] In the present invention, hydrogen and carbon monoxide are compressed and sent into a mixed storage tank by a hydrogen compression device and a carbon monoxide compression device.

[0031] The present invention also provides an operating method of the hydrogen and carbon monoxide mixed storage system, comprising the following steps:

[0032] Hydrogen is output from the hydrogen preparation device and transported to the mixed storage tank via the hydrogen control device and the hydrogen compression device; carbon monoxide is output from the carbon monoxide preparation device and transported to the mixed storage tank via the carbon monoxide control device and the carbon monoxide compression device; the hydrogen and carbon monoxide in the mixed storage tank are output via the discharge pipe.

[0033] In the present invention, the temperature of the mixing storage tank is preferably 0-150°C, more preferably 20-130°C, and more preferably 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, and 120°C; the pressure of the mixing storage tank is preferably 0-80MPa, more preferably 10-70MPa, and more preferably 20MPa, 30MPa, 40MPa, 50MPa, and 60MPa.

[0034] In the present invention, the volume ratio of hydrogen in the mixing storage tank is preferably 0-60%, more preferably 5-55%, and more preferably 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%.

[0035] The present invention also provides application of the hydrogen and carbon monoxide mixed storage system in methanol synthesis.

[0036] In the present invention, the mixing storage tank is connected to the synthetic methanol system through a discharge pipe.

[0037] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0038] In the embodiment, the stirring device in the mixing storage tank is an internal baffle, and the internal baffle is a spiral baffle, which has high heat exchange efficiency and reduces scaling, and the gas flow rate is 0.6m / s.

[0039] Example 1

[0040] The mixed storage system of hydrogen and carbon monoxide includes the following devices: a hydrogen preparation device, a hydrogen control device, a hydrogen compression device, a carbon monoxide preparation device, a carbon monoxide control device, a carbon monoxide compression device, a mixed storage tank, and a discharge pipeline.

[0041] In the hydrogen preparation device, alkaline water electrolysis is used to produce hydrogen using electricity generated by renewable energy. The resulting hydrogen is transported through a control valve in a hydrogen control device (the flow rate of the hydrogen is displayed by a flow meter), and then compressed in a hydrogen compression device, with the gas flow rate being kept stable by a pressure-regulating valve. The carbon monoxide obtained in the carbon monoxide preparation device is transported through a control valve in a carbon monoxide control device (the flow rate of the carbon monoxide is displayed by a flow meter), and then compressed in a carbon monoxide compression device, with the carbon monoxide flow rate being kept stable by a pressure-regulating valve. The volume ratio of hydrogen transported into the mixing storage tank is 45%, and the volume ratio of carbon monoxide transported into the mixing storage tank is 55%. The stirring device is turned on to ensure that the hydrogen and carbon monoxide in the mixing storage tank are evenly mixed. The temperature in the mixing storage tank is 60°C and the pressure is 30 MPa. When methanol is synthesized, the mixed gas in the mixing storage tank is transported through a discharge pipe.

[0042] Example 2

[0043] The mixed storage system of hydrogen and carbon monoxide includes the following devices: a hydrogen preparation device, a hydrogen control device, a hydrogen compression device, a carbon monoxide preparation device, a carbon monoxide control device, a carbon monoxide compression device, a mixed storage tank, and a discharge pipeline.

[0044] In the hydrogen preparation device, hydrogen is produced by proton exchange membrane electrolysis of water using electricity generated by renewable energy. The obtained hydrogen is transported through a control valve in a hydrogen control device (the flow rate of hydrogen is displayed by a flow meter), and then compressed in a hydrogen compression device, and the gas flow rate is kept stable under the action of a pressure regulating valve; the carbon monoxide obtained in the carbon monoxide preparation device is transported through a control valve in a carbon monoxide control device (the flow rate of carbon monoxide is displayed by a flow meter), and then compressed in a carbon monoxide compression device, and the carbon monoxide flow rate is kept stable under the action of a pressure regulating valve; the volume ratio of hydrogen transported into the mixing storage tank is 30%, and the volume ratio of carbon monoxide transported into the mixing storage tank is 70%, and the stirring device is turned on to ensure that the hydrogen and carbon monoxide in the mixing storage tank are evenly mixed; the temperature in the mixing storage tank is 50°C and the pressure is 50 MPa; when methanol is synthesized, the mixed gas in the mixing storage tank is transported through a discharge pipe.

[0045] Example 3

[0046] The mixed storage system of hydrogen and carbon monoxide includes the following devices: a hydrogen preparation device, a hydrogen control device, a hydrogen compression device, a carbon monoxide preparation device, a carbon monoxide control device, a carbon monoxide compression device, a mixed storage tank, and a discharge pipeline.

[0047] In the hydrogen preparation device, alkaline water electrolysis is used to produce hydrogen using electricity generated by renewable energy. The resulting hydrogen is transported through a control valve in a hydrogen control device (the flow rate of the hydrogen is displayed by a flow meter), and then compressed in a hydrogen compression device, with the gas flow rate being kept stable by a pressure regulating valve. The carbon monoxide obtained in the carbon monoxide preparation device is transported through a control valve in a carbon monoxide control device (the flow rate of the carbon monoxide is displayed by a flow meter), and then compressed in a carbon monoxide compression device, with the carbon monoxide flow rate being kept stable by a pressure regulating valve. The volume ratio of hydrogen transported into the mixing storage tank is 20%, and the volume ratio of carbon monoxide transported into the mixing storage tank is 80%. The stirring device is turned on to ensure that the hydrogen and carbon monoxide in the mixing storage tank are evenly mixed. The temperature in the mixing storage tank is 100°C and the pressure is 20 MPa. When methanol is synthesized, the mixed gas in the mixing storage tank is transported through a discharge pipe.

[0048] As can be seen from the examples, the present invention provides a mixed storage system for hydrogen and carbon monoxide, which effectively controls the rate at which the raw gas enters the mixed storage tank through the hydrogen control device and the carbon monoxide control device, ensuring that the proportion of the mixed gas can be directly used for the subsequent synthesis of methanol; the hydrogen compression device and the carbon monoxide compression device can pressurize hydrogen and carbon monoxide into the mixed storage tank, and the hydrogen and carbon monoxide are quickly mixed in the mixed storage tank by the stirring device, so as to achieve the purpose of long-term uniform mixed storage of hydrogen and carbon monoxide. After sufficient mixing, they are transported to the synthetic methanol system through the discharge pipe. The mixed storage of hydrogen and carbon monoxide of the present invention reduces the pre-mixing step of the gas before synthesizing methanol, simplifies the process flow, and reduces energy consumption and the cost of synthesizing methanol; at the same time, because of the presence of carbon monoxide in the mixed gas tank, it not only prevents the explosion of hydrogen and ensures the safety of the process, but also reduces the requirements for the tank body and avoids the occurrence of hydrogen embrittlement. Under the premise of ensuring high-quality methanol synthesis, the present invention reduces process requirements and costs, and is convenient for large-scale production.

[0049] 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 principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A mixed storage system of hydrogen and carbon monoxide, characterized in that: It includes the following devices: hydrogen preparation device, hydrogen control device, hydrogen compression device, carbon monoxide preparation device, carbon monoxide control device, carbon monoxide compression device, mixing storage tank, and discharge pipeline; The mixed storage tank is used for the co-storage of carbon monoxide and hydrogen.

2. The hydrogen and carbon monoxide mixed storage system according to claim 1, characterized in that: The hydrogen comes from a hydrogen preparation device and is transported to a hydrogen control device through a pipeline; the carbon monoxide comes from a carbon monoxide preparation device and is transported to a carbon monoxide control device through a pipeline.

3. The hydrogen and carbon monoxide mixed storage system according to claim 2, characterized in that: The hydrogen control device is used to regulate the hydrogen rate supplied by the hydrogen production device; the carbon monoxide control device is used to regulate the carbon monoxide rate supplied by the carbon monoxide production device.

4. The hydrogen and carbon monoxide mixed storage system according to claim 2 or 3, characterized in that: The mixing storage tank includes a stirring device; the hydrogen entering the mixing storage tank through the hydrogen control device and the hydrogen compression device and the carbon monoxide entering the mixing storage tank through the carbon monoxide control device and the carbon monoxide compression device are uniformly mixed under the action of the stirring device.

5. The method for operating the hydrogen and carbon monoxide mixed storage system according to any one of claims 1 to 4, characterized in that: The following steps are included: Hydrogen is output from the hydrogen preparation device and transported to the mixed storage tank via the hydrogen control device and the hydrogen compression device; carbon monoxide is output from the carbon monoxide preparation device and transported to the mixed storage tank via the carbon monoxide control device and the carbon monoxide compression device; the hydrogen and carbon monoxide in the mixed storage tank are output via the discharge pipe.

6. The operating method according to claim 5, characterized in that: The temperature of the mixing storage tank is 0-150° C., and the pressure of the mixing storage tank is 0-80 MPa.

7. The operating method according to claim 5 or 6, characterized in that: The volume proportion of hydrogen in the mixed storage tank is 0-60%.

8. Use of the hydrogen and carbon monoxide mixed storage system according to any one of claims 1 to 4 in methanol synthesis.

9. The use according to claim 8, characterized in that The mixed storage tank is connected to the synthetic methanol system through a discharge pipe.

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