WO2023098151A1 - Shipborne hydrogen fuel preparation system and hydrogen preparation method thereof - Google Patents

Shipborne hydrogen fuel preparation system and hydrogen preparation method thereof Download PDF

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Publication number
WO2023098151A1
WO2023098151A1 PCT/CN2022/113659 CN2022113659W WO2023098151A1 WO 2023098151 A1 WO2023098151 A1 WO 2023098151A1 CN 2022113659 W CN2022113659 W CN 2022113659W WO 2023098151 A1 WO2023098151 A1 WO 2023098151A1
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Prior art keywords
natural gas
hydrogen
carbon dioxide
hydrogen production
gas
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PCT/CN2022/113659
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French (fr)
Chinese (zh)
Inventor
李晓峰
许峰
陈俊
李鑫
周玮
杜鲁辉
朱越星
刘昊天
Original Assignee
上海船舶研究设计院（中国船舶集团有限公司第六〇四研究院）
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Priority to KR1020237012685A priority Critical patent/KR20230084514A/en
Publication of WO2023098151A1 publication Critical patent/WO2023098151A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63H—MARINE PROPULSION OR STEERING
    • B63H21/00—Use of propulsion power plant or units on vessels
    • B63H21/38—Apparatus or methods specially adapted for use on marine vessels, for handling power plant or unit liquids, e.g. lubricants, coolants, fuels or the like
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING 
    • B63B17/00—Vessels parts, details, or accessories, not otherwise provided for
    • B63B17/0027—Tanks for fuel or the like ; Accessories therefor, e.g. tank filler caps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING 
    • B63B25/00—Load-accommodating arrangements, e.g. stowing, trimming; Vessels characterised thereby
    • B63B25/02—Load-accommodating arrangements, e.g. stowing, trimming; Vessels characterised thereby for bulk goods
    • B63B25/08—Load-accommodating arrangements, e.g. stowing, trimming; Vessels characterised thereby for bulk goods fluid
    • B63B25/12—Load-accommodating arrangements, e.g. stowing, trimming; Vessels characterised thereby for bulk goods fluid closed
    • B63B25/16—Load-accommodating arrangements, e.g. stowing, trimming; Vessels characterised thereby for bulk goods fluid closed heat-insulated
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M21/00—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form
    • F02M21/02—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels
    • F02M21/0203—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels characterised by the type of gaseous fuel
    • F02M21/0209—Hydrocarbon fuels, e.g. methane or acetylene
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
    • F17D1/00—Pipe-line systems
    • F17D1/02—Pipe-line systems for gases or vapours
    • F17D1/04—Pipe-line systems for gases or vapours for distribution of gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
    • F17D3/00—Arrangements for supervising or controlling working operations
    • F17D3/01—Arrangements for supervising or controlling working operations for controlling, signalling, or supervising the conveyance of a product
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
    • F17D3/00—Arrangements for supervising or controlling working operations
    • F17D3/14—Arrangements for supervising or controlling working operations for eliminating water
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H01M8/04208—Cartridges, cryogenic media or cryogenic reservoirs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63H—MARINE PROPULSION OR STEERING
    • B63H21/00—Use of propulsion power plant or units on vessels
    • B63H2021/003—Use of propulsion power plant or units on vessels the power plant using fuel cells for energy supply or accumulation, e.g. for buffering photovoltaic energy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
    • H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/34—Hydrogen distribution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T70/00—Maritime or waterways transport
    • Y02T70/50—Measures to reduce greenhouse gas emissions related to the propulsion system
    • Y02T70/5218—Less carbon-intensive fuels, e.g. natural gas, biofuels

Definitions

  • the present application relates to the technical field of on-board fuel preparation, in particular to an on-board hydrogen fuel preparation system and a hydrogen production method thereof.
  • the purpose of this application is to provide an on-board hydrogen fuel preparation system and its hydrogen production method, so as to alleviate the difficulty, high cost, high risk, low volumetric energy density and large occupied space of liquefied hydrogen storage on board in the prior art , there may also be the problem of waste of cold and heat energy on board; or the technical problem of low energy density generated by high-pressure gaseous hydrogen storage.
  • the on-board hydrogen fuel preparation system includes: a natural gas storage tank, a low-temperature evaporator, a heater, and a natural gas hydrogen production device;
  • the natural gas storage tank is used to store liquid natural gas
  • the natural gas The storage compartment communicates with the low-temperature evaporator and the heater respectively, the liquid natural gas in the natural gas storage compartment can enter the heater through the low-temperature evaporator, and the evaporated gas in the natural gas storage compartment can enter to the heater,
  • the natural gas hydrogen production device is connected with the heater, the heater is configured to be able to heat natural gas, and transport the heated natural gas to the natural gas hydrogen production device, and the natural gas hydrogen production device
  • the hydrogen plant is configured to convert natural gas into hydrogen.
  • the heater is used to communicate with the valve group unit of the gas supply system of the internal combustion engine, and the heated natural gas in the heater is delivered to the valve group unit of the gas supply system of the internal combustion engine.
  • the hydrogen fuel preparation system on board also includes a hydrogen purification device; the hydrogen purification device is connected to the natural gas hydrogen production device, and the hydrogen in the natural gas hydrogen production device can enter the hydrogen In the purification device; the hydrogen purification device communicates with the low-temperature evaporator, and the heat in the hydrogen purification device can be transferred to the low-temperature evaporator.
  • the on-board hydrogen fuel preparation system further includes a carbon dioxide recovery device;
  • the preliminary hydrogen purification device is connected to the reaction gas discharged from the natural gas hydrogen production device, and the preliminary hydrogen purification device is configured to remove all
  • the natural gas hydrogen production device produces carbon dioxide and water contained in the reaction gas;
  • the carbon dioxide recovery device is connected to the waste gas discharged from the natural gas hydrogen production device via the heater, and the carbon dioxide recovery device is configured to add heat to the waste gas pressure, and remove the carbon dioxide and water contained in the waste gas produced by the natural gas hydrogen production plant in liquid form.
  • the coolants of the carbon dioxide recovery device and the hydrogen primary purification device are respectively communicated with the low-temperature evaporator to form a circulation loop, and the cold energy of the liquid natural gas is transferred from the low-temperature evaporator to the low-temperature evaporator.
  • the carbon dioxide recovery device and the hydrogen preliminary purification device are used for liquefied carbon dioxide.
  • the hydrogen production method based on the ship hydrogen fuel preparation system includes the following steps: hydrogen production step: storing liquid natural gas in the natural gas storage tank, and boosting the The liquid natural gas in the natural gas storage tank is pressurized and transported to the low-temperature evaporator, the liquid natural gas becomes low-temperature natural gas, and the low-temperature natural gas enters the heater together with the evaporated gas in the natural gas storage tank, and the heated natural gas is controlled Pressure, the natural gas suitable for the pressure required by the natural gas hydrogen production device enters the natural gas hydrogen production device, and the natural gas suitable for the pressure required by the internal combustion engine enters the valve group unit of the internal combustion engine gas supply system.
  • the hydrogen production step further includes the following steps: the hydrogen produced by the natural gas hydrogen production device enters the hydrogen preliminary purification device to remove water and carbon dioxide contained in the hydrogen, and the hydrogen preliminary purification device
  • the purified low-purity hydrogen can enter the hydrogen secondary purification device
  • the high-purity hydrogen purified by the hydrogen secondary purification device enters the hydrogen fuel cell stack after being decompressed by the buffer tank.
  • it also includes a carbon dioxide preservation step: the carbon dioxide produced by the hydrogen preliminary purification device and the carbon dioxide recovery device enters the carbon dioxide storage cabin in liquid form, and the coolant is stored in the carbon dioxide storage cabin and the carbon dioxide storage cabin.
  • the circulation between the low-temperature evaporators brings the cold energy of the liquefied natural gas in the low-temperature evaporators into the carbon dioxide storage compartment, which is required for the carbon dioxide storage compartment to store carbon dioxide in liquid or solid form.
  • it also includes a process of making full use of the cold energy contained in liquid natural gas and making full use of waste heat, including the following steps: After the heater precools the waste gas generated by the natural gas hydrogen production device, it enters the The above-mentioned carbon dioxide recovery device is used to capture carbon dioxide in the waste gas, so as to save high-grade cold energy and make full use of the waste heat of the waste gas; before the reaction gas of the natural gas hydrogen production device enters the hydrogen primary purification device, the reaction gas is converted to Part of the heat is transferred to the heater and/or low temperature evaporator.
  • the following steps are included: the residual tail gas produced by the hydrogen secondary purification device enters the natural gas hydrogen production device as fuel; the crude hydrogen purified by the hydrogen primary purification device enters the internal combustion engine supply In the valve block unit of the gas system.
  • the present application provides an onboard hydrogen fuel preparation system and its hydrogen production method.
  • a natural gas storage tank for storing liquefied natural gas By placing a natural gas storage tank for storing liquefied natural gas on board, the natural gas evaporator in the natural gas storage tank directly enters the heater, and the natural gas storage tank The liquefied natural gas in the liquefied natural gas is turned into low-temperature natural gas through the low-temperature evaporator, and the low-temperature natural gas enters the heater, and the heater increases the temperature of the natural gas, and transports the heated natural gas to the natural gas hydrogen production device, and uses the natural gas hydrogen production device Convert natural gas into hydrogen, use hydrogen as fuel for internal combustion engines and/or hydrogen fuel cells on board as power and/electric power systems, use hydrogen production on board instead of hydrogen storage on board, increase safety, effectively reduce risks, and alleviate existing technologies
  • the storage of liquefied hydrogen on board is difficult, costly, dangerous, low in volume energy density, takes up a lot of space, and there may be problems
  • Figure 1 is a schematic diagram of the overall structure of the on-board hydrogen fuel preparation system provided by the embodiment of the present application;
  • Fig. 2 is a flow chart of the on-board hydrogen fuel preparation system provided by the embodiment of the present application.
  • the terms “installation”, “installation”, “connection”, and “connection” should be understood in a broad sense, for example, it can be a fixed connection, It can also be a detachable connection or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediary, and it can be the internal communication of two components.
  • installation can be a fixed connection, It can also be a detachable connection or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediary, and it can be the internal communication of two components.
  • the embodiment of the first aspect of the present application provides a hydrogen fuel preparation system on board, including: a natural gas storage tank 1, a low-temperature evaporator 2, a heater 3 and a natural gas hydrogen production device 4; natural gas storage
  • the tank 1 is used to store liquid natural gas.
  • the natural gas storage tank 1 communicates with the low-temperature evaporator 2 and the heater 3 respectively.
  • the liquid natural gas in the natural gas storage tank 1 can enter the heater 3 through the low-temperature evaporator 2.
  • the natural gas storage tank 1 The evaporated gas inside can enter the heater 3, the natural gas hydrogen production device 4 is connected with the heater 3, the heater 3 is configured to be able to heat the natural gas, and transport the heated natural gas to the natural gas hydrogen production device 4 as fuel and raw material,
  • the natural gas hydrogen production device 4 is configured to convert natural gas into hydrogen.
  • the natural gas storage cabin 1 communicates with the heater 3 through the boil-off gas delivery pipeline, and the intake air of the boil-off gas delivery pipeline
  • the mouth is located at the top of the natural gas storage cabin 1, and the liquid natural gas is connected with the low-temperature evaporator 2 through the liquid natural gas delivery pipeline, and the natural gas delivery pipeline extends into the interior of the natural gas storage cabin 1, and the low-temperature evaporator 2 converts the liquid natural gas into low-temperature natural gas
  • the low-temperature natural gas has an appropriate pressure.
  • the low-temperature natural gas enters the heater 3 together with the pressurized boil-off gas.
  • the heater 3 heats the natural gas and controls the pressure.
  • the natural gas with a pressure suitable for the natural gas hydrogen production device 4 enters the natural gas production Hydrogen device 4.
  • the natural gas pressure difference required by the natural gas hydrogen production device 4 and the valve group unit 5 of the internal combustion engine gas supply system When it is larger, two or more sets of booster pumps, low-temperature evaporator 2 and heater 3 can be used; for another example, when the natural gas pressure required by all equipment is very close, only one set of heater outlet pipelines can be set; For example, the above process is suitable for internal combustion engines fueled by hydrogen and natural gas. If it is a 100% hydrogen fueled internal combustion engine, or if no internal combustion engine is provided, there is no need to provide the valve group unit pipeline from natural gas to the gas supply system of the internal combustion engine.
  • This embodiment provides a hydrogen fuel preparation system on board a ship and a hydrogen production method thereof.
  • a natural gas storage tank 1 for storing liquefied natural gas By placing a natural gas storage tank 1 for storing liquefied natural gas on board, the natural gas in the natural gas storage tank 1 is pressurized by an evaporator and directly enters the In the heater 3, the liquefied natural gas in the natural gas storage compartment 1 passes through the low-temperature evaporator 2 to turn the liquefied natural gas into low-temperature natural gas and has a suitable pressure, and the low-temperature natural gas enters the heater 3, and the heater 3 increases the temperature of the natural gas, and The heated natural gas is sent to the natural gas hydrogen production device 4, and the natural gas hydrogen production device 4 is used to convert the natural gas into hydrogen, and the hydrogen is used as fuel for the ship's internal combustion engine and/or hydrogen fuel cell as power and/or power system.
  • Hydrogen replaces hydrogen storage on board, which increases safety, effectively reduces risks, and alleviates the difficulty, high cost, high risk, low volumetric energy density, and large footprint of liquefied hydrogen storage on board existing in the prior art.
  • the heater 3 in the on-board hydrogen fuel preparation system provided in this embodiment is used to communicate with the valve group unit 5 of the gas supply system of the internal combustion engine, and the heater 3
  • the heated natural gas is delivered to the internal combustion engine for combustion through the valve group unit 5 of the gas supply system of the internal combustion engine; when natural gas and hydrogen are mixed, after mixing an appropriate proportion of natural gas and hydrogen in the valve group unit 5 of the gas supply system of the internal combustion engine, sent to the internal combustion engine for combustion.
  • the natural gas formed by heating with the heater 3 should have the required pressure suitable for the valve group unit 5 of the gas supply system of the internal combustion engine, and be supplied to the valve group unit 5 of the gas supply system of the internal combustion engine through a buffer tank.
  • the onboard hydrogen fuel preparation system also includes a hydrogen purification device; the hydrogen purification device is connected to the natural gas hydrogen production device 4, and the reaction gas containing hydrogen in the natural gas hydrogen production device 4 can enter the hydrogen preliminary purification device ; Before the reaction gas enters the hydrogen purification device, the heat can be transferred to the heater 3 and/or the low-temperature evaporator 2 through the heat exchanger, so as to realize the purpose of initially cooling the reaction gas and raising the temperature of the natural gas; The evaporator 2 is connected to realize heat transfer between the hydrogen preliminary purification device and the low-temperature evaporator 2 .
  • the hydrogen purification device of the hydrogen supply fuel cell includes a hydrogen primary purification device 6 and a hydrogen secondary purification device 7.
  • the hydrogen-containing reaction gas produced by the natural gas hydrogen production device 4 enters the hydrogen primary purification device 6 and the hydrogen secondary purification device sequentially.
  • hydrogen is sequentially purified.
  • the onboard hydrogen fuel preparation system also includes a carbon dioxide recovery device 8, which together with the hydrogen primary purification device 6 achieves the purpose of carbon dioxide recovery; the waste gas discharged by the carbon dioxide recovery device 8 and the natural gas hydrogen production device 4 passes through the heater 3 connected, the carbon dioxide recovery unit 8 is configured to be able to freeze the exhaust gas generated by the natural gas hydrogen production unit 4, and liquefy the carbon dioxide therein.
  • the heater 3 cools the waste gas produced by the natural gas hydrogen production device 4, and the cooled waste gas enters the carbon dioxide recovery device 8, and the liquid carbon dioxide produced by the carbon dioxide recovery device 8 and the hydrogen preliminary purification device 6 enters the carbon dioxide storage cabin 9, Solid or liquid carbon dioxide is stored in the carbon dioxide storage compartment 9 .
  • the coolant of the carbon dioxide recovery device 8 communicates with the low-temperature evaporator 2 , and the cold energy required in the carbon dioxide recovery device 8 is provided by the low-temperature evaporator 2 .
  • the heat source of the low-temperature evaporator 2 comes from the hydrogen primary purification device 6, the carbon dioxide recovery device 8, and the carbon dioxide storage cabin 9, and can also come from the initial cooling process of the reaction gas (the hydrogen-containing reaction gas produced by the natural gas hydrogen production device 4 enters the to the preliminary cooling before the hydrogen primary purification device 6), when these heat sources are insufficient, they are provided by the secondary heating system provided by the ship, and the heat source of the secondary heating system of the ship can come from the fresh water cooling system of the engine room, the cylinder jacket water system or boiler.
  • the inlet temperature of liquefied natural gas is about -162°C
  • the outlet temperature of natural gas depends on the temperature when the low-temperature coolant leaves the low-temperature evaporator 2
  • the choice of low-temperature coolant also depends on the temperature at this time, and when the low-temperature coolant leaves the low-temperature evaporator 2
  • the temperature depends on the temperature of carbon dioxide recovery and storage.
  • the heat source of the natural gas heater 3 comes from the heat contained in the waste gas of the natural gas hydrogen production unit 4, and can also come from the preliminary cooling process of the reaction gas (the hydrogen-containing reaction gas produced by the natural gas hydrogen production unit 4 enters the hydrogen preliminary purification unit 6 When the heat provided by the waste heat is insufficient, it is provided by the secondary heating system provided by the ship, and the natural gas outlet temperature is above 0°C.
  • the on-board hydrogen fuel preparation system provided in this example uses liquefied natural gas to produce hydrogen on board, and eliminates the sulfur removal step that is often used in land-based hydrogen production.
  • the main reason is that the natural gas used for land-based hydrogen production has a high sulfur content, which is likely to cause catalyst poisoning. ; while natural gas has to go through the process of desulfurization before being liquefied into liquefied natural gas, and most of the sulfur has been removed, so this step can be omitted.
  • the amount of sulfur and hydrogen sulfide in liquid natural gas is less than 1mg/m 3 , which is far less than the requirement of normal hydrogen production process that the sulfur content of natural gas should not exceed 0.1ppm.
  • the hydrogen production method based on the on-board hydrogen fuel preparation system includes the following steps: hydrogen production step: storing liquefied natural gas in the natural gas storage tank 1, and the booster pump stores the natural gas
  • the liquid natural gas in the cabin 1 is pressurized and transported to the low-temperature evaporator 2, and the liquid natural gas becomes low-temperature natural gas with a suitable pressure.
  • the low-temperature natural gas and the evaporated gas in the natural gas storage tank 1 are pressurized and enter the heater 3 together to control heating
  • the final natural gas pressure, the natural gas suitable for the pressure required by the natural gas hydrogen production device 4 enters the natural gas hydrogen production device 4, and the natural gas suitable for the pressure required by the internal combustion engine enters the valve group unit 5 of the internal combustion engine gas supply system, either alone or mixed with hydrogen Then supply the internal combustion engine as fuel.
  • the hydrogen production step also includes the following steps: the hydrogen-containing gas produced by the natural gas hydrogen production unit 4 enters the hydrogen preliminary purification unit 6 for preliminary purification, and greatly reduces the carbon dioxide and water therein.
  • the low-purity hydrogen generated by the hydrogen primary purification device 6 can enter the hydrogen secondary purification device 7, and the high-purity hydrogen purified by the hydrogen secondary purification device 7 enters the hydrogen fuel cell stack after being decompressed by the buffer tank; the hydrogen primary purification
  • the low-purity hydrogen generated by the device 6 can also enter the valve group unit 5 of the gas supply system of the internal combustion engine through the buffer tank, and be supplied to the internal combustion engine as fuel alone or mixed with natural gas.
  • a carbon dioxide storage step is also included: the carbon dioxide produced by the hydrogen preliminary purification device 6 enters the carbon dioxide storage compartment 9, and the carbon dioxide recovery device 8 freezes the carbon dioxide in the waste gas into liquid carbon dioxide and then enters the carbon dioxide storage compartment 9; the coolant in the carbon dioxide storage compartment 9 is connected to the low-temperature evaporator 2, and the cold energy in the low-temperature evaporator 2 enters the carbon dioxide storage compartment 9 through the coolant.
  • the waste gas initially cooled by the heater 3 enters the carbon dioxide recovery device 8, and the carbon dioxide recovery device 8 liquefies the carbon dioxide and water in the pressurized waste gas by freezing, and the remaining waste gas is discharged into the atmosphere and liquefied.
  • the carbon dioxide in the carbon dioxide enters the carbon dioxide storage compartment 9; the liquid carbon dioxide produced by the hydrogen primary purification device 6 also enters the carbon dioxide storage compartment 9.
  • the coolant in the carbon dioxide storage compartment 9 is connected to the low-temperature evaporator 2, and the cold energy in the low-temperature evaporator 2 enters the carbon dioxide storage compartment 9 through the coolant to maintain the carbon dioxide storage compartment 9 and store carbon dioxide in liquid or solid form.
  • the following steps are also included: the exhaust gas cooled by the heater 3 enters the carbon dioxide recovery device 8 ; the cold energy required by the carbon dioxide recovery device 8 to freeze the exhaust gas is provided by the low-temperature evaporator 2 .
  • the waste gas produced by the natural gas hydrogen production unit 4 is transferred to the heater 3 as a heat source;
  • the tail gas produced by the hydrogen secondary purification unit 7 enters the natural gas hydrogen production unit 4 as fuel or Raw materials:
  • the crude hydrogen purified by the hydrogen primary purification device 6 enters the valve group unit 5 of the gas supply system of the internal combustion engine.
  • natural gas reforming is taken as an example.
  • the raw material required for hydrogen production by natural gas reforming is natural gas, and the required pressure is usually 1.0MPa-2.2MPa.
  • the raw material water, oxygen and process water of appropriate quality are provided by the ship system.
  • the fuel required for heating in the hydrogen production process is provided by primary purified crude hydrogen or natural gas, while the remaining tail gas from the secondary purification of hydrogen can be used as fuel or raw material.
  • the difference between using different fuels is: using natural gas as fuel, the disadvantage is that the content of carbon dioxide in the combustion exhaust gas is high, if it is directly discharged, it will cause more carbon emissions for hydrogen production on board, so set up a carbon dioxide recovery device 8 to capture carbon.
  • the tail gas from secondary purification of hydrogen is used as fuel, which will slightly increase carbon emissions, and the tail gas from secondary purification is used as raw material, which will reduce the conversion efficiency of hydrogen production equipment.
  • the specific configuration can be selected according to actual needs, such as crude hydrogen and secondary Purify tail gas as fuel, then the waste gas from hydrogen production can be eliminated from entering the carbon dioxide recovery device 8, and the capture rate of carbon dioxide produced in the hydrogen production process can exceed 95% at the highest.
  • the combustion exhaust gas produced by the hydrogen production unit after preheating the natural gas raw material, enters the heater 3 (heating for low-temperature natural gas, and at the same time lowers its own temperature), and after cooling, enters the carbon dioxide recovery device 8 to capture carbon dioxide after pressurization, or directly discharge,
  • the wastewater generated by the hydrogen production unit re-enters the ship system and is reused after treatment.
  • the hydrogen production method of the on-board hydrogen fuel preparation system does not need to store a large amount of hydrogen or liquid hydrogen on a ship fueled by hydrogen, but stores liquefied natural gas and prepares the required hydrogen through a hydrogen production device;
  • the on-board hydrogen production device is combined with the LNG gas supply system to realize the utilization of the cold energy of the LNG and the waste heat of the hydrogen production device, and the cold energy of the LNG is fully utilized; in the process of preparing hydrogen on board, carbon capture and storage are used to realize The zero-carbon or near-zero carbon emission of hydrogen production on board can effectively reduce the carbon emission intensity of ships;
  • the hydrogen produced on board can be used alone or mixed with natural gas as fuel for internal combustion engines;
  • the high-purity hydrogen produced on board can be used on board
  • the high-power hydrogen fuel cell pack as the main power source of the ship's power system, further reduces the carbon emission intensity of the ship;
  • the high-power hydrogen fuel cell pack on board supplies power to the propulsion device, and serves as the propulsion power for small and micro

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Abstract

A shipborne hydrogen fuel preparation system and a hydrogen preparation method thereof, relating to the technical field of shipborne fuel preparation, and comprising: a natural gas storage compartment, a low-temperature evaporator, a heater and a natural gas hydrogen production apparatus. The natural gas storage compartment is used to store liquefied natural gas, and the natural gas storage compartment is in communication respectively with the low-temperature evaporator and the heater. Liquefied natural gas in the natural gas storage compartment can enter the heater by means of the low-temperature evaporator, and boil-off gas in the natural gas storage compartment can enter the heater. The natural gas hydrogen production apparatus is connected to the heater, and the heater is configured to be capable of heating the natural gas and conveying the heated natural gas into the natural gas hydrogen production apparatus. The natural gas hydrogen production apparatus is configured to be capable of converting the natural gas into hydrogen gas. In the present application, shipborne hydrogen production is used to replace shipborne hydrogen storage, increasing safety, effectively reducing risk, and alleviating the technical problems in the prior art of the high difficulty, high cost, high danger, and large space occupation of shipborne liquefied hydrogen gas storage.

Description

船上氢燃料制备系统及其制氢方法On-board hydrogen fuel preparation system and hydrogen production method thereof
相关申请related application
本申请要求于2021年12月01日递交的申请号为202111456500.2的中国发明专利申请的优先权，并引用上述专利申请公开的内容作为本申请的一部分。This application claims the priority of the Chinese invention patent application with application number 202111456500.2 submitted on December 01, 2021, and cites the disclosed content of the above patent application as a part of this application.
技术领域technical field
本申请涉及船上燃料制备技术领域，尤其是涉及一种船上氢燃料制备系统及其制氢方法。The present application relates to the technical field of on-board fuel preparation, in particular to an on-board hydrogen fuel preparation system and a hydrogen production method thereof.
背景技术Background technique
为了实现船舶碳减排，替代燃料或者碳捕捉必将在船舶上取得广泛的应用，而作为减排的终极燃料，氢气是可以实现零碳排放的。In order to reduce carbon emissions of ships, alternative fuels or carbon capture will be widely used on ships, and as the ultimate fuel for emission reduction, hydrogen can achieve zero carbon emissions.
在船上作为燃料的氢气的储存方法主要有两种，即液化氢气超低温储存和高压气态氢气储存。There are two main storage methods for hydrogen used as fuel on board, namely ultra-low temperature storage of liquefied hydrogen and storage of high-pressure gaseous hydrogen.
但是，液化氢气储存难度大，成本高，危险性高，体积能量密度低，占用空间大，还可能存在船上的冷能和热能浪费的问题，而高压气态氢气储存能力密度低，占地空间大。However, the storage of liquefied hydrogen is difficult, costly, dangerous, low in volume energy density, takes up a lot of space, and there may be problems of wasting cold and heat energy on board, while high-pressure gaseous hydrogen has a low capacity density and occupies a large space .
发明内容Contents of the invention
本申请的目的在于提供一种船上氢燃料制备系统及其制氢方法，以缓解现有技术中存在的在船上液化氢气储存难度大，成本高，危险性高，体积能量密度低，占用空间大，还可能存在船上的冷能和热能浪费的问题；或者高压气态氢气储存产生的能量密度低的技术问题。The purpose of this application is to provide an on-board hydrogen fuel preparation system and its hydrogen production method, so as to alleviate the difficulty, high cost, high risk, low volumetric energy density and large occupied space of liquefied hydrogen storage on board in the prior art , there may also be the problem of waste of cold and heat energy on board; or the technical problem of low energy density generated by high-pressure gaseous hydrogen storage.
第一方面，本申请实施例提供的船上氢燃料制备系统，包括：天然气储存舱、低温蒸发器、加热器和天然气制氢装置；所述天然气储存舱被用于储放液态天然气，所述天然气储存舱分别与所述低温蒸发器和所述加热器连通，所述天然气储存舱内的液态天然气能够通过所述低温蒸发器进入到所述加热器，所述天然气储存舱内的蒸发气能够进入到所述加热器中，所述天然气制氢装置与所述加热器连接，所述加热器配置为能够加热天然气，并将加热后的天然气输送到所述天然气制氢装置中，所述天然气制氢装置配置为能够将天然气转变为氢气。In the first aspect, the on-board hydrogen fuel preparation system provided by the embodiment of the present application includes: a natural gas storage tank, a low-temperature evaporator, a heater, and a natural gas hydrogen production device; the natural gas storage tank is used to store liquid natural gas, and the natural gas The storage compartment communicates with the low-temperature evaporator and the heater respectively, the liquid natural gas in the natural gas storage compartment can enter the heater through the low-temperature evaporator, and the evaporated gas in the natural gas storage compartment can enter to the heater, the natural gas hydrogen production device is connected with the heater, the heater is configured to be able to heat natural gas, and transport the heated natural gas to the natural gas hydrogen production device, and the natural gas hydrogen production device The hydrogen plant is configured to convert natural gas into hydrogen.
在可选的实施方式中，所述加热器被用于与内燃机供气系统的阀组单元连通，所述加热器中加热后的天然气输送到内燃机供气系统的阀组单元中。In an optional embodiment, the heater is used to communicate with the valve group unit of the gas supply system of the internal combustion engine, and the heated natural gas in the heater is delivered to the valve group unit of the gas supply system of the internal combustion engine.
在可选的实施方式中，所述船上氢燃料制备系统还包括氢气提纯装置；所述氢气提纯装 置与所述天然气制氢装置连接，所述天然气制氢装置内的氢气能够进入到所述氢气提纯装置中；所述氢气提纯装置与所述低温蒸发器连通，所述氢气提纯装置中的热量能够传递到所述低温蒸发器中。In an optional embodiment, the hydrogen fuel preparation system on board also includes a hydrogen purification device; the hydrogen purification device is connected to the natural gas hydrogen production device, and the hydrogen in the natural gas hydrogen production device can enter the hydrogen In the purification device; the hydrogen purification device communicates with the low-temperature evaporator, and the heat in the hydrogen purification device can be transferred to the low-temperature evaporator.
在可选的实施方式中，所述船上氢燃料制备系统还包括二氧化碳回收装置；氢气初步提纯装置与所述天然气制氢装置排出的反应气连接，氢气初步提纯装置配置为能够以液态形式去除所述天然气制氢装置产生反应气中所含的二氧化碳和水；所述二氧化碳回收装置经由所述的加热器与所述天然气制氢装置排出的废气连接，所述二氧化碳回收装置配置为能够为废气加压，并以液态形式去除所述天然气制氢装置产生废气中所含的二氧化碳和水。In an optional embodiment, the on-board hydrogen fuel preparation system further includes a carbon dioxide recovery device; the preliminary hydrogen purification device is connected to the reaction gas discharged from the natural gas hydrogen production device, and the preliminary hydrogen purification device is configured to remove all The natural gas hydrogen production device produces carbon dioxide and water contained in the reaction gas; the carbon dioxide recovery device is connected to the waste gas discharged from the natural gas hydrogen production device via the heater, and the carbon dioxide recovery device is configured to add heat to the waste gas pressure, and remove the carbon dioxide and water contained in the waste gas produced by the natural gas hydrogen production plant in liquid form.
在可选的实施方式中，所述二氧化碳回收装置和所述氢气初步提纯装置的冷却剂分别与所述低温蒸发器连通形成循环回路，将液态天然气的冷能从所述低温蒸发器传递给所述二氧化碳回收装置和所述氢气初步提纯装置，以供液化二氧化碳所用。In an optional embodiment, the coolants of the carbon dioxide recovery device and the hydrogen primary purification device are respectively communicated with the low-temperature evaporator to form a circulation loop, and the cold energy of the liquid natural gas is transferred from the low-temperature evaporator to the low-temperature evaporator. The carbon dioxide recovery device and the hydrogen preliminary purification device are used for liquefied carbon dioxide.
第二方面，本申请实施例提供的基于所述船上氢燃料制备系统的制氢方法，包括以下步骤：制氢步骤：将液态天然气储放在所述天然气储存舱中，增压泵将所述天然气储存舱内的液态天然气加压输送至所述低温蒸发器，液态天然气变成低温天然气，低温天然气与所述天然气储存舱内的蒸发气一同进入到所述加热器中，控制加热后的天然气压力，适合所述天然气制氢装置所需压力的天然气进入到所述天然气制氢装置中，适合内燃机所需压力的天然气进入到内燃机供气系统的阀组单元中。In the second aspect, the hydrogen production method based on the ship hydrogen fuel preparation system provided in the embodiment of the present application includes the following steps: hydrogen production step: storing liquid natural gas in the natural gas storage tank, and boosting the The liquid natural gas in the natural gas storage tank is pressurized and transported to the low-temperature evaporator, the liquid natural gas becomes low-temperature natural gas, and the low-temperature natural gas enters the heater together with the evaporated gas in the natural gas storage tank, and the heated natural gas is controlled Pressure, the natural gas suitable for the pressure required by the natural gas hydrogen production device enters the natural gas hydrogen production device, and the natural gas suitable for the pressure required by the internal combustion engine enters the valve group unit of the internal combustion engine gas supply system.
在可选的实施方式中，所述制氢步骤还包括以下步骤：所述天然气制氢装置制备的氢气进入到氢气初步提纯装置中去除氢气中所含的水和二氧化碳，所述氢气初步提纯装置提纯出的低纯度氢气能够进入到氢气二次提纯装置中，所述氢气二次提纯装置提纯出的高纯度氢气通过缓冲罐减压后进入到氢燃料电池组中。In an optional embodiment, the hydrogen production step further includes the following steps: the hydrogen produced by the natural gas hydrogen production device enters the hydrogen preliminary purification device to remove water and carbon dioxide contained in the hydrogen, and the hydrogen preliminary purification device The purified low-purity hydrogen can enter the hydrogen secondary purification device, and the high-purity hydrogen purified by the hydrogen secondary purification device enters the hydrogen fuel cell stack after being decompressed by the buffer tank.
在可选的实施方式中，还包括二氧化碳保存步骤：所述氢气初步提纯装置和所述二氧化碳回收装置产生的二氧化碳以液态形式进入到所述二氧化碳储存舱中，冷却剂在所述二氧化碳储存舱和所述低温蒸发器之间循环，将所述低温蒸发器中的液态天然气的冷能带入到二氧化碳储存舱中，供所述二氧化碳储存舱以液态或者固态形式储存二氧化碳所需。In an optional embodiment, it also includes a carbon dioxide preservation step: the carbon dioxide produced by the hydrogen preliminary purification device and the carbon dioxide recovery device enters the carbon dioxide storage cabin in liquid form, and the coolant is stored in the carbon dioxide storage cabin and the carbon dioxide storage cabin. The circulation between the low-temperature evaporators brings the cold energy of the liquefied natural gas in the low-temperature evaporators into the carbon dioxide storage compartment, which is required for the carbon dioxide storage compartment to store carbon dioxide in liquid or solid form.
在可选的实施方式中，还含有充分利用液态天然气所含冷能和充分利用废热的过程，包括以下步骤：所述加热器将所述天然气制氢装置产生的废气预冷后，进入到所述二氧化碳回收装置中以捕捉废气中的二氧化碳，以节省高品位冷能，充分利用废气的废热；所述的天然气制氢装置的反应气进入到氢气初步提纯装置之前，通过热交换器将反应气的部分热量传递给加热器和/或低温蒸发器。In an optional embodiment, it also includes a process of making full use of the cold energy contained in liquid natural gas and making full use of waste heat, including the following steps: After the heater precools the waste gas generated by the natural gas hydrogen production device, it enters the The above-mentioned carbon dioxide recovery device is used to capture carbon dioxide in the waste gas, so as to save high-grade cold energy and make full use of the waste heat of the waste gas; before the reaction gas of the natural gas hydrogen production device enters the hydrogen primary purification device, the reaction gas is converted to Part of the heat is transferred to the heater and/or low temperature evaporator.
在可选的实施方式中，包括以下步骤：所述氢气二次提纯装置产生的剩余尾气进入到所 述天然气制氢装置中作为燃料；所述氢气初步提纯装置提纯出的粗氢进入到内燃机供气系统的阀组单元内。In an optional embodiment, the following steps are included: the residual tail gas produced by the hydrogen secondary purification device enters the natural gas hydrogen production device as fuel; the crude hydrogen purified by the hydrogen primary purification device enters the internal combustion engine supply In the valve block unit of the gas system.
本申请提供的一种船上氢燃料制备系统及其制氢方法，通过在船上放置用于储放液态天然气的天然气储存舱，天然气储存舱中的天然气蒸发器直接进入到加热器中，天然气储存舱中的液态天然气通过低温蒸发器将液态天然气变成低温天然气，低温天然气进入到加热器中，加热器提高天然气的温度，并将加热后的天然气输送到天然气制氢装置中，利用天然气制氢装置将天然气转变为氢气，氢气作为燃料供船上内燃机和/或氢燃料电池作为动力和/电力系统使用，利用在船上制氢代替在船上储氢，增加安全性，有效减少风险，缓解了现有技术中存在的在船上液化氢气储存难度大，成本高，危险性高，体积能量密度低，占用空间大，还可能存在船上的冷能和热能浪费的问题；或者高压气态氢气储存产生的能量密度低的技术问题。The present application provides an onboard hydrogen fuel preparation system and its hydrogen production method. By placing a natural gas storage tank for storing liquefied natural gas on board, the natural gas evaporator in the natural gas storage tank directly enters the heater, and the natural gas storage tank The liquefied natural gas in the liquefied natural gas is turned into low-temperature natural gas through the low-temperature evaporator, and the low-temperature natural gas enters the heater, and the heater increases the temperature of the natural gas, and transports the heated natural gas to the natural gas hydrogen production device, and uses the natural gas hydrogen production device Convert natural gas into hydrogen, use hydrogen as fuel for internal combustion engines and/or hydrogen fuel cells on board as power and/electric power systems, use hydrogen production on board instead of hydrogen storage on board, increase safety, effectively reduce risks, and alleviate existing technologies The storage of liquefied hydrogen on board is difficult, costly, dangerous, low in volume energy density, takes up a lot of space, and there may be problems of wasting cold and heat energy on board; or the energy density generated by high-pressure gaseous hydrogen storage is low technical problems.
附图说明Description of drawings
为了更清楚地说明本申请具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本申请的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the accompanying drawings that need to be used in the description of the specific embodiments or prior art. Obviously, the accompanying drawings in the following description The figures show some implementations of the present application, and those skilled in the art can obtain other figures based on these figures without any creative effort.
图1为本申请实施例提供的船上氢燃料制备系统的整体结构示意图；Figure 1 is a schematic diagram of the overall structure of the on-board hydrogen fuel preparation system provided by the embodiment of the present application;
图2为本申请实施例提供的船上氢燃料制备系统的流程图。Fig. 2 is a flow chart of the on-board hydrogen fuel preparation system provided by the embodiment of the present application.
具体实施方式Detailed ways
为使本申请实施例的目的、技术方案和优点更加清楚，下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。通常在此处附图中描述和示出的本申请实施例的组件可以以各种不同的配置来布置和设计。In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments It is a part of the embodiments of this application, not all of them. The components of the embodiments of the application generally described and illustrated in the figures herein may be arranged and designed in a variety of different configurations.
因此，以下对在附图中提供的本申请的实施例的详细描述并非旨在限制要求保护的本申请的范围，而是仅仅表示本申请的选定实施例。基于本申请中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。Accordingly, the following detailed description of the embodiments of the application provided in the accompanying drawings is not intended to limit the scope of the claimed application, but merely represents selected embodiments of the application. Based on the embodiments in this application, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of this application.
应注意到：相似的标号和字母在下面的附图中表示类似项，因此，一旦某一项在一个附图中被定义，则在随后的附图中不需要对其进行进一步定义和解释。It should be noted that like numerals and letters denote similar items in the following figures, therefore, once an item is defined in one figure, it does not require further definition and explanation in subsequent figures.
在本申请的描述中，需要说明的是，术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，或者是 该发明产品使用时惯常摆放的方位或位置关系，仅是为了便于描述本申请和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请的限制。此外，术语“第一”、“第二”、“第三”等仅用于区分描述，而不能理解为指示或暗示相对重要性。In the description of this application, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer" etc. The indicated orientation or positional relationship is based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship that is usually placed when the product of the invention is used, and is only for the convenience of describing the application and simplifying the description, rather than indicating or implying References to devices or elements must have a particular orientation, be constructed, and operate in a particular orientation and therefore should not be construed as limiting the application. In addition, the terms "first", "second", "third", etc. are only used for distinguishing descriptions, and should not be construed as indicating or implying relative importance.
此外，术语“水平”、“竖直”、“悬垂”等术语并不表示要求部件绝对水平或悬垂，而是可以稍微倾斜。如“水平”仅仅是指其方向相对“竖直”而言更加水平，并不是表示该结构一定要完全水平，而是可以稍微倾斜。In addition, the terms "horizontal", "vertical", "overhanging" and the like do not mean that the components are absolutely horizontal or overhanging, but may be slightly inclined. For example, "horizontal" only means that its direction is more horizontal than "vertical", and it does not mean that the structure must be completely horizontal, but can be slightly inclined.
在本申请的描述中，还需要说明的是，除非另有明确的规定和限定，术语“设置”、“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以具体情况理解上述术语在本申请中的具体含义。In the description of this application, it should also be noted that, unless otherwise clearly stipulated and limited, the terms "installation", "installation", "connection", and "connection" should be understood in a broad sense, for example, it can be a fixed connection, It can also be a detachable connection or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediary, and it can be the internal communication of two components. Those of ordinary skill in the art can understand the specific meanings of the above terms in this application in specific situations.
下面结合附图，对本申请的一些实施方式作详细说明。在不冲突的情况下，下述的实施例及实施例中的特征可以相互组合。Some implementations of the present application will be described in detail below in conjunction with the accompanying drawings. In the case of no conflict, the following embodiments and features in the embodiments can be combined with each other.
如图1、图2所示，本申请第一方面的实施例提供一种船上氢燃料制备系统，包括：天然气储存舱1、低温蒸发器2、加热器3和天然气制氢装置4；天然气储存舱1被用于储放液态天然气，天然气储存舱1分别与低温蒸发器2和加热器3连通，天然气储存舱1内的液态天然气能够通过低温蒸发器2进入到加热器3，天然气储存舱1内的蒸发气能够进入到加热器3中，天然气制氢装置4与加热器3连接，加热器3配置为能够加热天然气，并将加热后的天然气输送到天然气制氢装置4作为燃料和原料，天然气制氢装置4配置为能够将天然气转变为氢气。As shown in Figure 1 and Figure 2, the embodiment of the first aspect of the present application provides a hydrogen fuel preparation system on board, including: a natural gas storage tank 1, a low-temperature evaporator 2, a heater 3 and a natural gas hydrogen production device 4; natural gas storage The tank 1 is used to store liquid natural gas. The natural gas storage tank 1 communicates with the low-temperature evaporator 2 and the heater 3 respectively. The liquid natural gas in the natural gas storage tank 1 can enter the heater 3 through the low-temperature evaporator 2. The natural gas storage tank 1 The evaporated gas inside can enter the heater 3, the natural gas hydrogen production device 4 is connected with the heater 3, the heater 3 is configured to be able to heat the natural gas, and transport the heated natural gas to the natural gas hydrogen production device 4 as fuel and raw material, The natural gas hydrogen production device 4 is configured to convert natural gas into hydrogen.
具体的，天然气储存舱1中储放有液态天然气，天然气储存舱1中具有挥发的天然气蒸发气，天然气储存舱1通过蒸发气输送管路与加热器3连通，蒸发气输送管路的进气口位于天然气储存舱1的内部顶部，液态天然气通过液态天然气输送管路与低温蒸发器2连通，天然气输送管路伸入到天然气储存舱1的内部，低温蒸发器2将液态天然气转换为低温天然气，低温天然气具有适当的压力，低温天然气随同加压后的蒸发气一同进入到加热器3中，加热器3加热天然气，并且控制压力，适合天然气制氢装置4所需压力的天然气进入到天然气制氢装置4。Specifically, there is liquid natural gas stored in the natural gas storage cabin 1, and there is volatilized natural gas vapor in the natural gas storage cabin 1. The natural gas storage cabin 1 communicates with the heater 3 through the boil-off gas delivery pipeline, and the intake air of the boil-off gas delivery pipeline The mouth is located at the top of the natural gas storage cabin 1, and the liquid natural gas is connected with the low-temperature evaporator 2 through the liquid natural gas delivery pipeline, and the natural gas delivery pipeline extends into the interior of the natural gas storage cabin 1, and the low-temperature evaporator 2 converts the liquid natural gas into low-temperature natural gas The low-temperature natural gas has an appropriate pressure. The low-temperature natural gas enters the heater 3 together with the pressurized boil-off gas. The heater 3 heats the natural gas and controls the pressure. The natural gas with a pressure suitable for the natural gas hydrogen production device 4 enters the natural gas production Hydrogen device 4.
另外，应根据内燃机供气系统的阀组单元5和天然气制氢装置4所需不同的压力进行调整，例如在天然气制氢装置4与内燃机供气系统的阀组单元5所需的天然气压力差异较大时，可使用两套甚至多套增压泵、低温蒸发器2和加热器3；再如，在所有设备所需天然气压力 非常接近时，可以只设置一套加热器出口管路；再如，上述流程适合于氢气和天然气混合燃料的内燃机，如果是100％氢燃料内燃机，或者不设置内燃机的情况，则此处不必提供天然气到内燃机供气系统的阀组单元管路。In addition, it should be adjusted according to the different pressures required by the valve group unit 5 of the internal combustion engine gas supply system and the natural gas hydrogen production device 4, for example, the natural gas pressure difference required by the natural gas hydrogen production device 4 and the valve group unit 5 of the internal combustion engine gas supply system When it is larger, two or more sets of booster pumps, low-temperature evaporator 2 and heater 3 can be used; for another example, when the natural gas pressure required by all equipment is very close, only one set of heater outlet pipelines can be set; For example, the above process is suitable for internal combustion engines fueled by hydrogen and natural gas. If it is a 100% hydrogen fueled internal combustion engine, or if no internal combustion engine is provided, there is no need to provide the valve group unit pipeline from natural gas to the gas supply system of the internal combustion engine.
本实施例提供的一种船上氢燃料制备系统及其制氢方法，通过在船上放置用于储放液态天然气的天然气储存舱1，天然气储存舱1中的天然气经蒸发器加压后直接进入到加热器3中，天然气储存舱1中的液态天然气通过低温蒸发器2将液态天然气变成低温天然气并具备合适的压力，低温天然气进入到加热器3中，加热器3提高天然气的温度，并将加热后的天然气输送到天然气制氢装置4中，利用天然气制氢装置4将天然气转变为氢气，氢气作为燃料供船上内燃机和/或氢燃料电池作为动力和/或电力系统使用，利用在船上制氢代替在船上储氢，增加安全性，有效减少风险，缓解了现有技术中存在的在船上液化氢气储存难度大，成本高，危险性高，体积能量密度低，占用空间大，还可能存在船上的冷能和热能浪费的问题；或者高压气态氢气储存产生的能量密度低的技术问题。This embodiment provides a hydrogen fuel preparation system on board a ship and a hydrogen production method thereof. By placing a natural gas storage tank 1 for storing liquefied natural gas on board, the natural gas in the natural gas storage tank 1 is pressurized by an evaporator and directly enters the In the heater 3, the liquefied natural gas in the natural gas storage compartment 1 passes through the low-temperature evaporator 2 to turn the liquefied natural gas into low-temperature natural gas and has a suitable pressure, and the low-temperature natural gas enters the heater 3, and the heater 3 increases the temperature of the natural gas, and The heated natural gas is sent to the natural gas hydrogen production device 4, and the natural gas hydrogen production device 4 is used to convert the natural gas into hydrogen, and the hydrogen is used as fuel for the ship's internal combustion engine and/or hydrogen fuel cell as power and/or power system. Hydrogen replaces hydrogen storage on board, which increases safety, effectively reduces risks, and alleviates the difficulty, high cost, high risk, low volumetric energy density, and large footprint of liquefied hydrogen storage on board existing in the prior art. The problem of wasted cooling and heating energy on board; or the technical problem of low energy density resulting from high-pressure gaseous hydrogen storage.
在上述实施例的基础上，在可选的实施方式中，本实施例提供的船上氢燃料制备系统中的加热器3被用于与内燃机供气系统的阀组单元5连通，加热器3中加热后的天然气经由内燃机供气系统的阀组单元5，输送到内燃机中燃烧；需要在天然气与氢气混合时，在内燃机供气系统的阀组单元5中将适当比例的天然气与氢气混合后，输送到内燃机中燃烧。On the basis of the above-mentioned embodiments, in an optional embodiment, the heater 3 in the on-board hydrogen fuel preparation system provided in this embodiment is used to communicate with the valve group unit 5 of the gas supply system of the internal combustion engine, and the heater 3 The heated natural gas is delivered to the internal combustion engine for combustion through the valve group unit 5 of the gas supply system of the internal combustion engine; when natural gas and hydrogen are mixed, after mixing an appropriate proportion of natural gas and hydrogen in the valve group unit 5 of the gas supply system of the internal combustion engine, sent to the internal combustion engine for combustion.
具体的，加热器3加热形成的天然气应具备适合内燃机供气系统的阀组单元5所需压力，经过缓冲罐供给内燃机供气系统的阀组单元5。Specifically, the natural gas formed by heating with the heater 3 should have the required pressure suitable for the valve group unit 5 of the gas supply system of the internal combustion engine, and be supplied to the valve group unit 5 of the gas supply system of the internal combustion engine through a buffer tank.
在可选的实施方式中，船上氢燃料制备系统还包括氢气提纯装置；氢气提纯装置与天然气制氢装置4连接，天然气制氢装置4内的含有氢气的反应气能够进入到氢气初步提纯装置中；反应气进入到氢气提纯装置前，可以通过热交换器将热量传递给加热器3和/或低温蒸发器2，实现反应气初步降温和天然气升温的目的；氢气初步提纯装置的冷却剂与低温蒸发器2连通，实现氢气初步提纯装置与低温蒸发器2之间的热量的传递。In an optional embodiment, the onboard hydrogen fuel preparation system also includes a hydrogen purification device; the hydrogen purification device is connected to the natural gas hydrogen production device 4, and the reaction gas containing hydrogen in the natural gas hydrogen production device 4 can enter the hydrogen preliminary purification device ; Before the reaction gas enters the hydrogen purification device, the heat can be transferred to the heater 3 and/or the low-temperature evaporator 2 through the heat exchanger, so as to realize the purpose of initially cooling the reaction gas and raising the temperature of the natural gas; The evaporator 2 is connected to realize heat transfer between the hydrogen preliminary purification device and the low-temperature evaporator 2 .
如果设置氢燃料电池，则需进行氢气二次提纯。If a hydrogen fuel cell is installed, secondary purification of hydrogen is required.
具体的，供氢燃料电池的氢气提纯装置包括氢气初步提纯装置6，以及氢气二次提纯装置7，天然气制氢装置4制成的含氢反应气依次进入到氢气初步提纯装置6和氢气二次提纯装置7中，对氢气依次提纯。Specifically, the hydrogen purification device of the hydrogen supply fuel cell includes a hydrogen primary purification device 6 and a hydrogen secondary purification device 7. The hydrogen-containing reaction gas produced by the natural gas hydrogen production device 4 enters the hydrogen primary purification device 6 and the hydrogen secondary purification device sequentially. In the purification device 7, hydrogen is sequentially purified.
在可选的实施方式中，船上氢燃料制备系统还包括二氧化碳回收装置8，与氢气初步提纯装置6一起实现二氧化碳回收的目的；二氧化碳回收装置8与天然气制氢装置4排除的废气经由加热器3连接，二氧化碳回收装置8配置为能够冷冻天然气制氢装置4产生的废气，使其中的二氧化碳液化。In an optional embodiment, the onboard hydrogen fuel preparation system also includes a carbon dioxide recovery device 8, which together with the hydrogen primary purification device 6 achieves the purpose of carbon dioxide recovery; the waste gas discharged by the carbon dioxide recovery device 8 and the natural gas hydrogen production device 4 passes through the heater 3 connected, the carbon dioxide recovery unit 8 is configured to be able to freeze the exhaust gas generated by the natural gas hydrogen production unit 4, and liquefy the carbon dioxide therein.
具体的，加热器3冷却天然气制氢装置4产生的废气，冷却后的废气进入到二氧化碳回收装置8中，二氧化碳回收装置8和氢气初步提纯装置6产生的液态二氧化碳进入到二氧化碳储存舱9中，二氧化碳储存舱9中储存固态或者液态的二氧化碳。Specifically, the heater 3 cools the waste gas produced by the natural gas hydrogen production device 4, and the cooled waste gas enters the carbon dioxide recovery device 8, and the liquid carbon dioxide produced by the carbon dioxide recovery device 8 and the hydrogen preliminary purification device 6 enters the carbon dioxide storage cabin 9, Solid or liquid carbon dioxide is stored in the carbon dioxide storage compartment 9 .
在可选的实施方式中，二氧化碳回收装置8的冷却剂与低温蒸发器2连通，二氧化碳回收装置8中所需要的冷能由低温蒸发器2提供。In an optional embodiment, the coolant of the carbon dioxide recovery device 8 communicates with the low-temperature evaporator 2 , and the cold energy required in the carbon dioxide recovery device 8 is provided by the low-temperature evaporator 2 .
具体的，低温蒸发器2的热源来自于氢气初步提纯装置6、二氧化碳回收装置8以及二氧化碳储存舱9，也可来自于反应气初步降温过程(天然气制氢装置4生产的含氢反应气在进入到氢气初步提纯装置6前的初步降温)，在这些热源不足时，由船舶提供的二次加热系统提供，船舶二次加热系统的热源，可以来自于机舱的淡水冷却系统，缸套水系统或者锅炉。Specifically, the heat source of the low-temperature evaporator 2 comes from the hydrogen primary purification device 6, the carbon dioxide recovery device 8, and the carbon dioxide storage cabin 9, and can also come from the initial cooling process of the reaction gas (the hydrogen-containing reaction gas produced by the natural gas hydrogen production device 4 enters the to the preliminary cooling before the hydrogen primary purification device 6), when these heat sources are insufficient, they are provided by the secondary heating system provided by the ship, and the heat source of the secondary heating system of the ship can come from the fresh water cooling system of the engine room, the cylinder jacket water system or boiler.
液态天然气进口温度为-162℃左右，天然气出口温度取决于低温冷却剂离开低温蒸发器2时的温度，低温冷却剂的选择也取决于此时的温度，而低温冷却剂离开低温蒸发器2时的温度取决于二氧化碳回收和储存的温度。The inlet temperature of liquefied natural gas is about -162°C, the outlet temperature of natural gas depends on the temperature when the low-temperature coolant leaves the low-temperature evaporator 2, and the choice of low-temperature coolant also depends on the temperature at this time, and when the low-temperature coolant leaves the low-temperature evaporator 2 The temperature depends on the temperature of carbon dioxide recovery and storage.
天然气加热器3的热源，来自于天然气制氢装置4的废气所含的热量，也可来自于反应气初步降温过程(天然气制氢装置4生产的含氢反应气在进入到氢气初步提纯装置6前的初步降温)，在废热提供的热量不足时，由船舶提供的二次加热系统提供，天然气出口温度为0℃以上。The heat source of the natural gas heater 3 comes from the heat contained in the waste gas of the natural gas hydrogen production unit 4, and can also come from the preliminary cooling process of the reaction gas (the hydrogen-containing reaction gas produced by the natural gas hydrogen production unit 4 enters the hydrogen preliminary purification unit 6 When the heat provided by the waste heat is insufficient, it is provided by the secondary heating system provided by the ship, and the natural gas outlet temperature is above 0°C.
本实施例提供的船上氢燃料制备系统，船上使用液态天然气制氢，取消了陆上制氢常有的除硫步骤，主要原因是陆上制氢所用的天然气含硫较高，容易造成催化剂中毒；而天然气在液化成液态天然气前要经过除硫的过程，已经出去绝大部分硫，故而可以省略此步骤。按照对液态天然气取样检测结果，液态天然气含硫和硫化氢的量都小于1mg/m 3，远小于通常制氢工艺对天然气含硫量不超过0.1ppm的要求。 The on-board hydrogen fuel preparation system provided in this example uses liquefied natural gas to produce hydrogen on board, and eliminates the sulfur removal step that is often used in land-based hydrogen production. The main reason is that the natural gas used for land-based hydrogen production has a high sulfur content, which is likely to cause catalyst poisoning. ; while natural gas has to go through the process of desulfurization before being liquefied into liquefied natural gas, and most of the sulfur has been removed, so this step can be omitted. According to the test results of liquid natural gas sampling, the amount of sulfur and hydrogen sulfide in liquid natural gas is less than 1mg/m 3 , which is far less than the requirement of normal hydrogen production process that the sulfur content of natural gas should not exceed 0.1ppm.
在上述实施例的基础上，本实施例提供的基于船上氢燃料制备系统的制氢方法，包括以下步骤：制氢步骤：将液态天然气储放在天然气储存舱1中，增压泵将天然气储存舱1内的液态天然气加压输送至低温蒸发器2，液态天然气变成具备合适压力的低温天然气，低温天然气与天然气储存舱1内的蒸发气加压后一同进入到加热器3中，控制加热后的天然气压力，适合天然气制氢装置4所需压力的天然气进入到天然气制氢装置4中，适合内燃机所需压力的天然气进入到内燃机供气系统的阀组单元5中，单独或者与氢气混合后供给内燃机作为燃料。On the basis of the above-mentioned embodiments, the hydrogen production method based on the on-board hydrogen fuel preparation system provided by this embodiment includes the following steps: hydrogen production step: storing liquefied natural gas in the natural gas storage tank 1, and the booster pump stores the natural gas The liquid natural gas in the cabin 1 is pressurized and transported to the low-temperature evaporator 2, and the liquid natural gas becomes low-temperature natural gas with a suitable pressure. The low-temperature natural gas and the evaporated gas in the natural gas storage tank 1 are pressurized and enter the heater 3 together to control heating The final natural gas pressure, the natural gas suitable for the pressure required by the natural gas hydrogen production device 4 enters the natural gas hydrogen production device 4, and the natural gas suitable for the pressure required by the internal combustion engine enters the valve group unit 5 of the internal combustion engine gas supply system, either alone or mixed with hydrogen Then supply the internal combustion engine as fuel.
在可选的实施方式中，制氢步骤还包括以下步骤：天然气制氢装置4制备的含氢气体进入到氢气初步提纯装置6中进行初步提纯，大幅度减少其内的二氧化碳和水。氢气初步提纯装置6生成的低纯度氢气可进入到氢气二次提纯装置7中，氢气二次提纯装置7提纯出的高 纯度氢气通过缓冲罐减压后进入到氢燃料电池组中；氢气初步提纯装置6生成的低纯度氢气，也可通过缓冲罐进入到内燃机供气系统的阀组单元5中，单独或者与天然气混合后供给内燃机作为燃料。In an optional embodiment, the hydrogen production step also includes the following steps: the hydrogen-containing gas produced by the natural gas hydrogen production unit 4 enters the hydrogen preliminary purification unit 6 for preliminary purification, and greatly reduces the carbon dioxide and water therein. The low-purity hydrogen generated by the hydrogen primary purification device 6 can enter the hydrogen secondary purification device 7, and the high-purity hydrogen purified by the hydrogen secondary purification device 7 enters the hydrogen fuel cell stack after being decompressed by the buffer tank; the hydrogen primary purification The low-purity hydrogen generated by the device 6 can also enter the valve group unit 5 of the gas supply system of the internal combustion engine through the buffer tank, and be supplied to the internal combustion engine as fuel alone or mixed with natural gas.
在可选的实施方式中，还包括二氧化碳储存步骤：氢气初步提纯装置6产生的二氧化碳进入到二氧化碳储存舱9中，二氧化碳回收装置8将废气中的二氧化碳冷冻成液体二氧化碳后也进入到二氧化碳储存舱9中；二氧化碳储存舱9的冷却剂与低温蒸发器2相连，低温蒸发器2中冷能通过冷却剂进入到二氧化碳储存舱9中。In an optional embodiment, a carbon dioxide storage step is also included: the carbon dioxide produced by the hydrogen preliminary purification device 6 enters the carbon dioxide storage compartment 9, and the carbon dioxide recovery device 8 freezes the carbon dioxide in the waste gas into liquid carbon dioxide and then enters the carbon dioxide storage compartment 9; the coolant in the carbon dioxide storage compartment 9 is connected to the low-temperature evaporator 2, and the cold energy in the low-temperature evaporator 2 enters the carbon dioxide storage compartment 9 through the coolant.
具体的，经加热器3初步冷却的废气进入到二氧化碳回收装置8中，二氧化碳回收装置8用冷冻的方式将加压后的废气中的二氧化碳和水液化，残余的废气排到大气中，而液化的二氧化碳进入到二氧化碳储存舱9中；氢气初步提纯装置6产生的液态二氧化碳也进入到二氧化碳储存舱9中。二氧化碳储存舱9的冷却剂与低温蒸发器2相连，低温蒸发器2中的冷能通过冷却剂进入到二氧化碳储存舱9中，维持二氧化碳储存舱9，以液态或者固态的形式储存二氧化碳。Specifically, the waste gas initially cooled by the heater 3 enters the carbon dioxide recovery device 8, and the carbon dioxide recovery device 8 liquefies the carbon dioxide and water in the pressurized waste gas by freezing, and the remaining waste gas is discharged into the atmosphere and liquefied. The carbon dioxide in the carbon dioxide enters the carbon dioxide storage compartment 9; the liquid carbon dioxide produced by the hydrogen primary purification device 6 also enters the carbon dioxide storage compartment 9. The coolant in the carbon dioxide storage compartment 9 is connected to the low-temperature evaporator 2, and the cold energy in the low-temperature evaporator 2 enters the carbon dioxide storage compartment 9 through the coolant to maintain the carbon dioxide storage compartment 9 and store carbon dioxide in liquid or solid form.
在可选的实施方式中，还包括以下步骤：经加热器3冷却的废气进入到二氧化碳回收装置8中；二氧化碳回收装置8冷冻废气所需的冷能由低温蒸发器2提供。In an optional embodiment, the following steps are also included: the exhaust gas cooled by the heater 3 enters the carbon dioxide recovery device 8 ; the cold energy required by the carbon dioxide recovery device 8 to freeze the exhaust gas is provided by the low-temperature evaporator 2 .
在可选的实施方式中，还包括以下步骤：天然气制氢装置4产生的废气作为热源传递到加热器3中；氢气二次提纯装置7产生的尾气进入到天然气制氢装置4中作为燃料或者原料；氢气初步提纯装置6提纯出的粗氢进入到内燃机供气系统的阀组单元5内。In an optional embodiment, the following steps are also included: the waste gas produced by the natural gas hydrogen production unit 4 is transferred to the heater 3 as a heat source; the tail gas produced by the hydrogen secondary purification unit 7 enters the natural gas hydrogen production unit 4 as fuel or Raw materials: The crude hydrogen purified by the hydrogen primary purification device 6 enters the valve group unit 5 of the gas supply system of the internal combustion engine.
本工艺流程中以天然气重整为例，天然气重整制氢，所需的原料为天然气，所需压力通常为1.0MPa～2.2MPa，合适品质的原料水和氧气以及工艺水由船舶系统提供，制氢过程加热所需的燃料，由初步提纯的粗氢或者天然气提供，而氢气二次提纯的剩余尾气，可以作为燃料或者原料。In this process flow, natural gas reforming is taken as an example. The raw material required for hydrogen production by natural gas reforming is natural gas, and the required pressure is usually 1.0MPa-2.2MPa. The raw material water, oxygen and process water of appropriate quality are provided by the ship system. The fuel required for heating in the hydrogen production process is provided by primary purified crude hydrogen or natural gas, while the remaining tail gas from the secondary purification of hydrogen can be used as fuel or raw material.
此处，采用不同燃料的差异为：采用天然气作为燃料，缺点是燃烧废气中二氧化碳含量较高，如果直接排放，会导致船上制氢的碳排放较多，因此设置二氧化碳回收装置8，捕捉碳。Here, the difference between using different fuels is: using natural gas as fuel, the disadvantage is that the content of carbon dioxide in the combustion exhaust gas is high, if it is directly discharged, it will cause more carbon emissions for hydrogen production on board, so set up a carbon dioxide recovery device 8 to capture carbon.
氢气二次提纯的尾气作为燃料，会略增加碳排放，二次提纯的尾气作为原料，则会降低制氢装置的转换效率，具体的配置可按照实际需要选择，比如在以粗氢和二次提纯尾气为燃料，则可取消制氢废气进入二氧化碳回收装置8，此时制氢过程产生二氧化碳捕捉率最高可超过95％。The tail gas from secondary purification of hydrogen is used as fuel, which will slightly increase carbon emissions, and the tail gas from secondary purification is used as raw material, which will reduce the conversion efficiency of hydrogen production equipment. The specific configuration can be selected according to actual needs, such as crude hydrogen and secondary Purify tail gas as fuel, then the waste gas from hydrogen production can be eliminated from entering the carbon dioxide recovery device 8, and the capture rate of carbon dioxide produced in the hydrogen production process can exceed 95% at the highest.
制氢装置产生的燃烧废气，在对天然气原料预热后，进入到加热器3(为低温天然气加热，同时自身温度降低)，降温后进入二氧化碳回收装置8加压后捕捉二氧化碳，或者直接排 放，制氢装置产生的废水重新进入船舶系统，处理后进行再利用。The combustion exhaust gas produced by the hydrogen production unit, after preheating the natural gas raw material, enters the heater 3 (heating for low-temperature natural gas, and at the same time lowers its own temperature), and after cooling, enters the carbon dioxide recovery device 8 to capture carbon dioxide after pressurization, or directly discharge, The wastewater generated by the hydrogen production unit re-enters the ship system and is reused after treatment.
本实施例提供的船上氢燃料制备系统的制氢方法，在以氢为燃料的船上，不需要储存大量的氢气或者液氢，而是储存液化天然气，通过制氢装置制备所需的氢气；船载的制氢装置与液化天然气的供气系统相结合，实现液态天然气冷能与制氢装置废热的利用，且液态天然气的冷能利用充分；船上制备氢气过程中，通过碳捕捉和储存，实现船上制氢的零碳或者接近零碳排放，从而有效降低船舶的碳排放强度；船上制备的氢气，可以单独或者与天然气混合后用作内燃机的燃料；船上制备的高纯度氢气，可用于船上搭载的大功率氢燃料电池组，作为船舶的电力系统主要电力来源，进一步降低船舶碳排放强度；船载大功率的氢燃料电池组，供电给推进装置，作为小型和微型船舶的推进动力。The hydrogen production method of the on-board hydrogen fuel preparation system provided in this embodiment does not need to store a large amount of hydrogen or liquid hydrogen on a ship fueled by hydrogen, but stores liquefied natural gas and prepares the required hydrogen through a hydrogen production device; The on-board hydrogen production device is combined with the LNG gas supply system to realize the utilization of the cold energy of the LNG and the waste heat of the hydrogen production device, and the cold energy of the LNG is fully utilized; in the process of preparing hydrogen on board, carbon capture and storage are used to realize The zero-carbon or near-zero carbon emission of hydrogen production on board can effectively reduce the carbon emission intensity of ships; the hydrogen produced on board can be used alone or mixed with natural gas as fuel for internal combustion engines; the high-purity hydrogen produced on board can be used on board The high-power hydrogen fuel cell pack, as the main power source of the ship's power system, further reduces the carbon emission intensity of the ship; the high-power hydrogen fuel cell pack on board, supplies power to the propulsion device, and serves as the propulsion power for small and micro ships.
最后应说明的是：以上各实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述各实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的范围。Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, rather than limiting them; although the application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the various embodiments of the present application. scope.

Claims (10)

  1. 一种船上氢燃料制备系统，其中，包括：天然气储存舱(1)、低温蒸发器(2)、加热器(3)和天然气制氢装置(4)；A hydrogen fuel preparation system on board, including: a natural gas storage tank (1), a low-temperature evaporator (2), a heater (3) and a natural gas hydrogen production device (4);
    所述天然气储存舱(1)被用于储放液态天然气，所述天然气储存舱(1)分别与所述低温蒸发器(2)和所述加热器(3)连通，所述天然气储存舱(1)内的液态天然气能够通过所述低温蒸发器(2)进入到所述加热器(3)，所述天然气储存舱(1)内的蒸发气能够进入到所述加热器(3)中，所述天然气制氢装置(4)与所述加热器(3)连接，所述加热器(3)配置为能够加热天然气，并将加热后的天然气输送到所述天然气制氢装置(4)中，所述天然气制氢装置(4)配置为能够将天然气转变为氢气。The natural gas storage tank (1) is used to store liquid natural gas, and the natural gas storage tank (1) communicates with the low-temperature evaporator (2) and the heater (3) respectively, and the natural gas storage tank ( The liquefied natural gas in 1) can enter the heater (3) through the low-temperature evaporator (2), and the evaporated gas in the natural gas storage tank (1) can enter the heater (3), The natural gas hydrogen production device (4) is connected to the heater (3), and the heater (3) is configured to be able to heat natural gas, and transport the heated natural gas to the natural gas hydrogen production device (4) , the natural gas hydrogen production device (4) is configured to be able to convert natural gas into hydrogen.
  2. 根据权利要求1所述的船上氢燃料制备系统，其中，The on-board hydrogen fuel preparation system according to claim 1, wherein,
    所述加热器(3)被用于与内燃机供气系统的阀组单元(5)连通，所述加热器(3)中加热后的天然气输送到内燃机供气系统的阀组单元(5)中。The heater (3) is used to communicate with the valve group unit (5) of the gas supply system of the internal combustion engine, and the natural gas heated in the heater (3) is delivered to the valve group unit (5) of the gas supply system of the internal combustion engine .
  3. 根据权利要求2所述的船上氢燃料制备系统，其中，The on-board hydrogen fuel preparation system according to claim 2, wherein,
    所述船上氢燃料制备系统还包括氢气提纯装置；The on-board hydrogen fuel preparation system also includes a hydrogen purification device;
    所述氢气提纯装置与所述天然气制氢装置(4)连接，所述天然气制氢装置(4)内的氢气能够进入到所述氢气提纯装置中；The hydrogen purification device is connected with the natural gas hydrogen production device (4), and the hydrogen in the natural gas hydrogen production device (4) can enter the hydrogen purification device;
    所述氢气提纯装置与所述低温蒸发器(2)连通，所述氢气提纯装置中的热量能够传递到所述低温蒸发器(2)中。The hydrogen purification device is in communication with the low-temperature evaporator (2), and the heat in the hydrogen purification device can be transferred to the low-temperature evaporator (2).
  4. 根据权利要求3所述的船上氢燃料制备系统，其中，The on-board hydrogen fuel preparation system according to claim 3, wherein,
    所述船上氢燃料制备系统还包括二氧化碳回收装置(8)；The on-board hydrogen fuel preparation system also includes a carbon dioxide recovery device (8);
    氢气初步提纯装置(6)与所述天然气制氢装置(4)排出的反应气连接，氢气初步提纯装置(6)配置为能够以液态形式去除所述天然气制氢装置(4)产生反应气中所含的二氧化碳和水；The hydrogen preliminary purification device (6) is connected to the reaction gas discharged from the natural gas hydrogen production device (4), and the hydrogen preliminary purification device (6) is configured to remove the reaction gas produced by the natural gas hydrogen production device (4) in liquid form. Contains carbon dioxide and water;
    所述二氧化碳回收装置(8)经由所述的加热器(3)与所述天然气制氢装置(4)排出的废气连接，所述二氧化碳回收装置(8)配置为能够为废气加压，并以液态形式去除所述天然气制氢装置(4)产生废气中所含的二氧化碳和水。The carbon dioxide recovery device (8) is connected to the waste gas discharged from the natural gas hydrogen production device (4) via the heater (3), and the carbon dioxide recovery device (8) is configured to be able to pressurize the waste gas, and to The carbon dioxide and water contained in the exhaust gas produced by the natural gas hydrogen production unit (4) are removed in liquid form.
  5. 根据权利要求4所述的船上氢燃料制备系统，其中，The on-board hydrogen fuel preparation system according to claim 4, wherein,
    所述二氧化碳回收装置(8)和所述氢气初步提纯装置(6)的冷却剂分别与所述低温蒸发器(2)连通形成循环回路，将液态天然气的冷能从所述低温蒸发器(2)传递给所述二氧化碳回收装置(8)和所述氢气初步提纯装置(6)，以供液化二氧化碳所用。The coolants of the carbon dioxide recovery device (8) and the hydrogen preliminary purification device (6) are respectively communicated with the low-temperature evaporator (2) to form a circulation loop, and the cold energy of the liquid natural gas is transferred from the low-temperature evaporator (2) ) is delivered to the carbon dioxide recovery unit (8) and the hydrogen primary purification unit (6) for use in liquefied carbon dioxide.
  6. 一种基于如权利要求1-5任一项所述的船上氢燃料制备系统的制氢方法，其中，包括 以下步骤：A hydrogen production method based on the on-board hydrogen fuel preparation system according to any one of claims 1-5, wherein, comprising the following steps:
    制氢步骤：将液态天然气储放在所述天然气储存舱(1)中，增压泵将所述天然气储存舱(1)内的液态天然气加压输送至所述低温蒸发器(2)，液态天然气变成低温天然气，低温天然气与所述天然气储存舱(1)内的蒸发气一同进入到所述加热器(3)中，控制加热后的天然气压力，适合所述天然气制氢装置(4)所需压力的天然气进入到所述天然气制氢装置(4)中，适合内燃机所需压力的天然气进入到内燃机供气系统的阀组单元(5)中。Hydrogen production step: store the liquefied natural gas in the natural gas storage cabin (1), and the booster pump pressurizes the liquefied natural gas in the natural gas storage cabin (1) to the low-temperature evaporator (2). The natural gas becomes low-temperature natural gas, and the low-temperature natural gas enters the heater (3) together with the evaporated gas in the natural gas storage cabin (1) to control the pressure of the heated natural gas, which is suitable for the natural gas hydrogen production device (4) The natural gas at the required pressure enters the natural gas hydrogen production device (4), and the natural gas at the pressure required by the internal combustion engine enters the valve group unit (5) of the gas supply system for the internal combustion engine.
  7. 根据权利要求6所述的船上氢燃料制备系统的制氢方法，其中，所述制氢步骤还包括以下步骤：The hydrogen production method of the on-board hydrogen fuel preparation system according to claim 6, wherein the hydrogen production step further comprises the following steps:
    所述天然气制氢装置(4)制备的氢气进入到氢气初步提纯装置(6)中去除氢气中所含的水和二氧化碳，所述氢气初步提纯装置(6)提纯出的低纯度氢气能够进入到氢气二次提纯装置(7)中，所述氢气二次提纯装置(7)提纯出的高纯度氢气通过缓冲罐减压后进入到氢燃料电池组中。The hydrogen produced by the natural gas hydrogen production unit (4) enters the hydrogen preliminary purification unit (6) to remove water and carbon dioxide contained in the hydrogen, and the low-purity hydrogen purified by the hydrogen preliminary purification unit (6) can enter the In the hydrogen secondary purification device (7), the high-purity hydrogen purified by the hydrogen secondary purification device (7) enters the hydrogen fuel cell stack after being decompressed by the buffer tank.
  8. 根据权利要求7所述的船上氢燃料制备系统的制氢方法，其中，还包括二氧化碳保存步骤：The hydrogen production method of the on-board hydrogen fuel preparation system according to claim 7, further comprising a carbon dioxide preservation step:
    所述氢气初步提纯装置(6)和二氧化碳回收装置(8)产生的二氧化碳以液态形式进入到二氧化碳储存舱(9)中，冷却剂在所述二氧化碳储存舱(9)和所述低温蒸发器(2)之间循环，将所述低温蒸发器(2)中的液态天然气的冷能带入到二氧化碳储存舱(9)中，供所述二氧化碳储存舱(9)以液态或者固态形式储存二氧化碳所需。The carbon dioxide produced by the hydrogen preliminary purification unit (6) and the carbon dioxide recovery unit (8) enters the carbon dioxide storage cabin (9) in liquid form, and the coolant is in the carbon dioxide storage cabin (9) and the low-temperature evaporator ( 2) circulating between them, bringing the cold energy of the liquefied natural gas in the low-temperature evaporator (2) into the carbon dioxide storage compartment (9), for the carbon dioxide storage compartment (9) to store carbon dioxide in liquid or solid form need.
  9. 根据权利要求8项所述的船上氢燃料制备系统的制氢方法，其中，还含有充分利用液态天然气所含冷能和充分利用废热的过程，包括以下步骤：The hydrogen production method of the on-board hydrogen fuel preparation system according to claim 8, wherein it also includes a process of making full use of the cold energy contained in the liquefied natural gas and making full use of waste heat, including the following steps:
    所述加热器(3)将所述天然气制氢装置(4)产生的废气预冷后，进入到所述二氧化碳回收装置(8)中以捕捉废气中的二氧化碳，以节省高品位冷能，充分利用废气的废热；The heater (3) precools the waste gas produced by the natural gas hydrogen production device (4), and then enters the carbon dioxide recovery device (8) to capture carbon dioxide in the waste gas, so as to save high-grade cold energy and fully Utilize the waste heat of the exhaust gas;
    所述的天然气制氢装置(4)的反应气进入到氢气初步提纯装置(6)之前，通过热交换器将反应气的部分热量传递给加热器(3)和/或低温蒸发器(2)。Before the reaction gas of the natural gas hydrogen production unit (4) enters the hydrogen preliminary purification unit (6), part of the heat of the reaction gas is transferred to the heater (3) and/or low temperature evaporator (2) through a heat exchanger .
  10. 根据权利要求9所述的船上氢燃料制备系统的制氢方法，其中，包括以下步骤：The hydrogen production method of the on-board hydrogen fuel preparation system according to claim 9, wherein, comprising the following steps:
    所述氢气二次提纯装置(7)产生的剩余尾气进入到所述天然气制氢装置(4)中作为燃料；The remaining tail gas produced by the hydrogen secondary purification unit (7) enters the natural gas hydrogen production unit (4) as fuel;
    所述氢气初步提纯装置(6)提纯出的粗氢进入到内燃机供气系统的阀组单元(5)内。The crude hydrogen purified by the hydrogen preliminary purification device (6) enters the valve group unit (5) of the gas supply system of the internal combustion engine.
PCT/CN2022/113659 2021-12-01 2022-08-19 Shipborne hydrogen fuel preparation system and hydrogen preparation method thereof WO2023098151A1 (en)

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