CN115285937B - Ammonia reforming and separating integrated device and hydrogen-ammonia hybrid power system comprising same - Google Patents

Ammonia reforming and separating integrated device and hydrogen-ammonia hybrid power system comprising same Download PDF

Info

Publication number
CN115285937B
CN115285937B CN202210814288.0A CN202210814288A CN115285937B CN 115285937 B CN115285937 B CN 115285937B CN 202210814288 A CN202210814288 A CN 202210814288A CN 115285937 B CN115285937 B CN 115285937B
Authority
CN
China
Prior art keywords
ammonia
reforming
hydrogen
cavity
air cavity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210814288.0A
Other languages
Chinese (zh)
Other versions
CN115285937A (en
Inventor
刘龙
许智淳
谭富升
赵容海
吴錾
赵保琳
邓楠楠
王鑫浩
刘译桥
陶天一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Engineering University
Original Assignee
Harbin Engineering University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Engineering University filed Critical Harbin Engineering University
Priority to CN202210814288.0A priority Critical patent/CN115285937B/en
Publication of CN115285937A publication Critical patent/CN115285937A/en
Application granted granted Critical
Publication of CN115285937B publication Critical patent/CN115285937B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/047—Decomposition of ammonia
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B43/00—Engines characterised by operating on gaseous fuels; Plants including such engines
    • F02B43/10—Engines or plants characterised by use of other specific gases, e.g. acetylene, oxyhydrogen
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

The invention provides an ammonia reforming and separating integrated device and a hydrogen-ammonia hybrid power system comprising the same, and belongs to the field of power energy. Solves the problems that the prior ammonia reformer and the separation device have complex structure and low efficiency and are mutually independent and do not realize the coupling work. The device comprises an ammonia micro-channel thermal reforming module and a hydrogen selective separation module which are communicated with each other; the ammonia micro-channel thermal reforming module comprises an ammonia air cavity, an exhaust gas heat exchange cavity, a reforming air cavity I, an ammonia reforming micro-channel and an electric heating layer, wherein a plurality of ammonia reforming micro-channels are uniformly arranged in the ammonia air cavity, the outer wall surface of the exhaust gas heat exchange cavity is wrapped with the electric heating layer, an engine exhaust gas inlet and an engine exhaust gas outlet are arranged on the exhaust gas heat exchange cavity, and a reforming gas outlet is formed in the reforming air cavity I; the hydrogen selective separation module comprises a reforming air cavity II, a hydrogen separation cavity, a reforming air cavity III and a hydrogen selective passing composite pipe. The invention is applicable to a hydrogen fuel cell-ammonia fuel compression ignition piston engine hybrid power system.

Description

Ammonia reforming and separating integrated device and hydrogen-ammonia hybrid power system comprising same
Technical Field
The invention belongs to the field of power energy, and particularly relates to an ammonia reforming and separating integrated device based on selective passage of hydrogen molecules and a hydrogen fuel cell-ammonia fuel compression ignition piston engine hybrid power system comprising the same.
Background
The engine is widely applied to the civil production fields of engineering, agriculture, ocean and the like, is a main source of CO2 emission, and is irreplaceable due to the advantages of power density, safety, reliability and the like of the engine. In order to achieve the aim of controlling carbon emission, the control source is concentrated on the optimization and perfection of the engine, and under the background, the development of a zero-carbon power technology is imperative.
The hydrogen energy source is a clean and efficient renewable energy source, and is used as a battery fuel to greatly promote the development of a hydrogen fuel battery. The fuel cell can directly convert chemical energy in fuel into electric energy, has the advantages of high efficiency, cleanness, environmental protection and the like, and gradually has certain scale application in the aspects of automobiles, shipping and the like. However, the fuel cell mostly adopts hydrogen as a fuel source, leakage easily occurs in the process of hydrogen storage and transportation, and the hydrogen can corrode the gas storage tank, so that potential safety hazards are caused. In order to avoid the difficult problems of storage and transportation, it is important to realize on-site hydrogen production by reforming raw materials. Ammonia is a hydrogen-rich substance, its theoretical hydrogen storage capacity can be up to 17.6wt%, and its thermal stability is good, and its hydrogen-releasing condition is moderate, and it can be used as hydrogen-storing material, and can release hydrogen gas on site for fuel cell operation. Thermal cracking is one of the main methods for producing hydrogen from ammonia fuel, and a part of the energy required can be obtained by recovering the waste heat of the engine exhaust gas.
The inorganic membrane material for hydrogen separation mainly comprises a metal membrane, a ceramic membrane, a molecular sieve membrane, a carbon membrane and the like, wherein the most widely applied inorganic membrane material is metal palladium and an alloy membrane thereof. The transport of hydrogen in metallic palladium follows a dissolution-diffusion mechanism: that is, hydrogen is chemically adsorbed and dissociated into hydrogen atoms on the surface of the palladium membrane, the dissociated hydrogen atoms are dissolved in the palladium membrane and diffused to the other side of the palladium membrane through gaps of metal atom lattices, and then separated out from the surface of the other side of the palladium membrane and recombined into hydrogen molecules. Since atoms or molecules of other elements have diameters larger than lattice gaps of palladium atoms, the palladium film can selectively pass hydrogen atoms only to block other gases, and has excellent hydrogen selectivity.
At present, an ammonia high-efficiency reforming device and a hydrogen separation device for reforming mixed gas, which are applicable to a novel hydrogen-ammonia hybrid power system, are not available, the existing ammonia reformer and the existing ammonia separation device have the problems of complex structure and low efficiency, and the existing ammonia reformer and the existing ammonia separation device are mutually independent and do not realize coupling work, so that the space size and the weight of the device are increased, and the overall effective thermal efficiency and the overall power density of the power device are reduced.
Disclosure of Invention
In view of the above, the invention aims to provide an ammonia reforming and separating integrated device so as to achieve the efficient cracking of ammonia gas and the efficient high-purity separation of hydrogen gas, realize the integrated coupling of ammonia reforming and hydrogen separation, simplify the system structure, reduce the size and weight, and enable the ammonia fuel to meet the fuel supply requirement of a hydrogen-ammonia hybrid power system.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
an ammonia reforming and separating integrated device comprises an ammonia micro-channel thermal reforming module and a hydrogen selective separating module which are communicated with each other;
the ammonia micro-channel thermal reforming module comprises an ammonia air cavity, an exhaust gas heat exchange cavity, a reforming air cavity I, an ammonia reforming micro-channel and an electric heating layer, wherein a plurality of ammonia reforming micro-channels are uniformly arranged in the ammonia air cavity, the ammonia air cavity and the reforming air cavity I are respectively arranged at the left end and the right end of the exhaust gas heat exchange cavity, the two ends of the ammonia reforming micro-channels are respectively communicated with the ammonia air cavity and the reforming air cavity I, an ammonia air inlet is formed in the ammonia air cavity, the outer wall surface of the exhaust gas heat exchange cavity is wrapped with the electric heating layer, an engine exhaust gas inlet and an engine exhaust gas outlet are formed in the exhaust gas heat exchange cavity, and a reformed gas outlet is formed in the reforming air cavity I;
the hydrogen selective separation module comprises a reforming air cavity II, a hydrogen separation cavity, a reforming air cavity III and a hydrogen selective passing composite pipe, wherein a plurality of hydrogen selective passing composite pipes are uniformly arranged in the hydrogen separation cavity, the reforming air cavity II and the reforming air cavity III are respectively arranged at the left end and the right end of the hydrogen separation cavity, the plurality of hydrogen selective passing composite pipes are respectively communicated with the reforming air cavity II and the reforming air cavity III, a reformed gas inlet is formed in the reforming air cavity II, a reformed gas outlet and a reformed gas inlet are communicated through a pipeline, a hydrogen outlet is formed in the hydrogen separation cavity, and a hydrogen rich ammonia reformed gas outlet is formed in the reforming air cavity III.
Furthermore, the ammonia reforming micro-channel is of a tubular structure and comprises an ammonia reforming micro-channel shell, a Ni catalytic layer is coated inside the ammonia reforming micro-channel shell, and a micro-channel reforming cavity is formed inside the ammonia reforming micro-channel shell.
Further, the hydrogen selectively passes through the composite pipe and comprises a palladium membrane layer and Pd/gamma-Al which are sequentially arranged from outside to inside 2 O 3 Layer and Pd/alpha-Al 2 O 3 A layer.
Further, the palladium membrane layer and Pd/gamma-Al 2 O 3 Layer and Pd/alpha-Al 2 O 3 The diameter of the membrane tube of the layer is 1.0-1.2mm.
Further, the ammonia air cavity is separated from the waste gas heat exchange cavity through a first partition plate, and the waste gas heat exchange cavity is separated from the reforming air cavity I through a second partition plate; the reforming air cavity II is separated from the hydrogen separation cavity through a third partition plate, the hydrogen separation cavity is separated from the reforming air cavity III through a fourth partition plate, and holes communicated with corresponding channels or composite pipes are uniformly formed in the four partition plates.
Still further, engine exhaust gas inlet and engine exhaust gas outlet set up respectively in the lower extreme and the upper end of waste gas heat transfer chamber, and engine exhaust gas inlet is close to the left end arrangement in waste gas heat transfer chamber, and engine exhaust gas outlet is close to the right-hand member in waste gas heat transfer chamber.
Furthermore, the ammonia gas inlet is arranged at the center of the left end face of the ammonia gas cavity, the reformed gas outlet is arranged at the center of the right end face of the first reforming gas cavity, the reformed gas inlet is arranged at the center of the left end face of the second reforming gas cavity, and the hydrogen-rich ammonia reformed gas outlet is arranged at the center of the right end face of the third reforming gas cavity.
Further, the hydrogen outlet is arranged at the upper end of the hydrogen separation chamber and is arranged near the right end of the hydrogen separation chamber.
Furthermore, the waste gas heat exchange cavity and the hydrogen separation cavity are both tubular structures.
The invention provides a hydrogen-ammonia hybrid power system, which comprises an ammonia storage tank, an ammonia fuel compression ignition type piston engine, a hydrogen fuel cell, a storage battery, a motor, a gear box and the ammonia reforming and separating integrated device, wherein the ammonia storage tank is communicated with an ammonia gas inlet of the ammonia reforming and separating integrated device, a hydrogen outlet of the ammonia reforming and separating integrated device is communicated with a fuel inlet of the hydrogen fuel cell, a hydrogen-rich ammonia reforming gas outlet of the ammonia reforming and separating integrated device is communicated with a fuel inlet of the ammonia fuel compression ignition type piston engine, an exhaust gas outlet of the ammonia fuel compression ignition type piston engine is communicated with an engine exhaust gas inlet of the ammonia reforming and separating integrated device, the hydrogen fuel cell is electrically connected with the storage battery and the motor, the storage battery is electrically connected with an electric heating layer, the motor is connected with the gear box, and an output end of the ammonia fuel compression ignition type piston engine is connected with the gear box.
Compared with the prior art, the ammonia reforming and separating integrated device has the beneficial effects that:
(1) The ammonia reforming and separating integrated device provided by the invention has the advantages that ammonia can be subjected to cracking reforming simultaneously through a plurality of reforming micro-channels, the heat transfer speed and the cracking efficiency can be improved through the design of the micro-channels and the shell and tube type, and the reaction of as much gas as possible in a limited tube side is ensured, so that sufficient fuel is provided for a subsequent hydrogen fuel cell.
(2) The ammonia reforming and separating integrated device provided by the invention has the advantages that most of heat required by cracking is from high-temperature waste gas discharged after the piston engine performs work, so that waste heat of the engine waste gas is recycled, the power of an electric heating layer can be intelligently regulated and controlled according to the temperature state of the reformer by means of the energy feedback management system and the temperature sensor component of the hybrid system, the stable and efficient operation of the reformer is realized, the heat efficiency and the energy utilization rate of fuel are greatly improved, and the reforming degree and the reformed gas component are stable and controllable.
(3) The invention provides an ammonia reforming and separating integrated device applied to a hydrogen-ammonia hybrid power system, which comprises a palladium membrane layer and Pd/gamma-Al 2 O 3 Layer and Pd/alpha-Al 2 O 3 The hydrogen formed by stacking layers is selectively and directly separated after ammonia reforming through the composite tubes, the composite palladium separation layer has good single selective permeability on hydrogen, the micro tube bundle is designed to increase the contact rate of gas and a wall surface, high-purity hydrogen is efficiently generated and supplied to a hydrogen fuel cell for use, each composite tube is a separation unit, the unitized design is convenient for mass production and standardization, and the number of the composite tubes is flexibly adjusted according to different requirements of reformed gas components and hydrogen supply amount, so that the fuel supply requirement of a hybrid power system under different working conditions is realized.
(4) According to the ammonia reforming and separating integrated device, the ammonia micro-channel thermal reforming module and the hydrogen selective separating module are integrally arranged, pure hydrogen and a hydrogen-rich ammonia reformer are directly separated after ammonia is cracked and reformed, and the pure hydrogen and the hydrogen-rich ammonia reformer are directly supplied to a fuel cell and a piston engine from two passages for use so as to control reformed gas components, prevent the components of reformed gas from changing in the long-distance transmission process, further influence the hydrogen separation amount and cause unstable power and efficiency of the hydrogen fuel cell; and the device has simple structure, compact layout and small weight size, and can be well matched with the mixing system.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and do not constitute an undue limitation on the invention. In the drawings:
FIG. 1 is a schematic view of an ammonia reforming separation integrated device according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of an ammonia reforming microchannel according to an embodiment of the invention;
FIG. 3 is a schematic view of the structure of hydrogen selectively passing through a composite layer;
fig. 4 is a structural diagram of a hybrid system of an ammonia reforming separation integrated device based on a hydrogen molecular selective passing technique to which the present invention is applied.
Reference numerals illustrate:
1. an ammonia gas inlet; 2. electric powerA thermal layer; 3. an ammonia reforming microchannel; 4. an exhaust gas heat exchange cavity; 5. a reformed gas outlet; 6. an engine exhaust gas inlet; 7. an engine exhaust outlet; 8. a reformed gas inlet; 9. the hydrogen selectively passes through the composite pipe; 10. a hydrogen separation chamber; 11. a hydrogen outlet; 12. a hydrogen-rich ammonia reformed gas outlet; 13. an ammonia reforming microchannel housing; 14. a Ni catalytic layer; 15. a microchannel reforming chamber; 16. a palladium membrane layer; 17. Pd/gamma-Al 2 O 3 A layer; 18. alpha-Al 2 O 3 A layer; 19. an ammonia storage tank; 20. an ammonia reforming and separating integrated device; 21. an ammonia fuel compression ignition piston engine; 22. a hydrogen fuel cell; 23. a storage battery; 24. a motor; 25. a gear box; 26. an ammonia gas chamber; 27. reforming the first air cavity; 28. a reforming air cavity II; 29. a reforming air cavity III; 30. a one-way valve.
Detailed Description
The present invention now will be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention disclosed herein without departing from the scope of the invention.
In the description of the present invention, it should be noted that, directions or positional relationships indicated by terms such as "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., are based on those shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the creation of the present invention will be understood in a specific case by those skilled in the art.
In addition, the technical features which are described below and which are involved in the various embodiments of the invention can be combined with one another as long as they do not conflict with one another.
As shown in fig. 1-3, an ammonia reforming and separation integrated device comprises an ammonia micro-channel thermal reforming module and a hydrogen selective separation module which are communicated with each other;
the ammonia micro-channel thermal reforming module comprises an ammonia air cavity 26, an exhaust gas heat exchange cavity 4, a first reforming air cavity 27, an ammonia reforming micro-channel 3 and an electric heating layer 2, wherein a plurality of ammonia reforming micro-channels 3 are uniformly arranged in the ammonia air cavity 26, the ammonia air cavity 26 and the first reforming air cavity 27 are respectively arranged at the left end and the right end of the exhaust gas heat exchange cavity 4, the two ends of the ammonia reforming micro-channels 3 are respectively communicated with the ammonia air cavity 26 and the first reforming air cavity 27, an ammonia air inlet 1 is arranged on the ammonia air cavity 26, the outer wall surface of the exhaust gas heat exchange cavity 4 is wrapped with the electric heating layer 2, an engine exhaust gas inlet 6 and an engine exhaust gas outlet 7 are arranged on the exhaust gas heat exchange cavity 4, and a reformed gas outlet 5 is formed in the first reforming air cavity 27;
the hydrogen selective separation module comprises a reforming air cavity II 28, a hydrogen separation cavity 10, a reforming air cavity III 29 and a hydrogen selective passing composite pipe 9, wherein a plurality of hydrogen selective passing composite pipes 9 are uniformly arranged in the hydrogen separation cavity 10, the reforming air cavity II 28 and the reforming air cavity III 29 are respectively arranged at the left end and the right end of the hydrogen separation cavity 10, a plurality of hydrogen selective passing composite pipes 9 are respectively communicated with the reforming air cavity II 28 and the reforming air cavity III 29, a reforming air inlet 8 is arranged on the reforming air cavity II 28, a reforming air outlet 5 and the reforming air inlet 8 are communicated through a pipeline, a check valve 30 is arranged on the pipeline, a hydrogen outlet 11 is arranged on the hydrogen separation cavity 10, and a hydrogen rich ammonia reforming air outlet 12 is arranged on the reforming air cavity III 29.
Ammonia gas is fed from an ammonia gas inlet 1The ammonia gas flows into the ammonia gas cavity, then flows into each reforming micro-channel 3 from the ammonia gas cavity, the ammonia gas absorbs heat from the waste gas heat exchange cavity 4 for cracking reforming, the reformed gas of each reforming micro-channel is collected into the first reforming gas cavity, and is led into the reformed gas inlet 8 of the hydrogen selective separation module through the reformed gas outlet 5 and the pipeline; the reformed gas enters a cavity of a reforming air cavity II from a reformed gas inlet 8, then flows into each hydrogen gas to selectively pass through a composite pipe 9, pure hydrogen gas enters a hydrogen separation cavity 10 from the hydrogen gas to selectively pass through the composite pipe 9 under the action of concentration gradient, then flows out of a hydrogen fuel cell 22 through a hydrogen outlet 11, the hydrogen gas selectively passes through the residual hydrogen-rich ammonia reformed gas in the composite pipe 9 to be converged into a reforming air cavity III, and flows out of an ammonia fuel compression ignition type piston engine 21 through a hydrogen-rich ammonia reformed gas outlet 12; the electric heating layer 2 is arranged on the peripheral wall surface of the waste gas heat exchange cavity 4, and a metal Ni coating 14 is coated in the ammonia reforming micro-channel 3 to catalyze the thermal cracking of ammonia; the electric heating layer 2 further heats the waste gas in a form of generating heat by electrifying, complements a cracked energy gap, ensures that hydrogen entering the hydrogen selective separation module selectively passes through the composite pipe 9 at more than 300 ℃ so as to avoid mechanical failure of a film caused by hydrogen embrittlement phenomenon generated by hydrogen selectively passing through the palladium film layer 17 in the composite pipe 9, and provides main heat for cracking in a starting stage; the composite tube 9 is made of Pd/alpha-Al 2 O 3 (17) The hollow fiber membrane is made with high selectivity to hydrogen, so that hydrogen enters the hydrogen separation chamber 10 under the action of concentration gradient and following the principle of dissolution-diffusion.
The ammonia reforming micro-channel 3 is of a tubular structure and comprises an ammonia reforming micro-channel shell 13, a Ni catalytic layer 14 is coated inside the ammonia reforming micro-channel shell 13, and a micro-channel reforming cavity 15 is formed inside the ammonia reforming micro-channel shell 13.
The hydrogen selectively passes through the composite pipe 9 and comprises a palladium membrane layer 16 and Pd/gamma-Al which are sequentially arranged from outside to inside 2 O 3 Layer 17 and Pd/alpha-Al 2 O 3 Layer 18.
The palladium membrane layer 16 and Pd/gamma-Al 2 O 3 Layer 17 and Pd/alpha-Al 2 O 3 The membrane tube diameter of layer 18 is 1.0-1.2mm. Pd/alpha-Al 2 O 3 Layer 18 has high temperature resistance, high hardness, stable property, and mainly plays a supporting role, pd/gamma-Al 2 O 3 The layer 17 has high porosity and is convenient to form, pd can be fully inlaid in the layer, the palladium membrane layer 16 is made of pure palladium, single selective passing of hydrogen is ensured, and the effect of isolating other components through hydrogen is achieved.
The ammonia gas cavity 26 is separated from the waste gas heat exchange cavity 4 by a first partition plate, and the waste gas heat exchange cavity 4 is separated from the reforming air cavity I27 by a second partition plate; the second reforming air cavity 28 is separated from the third hydrogen separation cavity 10 by a third partition plate, the third hydrogen separation cavity 10 is separated from the third reforming air cavity 29 by a fourth partition plate, and holes communicated with corresponding channels or composite pipes are uniformly formed in the four partition plates.
The engine exhaust gas inlet 6 and the engine exhaust gas outlet 7 are respectively arranged at the lower end and the upper end of the exhaust gas heat exchange cavity 4, the engine exhaust gas inlet 6 is arranged near the left end of the exhaust gas heat exchange cavity 4, and the engine exhaust gas outlet 7 is arranged near the right end of the exhaust gas heat exchange cavity 4. The arrangement scheme can enable high-temperature waste gas discharged after the piston engine works to be fully filled and flow through the waste heat exchange cavity 4, so that as much heat as possible is transferred to the ammonia reforming micro-channel 3. The ammonia gas inlet 1 is arranged at the center of the left end face of the ammonia gas cavity 26, the reformed gas outlet 5 is arranged at the center of the right end face of the first reforming gas cavity 27, the reformed gas inlet 8 is arranged at the center of the left end face of the second reforming gas cavity 28, the one-way circulation valve 30 is arranged on the channel, and the hydrogen-rich ammonia reformed gas outlet 12 is arranged at the center of the right end face of the third reforming gas cavity 29. The arrangement scheme can directly separate the hydrogen after the ammonia is reformed, avoids the problems of component change caused by long pipe distance transmission, safety caused by long-distance transmission of the hydrogen and the like, ensures compact layout and small size and weight of the device, and improves the overall power density and reliability of the hybrid system. The one-way flow valve 30 ensures one-way passage of reformed gas from the reforming module into the separation module, avoiding reverse flow of the gas. The hydrogen outlet 11 is provided at the upper end of the hydrogen separation chamber 10 and is disposed near the right end of the hydrogen separation chamber 10.
The waste gas heat exchange cavity 4 and the hydrogen separation cavity 10 are both of shell-and-tube structures.
As shown in fig. 4, a hydrogen-ammonia hybrid system, namely a hydrogen-fuel cell-ammonia compression ignition piston engine hybrid system, comprises an ammonia storage tank 19, an ammonia-fuel compression ignition piston engine 21, a hydrogen fuel cell 22, a storage battery 23, an electric motor 24, a gear box 25 and the ammonia reforming separation integrated device 20, wherein the ammonia storage tank 19 is communicated with an ammonia gas inlet 1 of the ammonia reforming separation integrated device 20, a hydrogen outlet 11 of the ammonia reforming separation integrated device is communicated with a fuel inlet of the hydrogen fuel cell 22, a hydrogen-rich ammonia reformed gas outlet 12 of the ammonia reforming separation integrated device 20 is communicated with a fuel inlet of the ammonia-fuel compression ignition piston engine 21, an exhaust gas outlet of the ammonia-fuel compression ignition piston engine 21 is communicated with an engine exhaust gas inlet 6 of the ammonia reforming separation integrated device, the hydrogen fuel cell 22 is electrically connected with the storage battery 23 and the electric motor 24, the storage battery 23 is electrically connected with the electric heating layer 2, the electric motor 24 is connected with the gear box 25, and an output end of the ammonia compression ignition piston engine 21 is connected with the gear box 25.
The high-temperature waste gas generated after the ammonia fuel compression ignition piston engine 21 does work flows in from an engine waste gas inlet 6, exchanges heat with an ammonia reforming micro-channel 3 in an waste gas heat exchange cavity 4 to provide energy required by cracking, ammonia in an ammonia storage tank 19 enters an ammonia cavity from the ammonia gas inlet 1 and flows into each reforming micro-channel 3 from the ammonia cavity, the ammonia absorbs heat from the waste gas heat exchange cavity 4 to carry out cracking reforming, the waste gas after heat exchange is discharged from an engine waste gas outlet 7, reformed gas of each reforming micro-channel is converged into a reforming cavity I, and is led into a reformed gas inlet 8 of a hydrogen selective separation module through a reformed gas outlet 5 and a pipeline; the reformed gas enters a cavity of the reforming air cavity II from the reformed gas inlet 8, then flows into each hydrogen gas to selectively pass through the composite pipe 9, pure hydrogen gas selectively passes through the composite pipe 9 to enter the hydrogen gas separation cavity 10 under the action of concentration gradient, then flows out through the hydrogen gas outlet 11 to be supplied to the hydrogen fuel cell 22, the hydrogen gas selectively passes through the residual hydrogen-rich ammonia reformed gas in the composite pipe 9 to be converged into the reforming air cavity III, flows out through the hydrogen-rich ammonia reformed gas outlet 12 to be supplied to the ammonia fuel compression ignition type piston engine 21, the hydrogen fuel cell 22 generates electricity to supply power to the motor 24, and the redundant electricity is stored in the storage battery 23, the storage battery 23 supplies power to the electric heating layer 2, and the working output end of the ammonia fuel compression ignition type piston engine 21 and the output end of the motor 24 are connected with the gear box 25. The fuel safety and high efficiency supply problem of a novel hydrogen fuel cell-ammonia fuel compression ignition piston engine hybrid power system is solved.
The inventive embodiments disclosed above are merely intended to help illustrate the inventive embodiments. The examples are not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention.

Claims (10)

1. An ammonia reforming separation integrated device which is characterized in that: comprises an ammonia micro-channel thermal reforming module and a hydrogen selective separation module which are communicated with each other;
the ammonia micro-channel thermal reforming module comprises an ammonia air cavity (26), an exhaust gas heat exchange cavity (4), a first reforming air cavity (27), an ammonia reforming micro-channel (3) and an electric heating layer (2), wherein a plurality of ammonia reforming micro-channels (3) are uniformly arranged in the ammonia air cavity (26), the ammonia air cavity (26) and the first reforming air cavity (27) are respectively arranged at the left end and the right end of the exhaust gas heat exchange cavity (4), the two ends of the ammonia reforming micro-channel (3) are respectively communicated with the ammonia air cavity (26) and the first reforming air cavity (27), an ammonia air inlet (1) is formed in the ammonia air cavity (26), a layer of electric heating layer (2) is wrapped on the outer wall surface of the exhaust gas heat exchange cavity (4), an engine exhaust gas inlet (6) and an engine exhaust gas outlet (7) are formed in the exhaust gas heat exchange cavity (4), and a reformed gas outlet (5) is formed in the first reforming air cavity (27);
the hydrogen selective separation module comprises a reforming air cavity II (28), a hydrogen separation cavity (10), a reforming air cavity III (29) and a hydrogen selective passing composite pipe (9), wherein a plurality of hydrogen selective passing composite pipes (9) are uniformly arranged in the hydrogen separation cavity (10), the reforming air cavity II (28) and the reforming air cavity III (29) are respectively arranged at the left end and the right end of the hydrogen separation cavity (10), the hydrogen selective passing composite pipes (9) are respectively communicated with the reforming air cavity II (28) and the reforming air cavity III (29), a reforming air inlet (8) is formed in the reforming air cavity II (28), a hydrogen outlet (11) is formed in the hydrogen separation cavity (10), and a hydrogen rich ammonia reforming air outlet (12) is formed in the reforming air cavity III (29).
2. The ammonia reforming separation integrated device of claim 1, wherein: the ammonia reforming micro-channel (3) is of a tubular structure and comprises an ammonia reforming micro-channel shell (13), a Ni catalytic layer (14) is coated inside the ammonia reforming micro-channel shell (13), and a micro-channel reforming cavity (15) is formed inside the ammonia reforming micro-channel shell (13).
3. The ammonia reforming separation integrated device of claim 1, wherein: the hydrogen selectively passes through the composite pipe (9) and comprises a palladium membrane layer (16) and Pd/gamma-Al which are sequentially arranged from outside to inside 2 O 3 Layer (17) and Pd/alpha-Al 2 O 3 A layer (18).
4. An ammonia reforming separation integrated unit according to claim 3, wherein: the palladium membrane layer (16) and Pd/gamma-Al 2 O 3 Layer (17) and Pd/alpha-Al 2 O 3 The diameter of the membrane tube of layer (18) is 1.0-1.2mm.
5. The ammonia reforming separation integrated device of claim 1, wherein: the ammonia gas cavity (26) is separated from the waste gas heat exchange cavity (4) through a first partition plate, and the waste gas heat exchange cavity (4) is separated from the reforming air cavity I (27) through a second partition plate; the reforming air cavity II (28) is separated from the hydrogen separation cavity (10) by a third partition plate, the hydrogen separation cavity (10) is separated from the reforming air cavity III (29) by a fourth partition plate, and holes communicated with corresponding channels or composite pipes are uniformly formed in the four partition plates.
6. The ammonia reforming separation integrated device of claim 1, wherein: the engine exhaust gas inlet (6) and the engine exhaust gas outlet (7) are respectively arranged at the lower end and the upper end of the exhaust gas heat exchange cavity (4), the engine exhaust gas inlet (6) is arranged close to the left end of the exhaust gas heat exchange cavity (4), and the engine exhaust gas outlet (7) is arranged close to the right end of the exhaust gas heat exchange cavity (4).
7. The ammonia reforming separation integrated device of claim 1, wherein: the ammonia gas inlet (1) is arranged at the center of the left end face of the ammonia gas cavity (26), the reformed gas outlet (5) is arranged at the center of the right end face of the first reforming gas cavity (27), the reformed gas inlet (8) is arranged at the center of the left end face of the second reforming gas cavity (28), and the hydrogen-rich ammonia reformed gas outlet (12) is arranged at the center of the right end face of the third reforming gas cavity (29).
8. The ammonia reforming separation integrated device of claim 1, wherein: the hydrogen outlet (11) is arranged at the upper end of the hydrogen separation chamber (10) and is arranged near the right end of the hydrogen separation chamber (10).
9. The ammonia reforming separation integrated device of claim 1, wherein: the waste gas heat exchange cavity (4) and the hydrogen separation cavity (10) are both of tubular structures.
10. A hydrogen-ammonia hybrid system characterized by: the fuel-air separator integrated device comprises an ammonia storage tank (19), an ammonia fuel compression ignition type piston engine (21), a hydrogen fuel cell (22), a storage battery (23), an electric motor (24), a gear box (25) and the ammonia reforming separation integrated device (20) as claimed in any one of claims 1-9, wherein the ammonia storage tank (19) is communicated with an ammonia air inlet (1) of the ammonia reforming separation integrated device (20), a hydrogen outlet (11) of the ammonia reforming separation integrated device is communicated with a fuel inlet of the hydrogen fuel cell (22), a hydrogen-rich ammonia reformed gas outlet (12) of the ammonia reforming separation integrated device (20) is communicated with a fuel inlet of the ammonia fuel compression ignition type piston engine (21), an exhaust gas outlet of the ammonia fuel type piston engine (21) is communicated with an engine exhaust gas inlet (6) of the ammonia reforming separation integrated device, the hydrogen fuel cell (22) is electrically connected with the storage battery (23) and the electric motor (24), the storage battery (23) is electrically connected with the electric heating layer (2), the electric motor (24) is connected with the gear box (25), and an output end of the ammonia fuel type piston engine (21) is connected with the gear box (25).
CN202210814288.0A 2022-07-12 2022-07-12 Ammonia reforming and separating integrated device and hydrogen-ammonia hybrid power system comprising same Active CN115285937B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210814288.0A CN115285937B (en) 2022-07-12 2022-07-12 Ammonia reforming and separating integrated device and hydrogen-ammonia hybrid power system comprising same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210814288.0A CN115285937B (en) 2022-07-12 2022-07-12 Ammonia reforming and separating integrated device and hydrogen-ammonia hybrid power system comprising same

Publications (2)

Publication Number Publication Date
CN115285937A CN115285937A (en) 2022-11-04
CN115285937B true CN115285937B (en) 2023-06-16

Family

ID=83822108

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210814288.0A Active CN115285937B (en) 2022-07-12 2022-07-12 Ammonia reforming and separating integrated device and hydrogen-ammonia hybrid power system comprising same

Country Status (1)

Country Link
CN (1) CN115285937B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008074688A (en) * 2006-09-25 2008-04-03 Aisin Seiki Co Ltd Reforming apparatus
JP2018025375A (en) * 2016-07-31 2018-02-15 寛治 泉 Constitution method for engine burning hydrogen and oxygen
JP2020087556A (en) * 2018-11-19 2020-06-04 株式会社豊田自動織機 Fuel cell system
CN114483290A (en) * 2022-01-27 2022-05-13 西安交通大学 Composite compressed air energy storage system and method for methanol reformer coupled internal combustion engine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008074688A (en) * 2006-09-25 2008-04-03 Aisin Seiki Co Ltd Reforming apparatus
JP2018025375A (en) * 2016-07-31 2018-02-15 寛治 泉 Constitution method for engine burning hydrogen and oxygen
JP2020087556A (en) * 2018-11-19 2020-06-04 株式会社豊田自動織機 Fuel cell system
CN114483290A (en) * 2022-01-27 2022-05-13 西安交通大学 Composite compressed air energy storage system and method for methanol reformer coupled internal combustion engine

Also Published As

Publication number Publication date
CN115285937A (en) 2022-11-04

Similar Documents

Publication Publication Date Title
JP6977082B2 (en) Ammonia decomposition equipment and system and hydrogen production method
CN103311560B (en) Solid oxide fuel cell power generating system and battery pile thereof
JP4557428B2 (en) Small fuel reformer using metal thin film and its system
US20090042071A1 (en) Multi-tube fuel reformer with augmented heat transfer
JP5785659B2 (en) Laminated hydrocarbon reformer using microchannel heater
CN110429308B (en) Methanol hydrogen production power generation system
CN1330034C (en) Reformer and fuel cell system having the same
CN101580227B (en) Self-heating type alcohol reforming hydrogen production micro channel reactor with micro-lug boss array structure
WO2011107279A1 (en) Apparatus for generating hydrogen from ammonia stored in solid materials and integration thereof into low temperature fuel cells
CN110801785B (en) Hydrogen production reactor with honeycomb SiC ceramic as catalyst carrier
CN109638324B (en) Pure hydrogen catalytic device and PEMFC power generation system of many sleeve structures of integration to multiple hydrocarbon fuel
CN111483978B (en) Reforming hydrogen production device and reforming hydrogen production method
CN113930799A (en) Heat recovery system for hydrogen production of solid oxide electrolytic cell
CN102502494B (en) Laminated type reactor for hydrogen production by reforming alcohols
JP2002198074A (en) Multi-stage combustion process for maintaining controllable reforming temperature profile
CN100379072C (en) Reformer and fuel cell system having the same
CN111661818A (en) Integrated hydrogen production reactor for autothermal reforming of hydrocarbon
CN111196596A (en) Micro-channel methanol hydrogen production reactor with uniformly distributed flow velocity and concentration
CN115285937B (en) Ammonia reforming and separating integrated device and hydrogen-ammonia hybrid power system comprising same
CN109761193B (en) Methanol reforming hydrogen production reactor
CN202346756U (en) Laminated type alcohol reforming hydrogen production reactor
CN111453697B (en) Multi-fuel universal reforming hydrogen production system and method for SOFC
CN110600774B (en) Integrated BOP system of solid oxide fuel cell integration
CN201427859Y (en) Self-heating type microchannel reactor with micro-boss array structure for reforming alcohol to make hydrogen
CN219892210U (en) Fuel cell stack

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant