CN111170273B - Combined cooling, heating and power supply system and power supply method based on ammonia energy ship - Google Patents
Combined cooling, heating and power supply system and power supply method based on ammonia energy ship Download PDFInfo
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- CN111170273B CN111170273B CN202010139304.1A CN202010139304A CN111170273B CN 111170273 B CN111170273 B CN 111170273B CN 202010139304 A CN202010139304 A CN 202010139304A CN 111170273 B CN111170273 B CN 111170273B
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- 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
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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
- B63H21/12—Use of propulsion power plant or units on vessels the vessels being motor-driven
- B63H21/17—Use of propulsion power plant or units on vessels the vessels being motor-driven by electric motor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63J—AUXILIARIES ON VESSELS
- B63J2/00—Arrangements of ventilation, heating, cooling, or air-conditioning
- B63J2/12—Heating; Cooling
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D9/00—Heat-exchange apparatus having stationary plate-like or laminated conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D9/00—Heat-exchange apparatus having stationary plate-like or laminated conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D9/04—Heat-exchange apparatus having stationary plate-like or laminated conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being formed by spirally-wound plates or laminae
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- 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
- H01M8/0625—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 in a modular combined reactor/fuel cell structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63J—AUXILIARIES ON VESSELS
- B63J2/00—Arrangements of ventilation, heating, cooling, or air-conditioning
- B63J2/12—Heating; Cooling
- B63J2002/125—Heating; Cooling making use of waste energy
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- 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
- C01B2203/0405—Purification by membrane separation
- C01B2203/041—In-situ membrane purification during hydrogen production
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- 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
- C01B2203/042—Purification by adsorption on solids
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- 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
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- 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
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- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
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- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y02T70/00—Maritime or waterways transport
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Abstract
The invention provides a combined cooling, heating and power system based on an ammonia energy ship, which comprises a hydrogen production system, a ship power supply system and a cooling, heating and power recovery heat exchange circulating system; the hydrogen production system comprises a marine liquid ammonia storage tank, a flow regulating valve group, a gasifier, a pressure regulating valve group, a drying filter, an ammonia preheater, an electric heater, an ammonia catalytic decomposition hydrogen separation unit, a hydrogen purifier, a hydrogen cooler and a hydrogen pressure flow regulating valve group which are sequentially communicated; the marine power supply system includes a hydrogen-air fuel cell, a motor propeller, and a battery; the cold and heat energy recovery and heat exchange circulating system comprises a waste heat boiler and a secondary refrigerant pump; the waste heat boiler is used for generating saturated steam to supply heat requirements of an auxiliary engine and a passenger cabin of the ship; the coolant pump is used for cooling the ship equipment and supplying the related cold demand of the ship. The invention solves the problem of large energy consumption caused by cutting and splitting the hydrogen production and hydrogen storage technology in the existing hydrogen production-hydrogen storage technology.
Description
Technical Field
The invention relates to the field of combined cooling, heating and power of a liquid ammonia energy system, in particular to a combined cooling, heating and power system of an ammonia energy ship and a power supply method, wherein the combined cooling, heating and power system utilizes liquid ammonia to carry hydrogen, catalyze and produce hydrogen, and a fuel cell generates power and recycles the cold and heat energy of the process.
Background
Since 2020, the world maritime organization has been required to impose global sulfur emission limits of less than 0.5%, and more than half of the carbon emissions of marine maritime vessels have been required to be reduced by 2050. This is a challenge for most current marine industries that use polysulfide, multi-particulate emissions of heavy oils. The environment pollution and the climate warming bring great pressure to the marine environment, so that the optimized energy use efficiency in the ship cold-hot electric system reasonably develops the high-efficiency clean energy and the related conversion technology thereof, and is a critical problem to be solved at present. Hydrogen is a completely clean and renewable final energy source, the heat value of the hydrogen is about 3 times that of gasoline, the hydrogen is far higher than that of natural gas, and the hydrogen is used for generating only water by a fuel cell, so that the discharge of sulfur oxides and particulate matters can be completely avoided, and most ships can be expected to select hydrogen as main ship fuel within 30 to 50 years. However, the free hydrogen exists in a very small amount in a natural state, and how to economically and economically enrich and purify the free hydrogen to produce the hydrogen is a great difficulty in popularization of hydrogen energy. Due to technical limitations, the current large-scale hydrogen production process (fossil fuel reforming, electrolyzed water and biological hydrogen production) has the problems of larger pollution discharge amount, higher power consumption, poor safety and economy and the like. In addition, the hydrogen storage after the production is a great difficulty, for example, the compressed hydrogen for vehicles can meet the requirement only by producing a hydrogen storage tank with the design pressure of 98MPa, the liquefied hydrogen is more difficult to store and transport, the hydrogen is required to be liquefied at minus 253 ℃, and the technical difficulty of the tank storage is higher. The above difficulties have hampered the development of hydrogen energy in various neighborhoods and there is an urgent need to find alternative methods for producing hydrogen from hydrogen storage with economy.
The ammonia is used as a clean and renewable organic substance with the hydrogen content of 17.6 percent, is widely used for basic products and chemical raw materials in the agriculture industry, and has the advantages of the production of China ammonia accounting for one third of the world, the network distribution of synthetic ammonia factories nationally, mature production technology, and low storage and transportation price. The ammonia can be completely cracked into hydrogen and nitrogen by adding a conventional catalyst at the normal pressure of about 600 ℃, the conversion rate is as high as 99.9%, and the catalyst has great hydrogen production potential. Compared with hydrogen, ammonia can be liquefied only at the normal pressure of-33 ℃ or the normal temperature pressure of about 7bar, the volume energy density of liquid ammonia is 1.53 times that of liquid hydrogen, and the energy storage and transportation rate is higher under the same volume condition. At present, the price of hydrogen in domestic hydrogen stations is about 70 yuan per kilogram, the price of liquid ammonia is about 3000 yuan per ton, the hydrogen obtained by decomposition is about 16.7 yuan per kilogram, and the difference of the costs of hydrogen and ammonia in storage, transportation, decomposition and the like is not compared. Ammonia is therefore an extremely promising technical form as a source of feed gas for hydrogen-carrying hydrogen production.
Summary the existing hydrogen production-storage technologies at present are concentrated on high energy consumption and high emission, the hydrogen production and storage technologies are purely split, and no subsequent technical connection of hydrogen storage and transportation is performed after hydrogen is produced, so that a great amount of energy consumption is performed again for subsequent compression, liquefaction and hydride storage and transportation. This mode of technology results in the overall hydrogen production-storage industry with a final cost of hydrogen far greater than fossil fuels and associated emissions management costs, and the energy efficiency of hydrogen is not offset by the energy consumption emissions of hydrogen production-storage.
Disclosure of Invention
According to the technical problem that the existing hydrogen production-hydrogen storage technology is split to cause a large amount of energy consumption, the combined system and the power supply method for the combined heat and power supply based on the ammonia energy ship are provided. The invention takes hydrogen storage and transportation as the beginning and takes the combined utilization of cold and heat in the hydrogen production and flow as the terminal, breaks through the complex process and extremely high cost of the traditional method of firstly producing hydrogen and then storing and transporting, takes hydrogen-rich liquid ammonia as a hydrogen storage carrier, and forms a set of integrated system and power supply method of cold, heat and electricity based on ammonia energy ships through a series of energy conversion systems and methods of liquid ammonia gasification, ammonia preheating, heating, catalytic decomposition, hydrogen purification, fuel cell power generation, waste nitrogen heat exchange, liquid ammonia gasification cold and heat recycling and the like.
The invention adopts the following technical means:
a combined system of combined heat and power based on ammonia energy ship comprises a hydrogen production system, a ship power supply system and a heat exchange and circulation system for recovering cold and heat energy;
the hydrogen production system comprises a marine liquid ammonia storage tank, a flow regulating valve group, a gasifier, a pressure regulating valve group, a drying filter, an ammonia preheater, an electric heater, an ammonia catalytic decomposition hydrogen separation unit, a hydrogen purifier, a hydrogen cooler and a hydrogen pressure flow regulating valve group which are sequentially communicated;
the marine power supply system includes a hydrogen-air fuel cell, a motor propeller, and a battery; the hydrogen cooler is used for leading hydrogen into the hydrogen-air fuel cell to generate electricity and transmitting the electricity to the storage battery to store; the hydrogen-air fuel cell transmits electric power to a motor of the ship, and the motor receives the electric power to push a propeller of the motor to rotate so as to enable the ship to travel; the ship power supply system can also supply power to other electric equipment of the ship;
the cold and heat energy recovery and heat exchange circulating system comprises a waste heat boiler and a secondary refrigerant pump; the waste heat boiler is communicated with the ammonia preheater through a pipeline, heat carried by waste gas nitrogen after a cracking reaction occurs in the ammonia catalytic decomposition hydrogen separation unit recovered by the cold and heat energy recovery heat exchange circulation system is supplied to the waste heat boiler through the ammonia preheater, and the waste heat boiler is used for generating saturated steam to supply heat requirements of an auxiliary engine and a passenger cabin of a ship; the refrigerating agent pump is respectively communicated with the gasifier through pipelines, and the cold and heat energy recovery heat exchange circulation system is used for carrying out cold energy recovery in the gasifier through refrigerating agent and is used for cooling ship equipment and supplying related cold energy requirements of ships.
Further, the cold and heat energy recovery heat exchange circulation system can supply cold energy obtained by recovering liquid ammonia in the gasifier through a secondary refrigerant for gasification to the hydrogen cooler.
Further, the heat carried by the waste gas nitrogen after the cracking reaction in the ammonia catalytic decomposition hydrogen separation unit and recovered by the cold and heat energy recovery heat exchange circulation system is firstly supplied to the ammonia preheater to heat the ammonia so as to reduce the power consumption of the heater, and then supplied to the waste heat boiler through the ammonia preheater.
Further, the secondary refrigerant is glycol aqueous solution or nitrogen and other explosion-proof secondary refrigerant.
Further, the ammonia catalytic decomposition hydrogen separation unit comprises an inlet manifold, an outlet manifold and a shell-and-tube cracking separation device; the shell-and-tube cracking separation device is filled with a catalyst; the shell-and-tube cracking separation device is provided with a nitrogen outlet; the inlet manifold is communicated with the inside of the shell-and-tube cracking separation device; the outlet manifold extends into the shell-and-tube cracking separation device; the inner wall of the outlet manifold is attached with a hydrogen permeable membrane.
Further, the catalyst is a metal-based ammonia decomposition catalyst such as Ru, ni, fe and the like; the hydrogen permeable membrane is a palladium-based alloy membrane.
Further, the purifier is filled with porous solid molecular sieve adsorbent for removing tiny moisture impurities, ammonia and nitrogen in hydrogen.
Further, the gasifier, the ammonia preheater, and the hydrogen cooler may be plate-fin, plate, wound-tube, or shell-and-tube heat exchangers; the gasifier, the ammonia preheater, and the hydrogen cooler may be perforated, corrugated, or zigzag fins inside.
And when the combined system of the heating, cooling and power is started, the storage battery is used for driving the hydrogen production system to start hydrogen production, the electric heater works at full load when the system is started, and the electric heater changes into a small-load working or intermittent working mode after hydrogen is produced.
The invention also provides a combined cooling, heating and power supply method based on the ammonia energy ship, which adopts the combined cooling, heating and power supply system based on the ammonia energy ship, and comprises the following steps:
step 1: liquid ammonia storage and transportation gasification
The liquid ammonia is stored in a marine liquid ammonia storage tank, the flow is regulated by a flow regulating valve group, then the liquid ammonia is introduced into a gasifier for gasification to be changed into ammonia, and cold energy is recovered in the gasifier through a cold and heat energy recovery and heat exchange circulating system; ammonia gas is introduced into a filter of the dryer, and the pressure in the gasifier and the flow of the output ammonia gas are controlled through a pressure regulating valve group;
step 2: ammonia drying, impurity removing and heating
Drying ammonia through a dryer filter to remove impurities, preheating the ammonia to 500 ℃ by using heat carried by waste gas nitrogen after cracking reaction in the ammonia catalytic decomposition hydrogen separation unit recovered by a cold and heat energy recovery heat exchange circulation system in an ammonia preheater, and then heating the ammonia to a catalytic cracking temperature of 650-700 ℃ by an electric heater 7 with a set temperature;
step 3: catalytic cracking separation of ammonia and purification of hydrogen
The heated ammonia gas is introduced into an ammonia catalytic decomposition hydrogen separation unit and is decomposed into hydrogen and nitrogen by a catalyst; the hydrogen is purified and cooled by a hydrogen purifier and a hydrogen cooler in sequence;
step 4: ship fuel cell power generation and supply
The hydrogen is introduced into a hydrogen-air fuel cell through a hydrogen pressure flow control valve group to generate electricity and is conveyed to the storage battery to be stored; the hydrogen-air fuel cell transmits electric power to a motor of the ship, and the motor receives the electric power to push a propeller of the motor to rotate so as to enable the ship to travel; the ship power supply system can also supply power for other electric equipment of the ship.
Compared with the prior art, the invention has the following advantages:
1. the combined system and the power supply method for the combined heat and power supply based on the ammonia energy ship provided by the invention abandon the unreasonable situation that the existing pure hydrogen production and hydrogen storage technology is split (namely hydrogen production is firstly carried out and then hydrogen storage is carried out), the technical process of hydrogen raw material storage and hydrogen carrying is firstly carried out, and the field hydrogen production is reproduced is provided, so that the technical engagement of no subsequent hydrogen storage and transportation after large-scale energy consumption hydrogen production in the prior art is overcome, and the compression, liquefaction and storage of hydrogen are carried out again to consume a large amount of energy even worse than the hydrogen production economy.
2. The combined system and the power supply method for the combined heating and cooling power based on the ammonia energy ship overcome the defects of high storage and transportation cost, combustibility, explosiveness and the like of the existing hydrogen and liquid hydrogen, and utilize the hydrogen-carrying raw material liquid ammonia to carry out storage and transportation, and because the liquid ammonia acquisition way is wide and has low cost (< 3000 per ton), the price of the existing hydrogen in a hydrogenation station is about 70 per kilogram as converted into 16.7 per kg of hydrogen, and the hydrogen storage amount per unit mass of the system is higher (17.6%) than that of other hydrogen-carrying systems, in addition, the volume energy density of the liquid ammonia is 1.53 times that of the liquid hydrogen, the fuel with the same volume, and the endurance mileage of the liquid ammonia is 1.53 times that of the liquid hydrogen.
3. The combined cooling, heating and power system and the power supply method based on the ammonia energy ship are different from the traditional diesel or LNG ship combined cooling, heating and power system, the diesel ship utilizes an engine to drive a generator to generate power, and utilizes electric power to drive a refrigeration and boiler device to supply cold and heat; the LNG ship generates power using an organic rankine cycle, and generates a cold and hot supply by heat recovery; compared with diesel and LNG engines, the hydrogen-air fuel cell is utilized without any emission pollution; in addition, compared with an LNG ship organic Rankine cycle combined heat and power generation system, the system is simple and clear, the energy utilization rate is high, and the restriction of LNG cold energy cascade utilization and organic Rankine cycle efficiency can not exist.
4. The combined system and the power supply method for the cold, heat and electricity based on the ammonia energy ship provided by the invention are economical, safe, environment-friendly and energy-saving, the expensive storage of LNG and liquid hydrogen and inflammable and explosive conditions are abandoned, no nitrogen-oxygen-carbon-oxygen particulate matter is discharged in the process, and the extra energy provided by the ammonia catalytic hydrogen production is completely recycled through a heat exchange network. In order to prevent the danger of inflammable and explosive hydrogen cooling, the invention does not directly utilize the decomposed hydrogen waste heat to gasify the raw material gas in the system, but skillfully sets other explosion-proof secondary refrigerant as medium to transfer and convert heat between the gasifier and the hydrogen cooler.
5. The combined system and the power supply method for the combined heat and power generation based on the ammonia energy ship can store and transport hydrogen-rich media and produce hydrogen with the purification rate of more than 99.9 percent on site as fuel of a fuel cell to generate power, and utilize an integrated heat exchange network to recycle the cold energy and the waste heat in the process so as to reduce the hydrogen production energy consumption, and simultaneously, the combined heat and power supply system also has the advantages of high efficiency, no pollution and economy, and meets the triple requirements of steam heat, cold energy and electric power in the ship running process.
In summary, the invention takes hydrogen storage and transportation as the beginning and takes combined utilization of cold and heat and electricity in the hydrogen production and flow as the terminal, breaks through the complex process and extremely high cost of the traditional method of firstly producing hydrogen and then storing and transporting, takes hydrogen-rich substance liquid ammonia as a hydrogen storage carrier, and forms a set of integrated system and power supply method of cold, heat and electricity triple supply based on ammonia energy ships through a series of energy conversion systems and methods of liquid ammonia gasification, ammonia preheating, heating, catalytic decomposition, hydrogen purification, fuel cell power generation, waste nitrogen heat exchange, liquid ammonia gasification cold and heat recycling and the like. Therefore, the technical scheme of the invention solves the problem of large energy consumption caused by the fact that the existing hydrogen production-hydrogen storage technology breaks apart the hydrogen production technology and the hydrogen storage technology. The system and the modularized method are suitable for the popularization and the use of the cold-heat cogeneration of the liquid ammonia energy system and related ammonia energy in the fields of ships, automobiles and the like.
Based on the reasons, the invention can be widely popularized in the fields of cold-heat cogeneration of liquid ammonia energy systems and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to the drawings without inventive effort to a person skilled in the art.
Fig. 1 is a frame diagram of a combined cooling, heating and power system based on an ammonia-energy ship.
Fig. 2 is a schematic diagram of the working principle of the cold and hot energy recovery heat exchange circulation system according to the invention.
FIG. 3 is a schematic diagram of an ammonia cracking hydrogen separation unit device according to the invention.
In the figure: 1. liquid ammonia storage tank for ship; 2. a flow regulating valve group; 3. a gasifier; 4. a pressure regulating valve block; 5. drying the filter; 6. an ammonia preheater; 7. an electric heater; 8. an ammonia catalytic decomposition hydrogen separation unit; 81. an inlet manifold; 82. a shell-and-tube cracking separation device; 83. an outlet manifold; 84. a nitrogen outlet; 9. a hydrogen purifier; 10. a hydrogen cooler; 11. a hydrogen pressure flow control valve group; 12. a hydrogen-air fuel cell; 13. a motor propeller; 14. a storage battery; 15. a waste heat boiler; 16. a coolant pump.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The relative arrangement of the components and steps, numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless it is specifically stated otherwise. Meanwhile, it should be clear that the dimensions of the respective parts shown in the drawings are not drawn in actual scale for convenience of description. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further discussion thereof is necessary in subsequent figures.
In the description of the present invention, it should be understood that the azimuth or positional relationships indicated by the azimuth terms such as "front, rear, upper, lower, left, right", "lateral, vertical, horizontal", and "top, bottom", etc., are generally based on the azimuth or positional relationships shown in the drawings, merely to facilitate description of the present invention and simplify the description, and these azimuth terms do not indicate and imply that the apparatus or elements referred to must have a specific azimuth or be constructed and operated in a specific azimuth, and thus should not be construed as limiting the scope of protection of the present invention: the orientation word "inner and outer" refers to inner and outer relative to the contour of the respective component itself.
Spatially relative terms, such as "above … …," "above … …," "upper surface at … …," "above," and the like, may be used herein for ease of description to describe one device or feature's spatial location relative to another device or feature as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as "above" or "over" other devices or structures would then be oriented "below" or "beneath" the other devices or structures. Thus, the exemplary term "above … …" may include both orientations of "above … …" and "below … …". The device may also be oriented 90 degrees or at other orientations and the spatially relative descriptors used herein interpreted accordingly.
In addition, the terms "first", "second", etc. are used to define the components, and are only for convenience of distinguishing the corresponding components, and the terms have no special meaning unless otherwise stated, and therefore should not be construed as limiting the scope of the present invention.
Example 1
1-3, the invention provides a combined cooling, heating and power system based on an ammonia energy ship, which comprises a hydrogen production system, a ship power supply system and a cooling, heating and power recovery heat exchange circulation system;
the hydrogen production system for producing hydrogen comprises a marine liquid ammonia storage tank 1, a flow regulating valve group 2, a gasifier 3, a pressure regulating valve group 4, a drying filter 5, an ammonia preheater 6, an electric heater 7, an ammonia catalytic decomposition hydrogen separation unit 8, a hydrogen purifier 9, a hydrogen cooler 10 and a hydrogen pressure flow control valve group 11 which are sequentially communicated; all the devices of the hydrogen production system are communicated through pipelines;
the hydrogen production process of the hydrogen production system sequentially comprises liquid ammonia storage, gasification, impurity removal, ammonia heating, catalytic pyrolysis conversion hydrogen production, separation and purification, and the specific process comprises the following steps: the flow rate of the liquid ammonia flowing from the liquid ammonia storage tank 1 is regulated by the flow regulating valve group 2, the liquid ammonia enters the gasifier 3 to be gasified into ammonia, the pressure of the ammonia is regulated by the pressure regulating valve group 4, trace impurities and moisture are removed by the drying filter 5, the ammonia enters the ammonia preheater 6, the temperature of the ammonia is raised to the reaction temperature by the electric heater 7, the raw material ammonia is catalyzed by the ammonia catalytic decomposition hydrogen separation unit 8 to be cracked into hydrogen and nitrogen, and finally the hydrogen and the nitrogen sequentially pass through the hydrogen purifier 9 and the hydrogen cooler 10, and the pressure and the flow rate of the ammonia are regulated by the hydrogen pressure flow regulating valve group 11, so that the supplied fuel of the hydrogen-air fuel cell 12 in the ship power supply system enables the hydrogen-air fuel cell 12 to generate electricity;
the marine power supply system includes a hydrogen-air fuel cell 12, a motor propeller 13, and a battery 14; the hydrogen cooler 10 passes hydrogen gas to the hydrogen-air fuel cell 12 to generate electricity and delivers the electricity to the battery 14 for storage; the hydrogen-air fuel cell 12 transmits electric power to a motor of the ship, and the motor receives the electric power to push the motor propeller 13 to rotate so as to enable the ship to travel; the ship power supply system can also supply power to other electric equipment of the ship;
the cold and heat energy recovery and heat exchange circulating system comprises a waste heat boiler 15 and a secondary refrigerant pump 16; the waste heat boiler 15 is communicated with the ammonia gas preheater 6 through a pipeline, heat carried by waste gas nitrogen after a cracking reaction in the ammonia catalytic decomposition hydrogen separation unit 8 recovered by the cold and heat energy recovery heat exchange circulation system is supplied to the waste heat boiler 15 through the ammonia gas preheater 6, and the waste heat boiler 15 is used for generating saturated steam to supply heat requirements of auxiliary machinery of a ship and a passenger cabin;
specifically, the recovered high-temperature waste nitrogen gas waste heat firstly reaches the reaction temperature to the ammonia gas preheater 6 as soon as possible, so that the power consumption of the heater 7 is reduced, and the rest of heat is released to the waste heat boiler 15, so that the heat requirements of the saturated steam supply ship auxiliary machine and the passenger cabin are generated;
the secondary refrigerant pump 16 is respectively communicated with the gasifier 3 through pipelines, and the cold and heat energy recovery heat exchange circulation system is used for carrying out cold recovery in the gasifier 3 through secondary refrigerant so as to cool ship equipment and supply related cold demands of ships;
the invention comprises two energy recovery heat exchange networks, wherein the cold energy recovery heat exchange networks are respectively used for recycling the cold energy of liquid ammonia gasification in the gasifier 3 by pumping the secondary refrigerant circulation so as to supply the cold energy to a ship; the heat recovery and heat exchange network circularly heats gasified low Wen Anqi by utilizing decomposed high-temperature nitrogen in the preheater 6 so as to save the power consumption of the electric heater 7. The design makes the system more energy-saving and environment-friendly, the power consumption components of the system are only the secondary refrigerant circulating pump 16 and the electric heater 7, when the system is started, the electric heater 7 is driven by the storage battery 14 to heat ammonia gas to start reaction for hydrogen production, when the system is started, the electric heater works at full load, and when hydrogen is produced, the heater changes into a small-load working or intermittent working mode.
Further, the cold and heat energy recovery heat exchange cycle can supply the cold energy obtained by recovering the liquid ammonia in the vaporizer 3 by the coolant to the hydrogen cooler 10.
Further, the heat carried by the waste gas nitrogen after the cracking reaction in the ammonia catalytic decomposition hydrogen separation unit 8 recovered by the cold and heat energy recovery heat exchange circulation system is first supplied to the ammonia preheater 6 to raise the temperature of the ammonia gas so as to reduce the power consumption of the heater 7, and then supplied to the waste heat boiler 15 through the ammonia preheater 6.
Further, the coolant circulated by the gasifier 2, the hydrogen cooler 10, and the vessel cooling needs is glycol aqueous solution, nitrogen, or other explosion-proof coolant.
Further, as shown in fig. 3, the ammonia catalytic decomposition hydrogen separation unit 8 includes an inlet manifold 81, an outlet manifold 83, and a shell-and-tube cracking separation device 82; the shell-and-tube cracking separation device 82 is filled with a catalyst; the shell-and-tube cracking separation device 82 is provided with a nitrogen outlet 84; the inlet manifold 81 is communicated with the inside of the shell-and-tube cracking separation device 82; the outlet manifold 83 extends into the interior of the shell-and-tube pyrolysis separation unit 82; a hydrogen permeable membrane is attached to the inner wall of the outlet manifold 83;
through setting up the manifold, can increase reaction area and reduce catalyst poisoning inefficacy phenomenon, make ammonia be divided into several strands and let in the shell-and-tube pyrolysis separator in through the import manifold, by catalyst schizolysis into hydrogen and nitrogen, export manifold is with hydrogen membrane only hydrogen can get into in the pipe and export, and the hydrogen of each strand of export is assembled by the exit end manifold of export manifold and is discharged.
Further, the catalyst is a metal-based ammonia decomposition catalyst such as Ru, ni and Fe and the like and the hydrogen permeable membrane is a palladium-based alloy membrane and the like.
Further, the purifier 9 is filled with porous solid molecular sieve adsorbent for removing tiny moisture impurities, ammonia and nitrogen in the hydrogen; the porous solid molecular sieve adsorbent is a crystalline aluminosilicate or similar material.
Further, the gasifier 2, the ammonia preheater 6 and the hydrogen cooler 9 may be plate-fin, plate, wound-tube or shell-and-tube heat exchangers; the inside of the gasifier 2, the ammonia preheater 6 and the hydrogen cooler 9 may be perforated, corrugated or zigzag fins.
Further, when the combined cooling, heating and power system is started, the storage battery 14 is used for driving the hydrogen production system to start hydrogen production, the electric heater 7 works at full load when the combined cooling, heating and power system is started, and the electric heater 7 changes into a small-load working mode or an intermittent working mode after hydrogen is produced.
Further, the additional power consumption components of the combined cooling, heating and power system are the coolant circulating pump 16 and the ammonia gas electric heater 7, and no other power consumption equipment exists.
Further, in the ammonia catalytic decomposition hydrogen separation unit 8, the raw material gas is reacted and decomposed into hydrogen and nitrogen by a catalyst at a certain temperature of 650-700 ℃ under normal pressure, and the process can be represented as follows:
ΔH＝47.3kJ/mol
the process is an endothermic expansion reaction, namely, unit mole ammonia gas is cracked into 75% hydrogen and 25% ammonia gas under the catalysis of a certain temperature and absorbs 47.3kJ heat, so that the dynamic decomposition of ammonia is facilitated by increasing the temperature and reducing the pressure, and the ammonia cracking conversion rate can reach 99.9% at the temperature of about 650 ℃ under normal pressure generally.
The invention also provides a combined cooling, heating and power supply method based on the ammonia energy ship, which adopts the combined cooling, heating and power supply system based on the ammonia energy ship, and comprises the following steps:
step 1: liquid ammonia storage and transportation gasification
Ammonia is converted into liquid state to be stored in a marine liquid ammonia storage tank 1 when being pressurized at normal temperature and 0.86MPa or normal pressure and low temperature of minus 33 ℃, the flow is regulated by a flow regulating valve group 2 and then is introduced into a gasifier 3 to be gasified into ammonia, and cold energy is recovered in the gasifier 3 through a cold and heat energy recovery and heat exchange circulating system; the ammonia gas is introduced into a dryer filter 5, and the pressure in the gasifier 3 and the flow of the output ammonia gas are controlled through a pressure regulating valve group 4;
step 2: ammonia drying, impurity removing and heating
Drying and impurity removing are carried out on the ammonia gas through a dryer filter 5, the ammonia gas is preheated to about 500 ℃ by utilizing heat carried by waste gas nitrogen after the cracking reaction in the ammonia catalytic decomposition hydrogen separation unit 8 recovered by a cold and heat energy recovery heat exchange circulation system in an ammonia gas preheater 6, and then the ammonia gas is heated to about 650-700 ℃ by an electric heater 7 with a set temperature;
step 3: catalytic cracking separation of ammonia and purification of hydrogen
The raw material gas under the process condition is introduced into an ammonia catalytic decomposition hydrogen separation unit 8, and is decomposed into hydrogen and nitrogen by a catalyst at a certain temperature; the hydrogen is purified and cooled by a hydrogen purifier 9 and a hydrogen cooler 10 in sequence;
the ammonia catalytic decomposition hydrogen separation unit 8 passes through a palladium metal-based hydrogen permeable membrane attached to a pipe layer, only hydrogen can enter the purifier 9 after decomposed gas passes through the hydrogen permeable membrane, tiny moisture impurities, ammonia, nitrogen and the like in the hydrogen permeable membrane are adsorbed by a molecular sieve, and the remaining hydrogen is led out as fuel;
step 4: ship fuel cell power generation and supply
The hydrogen is introduced into a hydrogen-air fuel cell 12 through a hydrogen pressure flow control valve group 11 to generate electricity and is conveyed to a storage battery 14 to be stored; the hydrogen-air fuel cell 12 transmits electric power to the electric motor of the ship, and the electric motor receives the electric power to push the motor propeller 13 to rotate so as to enable the ship to travel; the ship power supply system can also supply power to other electric equipment of the ship;
the invention discloses a combined cooling, heating and power supply method based on an ammonia energy ship, which comprises the following steps of:
the separated waste gas nitrogen and the purified hydrogen enter a system heat exchange network for energy recycling, the system is in a cold and heat energy recycling heat exchange network supply cycle, namely, the heat carried by the waste gas nitrogen after ammonia temperature rising and cracking reaction is recycled, the high-temperature waste nitrogen waste heat recycled by the heat exchange network firstly reaches the reaction temperature as soon as possible for the ammonia preheater 6, so that the power consumption of the heater 7 is reduced, and the rest of the waste gas nitrogen waste heat is released for the waste heat boiler 15 to generate saturated steam for supplying heat requirements of ships. The liquid ammonia gasification cold recovery heat exchange network circulates through the coolant for cold recovery in the gasifier 3 via the coolant pump 16 and associated piping to supply the associated refrigeration demand of the ship.
As shown in fig. 1, the technological process and design thought of a combined cooling heating and power integrated system are provided, wherein the technological process comprises the steps of fuel storage, gasification, temperature rising, decomposition and conversion for hydrogen production, fuel cell power generation, waste nitrogen serving as a heat source and the combined cooling heating and power integrated system based on the process.
As shown in fig. 2, the system is provided with a heat exchange network for recovering heat carried by the waste gas nitrogen after the ammonia temperature-rising cracking reaction, and the high-temperature waste nitrogen waste heat recovered by the heat exchange network is firstly supplied to the ammonia preheater 6 to enable the ammonia preheater 6 to reach the reaction temperature as soon as possible so as to reduce the power consumption of the heater 7, and the rest is released to the waste heat boiler 16 to generate saturated steam for supplying the heat demand of the ship. The liquid ammonia gasification cold recovery heat exchange network circulates through the coolant for cold recovery in the gasifier 3 via the coolant pump 16 and associated piping to supply the associated refrigeration demand of the ship.
The invention can store and transport hydrogen-rich medium and produce hydrogen with purification rate of more than 99.9% on site as fuel cell fuel for power generation, and utilizes the integrated heat exchange network to recycle the cold and waste heat in the process so as to reduce hydrogen production energy consumption, and simultaneously has the advantages of high efficiency, no pollution and economy, and satisfies the triple requirements of steam heat, cold and electric power in ship running.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced with equivalents; such modifications and substitutions do not depart from the spirit of the technical solutions according to the embodiments of the present invention.
Claims (8)
1. The combined system is characterized by comprising a hydrogen production system, a ship power supply system and a cold and hot energy recovery heat exchange circulating system;
the hydrogen production system comprises a marine liquid ammonia storage tank (1), a flow regulating valve group (2), a gasifier (3), a pressure regulating valve group (4), a drying filter (5), an ammonia preheater (6), an electric heater (7), an ammonia catalytic decomposition hydrogen separation unit (8), a hydrogen purifier (9), a hydrogen cooler (10) and a hydrogen pressure flow control valve group (11) which are sequentially communicated;
the marine power supply system includes a hydrogen-air fuel cell (12), a motor propeller (13), and a battery (14); the hydrogen cooler (10) is used for leading hydrogen into the hydrogen-air fuel cell (12) to generate electricity and transmitting the electricity to the storage battery (14) for storage; the hydrogen-air fuel cell (12) transmits electric power to a motor of the ship, and the motor receives the electric power to push the motor propeller (13) to rotate so as to enable the ship to travel; the ship power supply system can also supply power to other electric equipment of the ship;
the cold and heat energy recovery heat exchange circulating system comprises a waste heat boiler (15) and a secondary refrigerant pump (16); the waste heat boiler (15) is communicated with the ammonia preheater (6) through a pipeline, heat carried by waste gas nitrogen after a cracking reaction in the ammonia catalytic decomposition hydrogen separation unit (8) recovered by the cold and heat energy recovery heat exchange circulation system is supplied to the waste heat boiler (15) through the ammonia preheater (6), and the waste heat boiler (15) is used for generating saturated steam to supply heat requirements of a ship auxiliary machine and a passenger cabin; the refrigerating medium pump (16) is respectively communicated with the gasifier (3) through pipelines, and the cold and heat energy recovery and heat exchange circulating system is used for carrying out cold energy recovery in the gasifier (3) through refrigerating medium and is used for cooling ship equipment and supplying related cold energy requirements of ships;
the power consumption component of the combined cooling, heating and power system is only a refrigerating pump (16) and an electric heater (7); when the combined cooling, heating and power system is started, the storage battery (14) is used for driving the hydrogen production system to start hydrogen production, the electric heater (7) works in full load when hydrogen production is started, and the electric heater (7) changes into a small-load working mode or an intermittent working mode after hydrogen is produced;
the ammonia catalytic decomposition hydrogen separation unit (8) comprises an inlet manifold (81), an outlet manifold (83) and a shell-and-tube cracking separation device (82); the shell-and-tube cracking separation device (82) is filled with a catalyst; the shell-and-tube cracking separation device (82) is provided with a nitrogen outlet (84); the inlet manifold (81) is communicated with the inside of the shell-and-tube cracking separation device (82); the outlet manifold (83) extends into the interior of the shell-and-tube cracking separation device (82); a hydrogen permeable membrane is attached to the inner wall of the outlet manifold (83).
2. The combined cooling, heating and power system based on the ammonia-energy ship according to claim 1, wherein the cold energy recovery and heat exchange circulation system can supply the cold energy of the gasification of the recovered liquid ammonia in the gasifier (3) to the hydrogen cooler (10) through a secondary refrigerant.
3. The combined cooling, heating and power system based on the ammonia-based ship according to claim 1, wherein the heat carried by the waste gas nitrogen after the cracking reaction occurring in the ammonia catalytic decomposition hydrogen separation unit (8) recovered by the cold-heat energy recovery heat exchange cycle system is first supplied to the ammonia preheater (6) to raise the temperature of the ammonia gas so as to reduce the power consumption of the electric heater (7), and then supplied to the waste heat boiler (15) through the ammonia preheater (6).
4. The ammonia-based marine vessel cogeneration system of claim 1, wherein the coolant is an aqueous glycol solution or nitrogen.
5. The ammonia energy ship based combined heat and power system of claim 1, wherein the catalyst is a metal-based ammonia decomposition catalyst; the hydrogen permeable membrane is a palladium-based alloy membrane.
6. The combined heat and power system based on the ammonia energy ship according to claim 1, wherein the hydrogen purifier (9) is filled with porous solid molecular sieve adsorbent for removing tiny moisture impurities, ammonia and nitrogen in hydrogen.
7. The combined cooling, heating and power system based on the ammonia-based energy ship according to claim 1, characterized in that the gasifier (3), the ammonia preheater (6) and the hydrogen cooler (10) are plate-fin, plate, wound-tube or shell-tube heat exchangers; the gasifier (3), the ammonia gas preheater (6) and the hydrogen cooler (10) are internally provided with punching, corrugated or zigzag fins.
8. The combined cooling, heating and power supply method based on the ammonia energy ship adopts the combined cooling, heating and power supply system based on the ammonia energy ship as claimed in claim 1, and is characterized by comprising the following steps:
step 1: liquid ammonia storage and transportation gasification
The liquid ammonia is stored in a marine liquid ammonia storage tank (1), the flow is regulated by a flow regulating valve group (2), then the liquid ammonia is introduced into a gasifier (3) for gasification to be changed into ammonia, and cold energy is recovered in the gasifier (3) through a cold and heat energy recovery and heat exchange circulating system; the ammonia gas is introduced into a drying filter (5), and the pressure in the gasifier (3) and the flow of the output ammonia gas are controlled through a pressure regulating valve group (4);
step 2: ammonia drying, impurity removing and heating
Drying and impurity removing are carried out on ammonia gas through a drying filter (5), the ammonia gas is preheated to 500 ℃ by utilizing heat carried by waste gas nitrogen after cracking reaction in an ammonia catalytic decomposition hydrogen separation unit (8) recovered by a cold and heat energy recovery heat exchange circulation system in an ammonia gas preheater (6), and then the ammonia gas is heated to a catalytic cracking temperature of 650-700 ℃ through an electric heater (7) with a set temperature;
step 3: catalytic cracking separation of ammonia and purification of hydrogen
The heated ammonia gas is introduced into an ammonia catalytic decomposition hydrogen separation unit (8) and is decomposed into hydrogen and nitrogen by a catalyst; the hydrogen is purified and cooled by a hydrogen purifier (9) and a hydrogen cooler (10) in sequence;
step 4: ship fuel cell power generation and supply
The hydrogen is introduced into a hydrogen-air fuel cell (12) through a hydrogen pressure flow control valve group (11) to generate electricity and is conveyed to a storage battery (14) to be stored; a hydrogen-air fuel cell (12) transmits electric power to a motor of the ship, and the motor receives the electric power to push a motor propeller (13) to rotate so as to enable the ship to travel; the ship power supply system can also supply power for other electric equipment of the ship.
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