CN212356521U - Combined cooling heating and power system based on ammonia energy ship - Google Patents

Abstract

The utility model 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 and heating energy recovery heat exchange circulating system; the hydrogen production system comprises a marine liquid ammonia storage tank, a flow regulating valve bank, a gasifier, a pressure regulating valve bank, a drying filter, an ammonia gas preheater, an electric heater, an ammonia catalytic decomposition hydrogen separation unit, a hydrogen purifier, a hydrogen cooler and a hydrogen pressure flow control valve bank which are sequentially communicated; the ship power supply system comprises a hydrogen-air fuel cell, a motor propeller and a storage battery; the cold and heat energy recovery and heat exchange circulating system comprises a waste heat boiler and a coolant pump; the waste heat boiler is used for generating saturated steam to supply heat requirements for the ship auxiliary engine and the passenger cabin; the coolant pump is used to cool the ship equipment and to supply the relevant refrigeration requirements of the ship. The utility model solves the problem that hydrogen production and hydrogen storage technologies are split by the hydrogen production-hydrogen storage technology to cause a large amount of energy consumption.

Description

Combined cooling heating and power system based on ammonia energy ship

Technical Field

The utility model relates to a liquid ammonia energy system combined cooling heating and power field particularly, especially relates to an utilize liquid ammonia to carry hydrogen, catalysis hydrogen manufacturing, fuel cell power generation and the cold and hot electricity trigeminy of ammonia energy boats and ships of this process of recycle supply combined system.

Background

Since 2020, the international maritime organization required the world shipping industry to enforce global sulfur emission limits of less than 0.5%, while it was necessary to reduce the carbon emissions of marine vessels by more than half before 2050. This is a challenge for the current marine industry, which is mostly using polysulfide, multiparticulate emissions of heavy oils. Environmental pollution and climate warming bring huge pressure to marine environment, so that the optimization of energy use efficiency in a ship cooling, heating and power system, the reasonable development of high-efficiency clean energy and related conversion technology thereof are key problems to be solved urgently at present. Hydrogen is a completely clean renewable ultimate energy source, the calorific value of the hydrogen is about 3 times of that of gasoline, the calorific value of the hydrogen is far higher than that of natural gas, the hydrogen is only used for generating water in a fuel cell, the emission of sulfur oxides and particulate matters can be completely avoided, and most ships can select hydrogen as main marine fuel within 30 to 50 years in the future. However, the existing amount of free hydrogen in the natural state is very small, and how to produce hydrogen by enrichment and purification with low carbon and environmental protection is a big problem of popularization of hydrogen energy. Due to technical limitation, the current large-scale hydrogen production process (fossil fuel reforming, water electrolysis and biological hydrogen production) has the problems of large pollution emission, higher power consumption, poorer safety and economy and the like. In addition, hydrogen storage after production is a difficult problem, for example, compressed hydrogen for vehicles needs to be produced by a hydrogen storage tank with the design pressure of 98MPa to meet the requirement, liquid hydrogen storage and transportation are more difficult, the hydrogen needs to be liquefied at the temperature of 253 ℃ below zero, and the requirement on storage tank technology difficulty materials is higher. The above difficulties have always hindered the development of hydrogen energy in various areas, and alternative methods for producing hydrogen by storing hydrogen economically are urgently sought.

Ammonia is used as a clean and renewable organic substance containing 17.6% of hydrogen by mass, is widely applied to basic products of agricultural industry and chemical raw materials, currently, the ammonia yield of China accounts for one third of the world, and synthetic ammonia manufacturers are distributed nationwide in a network manner, and the production technology is mature and the storage and transportation cost is low. The ammonia can be completely cracked into hydrogen and nitrogen by adding the conventional catalyst at about 600 ℃ under normal pressure, the conversion rate is as high as 99.9 percent, and the catalyst has great hydrogen production potential. Compared with hydrogen, ammonia can be liquefied only at the temperature of normal pressure to 33 ℃ or the normal temperature of about 7bar, the volume energy density of liquid ammonia is 1.53 times of 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, while the price of liquid ammonia is about 3000 yuan per ton, and the hydrogen obtained by decomposition is about 16.7 yuan per kilogram, wherein the price difference of the costs of hydrogen and ammonia in storage, transportation, decomposition and the like does not exist. Therefore, ammonia is an extremely promising technology as a source of hydrogen-bearing hydrogen production raw material gas.

In summary, the existing hydrogen production and storage technologies focus on high energy consumption and high emission, and the hydrogen production and storage technologies are purely split, so that the subsequent technical connection of hydrogen storage and transportation is not performed after hydrogen is produced, and a large amount of energy is consumed again in the subsequent compression, liquefaction and hydride storage and transportation. The final cost of hydrogen consumption in the whole hydrogen production-storage industry is far higher than that of fossil fuel and related emission treatment due to the technical mode, and the energy consumption emission in the hydrogen production-storage industry is not offset by the energy efficiency in the hydrogen consumption.

SUMMERY OF THE UTILITY MODEL

According to the technical problem that hydrogen production and hydrogen storage technologies are split to cause large energy consumption by the existing hydrogen production-hydrogen storage technologies, the combined cooling, heating and power supply system based on the ammonia energy ship is provided. The utility model discloses subversive use the warehousing and transportation of hydrogen to be the beginning, and the combined use of cold and hot electricity in hydrogen manufacturing and the flow is the terminal, has broken the complicated process and the high cost of the first hydrogen manufacturing back warehousing and transportation of traditional approach, the utility model discloses use hydrogen-rich thing liquid ammonia to store hydrogen the carrier, through liquid ammonia gasification, ammonia preheat, heating, catalytic decomposition and hydrogen purification, fuel cell electricity generation, a series of energy conversion systems and methods such as waste nitrogen heat transfer, liquid ammonia gasification cold and heat recovery utilize form one set of cold and hot electricity trigeminy based on ammonia energy boats and ships and supply integrated system.

The utility model discloses a technical means as follows:

a combined cooling heating and power system based on an ammonia energy ship comprises a hydrogen production system, a ship power supply system and a cooling and heating energy recovery and heat exchange circulating system;

the hydrogen production system comprises a marine liquid ammonia storage tank, a flow regulating valve bank, a gasifier, a pressure regulating valve bank, a drying filter, an ammonia gas preheater, an electric heater, an ammonia catalytic decomposition hydrogen separation unit, a hydrogen purifier, a hydrogen cooler and a hydrogen pressure flow control valve bank which are sequentially communicated;

the ship power supply system comprises a hydrogen-air fuel cell, a motor propeller and a storage battery; the hydrogen cooler is used for introducing hydrogen into the hydrogen-air fuel cell to generate electricity and transmitting the electricity to the storage battery to be stored; the hydrogen-air fuel cell transmits power to a motor of the ship, and the motor receives the power to drive the motor propeller to rotate so as to enable the ship to advance; the ship power supply system can also supply power for other electric equipment of the ship;

the cold and heat energy recovery and heat exchange circulating system comprises a waste heat boiler and a coolant pump; the waste heat boiler is communicated with the ammonia gas preheater through a pipeline, heat carried by waste gas nitrogen after cracking reaction in the ammonia catalytic decomposition hydrogen separation unit recovered by the cold and heat energy recovery and heat exchange circulating system is supplied to the waste heat boiler through the ammonia gas preheater, and the waste heat boiler is used for generating saturated steam to supply heat requirements for a marine auxiliary engine and a cabin; the cold-carrying agent pump is respectively communicated with the gasifier through pipelines, and the cold-heat energy recovery heat exchange circulation system is used for cooling ship equipment and supplying related cold quantity requirements to ships by carrying out cold quantity recovery on cold medium in the gasifier.

Further, the cold and heat energy recovery heat exchange circulation system can recover cold energy from the gasification of the liquid ammonia in the vaporizer by using a refrigerant and supply the cold energy to the hydrogen cooler.

Further, heat carried by the waste gas nitrogen after the cracking reaction in the ammonia catalytic decomposition hydrogen separation unit recovered by the cold and heat energy recovery and heat exchange circulation system is firstly supplied to the ammonia preheater to heat the ammonia gas so as to reduce the power consumption of the heater, and then the heat is supplied to the waste heat boiler through the ammonia gas preheater.

Further, the refrigerating medium is glycol aqueous solution or nitrogen and other explosion-proof refrigerating mediums.

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 interior of the shell-and-tube cracking separation device; the outlet manifold extends into the interior of 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 and Fe; the hydrogen permeable membrane is a palladium-based alloy membrane.

Further, the purifier is filled with porous solid molecular sieve adsorbent for removing micro-moisture impurities in the hydrogen and ammonia and nitrogen.

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 gas preheater and the hydrogen cooler can be internally provided with perforated, corrugated or sawtooth fins.

Further, when the combined cooling heating and power system 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 combined cooling heating and power system is started, and the electric heater is changed into a low-load working mode or an intermittent working mode after hydrogen is produced.

Compared with the prior art, the utility model has the advantages of it is following:

1. the utility model provides a cold and hot electricity trigeminy supplies combined system based on ammonia energy boats and ships has abandoned present pure hydrogen manufacturing and hydrogen storage technology to split (hydrogen manufacturing is warehousing and transportation hydrogen earlier promptly), pioneering's proposition stores up earlier and carries the hydrogen raw materials, reappear the technical process of hydrogen manufacturing, overcome prior art and have not had the technique of follow-up hydrogen warehousing and transportation behind extensive power consumption hydrogen manufacturing and link up to the compression of hydrogen, liquefaction warehousing and transportation carry out a large amount of energy resource consumptions once more and even than this unreasonable situation that hydrogen manufacturing economy is worse.

2. The utility model provides a cold, heat and electricity trigeminy supplies combined system based on ammonia energy boats and ships, overcome present hydrogen, liquid hydrogen warehousing and transportation are with high costs, shortcomings such as inflammable and explosive, utilize and carry hydrogen raw materials liquid ammonia through the warehousing and transportation, because liquid ammonia obtains the extensive low cost (<3000 this ton) of route, convert into hydrogen and be 16.7 this hydrogen price of hydrogen station about 70 this hydrogen price, and carry hydrogen system unit mass hydrogen storage capacity than other (17.6%) and the volume energy density of liquid ammonia is 1.53 times of liquid hydrogen in addition, the fuel of the same volume, the continuation of the journey mileage of liquid ammonia is 1.53 times of liquid hydrogen.

3. The utility model provides a cooling, heating and power trigeminy supplies combined system based on ammonia energy boats and ships, different from traditional diesel oil or LNG boats and ships cold and heat electricity trigeminy, the diesel oil boats and ships utilize the engine to drive the generator electricity generation, utilize electric drive refrigeration, boiler plant to carry out cold and heat supply; an LNG ship generates power by using an organic Rankine cycle, and generates cold and hot supply by heat recovery; compared with diesel oil and LNG engines, the hydrogen-air fuel cell has no emission pollution; in addition the utility model discloses compare in LNG boats and ships organic rankine cycle combined cooling heating and power system simple and clear, energy utilization is high, can not have the LNG cold energy cascade utilization moreover and organic rankine cycle efficiency's restriction.

4. The utility model provides a cold and hot electricity trigeminy supplies combined system based on ammonia energy boats and ships, economy, safety, environmental protection, energy-conservation have abandoned LNG, and liquid hydrogen's expensive storage and flammable and explosive condition do not produce any nitrogen oxygen-carbon oxygen particulate matter emission at the in-process, through the extra energy that heat transfer network complete recycle ammonia catalysis hydrogen manufacturing provided. In order to prevent the danger of flammability and explosiveness when the hydrogen is cooled, the utility model discloses do not directly utilize the hydrogen waste heat after decomposing to gasify the feed gas in the system, but ingenious setting up other anti-explosion secondary refrigerant and carrying out thermal transmission and conversion between vaporizer and hydrogen cooler as the medium.

5. The utility model provides a cold and hot electricity trigeminy supplies combined system based on ammonia energy boats and ships not only can the rich hydrogen medium of warehousing and transportation and the on-the-spot hydrogen of making more than the purification rate 99.9% as fuel cell fuel electricity generation, utilizes integrated heat transfer network to retrieve this process cold volume and used heat in order to reduce the hydrogen manufacturing energy consumption moreover, has still compromise high efficiency, pollution-free and economic nature simultaneously, has satisfied the triple demand of steam heat, cold volume and electric power in the boats and ships travel.

To sum up, use the utility model discloses the storage and transportation of subversive use hydrogen is the beginning, and the combined use of cold and hot electricity in hydrogen manufacturing and the flow is the terminal, has broken the complex process and the high cost of the earlier hydrogen manufacturing back storage and transportation of traditional approach, the utility model discloses use hydrogen-rich thing liquid ammonia to store up hydrogen carrier, through liquid ammonia gasification, ammonia preheat, heating, catalytic decomposition and hydrogen purification, fuel cell electricity generation, a series of energy conversion systems and methods such as waste nitrogen heat transfer, liquid ammonia gasification cold and heat recovery utilization form one set of cold and hot electricity trigeminy based on ammonia energy boats and ships and supply integrated system. Therefore, the technical proposal of the utility model solves the problem that the prior hydrogen production-hydrogen storage technology splits the hydrogen production and hydrogen storage technology to cause a large amount of energy consumption. The system and the modularization method are suitable for the combined production of cold, heat and power of the liquid ammonia energy system and the popularization and the application of related ammonia energy in the fields of ships, automobiles and the like.

Based on the above reason the utility model discloses can extensively promote in fields such as liquid ammonia energy system combined cooling heating and power.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required to be used in the description of the embodiments or the prior art are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive labor.

Fig. 1 is a frame diagram of the cooling, heating and power triple supply composite system based on the ammonia energy ship.

Fig. 2 is the working principle schematic diagram of the cold and heat energy recovery heat exchange cycle system of the present invention.

FIG. 3 is a schematic diagram of the ammonia cracking hydrogen separation unit device of the present invention.

In the figure: 1. a marine liquid ammonia storage tank; 2. a flow regulating valve group; 3. a gasifier; 4. a pressure regulating valve group; 5. drying the filter; 6. an ammonia gas 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, in the present invention, the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in 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 obvious 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 illustrative in nature and is in no way intended to limit the invention, its application, or uses. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative work belong to the protection scope of the present 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 example embodiments in accordance with the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.

Unless specifically stated otherwise, the relative arrangement of the components and steps, the numerical expressions, and numerical values set forth in these embodiments do not limit the scope of the present invention. Meanwhile, it should be understood that the sizes of the respective portions shown in the drawings are not drawn in an actual proportional relationship for the 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. Any specific values in all examples shown and discussed herein are to be construed as exemplary only and not as limiting. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.

In the description of the present invention, it should be understood that the orientation or positional relationship indicated by the orientation words such as "front, back, up, down, left, right", "horizontal, vertical, horizontal" and "top, bottom", etc. are usually based on the orientation or positional relationship shown in the drawings, and are only for convenience of description and simplicity of description, and in the case of not making a contrary explanation, these orientation words do not indicate and imply that the device or element in question must have a specific orientation or be constructed and operated in a specific orientation, and therefore should not be construed as limiting the scope of the present invention: the terms "inner and outer" refer to the inner and outer relative to the profile of the respective component itself.

Spatially relative terms, such as "above … …," "above … …," "above … …," "above," and the like, may be used herein for ease of description to describe one device or feature's spatial relationship 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 of the device in use or operation in addition to the orientation depicted in the figures. For example, if a device in the figures is turned over, devices described as "above" or "on" other devices or configurations would then be oriented "below" or "under" the other devices or configurations. Thus, the exemplary term "above … …" can include both an orientation 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.

It should be noted that the terms "first", "second", and the like are used to define the components, and are only used for convenience of distinguishing the corresponding components, and if not stated otherwise, the terms have no special meaning, and therefore, the scope of the present invention should not be construed as being limited.

Example 1

As shown in fig. 1-3, the utility model 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 and heating energy recovery heat exchange circulation system;

the hydrogen production system for producing hydrogen comprises a marine liquid ammonia storage tank 1, a flow regulating valve bank 2, a gasifier 3, a pressure regulating valve bank 4, a drying filter 5, an ammonia gas 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 bank 11 which are communicated in sequence; all 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 gas temperature rise, catalytic cracking conversion hydrogen production and separation purification, and the specific process comprises the following steps: liquid ammonia flowing from the liquid ammonia storage tank 1 enters the vaporizer 3 to be vaporized into ammonia gas after the flow rate of the liquid ammonia is adjusted by the flow rate adjusting valve bank 2, the ammonia gas is subjected to pressure adjustment by the pressure adjusting valve bank 4 and enters the ammonia gas preheater 6 after trace impurities and moisture are removed by the drying filter 5, the temperature of the ammonia gas is raised to the reaction temperature by the electric heater 7, the ammonia gas serving as a raw material is catalyzed by the ammonia catalytic decomposition hydrogen separation unit 8 to be cracked into hydrogen gas and nitrogen gas, and finally the hydrogen gas passes through the hydrogen purifier 9 and the hydrogen cooler 10 in sequence, and the pressure and the flow rate are adjusted by the hydrogen pressure flow rate controlling valve bank 11 to become fuel supplied to the hydrogen-air fuel cell 12 in the ship power supply system so as to enable the hydrogen-air fuel cell 12 to generate power;

the marine vessel power supply system includes a hydrogen-air fuel cell 12, a motor propeller 13, and a storage battery 14; the hydrogen cooler 10 passes hydrogen gas into the hydrogen-air fuel cell 12 to generate electricity and transmits the electricity to the storage battery 14 to be stored; the hydrogen-air fuel cell 12 transmits power to a motor of the ship, and the motor receives the power to drive the motor propeller 13 to rotate so as to enable the ship to run; the ship power supply system can also supply power for 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 coolant carrying pump 16; the waste heat boiler 15 is communicated with the ammonia gas preheater 6 through a pipeline, 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 and heat exchange circulating 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 for a marine auxiliary machine and a cabin;

specifically, the recovered waste heat of the high-temperature waste nitrogen gas is firstly fed to the ammonia gas preheater 6 to reach the reaction temperature as soon as possible, so that the power consumption of the heater 7 is reduced, and the rest heat is released to the waste heat boiler 15 to generate saturated steam to supply heat requirements of the ship auxiliary engine and the passenger cabin;

the coolant pump 16 is respectively communicated with the gasifier 3 through a pipeline, and the cold and heat energy recovery heat exchange circulation system is used for cooling ship equipment and supplying related cold energy requirements to ships by carrying out cold energy recovery on cold medium in the gasifier 3;

the utility model comprises two energy recovery heat exchange networks, wherein the cold energy recovery heat exchange networks are respectively used for recovering the cold energy gasified by the liquid ammonia in the gasifier 3 by utilizing the circulation of the pumping secondary refrigerant so as to supply the cold energy to the cold energy demand side of the ship; the heat recovery heat exchange network utilizes the decomposed high-temperature nitrogen to circularly heat the gasified low-temperature ammonia gas in the preheater 6, thereby saving the power consumption of the electric heater 7. The design enables the system to be more energy-saving and environment-friendly, power consumption components of the system are only the secondary refrigerant circulating pump 16 and the electric heater 7, the electric heater 7 is driven by the storage battery 14 to heat ammonia gas to start reaction to produce hydrogen when the system is started, the electric heater works at full load when the system is started circularly, and the heater becomes a small-load working mode or an intermittent working mode after hydrogen is produced.

Further, the cold and heat energy recovery heat exchange cycle system can recover cold energy generated by gasifying liquid ammonia in the vaporizer 3 by using a refrigerant and supply the cold energy 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 and heat exchange circulation system is first supplied to the ammonia preheater 6 to heat the ammonia gas so as to reduce the power consumption of the heater 7, and then supplied to the exhaust-heat boiler 15 through the ammonia preheater 6.

Further, the coolant circulated by the gasifier 2, the hydrogen cooler 10 and the cooling requirement of the ship 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 type 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 type cracking separation device 82; the outlet manifold 83 extends into the interior of the shell-and-tube cracking 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 the ammonia pass through in the inlet manifold and be divided into several strands and let in shell and tube type schizolysis separator, be hydrogen and nitrogen gas by the catalyst schizolysis, export manifold is with hydrogen and passes through the membrane and only hydrogen can the admission pipe and derive, and the hydrogen that every thigh was derived 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 substance molecular sieve adsorbent for removing micro moisture impurities in the hydrogen gas, ammonia and nitrogen; the porous solid substance molecular sieve adsorbent is a crystalline aluminosilicate and other similar materials.

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 gasifier 2, the ammonia gas preheater 6 and the hydrogen gas cooler 9 can be internally provided with perforated, corrugated or sawtooth 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 is changed into a small-load working mode or an intermittent working mode after hydrogen is produced.

Furthermore, the additional power consumption components of the combined cooling heating and power system are the coolant circulating pump 16 and the ammonia electric heater 7 without other power consumption devices.

Further, in the separation unit 8 for catalytically decomposing ammonia into hydrogen and nitrogen, the raw material gas is reacted and decomposed into hydrogen and nitrogen by the catalyst at a certain temperature of about 650 to 700 ℃ and under normal pressure, and the process can be embodied as follows:

the process is endothermic expansion reaction, i.e. unit mole of 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 temperature is increased and the pressure is reduced to facilitate the dynamic decomposition of ammonia, and the ammonia gas cracking conversion rate can reach 99.9% at normal pressure and about 650 ℃.

Adopt the combined cooling heating and power system specifically includes following step when supplying power based on ammonia energy boats and ships's combined cooling heating and power system:

step 1: liquid ammonia storage, transportation and gasification

Ammonia is converted into liquid state under the condition of normal temperature pressurization of 0.86MPa or normal pressure and low temperature of-33 ℃ and is stored in a marine liquid ammonia storage tank 1, the flow is regulated by a flow regulating valve group 2 and then is introduced into a gasifier 3 for gasification to form ammonia, and cold energy recovery and heat exchange circulation system is used for cold energy recovery in the gasifier 3; introducing ammonia gas into a dryer filter 5, and controlling the pressure in the gasifier 3 and the flow of the output ammonia gas through a pressure regulating valve group 4;

step 2: drying, impurity removing and heating of ammonia gas

The ammonia gas is dried and purified through a dryer filter 5, in an ammonia gas preheater 6, the ammonia gas is preheated to about 500 ℃ by using the heat carried by the waste gas and the nitrogen after the cracking reaction in the ammonia catalytic decomposition hydrogen separation unit 8 recovered by a cold and heat energy recovery and heat exchange circulating system, and then the ammonia gas is heated to about the catalytic cracking temperature of 650-700 ℃ through an electric heater 7 with a set temperature;

and step 3: catalytic cracking separation of ammonia and purification of hydrogen

Introducing feed gas under the process condition into an ammonia catalytic decomposition hydrogen separation unit 8, and decomposing the feed gas into hydrogen and nitrogen by a catalyst at a certain temperature; the hydrogen gas 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 tube layer, decomposed gas passes through the hydrogen permeable membrane, only hydrogen can enter the purifier 9, micro water impurities, ammonia, nitrogen and the like in the decomposed gas are adsorbed by the molecular sieve, and the remaining hydrogen is led out to be used as fuel;

and 4, step 4: fuel cell power generation and supply for ships

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 the storage battery 14 to be stored; the hydrogen-air fuel cell 12 transmits power to a motor of the ship, and the motor receives the power to drive the motor propeller 13 to rotate so as to enable the ship to run; the ship power supply system can also supply power for other electric equipment of the ship;

cold and heat electricity trigeminy power supply method based on ammonia energy boats and ships, system heat transfer network energy recycle flow specifically do including:

the separated waste gas nitrogen and the purified hydrogen enter a system heat exchange network for energy recovery and utilization, the system is supplied and circulated by a cold and hot energy recovery heat exchange network, namely, the heat carried by the waste gas nitrogen after the ammonia heating cracking reaction is recovered, the waste heat of the high-temperature waste nitrogen recovered by the heat exchange network is firstly supplied to an ammonia gas preheater 6 to enable the ammonia gas preheater 6 to reach the reaction temperature as soon as possible so as to reduce the power consumption of a heater 7, and the rest of the waste nitrogen is released to a waste heat boiler 15 so as to generate saturated steam for supplying the heat demand of ships. The liquid ammonia gasification cold energy recovery heat exchange network circularly carries out cold energy recovery in the gasifier 3 through a cold carrier, and the cold carrier is used for supplying relevant cold energy requirements of ships through a cold carrier pump 16 and relevant pipelines.

As shown in fig. 1, a process flow and a design concept of a combined cooling heating and power system based on the process are provided, wherein the integrated cooling heating and power system comprises a fuel storage, gasification, heating, decomposition and conversion for hydrogen production, a fuel cell for power generation, and waste nitrogen as a heat source in an ammonia energy ship.

As shown in fig. 2, the system supplies circulation by using a cold and hot energy recovery heat exchange network, that is, heat carried by the waste gas nitrogen after the ammonia heating and cracking reaction is recovered, the waste heat of the high-temperature waste nitrogen recovered by the heat exchange network is firstly sent to 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 energy recovery heat exchange network circularly carries out cold energy recovery in the gasifier 3 through a cold carrier, and the cold carrier is used for supplying relevant cold energy requirements of ships through a cold carrier pump 16 and relevant pipelines.

The utility model discloses not only can the hydrogen-rich medium of warehousing and transportation and the on-the-spot hydrogen of making more than the purification rate 99.9% be as fuel cell fuel power generation, utilize integrated heat transfer network to retrieve this process cold volume and used heat in order to reduce the hydrogen manufacturing energy consumption moreover, still compromise high-efficient, pollution-free and economic nature simultaneously, satisfied the triple demand of steam heat, cold volume and electric power during boats and ships travel.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the embodiments of the present invention.

Claims (9)

1. A combined cooling heating and power system based on an ammonia energy ship is characterized by comprising a hydrogen production system, a ship power supply system and a cooling and heating energy recovery heat exchange circulating system;

the hydrogen production system comprises a marine liquid ammonia storage tank (1), a flow regulating valve bank (2), a gasifier (3), a pressure regulating valve bank (4), a drying filter (5), an ammonia gas 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 bank (11) which are communicated in sequence;

the marine vessel power supply system includes a hydrogen-air fuel cell (12), a motor propeller (13), and a storage battery (14); the hydrogen cooler (10) passes hydrogen gas into the hydrogen-air fuel cell (12) to generate electricity and transmits the electricity to the storage battery (14) to be stored; the hydrogen-air fuel cell (12) transmits power to a motor of the ship, and the motor receives the power to drive the motor propeller (13) to rotate so as to enable the ship to advance; the ship power supply system can also supply power for 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 coolant carrying 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 cracking reaction in the ammonia catalytic decomposition hydrogen separation unit (8) recovered by the cold and heat energy recovery heat exchange circulating 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 a ship auxiliary machine and a cabin; the coolant pump (16) is respectively communicated with the gasifier (3) through pipelines, and the cold and heat energy recovery heat exchange circulation system carries out cold recovery in the gasifier (3) through a coolant for cooling ship equipment and supplying related cold requirements of ships.

2. The combined cooling, heating and power system for an ammonia-based vessel according to claim 1, wherein the cooling heat energy recovery heat exchange cycle system can supply the cooling energy generated by gasifying the liquid ammonia recovered in the gasifier (3) by a cooling agent to the hydrogen cooler (10).

3. The combined cooling, heating and power system for the ammonia-based ship is characterized in that the heat carried by the waste gas nitrogen after the cracking reaction in the ammonia catalytic decomposition and hydrogen separation unit (8) recovered by the cold and heat energy recovery and heat exchange circulating system is firstly supplied to the ammonia gas preheater (6) to heat the ammonia gas so as to reduce the power consumption of the electric heater (7), and then is supplied to the waste heat boiler (15) through the ammonia gas preheater (6).

4. The combined cooling, heating and power system of claim 1, wherein the coolant is glycol water solution or nitrogen or other explosion-proof coolant.

5. The combined cooling, heating and power system for an ammonia-based vessel as claimed in claim 1, wherein 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 interior of the shell-and-tube cracking separation device (82); said outlet manifold (83) extending into the interior of said shell and tube cracking separation unit (82); the inner wall of the outlet manifold (83) is attached with a hydrogen permeable membrane.

6. The combined cooling, heating and power system based on the ammonia-powered vessel as claimed in claim 5, wherein the catalyst is a metal-based ammonia decomposition catalyst; the hydrogen permeable membrane is a palladium-based alloy membrane.

7. The combined cooling, heating and power system of claim 1, wherein the hydrogen purifier (9) is filled with porous solid molecular sieve adsorbent for removing micro water impurities, ammonia and nitrogen from hydrogen.

8. The combined cooling, heating and power system for ammonia-based ships according to claim 1, wherein the gasifier (3), the ammonia preheater (6) and the hydrogen cooler (10) can be plate-fin, plate, wound-tube or shell-and-tube heat exchangers; the gasifier (3), the ammonia gas preheater (6) and the hydrogen cooler (10) can be internally provided with perforated, corrugated or sawtooth fins.

9. The combined cooling heating and power system based on the ammonia energy ship as claimed in claim 1, wherein the storage battery (14) is used to drive the hydrogen production system to start hydrogen production when the combined cooling heating and power system is started, the electric heater (7) is operated at full load when hydrogen production is started, and the electric heater (7) is changed to a low-load operation mode or an intermittent operation mode after hydrogen is produced.

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