CN108469150B - Hydrogen liquefying device - Google Patents

Hydrogen liquefying device Download PDF

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Publication number
CN108469150B
CN108469150B CN201810522479.3A CN201810522479A CN108469150B CN 108469150 B CN108469150 B CN 108469150B CN 201810522479 A CN201810522479 A CN 201810522479A CN 108469150 B CN108469150 B CN 108469150B
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hydrogen
channel
heat exchanger
circulating
liquid
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CN108469150A (en
Inventor
况开锋
倪中华
严岩
魏蔚
邬海强
郭道峰
王秋霞
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Jiangsu Guofu Hydrogen Energy Technology Equipment Co Ltd
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Jiangsu Guofu Hydrogen Energy Technology Equipment Co Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0235—Heat exchange integration
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0257—Construction and layout of liquefaction equipments, e.g. valves, machines
    • F25J1/0262—Details of the cold heat exchange system
    • F25J1/0264—Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams
    • F25J1/0265—Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams comprising cores associated exclusively with the cooling of a refrigerant stream, e.g. for auto-refrigeration or economizer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0005—Light or noble gases
    • F25J1/001—Hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/005—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by expansion of a gaseous refrigerant stream with extraction of work
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/0062—Light or noble gases, mixtures thereof
    • F25J1/0067—Hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/007—Primary atmospheric gases, mixtures thereof
    • F25J1/0072—Nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0203—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a single-component refrigerant [SCR] fluid in a closed vapor compression cycle
    • F25J1/0205—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a single-component refrigerant [SCR] fluid in a closed vapor compression cycle as a dual level SCR refrigeration cascade
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0235—Heat exchange integration
    • F25J1/0237—Heat exchange integration integrating refrigeration provided for liquefaction and purification/treatment of the gas to be liquefied, e.g. heavy hydrocarbon removal from natural gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0244—Operation; Control and regulation; Instrumentation
    • F25J1/0245—Different modes, i.e. 'runs', of operation; Process control
    • F25J1/0249—Controlling refrigerant inventory, i.e. composition or quantity
    • F25J1/025—Details related to the refrigerant production or treatment, e.g. make-up supply from feed gas itself
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0285—Combination of different types of drivers mechanically coupled to the same refrigerant compressor, possibly split on multiple compressor casings
    • F25J1/0288—Combination of different types of drivers mechanically coupled to the same refrigerant compressor, possibly split on multiple compressor casings using work extraction by mechanical coupling of compression and expansion of the refrigerant, so-called companders
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/82—Processes or apparatus using other separation and/or other processing means using a reactor with combustion or catalytic reaction
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/10—Hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/02—Separating impurities in general from the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2240/00—Processes or apparatus involving steps for expanding of process streams
    • F25J2240/60—Expansion by ejector or injector, e.g. "Gasstrahlpumpe", "venturi mixing", "jet pumps"
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/90—Processes or apparatus involving steps for recycling of process streams the recycled stream being boil-off gas from storage
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/14—External refrigeration with work-producing gas expansion loop
    • F25J2270/16—External refrigeration with work-producing gas expansion loop with mutliple gas expansion loops of the same refrigerant

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

The invention discloses a hydrogen liquefying device, which comprises: the device comprises a first compressor unit, a purification device, a first cold box, a second cold box, a throttling expansion valve, a liquid hydrogen storage tank, a liquid nitrogen precooling device, a second compressor unit and a third compressor unit, wherein the liquid nitrogen precooling device provides cold energy for the first cold box. The hydrogen liquefying device can recycle low-temperature gaseous hydrogen gasified in the liquid hydrogen storage tank, so that potential safety hazards and energy waste caused by directly releasing the low-temperature gaseous hydrogen can be avoided, cold energy can be provided for hydrogen liquefying, energy consumption required by hydrogen liquefying is reduced, and cost is reduced; in addition, the hydrogen liquefying device can prepare high-purity liquid hydrogen with the concentration of para-hydrogen not lower than 98%, so that the concentration of ortho-hydrogen which can spontaneously generate ortho-para-conversion in the liquid hydrogen is effectively reduced, the evaporation loss of the liquid hydrogen is small, blockage phenomena of various gases, liquid channels and pipelines in the hydrogen liquefying device are not easy to occur, and potential safety hazards are reduced.

Description

Hydrogen liquefying device
Technical Field
The invention relates to a hydrogen liquefying technology, in particular to a hydrogen liquefying device.
Background
With the development of industry and the improvement of the living standard of people, the demand of energy is also increasing. Because fossil energy sources such as coal, petroleum and the like inevitably pollute the environment when in use, and because of limited reserves, mankind is faced with the difficult challenge of developing efficient and clean secondary energy sources, so that the search for renewable green energy sources is urgent. Hydrogen, one of the important bridges for the transition from fossil to renewable energy, is an ideal energy carrier available from a variety of sources, and will provide a new and important form for end-use energy utilization.
The utilization of hydrogen energy needs to solve a series of problems of preparation, storage, transportation, application and the like, and the storage and the transportation are important keys for the application of the hydrogen energy. Current hydrogen energy utilization is generally "on-site production, on-site consumption", mainly due to hydrogen storage and transportation difficulties. Currently, there are two main ways of hydrogen storage: high-pressure gas storage and low-temperature liquid storage, the high-pressure gas storage is the most common and direct hydrogen storage mode, hydrogen is stored in a storage tank through pressurization, but the hydrogen storage mode has small hydrogen storage capacity, needs a thick pressure-resistant storage tank, and has very high transportation cost. While cryogenic liquid storage technology is currently immature, many researchers have conducted a great deal of theoretical and experimental research around improving the efficiency and reducing the cost of liquefying hydrogen for the past half a century. However, facing the large-scale industrial demand, the existing hydrogen liquefying device generally has the problems of low liquefying efficiency, large investment and the like.
Disclosure of Invention
The liquid hydrogen is liquid obtained by cooling hydrogen, is colorless and odorless high-energy low-temperature liquid fuel, and is a mixture of para-hydrogen (p-H2) and ortho-hydrogen (o-H2). Ortho-hydrogen and para-hydrogen are two spin isomers of molecular hydrogen, which isomerism arises from the two possible couplings of the nuclear spins of the two hydrogen atoms. The spins of the two nuclei in orthohydrogen are parallel and the spins of the two nuclei in para-hydrogen are antiparallel. The magnetic moment of para-hydrogen molecules is zero and the magnetic moment of ortho-hydrogen molecules is twice the magnetic moment of protons. Para-hydrogen has the same chemical properties as ortho-hydrogen, and is different in physical properties, and is represented by lower ground state energy than ortho-hydrogen. At or above room temperature, the equilibrium composition of normal and para-hydrogen is 75:25, known as standard hydrogen (n-H2) or normal hydrogen. At a temperature lower than normal temperature, the equilibrium composition of the normal para-hydrogen changes, and the proportion of para-hydrogen increases. The normal-to-secondary conversion of gaseous hydrogen occurs in the presence of a catalyst, whereas liquid hydrogen spontaneously occurs in the absence of a catalyst, converting from normal to para-hydrogen. The positive secondary conversion of liquid hydrogen is an exothermic reaction, and the amount of heat evolved during the conversion is related to the temperature at which the conversion occurs. In order to reduce the evaporation loss of liquid hydrogen caused by the exothermic heat of conversion of normal and para-hydrogen, all liquid hydrogen products are required to have para-hydrogen content at least above 95%, i.e. the normal hydrogen is required to be substantially catalytically converted into para-hydrogen during liquefaction.
The technical problems to be solved by the invention are as follows: the low-temperature gaseous hydrogen recycling device is low in energy consumption, safe and reliable, and the concentration of para-hydrogen in liquid hydrogen prepared by the hydrogen liquefying device is not lower than 98%.
In order to solve the problems, the invention adopts the following technical scheme: the hydrogen liquefying device comprises: the device comprises a first compressor unit, a purification device, a first cold box, a second cold box, a throttling expansion valve, a liquid hydrogen storage tank, a liquid nitrogen precooling device, a second compressor unit and a third compressor unit, wherein the liquid nitrogen precooling device provides cold energy for the first cold box.
The first cold box comprises: a heat exchanger a and a first reactor; the heat exchanger A is provided with a hydrogen channel A, a first liquid nitrogen channel, a circulating hydrogen channel A, a first circulating hydrogen return channel A and a second circulating hydrogen return channel A, wherein the hydrogen channel A, the first liquid nitrogen channel, the circulating hydrogen channel A, the first circulating hydrogen return channel A and the second circulating hydrogen return channel A are mutually independent; the first reactor is provided with a second liquid nitrogen channel, a first hydrogen channel, a first normal-secondary conversion channel, a first liquid hydrogen channel and a first circulating hydrogen channel, wherein the second liquid nitrogen channel, the first hydrogen channel, the first normal-secondary conversion channel, the first liquid hydrogen channel and the first circulating hydrogen channel are mutually independent.
The second cold box includes: a heat exchanger B, a heat exchanger C, a heat exchanger D, a heat exchanger E, a heat exchanger F, a second reactor, a second turboexpander set and a third turboexpander set; the heat exchanger B is provided with a liquid hydrogen channel B, a circulating hydrogen channel B, a first circulating hydrogen return channel B and a second circulating hydrogen return channel B, wherein the liquid hydrogen channel B, the circulating hydrogen channel B, the first circulating hydrogen return channel B and the second circulating hydrogen return channel B are mutually independent; the heat exchanger C is provided with a liquid hydrogen channel C, a circulating hydrogen channel C, a first circulating hydrogen return channel C and a second circulating hydrogen return channel C, wherein the liquid hydrogen channel C, the circulating hydrogen channel C, the first circulating hydrogen return channel C and the second circulating hydrogen return channel C are mutually independent; the heat exchanger D is provided with a liquid hydrogen channel D, a circulating hydrogen channel D, a first circulating hydrogen return channel D, a second circulating hydrogen return channel D and a hydrogen expansion channel, wherein the liquid hydrogen channel D, the circulating hydrogen channel D, the first circulating hydrogen return channel D, the second circulating hydrogen return channel D and the hydrogen expansion channel are mutually independent; the heat exchanger E is provided with a liquid hydrogen channel E, a circulating hydrogen channel E, a first circulating hydrogen return channel E and a second circulating hydrogen return channel E, wherein the liquid hydrogen channel E, the circulating hydrogen channel E, the first circulating hydrogen return channel E and the second circulating hydrogen return channel E are mutually independent; the heat exchanger F is provided with a liquid hydrogen channel F, a circulating hydrogen channel F and a first circulating hydrogen return channel F, wherein the liquid hydrogen channel F, the circulating hydrogen channel F and the first circulating hydrogen return channel F are mutually independent; the second reactor is provided with a second liquid hydrogen channel, a second normal-secondary conversion channel, a third liquid hydrogen channel and a first circulating hydrogen return channel G, wherein the second liquid hydrogen channel, the second normal-secondary conversion channel, the third liquid hydrogen channel and the first circulating hydrogen return channel G are mutually independent.
The raw material hydrogen is sequentially connected with a first compressor unit, a purification device, a hydrogen channel A in a heat exchanger A and an air inlet of a first hydrogen channel in a first reactor through a hydrogen conveying pipeline, an air outlet of the first hydrogen channel is connected with an air inlet of a first positive-to-secondary conversion channel through a first connecting pipeline, an air outlet of the first positive-to-secondary conversion channel is connected with an air inlet of a first liquid hydrogen channel through a second connecting pipeline, an air outlet of the first liquid hydrogen channel sequentially passes through a liquid hydrogen conveying pipeline to be connected with a liquid hydrogen channel B in a heat exchanger B, a liquid hydrogen channel C in a heat exchanger C, a liquid hydrogen channel D in a heat exchanger D, a liquid hydrogen channel E in a heat exchanger E, a liquid hydrogen channel F in a heat exchanger F, a throttling expansion valve and an air inlet of a second liquid hydrogen channel in a second reactor, an air outlet of the second liquid hydrogen channel is connected with an air inlet of a second positive-to-secondary conversion channel through a third connecting pipeline, and an air outlet of the second positive-to-secondary conversion channel is connected with an air inlet of a third liquid hydrogen channel through a fifth connecting pipeline, and an air outlet of the third liquid hydrogen channel is connected with a liquid hydrogen storage tank through a fifth connecting pipeline.
A first branch pipeline and a second branch pipeline are arranged at an evaporation gas outlet of the liquid hydrogen storage tank, and the first branch pipeline is connected with a throttling expansion valve; the second branch pipeline is connected with a second compressor unit, and the second compressor unit is sequentially connected with a circulating hydrogen channel A in the heat exchanger A, a first circulating hydrogen channel in the first reactor, a third compressor unit and an air inlet of a circulating hydrogen channel B in the heat exchanger B through circulating pipelines; a third branch pipeline and a fourth branch pipeline are arranged at the air outlet of the circulating hydrogen channel B:
The third branch pipeline is connected with a circulating hydrogen channel C in the heat exchanger C, the circulating hydrogen channel C in the heat exchanger C is sequentially connected with a circulating hydrogen channel D in the heat exchanger D, a circulating hydrogen channel E in the heat exchanger E and a circulating hydrogen channel F in the heat exchanger F through a first circulating hydrogen return pipeline, the air outlet of the first circulating hydrogen return channel G is sequentially connected with the first circulating hydrogen return channel F of the heat exchanger F, the first circulating hydrogen return channel E of the heat exchanger E, the first circulating hydrogen return channel D of the heat exchanger D, the first circulating hydrogen return channel C in the heat exchanger C, the first circulating hydrogen return channel B in the heat exchanger B and the first circulating hydrogen return channel A in the heat exchanger A through a first circulating hydrogen return pipeline, and then the air outlet of the first circulating hydrogen return channel G is connected with the second branch pipeline in a converging mode, and is connected with the second compressor unit.
The fourth branch pipeline is connected with a second turboexpander unit, the second turboexpander unit is sequentially connected with a hydrogen expansion channel in the heat exchanger D through a second circulating pipeline, the third turboexpander unit is connected with an air inlet of a second circulating hydrogen return channel E in the heat exchanger E, an air outlet of the second circulating hydrogen return channel E is sequentially connected with the second circulating hydrogen return channel D in the heat exchanger D, the second circulating hydrogen return channel C in the heat exchanger C, the second circulating hydrogen return channel B in the heat exchanger B and the second circulating hydrogen return channel A in the heat exchanger A through a second circulating hydrogen return pipeline, and then the second circulating hydrogen return channel E is connected with the second branch pipeline in a merging mode, and is connected with the second compressor unit.
Further, in the foregoing hydrogen liquefying apparatus, the first compressor unit is composed of a first low-pressure compressor and a first high-pressure compressor, and raw hydrogen is sequentially connected with the first low-pressure compressor and the first high-pressure compressor through a hydrogen conveying pipeline; the second compressor unit consists of a second low-pressure compressor and a second high-pressure compressor; the second branch pipeline is connected with the second low-pressure compressor and the second high-pressure compressor in sequence; the third compressor unit consists of a third low-pressure compressor and a third high-pressure compressor; the circulating pipeline is connected with the circulating hydrogen channel A in the heat exchanger A, the first circulating hydrogen channel in the first reactor, the third low-pressure compressor and the third high-pressure compressor in sequence.
Further, the aforementioned hydrogen liquefying apparatus, wherein the purifying apparatus comprises: an absolute adsorber, a catalytic refining device, a drying device and an adsorber capable of removing high boiling point impurities; raw material hydrogen is sequentially connected with a first compressor unit, an oil purification absorber, a catalytic refining device, a drying device, an absorber capable of removing high-boiling impurities, a hydrogen channel A in a heat exchanger A and an air inlet of a first hydrogen pipeline in a first reactor through a hydrogen conveying pipeline.
Further, the foregoing hydrogen liquefying apparatus, wherein the liquid nitrogen precooling apparatus includes: a compressor, a KT turbine expansion compressor, a first heat exchanger, a second heat exchanger and a gas-liquid separator; a nitrogen channel and a first circulating channel are arranged in the first heat exchanger, and the nitrogen channel and the first circulating channel are mutually independent; a liquid nitrogen channel and a second circulating channel are arranged in the second heat exchanger, and the liquid nitrogen channel and the second circulating channel are mutually independent; the method comprises the steps that raw nitrogen is sequentially connected with a compressor and a K loop of a KT turbine expansion compressor through a first nitrogen connecting pipeline and a gas inlet of a nitrogen channel in a first heat exchanger, a first branch nitrogen pipeline and a second branch nitrogen pipeline are arranged at a gas outlet of the nitrogen channel, the gas outlet of the nitrogen channel is respectively connected with the first branch nitrogen pipeline and the second branch nitrogen pipeline, the nitrogen channel is sequentially connected with a liquid nitrogen channel and a gas-liquid separator in the second heat exchanger through the first branch nitrogen pipeline, and a liquid nitrogen outlet of the gas-liquid separator is sequentially connected with a first cold box and the compressor through a second nitrogen connecting pipeline to form a first nitrogen refrigerating circulation loop; the nitrogen channel is sequentially connected with a T loop of the KT turbine expansion compressor, a second circulating channel in the second heat exchanger, a first circulating channel in the first heat exchanger and the compressor through a second branch nitrogen pipeline to form a second nitrogen refrigeration circulating loop; the nitrogen outlet in the gas-liquid separator is connected with the air inlet of the second circulating channel in the second heat exchanger through a third connecting nitrogen pipeline.
Further, in the foregoing hydrogen liquefying apparatus, the compressor is an oil-free centrifugal turbo compressor; a first stop valve is arranged on a first branch nitrogen pipeline between an air outlet of a liquid nitrogen channel in the second heat exchanger and the gas-liquid separator; a second stop valve is arranged on a second nitrogen connecting pipeline between a liquid nitrogen outlet of the gas-liquid separator and the first cold box; and a third branch nitrogen pipeline is further arranged on a second nitrogen connecting pipeline between the liquid nitrogen outlet of the gas-liquid separator and the first cold box, and the third branch nitrogen pipeline is connected with at least one liquid nitrogen storage tank.
Further, in the foregoing hydrogen liquefying apparatus, a first low-temperature double-unit conversion adsorber is further disposed on the first connecting pipeline, where the first low-temperature double-unit conversion adsorber is composed of a first adsorber and a second adsorber, and adsorbents in the first adsorber and the second adsorber can be thermally regenerated; when the first low-temperature double-unit conversion absorber works normally, if the first absorber works normally, the second absorber thermally regenerates; otherwise, if the second adsorber works normally, the first adsorber is thermally regenerated.
Further, in the aforementioned hydrogen liquefying apparatus, a first filter is provided on a first connecting pipe located at the air inlet end of the first low-temperature double-unit conversion adsorber.
Further, in the aforementioned hydrogen liquefying apparatus, a third adsorber is provided on a circulation line between the gas outlet of the first circulation hydrogen passage in the first reactor and the third compressor unit.
Further, in the foregoing hydrogen liquefying apparatus, a second low-temperature double-unit conversion adsorber is disposed on a circulation pipeline between an air outlet of the first circulation hydrogen channel in the first reactor and the third compressor unit, and the second low-temperature double-unit conversion adsorber consists of a third adsorber and a fourth adsorber, where the adsorbents in the third adsorber and the fourth adsorber can be thermally regenerated; when the second low-temperature double-unit conversion adsorber works normally, if the third adsorber works normally, the fourth adsorber regenerates thermally; otherwise, if the fourth adsorber works normally, the third adsorber is thermally regenerated.
Further, in the aforementioned hydrogen liquefying apparatus, a second mechanical filter is provided on the circulation line located at the air inlet end of the second low-temperature double-unit conversion adsorber.
Further, in the aforementioned hydrogen liquefying apparatus, a temperature sensor, a pressure sensor, and a flow sensor are respectively provided in the heat exchanger a, the first reactor, the heat exchanger B, the heat exchanger C, the heat exchanger D, the heat exchanger E, the heat exchanger F, and the second reactor; a hydrogen safety sensor and a smoke sensor are arranged in the hydrogen liquefying environment, and the hydrogen safety sensor and the smoke sensor are respectively connected with a control device for controlling the hydrogen liquefying device.
The beneficial effects of the invention are as follows: (1) the adoption of the hydrogen liquefying device can prepare high-purity liquid hydrogen with the concentration of para-hydrogen not lower than 98%, so that the concentration of ortho-hydrogen which can spontaneously undergo ortho-para conversion in the liquid hydrogen is effectively reduced, the evaporation loss of the liquid hydrogen is small, in addition, the blockage phenomenon of each gas, each liquid channel and each pipeline in the hydrogen liquefying device is not easy to occur, and the potential safety hazard is reduced; (2) the method can recycle the gasified low-temperature gaseous hydrogen in the liquid hydrogen storage tank, can avoid potential safety hazard and energy waste caused by directly releasing the low-temperature gaseous hydrogen, can provide cold for hydrogen liquefaction, reduces energy consumption required by the hydrogen liquefaction and reduces cost; (3) the low-temperature gaseous hydrogen recycled through the nitrogen refrigeration cycle loop provides cold for the first reactor, so that the consumption of liquid nitrogen is reduced by about 30% compared with that of the traditional nitrogen refrigeration cycle loop, the energy consumption required by hydrogen liquefaction is further reduced, and the cost is reduced.
Drawings
Fig. 1 is a schematic structural view of a hydrogen liquefying apparatus according to the present invention.
Fig. 2 is a schematic diagram of a connection structure of the first compressor unit, the purifying device, the liquid nitrogen precooling device and the first cold box in fig. 1.
Fig. 3 is a schematic view of the first cooling box in fig. 2.
Fig. 4 is a schematic structural view of the liquid nitrogen precooling apparatus in fig. 1.
Fig. 5 is a schematic diagram of the connection structure of the second cold box, the liquid hydrogen storage tank and the throttle expansion valve in fig. 1.
Fig. 6 is a schematic diagram showing the connection structure of the heat exchanger B, the heat exchanger C and the second turboexpander of fig. 5.
FIG. 7 is a schematic diagram of the connection of heat exchanger D, heat exchanger E and third turboexpander of FIG. 5.
Fig. 8 is a schematic diagram showing a connection structure of the heat exchanger F and the second reactor in fig. 5.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the attached drawings and the preferred embodiments.
As shown in fig. 1, the structure of the hydrogen liquefying device is as follows: the device comprises a first compressor unit, a purifying device, a first cold box 101, a second cold box 102, a throttling expansion valve, a liquid hydrogen storage tank, a liquid nitrogen precooling device, a second compressor unit and a third compressor unit 9.
The first compressor unit includes: the first low-pressure compressor can adopt a low-pressure unit-spiral oil-filled compressor or a low-pressure dry piston multi-stage compressor, and the first high-pressure compressor can adopt a high-pressure unit-dry piston multi-stage compressor.
The purification device comprises: absolute adsorber, catalytic refining unit, drying device and can clear away the adsorber of high boiling impurity. The adsorbent in the absolute adsorber is activated carbon, and the activated carbon cannot be regenerated, so that the activated carbon needs to be replaced periodically. The catalyst adopted in the catalytic refining device is a metal catalyst, the metal catalyst is one of platinum, nickel and palladium, the surface of a carrier for catalytic refining is generally set to be an extended surface, and the extended surface is uniformly coated with the metal catalyst. The drying device is provided with the fine pore zeolite, the fine pore zeolite can be regenerated by heating, and gaseous hydrogen is dried through the fine pore zeolite which can be regenerated by heating, wherein the heating mode of the fine pore zeolite can adopt indirect electric heating modes such as a heat carrier and the like, so that potential safety hazards can be reduced.
As shown in fig. 2 and 3, the first cooling box 101 includes: a heat exchanger A1, a first reactor 2, a first adsorber 301 capable of removing impurities, a second adsorber 302 capable of removing impurities, and a third adsorber 303 capable of removing impurities. The heat exchanger A1 is provided with a hydrogen channel A11, a first liquid nitrogen channel 12, a circulating hydrogen channel A13, a first circulating hydrogen return channel A14 and a second circulating hydrogen return channel A, wherein the hydrogen channel A11, the first liquid nitrogen channel 12, the circulating hydrogen channel A13, the first circulating hydrogen return channel A14 and the second circulating hydrogen return channel A are mutually independent and do not interfere with each other. The first reactor 2 is provided with a second liquid nitrogen channel, a first hydrogen channel 21, a first positive-secondary conversion channel 22, a first liquid hydrogen channel 23 and a first circulating hydrogen channel 24, wherein the second liquid nitrogen channel, the first hydrogen channel 21, the first positive-secondary conversion channel 22, the first liquid hydrogen channel 23 and the first circulating hydrogen channel 24 are mutually independent and do not interfere with each other.
As shown in fig. 4, 5, 6 and 7, the second cooling tank 102 includes: heat exchanger B3, heat exchanger C4, heat exchanger D5, heat exchanger E6, heat exchanger F7, second reactor 8, second turboexpander train and third turboexpander train. The heat exchanger B3 is provided with a liquid hydrogen channel B31, a circulating hydrogen channel B32, a first circulating hydrogen return channel B33 and a second circulating hydrogen return channel B, wherein the liquid hydrogen channel B31, the circulating hydrogen channel B32, the first circulating hydrogen return channel B33 and the second circulating hydrogen return channel B are mutually independent and do not interfere with each other. The heat exchanger C4 is provided with a liquid hydrogen channel C41, a circulating hydrogen channel C42, a first circulating hydrogen return channel C43 and a second circulating hydrogen return channel C, wherein the liquid hydrogen channel C41, the circulating hydrogen channel C42, the first circulating hydrogen return channel C43 and the second circulating hydrogen return channel C are mutually independent and do not interfere with each other. The heat exchanger D5 is provided with a liquid hydrogen channel D51, a circulating hydrogen channel D52, a first circulating hydrogen return channel D53, a second circulating hydrogen return channel D and a hydrogen expansion channel 54, wherein the liquid hydrogen channel D51, the circulating hydrogen channel D52, the first circulating hydrogen return channel D53, the second circulating hydrogen return channel D and the hydrogen expansion channel 54 are mutually independent and do not interfere with each other. The heat exchanger E6 is provided with a liquid hydrogen channel E61, a circulating hydrogen channel E62, a first circulating hydrogen return channel E63 and a second circulating hydrogen return channel E, wherein the liquid hydrogen channel E61, the circulating hydrogen channel E62, the first circulating hydrogen return channel E63 and the second circulating hydrogen return channel E are mutually independent and do not interfere with each other. The heat exchanger F7 is provided with a liquid hydrogen channel F71, a circulating hydrogen channel F72 and a first circulating hydrogen return channel F, wherein the liquid hydrogen channel F71, the circulating hydrogen channel F72 and the first circulating hydrogen return channel F are mutually independent and do not interfere with each other. The second reactor 8 is provided with a second liquid hydrogen channel 81, a second normal-secondary conversion channel 82, a third liquid hydrogen channel 83 and a first circulating hydrogen return channel G, wherein the second liquid hydrogen channel 81, the second normal-secondary conversion channel 82, the third liquid hydrogen channel 83 and the first circulating hydrogen return channel G are mutually independent and do not interfere with each other.
As shown in fig. 4, the liquid nitrogen pre-cooling device includes: a compressor 601 and a nitrogen liquefaction cold box 600. The nitrogen liquefaction cooling tank 600 includes: KT turboexpander compressor 602, first heat exchanger 603, second heat exchanger 604, and gas-liquid separator 605. The compressor 601 may here be an oil-free centrifugal turbo compressor.
The first heat exchanger 603 is provided with a nitrogen passage and a first circulation passage, which are independent of each other and do not interfere with each other. The second heat exchanger 604 is provided with a liquid nitrogen passage and a second circulation passage, which are independent of each other and do not interfere with each other.
As shown in fig. 4, raw nitrogen is sequentially connected with a K loop of a compressor 601 and a KT turboexpansion compressor 602 through a first nitrogen connecting pipeline 701, and is connected with an air inlet of a nitrogen channel in a first heat exchanger 603, a first branch nitrogen pipeline 702 and a second branch nitrogen pipeline 703 are arranged at an air outlet of the nitrogen channel, and a gas-liquid mixture output from the nitrogen channel in the first heat exchanger 603 enters a subsequent process in two ways, wherein one way is: liquefied nitrogen in the nitrogen channel is sequentially connected with the nitrogen channel in the second heat exchanger 604 and the gas-liquid separator 605 through the first branch nitrogen pipeline 702, and a liquid nitrogen outlet of the gas-liquid separator 605 is sequentially connected with the first cold box 101 and the compressor 601 through the second nitrogen connecting pipeline 704 to form a first nitrogen refrigerating circulation loop. The other path is as follows: the non-liquefied gaseous nitrogen in the nitrogen channel is sequentially connected with the T loop of the KT turbine expansion compressor 602, the second circulating channel in the second heat exchanger 604, the first circulating channel in the first heat exchanger 603 and the compressor 601 through the second branch nitrogen pipeline 703 to form a second nitrogen refrigeration circulating loop. In the actual use process, the gaseous nitrogen gasified and separated from the gas-liquid separator 605 is also recycled and utilized in the liquid nitrogen precooling device, and a nitrogen outlet in the gas-liquid separator 605 is connected with an air inlet of the second circulation channel in the second heat exchanger 604 through a third connecting nitrogen pipeline 705.
In the actual use process, in order to control the liquid nitrogen precooling device conveniently, a third stop valve 606 is arranged on the first branch nitrogen pipeline 702 between the air outlet of the liquid nitrogen channel in the second heat exchanger 604 and the gas-liquid separator 605, and the third stop valve 606 is used for adjusting flow, cutting off the first branch nitrogen pipeline 702 between the liquid nitrogen channel and the gas-liquid separator 5, and the like. A fourth shut-off valve 607 is provided on the second connecting nitrogen line 704 between the liquid nitrogen outlet of the gas-liquid separator 605 and the first cold box 101, the fourth shut-off valve 607 being operable to regulate the flow, shut off the second connecting nitrogen line 704 between the liquid nitrogen outlet of the gas-liquid separator 605 and the first cold box 101, etc.
In the actual use process, a third branch nitrogen pipeline is further arranged on the second connecting nitrogen pipeline 704 between the liquid nitrogen outlet of the gas-liquid separator 605 and the first cold box 101, and the third branch nitrogen pipeline is connected with at least one liquid nitrogen storage tank, so that even if the liquid nitrogen precooling device is stopped briefly, enough cooling medium liquid nitrogen can be provided for the first cold box 101.
The second compressor unit includes: the second low-pressure compressor can adopt a low-pressure unit-spiral oil-filled compressor or a low-pressure dry piston multi-stage compressor, and the second high-pressure compressor can adopt a high-pressure unit-dry piston multi-stage compressor.
The third compressor unit includes: the third low-pressure compressor can adopt a low-pressure unit-spiral oil-filled compressor or a low-pressure dry piston multi-stage compressor, and the third high-pressure compressor can adopt a high-pressure unit-dry piston multi-stage compressor.
Referring to fig. 1 and 2, raw hydrogen is sequentially connected to a first low-pressure compressor, a first high-pressure compressor, a clean oil adsorber, a catalytic refining device, a drying device, an adsorber capable of removing high-boiling impurities, a hydrogen channel a11 in a heat exchanger A1, an air inlet of a first hydrogen channel 21 in a first reactor 2 through a first connecting pipe 202, an air outlet of the first hydrogen channel 21 is connected to an air inlet of a first normal-secondary conversion channel 22 through a second connecting pipe 203, an air outlet of the first normal-secondary conversion channel 22 is connected to an air inlet of a first liquid hydrogen channel 23 through a second connecting pipe 203, an air outlet of the first liquid hydrogen channel 23 is sequentially connected to a liquid hydrogen channel B31 in a heat exchanger B3 through a liquid hydrogen conveying pipe 204, a liquid hydrogen channel C41 in a heat exchanger C4, a liquid hydrogen channel D51 in a heat exchanger D5, a liquid hydrogen channel E61 in a heat exchanger E6, a liquid hydrogen channel F71 in a heat exchanger F7, a throttle expansion valve, an air inlet of a second liquid hydrogen channel 81 in a second reactor 8 through a third connecting pipe 205, an air outlet of the second liquid hydrogen channel 81 is connected to an air outlet of the third normal-conversion channel 82 through a third connecting pipe 82, and an air outlet of the second normal-secondary conversion channel 82 is connected to a third liquid hydrogen channel 82 through a third connecting pipe 82.
Referring to fig. 1 and 2, a low-temperature double-unit conversion adsorber is further disposed on the first connection pipe 202, and the low-temperature double-unit conversion adsorber is composed of a first adsorber 301 and a second adsorber 302, wherein the first adsorber 301 and the second adsorber 302 can remove low-boiling impurities such as N 2 CO, and fine purification of high boiling impurities. The adsorbents in the first adsorber 301 and the second adsorber 302 are fine pore zeolite that can be regenerated thermally; when the low-temperature double-unit conversion absorber works normally, if the first absorber 301 works normally, the second absorber 302 regenerates thermally; conversely, if the second adsorber 302 is operating normally, the first adsorber 301 is thermally regenerated. The first adsorber 301 and the second adsorber 302 may employ a sleeve structure for supplying a heat carrier, and thermal vacuum regeneration may be employed, such as using a separate high vacuum shield or a multi-layer vacuum shield insulation shield, in order to enhance regeneration strength of the adsorbent in the first adsorber 301 and the second adsorber 302. In order to ensure that the adsorbents in the first adsorber 301 and the second adsorber 302 are not affected by the mechanically damaging substances of the adsorbents during the actual use, a filter (not shown) is usually disposed on the first connecting pipe 202 at the air inlet end of the low-temperature double-unit conversion adsorber, and the filter may be a mechanical filter, where the filtration precision of the metal filter element is not more than 40 micrometers, and a filter element with filtration precision not more than 10 micrometers may be generally used. The mechanical filter can be regenerated by heating/precooling mode to perform self-purification.
Referring to fig. 1, 5, 6, 7 and 8, a first branch pipeline 401 and a second branch pipeline 402 are arranged at an evaporation gas outlet of a liquid hydrogen storage tank, the first branch pipeline 401 is connected with a throttling expansion valve, and low-temperature gaseous hydrogen gasified in the liquid hydrogen storage tank enters a preceding process in two ways: the first path of low-temperature gaseous hydrogen enters the throttling expansion valve through the first branch pipeline 401 and is combined with the mixed liquid hydrogen entering the throttling expansion valve.
The second branch pipe 402 is connected to a second low-pressure compressor, which is connected to the second high-pressure compressor, the circulating hydrogen passage a13 in the heat exchanger A1, the first circulating hydrogen passage 24 in the first reactor 2, the third low-pressure compressor, the third high-pressure compressor, and the air inlet of the circulating hydrogen passage B32 in the heat exchanger B3 in this order through a circulating pipe 403. A third branch pipe 404 and a fourth branch pipe 405 are provided at the outlet of the circulation hydrogen passage B32:
the third branch pipe 404 is connected to the circulating hydrogen passage C42 in the heat exchanger C4, the circulating hydrogen passage C42 in the heat exchanger C4 is connected to the circulating hydrogen passage D52 in the heat exchanger D5, the circulating hydrogen passage E62 in the heat exchanger E6, and the circulating hydrogen passage F72 in the heat exchanger F7 in this order through the first circulating pipe 406, and the air inlet of the first circulating hydrogen return passage G in the second reactor 8 is connected to the first circulating hydrogen return passage F of the heat exchanger F7, the first circulating hydrogen return passage E63 of the heat exchanger E6, the first circulating hydrogen return passage D53 of the heat exchanger D5, the first circulating hydrogen return passage C43 in the heat exchanger C4, the first circulating hydrogen return passage B33 in the heat exchanger B3, the first circulating hydrogen return passage a14 in the heat exchanger A1 in this order through the first circulating hydrogen return pipe 407, and then is connected to the second branch pipe 402, and is connected to the second compressor unit.
The fourth branch pipe 405 is connected to a second turboexpander, which is sequentially connected to the hydrogen expansion channel 54 in the heat exchanger D5 and the air inlet of the second circulating hydrogen return channel E in the heat exchanger E6 through the second circulating pipe 408, and the air outlet of the second circulating hydrogen return channel E is sequentially connected to the second circulating hydrogen return channel D in the heat exchanger D5, the second circulating hydrogen return channel C in the heat exchanger C4, the second circulating hydrogen return channel B in the heat exchanger B3, the second circulating hydrogen return channel a in the heat exchanger A1, and then to the second branch pipe 402 through the second circulating hydrogen return pipe 409.
As shown in fig. 5, the gasified low-temperature gaseous hydrogen in the liquid hydrogen storage tank enters the previous process in two ways: the second path of low-temperature gaseous hydrogen enters a circulating hydrogen channel B32 in a heat exchanger B3 through a second low-pressure compressor, a second high-pressure compressor, a circulating hydrogen channel A13 in a heat exchanger A1, a first circulating hydrogen channel 24 in a first reactor 2, a third low-pressure compressor and a third high-pressure compressor, and the low-temperature gaseous hydrogen output from an air outlet of the circulating hydrogen channel B32 is circulated in two paths of circulating hydrogen:
The first path of circulating hydrogen enters a first circulating hydrogen return channel G in the second reactor 8 through a circulating hydrogen channel C42 in the heat exchanger C4, a circulating hydrogen channel D52 in the heat exchanger D5, a circulating hydrogen channel E62 in the heat exchanger E6 and a circulating hydrogen channel F72 in the heat exchanger F7, then sequentially passes through a first circulating hydrogen return channel F of the heat exchanger F7, a first circulating hydrogen return channel E63 of the heat exchanger E6, a first circulating hydrogen return channel D53 of the heat exchanger D5, a first circulating hydrogen return channel C43 in the heat exchanger C4, a first circulating hydrogen return channel B33 in the heat exchanger B3 and a first circulating hydrogen return channel A14 in the heat exchanger A1 from an air outlet of the first circulating hydrogen return channel G, and then enters a second low-pressure compressor again to form a first path of hydrogen refrigeration cycle.
The other path of circulating hydrogen enters a second circulating hydrogen return channel E in a heat exchanger E6 through a second turboexpander, a hydrogen expansion channel in a heat exchanger D5 and a third turboexpander, then sequentially passes through a second circulating hydrogen return channel D in the heat exchanger D5, a second circulating hydrogen return channel C in a heat exchanger C4, a second circulating hydrogen return channel B in a heat exchanger B3 and a second circulating hydrogen return channel A in a heat exchanger A1 from an air outlet of the second circulating hydrogen return channel E, and then enters a second low-pressure compressor again after being combined with a second path of low-temperature gaseous hydrogen in a second branch pipeline 402 to form a second path of hydrogen refrigeration cycle.
And defining the gas circulated in the first path of hydrogen refrigeration circulation loop and the gas circulated in the second path of hydrogen refrigeration circulation loop as circulating hydrogen, and converging the circulating hydrogen in the first path of hydrogen refrigeration circulation loop, the circulating hydrogen in the second path of hydrogen refrigeration circulation loop and the second path of low-temperature liquid hydrogen to form low-temperature circulating hydrogen.
Referring to fig. 1 and 2, a third adsorber 303 capable of removing impurities is disposed on a circulation pipe 403 between an air outlet of the first circulation hydrogen passage 24 and the third low pressure compressor in the first reactor 2, and since the amount of impurities in the low temperature circulation hydrogen is limited, the use requirement can be satisfied by using one third adsorber 303, and when the third adsorber 303 is regenerated, the circulation pipe 403 between the air outlet of the first circulation hydrogen passage 24 and the third low pressure compressor in the first reactor 2 is disconnected, and when the third adsorber 303 is regenerated, the circulation pipe 403 between the air outlet of the first circulation hydrogen passage 24 and the third low pressure compressor in the first reactor 2 is unobstructed. Of course, in the actual use process, instead of the single third adsorber 303, a low-temperature double-unit conversion adsorber may be used, where the low-temperature double-unit conversion adsorber is composed of a third adsorber 303 capable of removing impurities and a fourth adsorber capable of removing impurities, and the adsorbents in the third adsorber 303 and the fourth adsorber are fine pore zeolite capable of thermal regeneration; when the low-temperature double-unit conversion absorber works normally, if the third absorber 303 works normally, the fourth absorber thermally regenerates; conversely, if the fourth adsorber is operating normally, the third adsorber 303 is thermally regenerated. The third adsorber 303 and the fourth adsorber may be sleeve structures for supplying heat carrier, and thermal vacuum regeneration may be used, such as using a separate high vacuum shield or a multi-layer vacuum shield insulation shield, in order to increase regeneration strength of the adsorbent in the third adsorber 303 and the fourth adsorber. In practical use, to ensure that the adsorbents in the third adsorber 303 and the fourth adsorber are not affected by the mechanically damaging substances of the adsorbents, a filter (not shown) is typically disposed on the circulation conduit 403 at the air inlet end of the low-temperature double-unit conversion adsorber, where the filter may be a mechanical filter, and the metal filter element in the mechanical filter may have a filtration accuracy of not more than 40 micrometers, and may generally also have a filtration accuracy of not more than 10 micrometers. The mechanical filter can be regenerated by heating/precooling to perform self-purification.
In the actual use process, in order to monitor the working conditions among the components of the hydrogen liquefying device, a temperature sensor, a pressure sensor and a flow sensor are generally respectively arranged in the heat exchanger A1, the first reactor 2, the heat exchanger B3, the heat exchanger C4, the heat exchanger D5, the heat exchanger E6, the heat exchanger F7 and the second reactor 8; a hydrogen safety sensor and a smoke sensor are arranged in the hydrogen liquefying process environment, and the hydrogen safety sensor and the smoke sensor are respectively connected with a control device for controlling the hydrogen liquefying device. The control components such as a stop valve can be arranged at each important part of the hydrogen liquefying device for controlling the hydrogen liquefying process flow, for example: the first stop valve is arranged on the hydrogen conveying pipeline 201 positioned at the air inlet end of the first compressor unit, the second stop valve is arranged on the second branch pipeline 402 positioned at the air inlet end of the second compressor unit, and the first stop valve, the second stop valve, the third stop valve, the fourth stop valve and other control components are controlled by the control device. The hydrogen liquefying device has the advantages of flexible adjustment, safety, reliability, convenient maintenance, lower energy consumption and the like.
The specific steps of a hydrogen liquefying process matched with the hydrogen liquefying device are as follows:
the first step: compressing and purifying raw material hydrogen: firstly, compressing raw material hydrogen into gaseous hydrogen with the pressure of 2.5 MPa+/-10% by a first compressor unit; and then the oil in the gaseous hydrogen is adsorbed by the absolute adsorber, so that the volume content of the oil in the gaseous hydrogen is not more than 10ppbV, and the adsorbent of the absolute adsorber is activated carbon. Then, carrying out catalytic refining on the gaseous hydrogen to remove oxygen impurities in the gaseous hydrogen, so that the volume content of the oxygen impurities in the gaseous hydrogen is not more than 2ppbV; the catalyst used in the catalytic refining is a metal catalyst, and the metal catalyst is one of platinum, nickel and palladium. Then the gaseous hydrogen is dried to make the moisture in the gaseous hydrogen be in a bodyThe integrated content is not more than 1ppmV, and the temperature of gaseous hydrogen obtained after drying treatment is controlled at the condensation point temperature of minus 100 ℃ to minus 70 ℃; the gaseous hydrogen may be subjected to a drying treatment using a fine pore zeolite which can be regenerated by heating. Finally, CO in gaseous hydrogen is removed by an absorber capable of removing high-boiling impurities 2 、H 2 S and high boiling point impurities are adsorbed to enable CO in gaseous hydrogen 2 、H 2 The total volume content of S and high boiling impurities is not more than 1ppmV.
And a second step of: the compressed and purified gaseous hydrogen is subjected to gaseous hydrogen positive-secondary conversion: the compressed and purified gaseous hydrogen is precooled to 102.7+/-10K through a heat exchanger A, enters a first hydrogen channel of a first reactor, is output from an air outlet of the first hydrogen channel, and returns to enter a first positive-secondary conversion channel of the first reactor to carry out positive-secondary conversion of the gaseous hydrogen to obtain mixed liquid hydrogen with the temperature of 81.2+/-5K and the secondary hydrogen concentration of 46.3% -55%; wherein the cold in heat exchanger a is provided by liquid nitrogen and low temperature recycle hydrogen.
The liquid nitrogen is prepared by a liquid nitrogen precooling process, and the specific steps of the liquid nitrogen precooling process are as follows:
(1) Initially pressurizing raw nitrogen to gaseous nitrogen with the pressure of 0.9MPa and the temperature of 300K-313K through a compressor 601; the compressor 601 described herein may employ an oil-free centrifugal turbo compressor;
(2) Delivering the primarily pressurized gaseous nitrogen into a K loop in a KT turbine expansion compressor 602 for secondary pressurization, expansion, throttling and cooling to obtain the gaseous nitrogen with the pressure of 0.128-0.13 MPa and the temperature of 120 K+/-5K;
(3) Delivering the gaseous nitrogen subjected to secondary pressurization, expansion throttling and cooling into a first heat exchanger 603 for primary cooling and liquefying treatment to obtain a gas-liquid mixture of the gaseous nitrogen and liquid nitrogen with the temperature of 79.2 K+/-2K; the non-liquefied gaseous nitrogen in the gas-liquid mixture is conveyed into a T loop in the KT turbine expansion compressor 602 for expansion, throttling and cooling, then is combined with the gaseous nitrogen separated from the gas-liquid separator 605 to be used as cooling media of the first heat exchanger 603 and the second heat exchanger 604, and then is sequentially conveyed into the second heat exchanger 604 and the first heat exchanger 603, and the cooling capacity is provided for the second heat exchanger 604 and the first heat exchanger 603 and then is returned to the compressor 601 for preliminary pressurization; delivering liquefied liquid nitrogen in the gas-liquid mixture to a second heat exchanger 604 for secondary cooling and liquefying treatment, and delivering to a gas-liquid separator 605 for gas-liquid separation to obtain liquid nitrogen with the pressure of 0.123-0.128 MPa and the temperature of 70K-79.2K;
(4) The liquid nitrogen obtained after gas-liquid separation is conveyed into a first cold box in a hydrogen liquefying device, and the liquid nitrogen is taken as a cooling medium of the first cold box, and returns to a compressor for preliminary pressurization after providing cooling capacity for the first cold box; wherein the first cold box includes: the liquid nitrogen obtained after gas-liquid separation is sequentially conveyed into the first reactor and the heat exchanger A to provide cold energy for the first reactor and the heat exchanger A; wherein the temperature of the liquid nitrogen entering the first cooling box 101 is 70K-79.2K;
(5) And circulating the steps.
And continuously sampling and analyzing the compressed and purified gaseous hydrogen, so as to ensure that the gaseous hydrogen before the purified and liquefied hydrogen meets the impurity component requirement of the hydrogen in the first table. Of course, this is also a means of detecting whether the purge is satisfactory.
TABLE I gaseous Hydrogen composition requirement before liquefaction after purification
Aiming at the requirement, gas analysis equipment for detecting the trace concentration of the impurities is not needed, the value is a reference value, and the low-temperature adsorption can be realized at-80K. According to the industry standard, the volume content of nitrogen in the liquid hydrogen must not exceed 200ppbV, but in order to allow the subsequent liquefaction to continue, it is only necessary that the volume content of concentrated nitrogen in the gaseous hydrogen after compression and purification does not exceed 600ppbV, and according to the reference annex b of GOST R56248-2014, this amount of nitrogen is soluble in the liquid hydrogen at a temperature exceeding 20.64K or at an equilibrium pressure exceeding 0.115 mpa (absolute), which is the minimum for the storage of liquid hydrogen.
The selection of oxygen content requirements is detailed in Table one, where the values noted here are critical values according to industry standards and meet product temperatures of 22.15K or equilibrium pressures of 0.17 megapascals; the oxygen concentration is reduced and is monitored until the volume content reaches 0.5 ppbV without exceeding the range, so that the hydrogen liquefying device can be operated under the condition that accumulated solid oxygen does not exist, and each gas, liquid channel and pipeline in the hydrogen liquefying device is not easy to be blocked, and if the blocking phenomenon occurs, explosion is extremely easy to occur, so that the potential safety hazard of the hydrogen liquefying device is effectively reduced through the arrangement.
And a third step of: the liquid hydrogen is subjected to liquid hydrogen positive-secondary conversion: the mixed liquid hydrogen output from the gas outlet of the first normal-secondary conversion channel 22 of the first reactor 2 is returned to the first liquid hydrogen channel 23 of the first reactor 2, then output from the gas outlet of the first liquid hydrogen channel 23, sequentially cooled to 23.6+/-10K by a heat exchanger B3, a heat exchanger C4, a heat exchanger D5, a heat exchanger E6, a heat exchanger F7 and a throttling expansion valve, then enters the second liquid hydrogen channel 81 of the second reactor 8, and then output from the gas outlet of the second liquid hydrogen channel 81, and then returns to the second normal-secondary conversion channel 82 of the second reactor 8 to perform normal-secondary conversion of the liquid hydrogen, so that the liquid hydrogen with the temperature of 2.13K-5K and the secondary hydrogen concentration of not lower than 98% is obtained.
Fourth step: liquid hydrogen storage: the liquid hydrogen output from the gas outlet of the second normal-secondary conversion channel 82 of the second reactor 8 is returned to the third liquid hydrogen channel 83 of the second reactor 8, and then the liquid hydrogen output from the gas outlet of the third liquid hydrogen channel 83 is stored in a liquid hydrogen storage tank; the gasified low-temperature gaseous hydrogen in the liquid hydrogen storage tank enters the prior process in two ways: the first path of low-temperature gaseous hydrogen is converged with the mixed liquid hydrogen entering the throttling expansion valve through the throttling expansion valve; the second path of low-temperature gaseous hydrogen is compressed into low-temperature gaseous hydrogen with the pressure of 2.5MPa plus or minus 10 percent by a second compressor unit, and then enters a heat exchanger A1, a first reactor 2, a third compressor unit and a heat exchanger B3 in sequence, and then enters the previous process by two paths of circulating hydrogen: one path of circulating hydrogen sequentially passes through the heat exchanger C4, the heat exchanger D5, the heat exchanger E6, the heat exchanger F7 and the second reactor 8 and then returns to the heat exchanger F7, and then sequentially passes through the heat exchanger E6, the heat exchanger D5, the heat exchanger C4, the heat exchanger B3 and the heat exchanger A1 and then is converged with a second path of low-temperature gaseous hydrogen and then enters the second compressor unit to form a first path of hydrogen refrigeration cycle. The other path of circulating hydrogen is compressed and expanded by a second turbo-expander set and then enters a heat exchanger D5, then compressed and expanded by a third turbo-expander set and then enters a heat exchanger E6, and then sequentially returns to the heat exchanger D5, the heat exchanger C4, the heat exchanger B3 and the heat exchanger A1, and then enters a second path of hydrogen refrigeration circulation loop after being combined with a second path of low-temperature gaseous hydrogen. The circulating hydrogen in the first path of hydrogen refrigeration cycle loop, the circulating hydrogen in the second path of hydrogen refrigeration cycle loop and the second path of low-temperature liquid hydrogen are combined to form low-temperature circulating hydrogen, and the low-temperature circulating hydrogen provides cooling capacity for the heat exchanger A1, the first reactor 2, the heat exchanger B3, the heat exchanger C4, the heat exchanger D5, the heat exchanger E6, the heat exchanger F7 and the second reactor 8; the expansion pressure of the second turbo-expander set is 1.58MPaA, and the expansion pressure of the third turbo-expander set is 0.25MPaA.
The first compressor unit in the first step is composed of a first low-pressure compressor and a first high-pressure compressor, raw material hydrogen is compressed into gaseous hydrogen with the pressure of 0.29 MPa+/-10% by the first low-pressure compressor, and then the gaseous hydrogen with the pressure of 2.5 MPa+/-10% is compressed by the first high-pressure compressor; the first low-pressure compressor can be a low-pressure unit-spiral oil-filled compressor or a low-pressure dry piston multi-stage compressor, and the first high-pressure compressor can be a high-pressure unit-dry piston multi-stage compressor.
The second compressor unit in the fourth step is composed of a second low-pressure compressor and a second high-pressure compressor, the low-temperature circulating hydrogen is compressed into low-temperature circulating hydrogen with the pressure of 0.29 MPa+/-10% by the second low-pressure compressor, and then the low-temperature circulating hydrogen is compressed into low-temperature circulating hydrogen with the pressure of 2.5 MPa+/-10% by the second high-pressure compressor; the second low-pressure compressor can be a low-pressure unit-spiral oil-filled compressor or a low-pressure dry piston multi-stage compressor, and the second high-pressure compressor can be a high-pressure unit-dry piston multi-stage compressor.
The third compressor group in the fourth step is composed of a third low-pressure compressor and a third high-pressure compressor, the low-temperature circulating hydrogen outputted from the first reactor 2 is compressed into the low-temperature circulating hydrogen with the pressure of 0.29MPa +/-10% by the third low-pressure compressor, and then is compressed into the low-temperature circulating hydrogen with the pressure of 2.5MPa +/-10% by the third high-pressure compressor. The third low-pressure compressor can be a low-pressure unit-spiral oil-filled compressor or a low-pressure dry piston multistage compressor, and the third high-pressure compressor can be a high-pressure unit-dry piston multistage compressor.
To increase the purification purity of the final liquid hydrogen, the adsorption is usually carried out again in the second step, in particular as follows: the compressed and purified gaseous hydrogen is precooled to 102.7+/-10K through a heat exchanger A1, enters a first hydrogen channel 21 of a first reactor 2, is output from an air outlet of the first hydrogen channel 21, is adsorbed through a low-temperature double-unit conversion adsorber, and returns to enter a first positive-secondary conversion channel 22 of the first reactor 2 after being adsorbed to carry out positive-secondary conversion of the gaseous hydrogen to obtain mixed liquid hydrogen with the temperature of 81.2+/-5K and the secondary hydrogen concentration of 46.3% -55%; the low-temperature double-unit conversion absorber consists of a first absorber 301 and a second absorber 302; when the compressed and purified gaseous hydrogen is adsorbed by the first adsorber 301, the second adsorber 302 is thermally regenerated; when the compressed and purified gaseous hydrogen is adsorbed by the second adsorber 302, the first adsorber 301 is thermally regenerated; in the step (4), the second path of low-temperature gaseous hydrogen is compressed into low-temperature gaseous hydrogen with the pressure of 2.5 MPa+/-10% by a second compressor unit, and then sequentially enters a heat exchanger A1, a first reactor 2 and a third adsorber 303 and then enters a third compressor unit.
And respectively performing water cooling or air cooling heat dissipation on the oil-free centrifugal compressor, the first compressor unit, the second compressor unit and the third compressor unit. A temperature sensor, a pressure sensor and a flow sensor are respectively arranged in the heat exchanger A1, the first reactor 2, the heat exchanger B3, the heat exchanger C4, the heat exchanger D5, the heat exchanger E6, the heat exchanger F7 and the second reactor 8; the hydrogen liquefying process environment is provided with a hydrogen safety sensor and a smoke sensor which are respectively connected with a control device for controlling the hydrogen liquefying process flow.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any other way, but any modifications or equivalent variations according to the technical spirit of the present invention are still included in the scope of the present invention.
The invention has the advantages that: (1) the adoption of the hydrogen liquefying device can prepare high-purity liquid hydrogen with the concentration of para-hydrogen not lower than 98%, so that the concentration of ortho-hydrogen which can spontaneously undergo ortho-para conversion in the liquid hydrogen is effectively reduced, the evaporation loss of the liquid hydrogen is small, in addition, the blockage phenomenon of each gas, each liquid channel and each pipeline in the hydrogen liquefying device is not easy to occur, and the potential safety hazard is reduced; (2) the method can recycle the gasified low-temperature gaseous hydrogen in the liquid hydrogen storage tank, can avoid potential safety hazard and energy waste caused by directly releasing the low-temperature gaseous hydrogen, can provide cold for hydrogen liquefaction, reduces energy consumption required by the hydrogen liquefaction and reduces cost; (3) the low-temperature gaseous hydrogen recycled through the nitrogen refrigeration cycle loop provides cold for the first reactor 2, so that compared with the traditional nitrogen refrigeration cycle loop, the liquid nitrogen consumption is reduced by about 30%, the energy consumption required by hydrogen liquefaction is further reduced, and the cost is reduced.

Claims (11)

1. The hydrogen liquefying device is characterized in that: comprising the following steps: the liquid nitrogen pre-cooling device provides cold energy for the first cold box;
The first cold box comprises: a heat exchanger a and a first reactor; the heat exchanger A is provided with a hydrogen channel A, a first liquid nitrogen channel, a circulating hydrogen channel A, a first circulating hydrogen return channel A and a second circulating hydrogen return channel A, wherein the hydrogen channel A, the first liquid nitrogen channel, the circulating hydrogen channel A, the first circulating hydrogen return channel A and the second circulating hydrogen return channel A are mutually independent; the first reactor is provided with a second liquid nitrogen channel, a first hydrogen channel, a first normal-secondary conversion channel, a first liquid hydrogen channel and a first circulating hydrogen channel, wherein the second liquid nitrogen channel, the first hydrogen channel, the first normal-secondary conversion channel, the first liquid hydrogen channel and the first circulating hydrogen channel are mutually independent;
the second cold box includes: a heat exchanger B, a heat exchanger C, a heat exchanger D, a heat exchanger E, a heat exchanger F, a second reactor, a second turboexpander set and a third turboexpander set; the heat exchanger B is provided with a liquid hydrogen channel B, a circulating hydrogen channel B, a first circulating hydrogen return channel B and a second circulating hydrogen return channel B, wherein the liquid hydrogen channel B, the circulating hydrogen channel B, the first circulating hydrogen return channel B and the second circulating hydrogen return channel B are mutually independent; the heat exchanger C is provided with a liquid hydrogen channel C, a circulating hydrogen channel C, a first circulating hydrogen return channel C and a second circulating hydrogen return channel C, wherein the liquid hydrogen channel C, the circulating hydrogen channel C, the first circulating hydrogen return channel C and the second circulating hydrogen return channel C are mutually independent; the heat exchanger D is provided with a liquid hydrogen channel D, a circulating hydrogen channel D, a first circulating hydrogen return channel D, a second circulating hydrogen return channel D and a hydrogen expansion channel, wherein the liquid hydrogen channel D, the circulating hydrogen channel D, the first circulating hydrogen return channel D, the second circulating hydrogen return channel D and the hydrogen expansion channel are mutually independent; the heat exchanger E is provided with a liquid hydrogen channel E, a circulating hydrogen channel E, a first circulating hydrogen return channel E and a second circulating hydrogen return channel E, wherein the liquid hydrogen channel E, the circulating hydrogen channel E, the first circulating hydrogen return channel E and the second circulating hydrogen return channel E are mutually independent; the heat exchanger F is provided with a liquid hydrogen channel F, a circulating hydrogen channel F and a first circulating hydrogen return channel F, wherein the liquid hydrogen channel F, the circulating hydrogen channel F and the first circulating hydrogen return channel F are mutually independent; a second liquid hydrogen channel, a second normal-to-secondary conversion channel, a third liquid hydrogen channel and a first circulating hydrogen return channel G are arranged in the second reactor, and the second liquid hydrogen channel, the second normal-to-secondary conversion channel, the third liquid hydrogen channel and the first circulating hydrogen return channel G are mutually independent;
The raw material hydrogen is sequentially connected with a first compressor unit, a purification device, a hydrogen channel A in a heat exchanger A and an air inlet of a first hydrogen channel in a first reactor through a hydrogen conveying pipeline, an air outlet of the first hydrogen channel is connected with an air inlet of a first normal-to-secondary conversion channel through a first connecting pipeline, an air outlet of the first normal-to-secondary conversion channel is connected with an air inlet of a first liquid hydrogen channel through a second connecting pipeline, an air outlet of the first liquid hydrogen channel is sequentially connected with a liquid hydrogen channel B in a heat exchanger B, a liquid hydrogen channel C in a heat exchanger C, a liquid hydrogen channel D in a heat exchanger D, a liquid hydrogen channel E in a heat exchanger E, a liquid hydrogen channel F in a heat exchanger F, a throttling expansion valve and an air inlet of a second liquid hydrogen channel in a second reactor through a third connecting pipeline, an air outlet of the second normal-to-secondary conversion channel is connected with an air inlet of a third liquid hydrogen channel through a fourth connecting pipeline, and an air outlet of the third liquid hydrogen channel is connected with a liquid hydrogen storage tank through a fifth connecting pipeline;
a first branch pipeline and a second branch pipeline are arranged at an evaporation gas outlet of the liquid hydrogen storage tank, and the first branch pipeline is connected with a throttling expansion valve; the second branch pipeline is connected with a second compressor unit, and the second compressor unit is sequentially connected with a circulating hydrogen channel A in the heat exchanger A, a first circulating hydrogen channel in the first reactor, a third compressor unit and an air inlet of a circulating hydrogen channel B in the heat exchanger B through circulating pipelines; a third branch pipeline and a fourth branch pipeline are arranged at the air outlet of the circulating hydrogen channel B:
The third branch pipeline is connected with a circulating hydrogen channel C in the heat exchanger C, the circulating hydrogen channel C in the heat exchanger C is sequentially connected with a circulating hydrogen channel D in the heat exchanger D, a circulating hydrogen channel E in the heat exchanger E and a circulating hydrogen channel F in the heat exchanger F through a first circulating hydrogen return pipeline, the air outlet of the first circulating hydrogen return channel G is sequentially connected with a first circulating hydrogen return channel F of the heat exchanger F, a first circulating hydrogen return channel E of the heat exchanger E, a first circulating hydrogen return channel D of the heat exchanger D, a first circulating hydrogen return channel C in the heat exchanger C, a first circulating hydrogen return channel B in the heat exchanger B, a first circulating hydrogen return channel A in the heat exchanger A and then is connected with a second branch pipeline in a converging manner through a first circulating hydrogen return pipeline, and then is connected with a second compressor unit;
the fourth branch pipeline is connected with a second turboexpander unit, the second turboexpander unit is sequentially connected with a hydrogen expansion channel in the heat exchanger D through a second circulating pipeline, the third turboexpander unit is connected with an air inlet of a second circulating hydrogen return channel E in the heat exchanger E, an air outlet of the second circulating hydrogen return channel E is sequentially connected with the second circulating hydrogen return channel D in the heat exchanger D, the second circulating hydrogen return channel C in the heat exchanger C, the second circulating hydrogen return channel B in the heat exchanger B and the second circulating hydrogen return channel A in the heat exchanger A through a second circulating hydrogen return pipeline, and then the second circulating hydrogen return channel E is connected with the second branch pipeline in a merging mode, and is connected with the second compressor unit.
2. The hydrogen liquefying apparatus according to claim 1, wherein: the first compressor unit consists of a first low-pressure compressor and a first high-pressure compressor, and raw material hydrogen is sequentially connected with the first low-pressure compressor and the first high-pressure compressor through hydrogen conveying pipelines; the second compressor unit consists of a second low-pressure compressor and a second high-pressure compressor; the second branch pipeline is connected with the second low-pressure compressor and the second high-pressure compressor in sequence; the third compressor unit consists of a third low-pressure compressor and a third high-pressure compressor; the circulating pipeline is connected with the circulating hydrogen channel A in the heat exchanger A, the first circulating hydrogen channel in the first reactor, the third low-pressure compressor and the third high-pressure compressor in sequence.
3. The hydrogen liquefying apparatus according to claim 1 or 2, wherein: the purification device comprises: an absolute adsorber, a catalytic refining device, a drying device and an adsorber capable of removing high boiling point impurities; raw material hydrogen is sequentially connected with a first compressor unit, an oil purification absorber, a catalytic refining device, a drying device, an absorber capable of removing high-boiling impurities, a hydrogen channel A in a heat exchanger A and an air inlet of a first hydrogen pipeline in a first reactor through a hydrogen conveying pipeline.
4. The hydrogen liquefying apparatus according to claim 1, wherein: the liquid nitrogen precooling device comprises: a compressor, a KT turbine expansion compressor, a first heat exchanger, a second heat exchanger and a gas-liquid separator; a nitrogen channel and a first circulating channel are arranged in the first heat exchanger, and the nitrogen channel and the first circulating channel are mutually independent; a liquid nitrogen channel and a second circulating channel are arranged in the second heat exchanger, and the liquid nitrogen channel and the second circulating channel are mutually independent; the method comprises the steps that raw nitrogen is sequentially connected with a compressor and a K loop of a KT turbine expansion compressor through a first nitrogen connecting pipeline and a gas inlet of a nitrogen channel in a first heat exchanger, a first branch nitrogen pipeline and a second branch nitrogen pipeline are arranged at a gas outlet of the nitrogen channel, the gas outlet of the nitrogen channel is respectively connected with the first branch nitrogen pipeline and the second branch nitrogen pipeline, the nitrogen channel is sequentially connected with a liquid nitrogen channel and a gas-liquid separator in the second heat exchanger through the first branch nitrogen pipeline, and a liquid nitrogen outlet of the gas-liquid separator is sequentially connected with a first cold box and the compressor through a second nitrogen connecting pipeline to form a first nitrogen refrigerating circulation loop; the nitrogen channel is sequentially connected with a T loop of the KT turbine expansion compressor, a second circulating channel in the second heat exchanger, a first circulating channel in the first heat exchanger and the compressor through a second branch nitrogen pipeline to form a second nitrogen refrigeration circulating loop; the nitrogen outlet in the gas-liquid separator is connected with the air inlet of the second circulating channel in the second heat exchanger through a third connecting nitrogen pipeline.
5. The hydrogen liquefying apparatus according to claim 4, wherein: the compressor is an oil-free centrifugal turbine compressor; a first stop valve is arranged on a first branch nitrogen pipeline between an air outlet of a liquid nitrogen channel in the second heat exchanger and the gas-liquid separator; a second stop valve is arranged on a second nitrogen connecting pipeline between a liquid nitrogen outlet of the gas-liquid separator and the first cold box; and a third branch nitrogen pipeline is further arranged on a second nitrogen connecting pipeline between the liquid nitrogen outlet of the gas-liquid separator and the first cold box, and the third branch nitrogen pipeline is connected with at least one liquid nitrogen storage tank.
6. The hydrogen liquefying apparatus according to claim 1, wherein: the first connecting pipeline is also provided with a first low-temperature double-unit conversion absorber, the first low-temperature double-unit conversion absorber consists of a first absorber and a second absorber, and the adsorbents in the first absorber and the second absorber can be regenerated thermally; when the first low-temperature double-unit conversion absorber works normally, if the first absorber works normally, the second absorber thermally regenerates; otherwise, if the second adsorber works normally, the first adsorber is thermally regenerated.
7. The hydrogen liquefying apparatus according to claim 6, wherein: a first filter is disposed on a first connecting line at the air inlet end of the first low temperature dual unit conversion adsorber.
8. The hydrogen liquefying apparatus according to claim 1 or 6, wherein: a third adsorber is disposed on the circulation conduit between the outlet of the first circulation hydrogen passage in the first reactor and the third compressor unit.
9. The hydrogen liquefying apparatus according to claim 8, wherein: a second low-temperature double-unit conversion absorber is arranged on a circulating pipeline between an air outlet of a first circulating hydrogen channel in the first reactor and the third compressor unit, the second low-temperature double-unit conversion absorber consists of a third absorber and a fourth absorber, and the adsorbents in the third absorber and the fourth absorber can be regenerated thermally; when the second low-temperature double-unit conversion adsorber works normally, if the third adsorber works normally, the fourth adsorber regenerates thermally; otherwise, if the fourth adsorber works normally, the third adsorber is thermally regenerated.
10. The hydrogen liquefying apparatus according to claim 9, wherein: a second mechanical filter is disposed on the circulation line at the air inlet end of the second low temperature dual unit conversion adsorber.
11. The hydrogen liquefying apparatus according to claim 1, wherein: a temperature sensor, a pressure sensor and a flow sensor are respectively arranged in the heat exchanger A, the first reactor, the heat exchanger B, the heat exchanger C, the heat exchanger D, the heat exchanger E, the heat exchanger F and the second reactor; a hydrogen safety sensor and a smoke sensor are arranged in the hydrogen liquefying environment, and the hydrogen safety sensor and the smoke sensor are respectively connected with a control device for controlling the hydrogen liquefying device.
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CN112361713A (en) * 2020-10-30 2021-02-12 北京航天试验技术研究所 Hydrogen liquefaction equipment provided with parallel turboexpander units
CN112361711A (en) * 2020-10-30 2021-02-12 北京航天试验技术研究所 Hydrogen liquefaction equipment provided with three turboexpander units connected in series
CN114034158B (en) * 2021-07-26 2022-09-20 中国科学院理化技术研究所 Hydrogen liquefaction device
CN114087845B (en) * 2021-11-19 2022-07-15 北京大臻科技有限公司 Liquid hydrogen production device, system and method based on parahydrogen circulation

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