CN115854651B - Hydrogen liquefaction method and device for precooling by utilizing refrigerator - Google Patents
Hydrogen liquefaction method and device for precooling by utilizing refrigerator Download PDFInfo
- Publication number
- CN115854651B CN115854651B CN202211490038.2A CN202211490038A CN115854651B CN 115854651 B CN115854651 B CN 115854651B CN 202211490038 A CN202211490038 A CN 202211490038A CN 115854651 B CN115854651 B CN 115854651B
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- para
- conversion reactor
- refrigerator
- hydrogen conversion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 196
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 196
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 170
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000003860 storage Methods 0.000 claims abstract description 27
- 238000001816 cooling Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011152 fibreglass Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 description 7
- 238000005057 refrigeration Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- OOYGSFOGFJDDHP-KMCOLRRFSA-N kanamycin A sulfate Chemical group OS(O)(=O)=O.O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N OOYGSFOGFJDDHP-KMCOLRRFSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- F25J1/0032—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 the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
- F25J1/004—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 the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by flash gas recovery
-
- 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
- F25J1/0225—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 other external refrigeration means not provided before, e.g. heat driven absorption chillers
-
- 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
- F25J2240/00—Processes or apparatus involving steps for expanding of process streams
- F25J2240/40—Expansion without extracting work, i.e. isenthalpic throttling, e.g. JT valve, regulating valve or venturi, or isentropic nozzle, e.g. Laval
-
- 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
- F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
- F25J2270/908—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by regenerative chillers, i.e. oscillating or dynamic systems, e.g. Stirling refrigerator, thermoelectric ("Peltier") or magnetic refrigeration
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Separation By Low-Temperature Treatments (AREA)
Abstract
The invention discloses a hydrogen liquefying method and device pre-cooled by a refrigerator, wherein the hydrogen liquefying device comprises a high-pressure hydrogen source, a pressure reducing valve, a first normal-para-hydrogen conversion reactor, a second normal-para-hydrogen conversion reactor, a first throttle valve, a third normal-para-hydrogen conversion reactor, a second throttle valve and a liquid hydrogen storage tank which are connected in sequence; the first positive para-hydrogen conversion reactor, the second positive para-hydrogen conversion reactor and the third positive para-hydrogen conversion reactor are respectively connected with a first refrigerator, a second refrigerator and a third refrigerator; wherein, the first refrigerator, the second refrigerator and the third refrigerator all adopt one or more refrigerators. The invention has the advantages of convenient start and stop and simple operation, and has higher energy efficiency.
Description
Technical Field
The invention belongs to the field of hydrogen liquefaction, and particularly relates to a hydrogen liquefaction method and device for precooling by using a refrigerator.
Background
Hydrogen is a difficult-to-liquefy gas, and the hydrogen can be liquefied only by reducing the temperature to 20K under normal pressure. Meanwhile, due to the difference in the spin directions of two hydrogen nuclei in a hydrogen molecule, hydrogen is divided into orthohydrogen and para-hydrogen, and the balance ratio of the orthohydrogen and para-hydrogen is directly related to temperature. At the liquid hydrogen temperature, secondary hydrogen is the main component, and at normal temperature, normal hydrogen is the main component. Heat is released when converting from normal hydrogen to para-hydrogen. Therefore, in the cooling and liquefying process of hydrogen, not only cooling capacity for cooling is needed, but also cooling capacity needed by normal-para-hydrogen conversion is needed.
The chinese patent publication No. CN114001273a discloses a hydrogen liquefaction and hydrogen storage system, which comprises a hydrogen liquefaction system and a hydrogen storage system, wherein the hydrogen liquefaction system comprises a hydrogen source, a precooling system, a first catalytic converter and a cooling system which are sequentially communicated along the flow direction of hydrogen, the hydrogen storage system comprises a liquid hydrogen storage tank and a gas hydrogen storage tank, the liquid hydrogen storage tank can store liquid hydrogen, vaporized hydrogen in the liquid hydrogen storage tank can be stored into the gas hydrogen storage tank through a recovery pipeline, and the recovery pipeline is penetrated through the precooling system. In the system, part of vaporized hydrogen in the liquid hydrogen storage tank can be stored into the gas hydrogen storage tank through the recovery pipeline, so that the waste of the part of hydrogen is avoided, the precooling system is penetrated through the recovery pipeline, the vaporized hydrogen can cool the hydrogen to be liquefied in the precooling system, and the cold energy in the part of hydrogen is fully utilized. However, this patent does not recycle the cold energy of the vaporized hydrogen gas converted from para-hydrogen to ortho-hydrogen, and requires the use of an expander operating at the liquid hydrogen temperature, which is costly in terms of equipment and difficult to implement.
Chinese patent publication No. CN114739114a discloses a hydrogen liquefying apparatus. The hydrogen liquefying device comprises a precooling structure, a Stirling cycle structure and at least one refrigeration cycle structure; the precooling structure is provided with a first hydrogen channel, a first precooling channel and a second precooling channel, and the second precooling channel is filled with precooling agent; the refrigerating circulation structure comprises a refrigerating heat exchanger, a compressor, a cooler and an expansion valve, wherein the refrigerating heat exchanger is provided with a second hydrogen channel and a first refrigerating channel, the second hydrogen channel is connected with the first hydrogen channel, the outlet end of the first refrigerating channel, the compressor and the cooler are sequentially connected, the inlet end of the first refrigerating channel is connected with the outlet end of the first precooling channel through the expansion valve, the outlet end of the cooler is connected with the first precooling channel, and the refrigerating circulation structure is filled with refrigerant; the Stirling cycle structure is provided with a third hydrogen passage connected to the second hydrogen passage. The device can economically and efficiently convert hydrogen into liquid hydrogen, thereby more effectively transporting and storing hydrogen. However, the patent uses multi-stage mixed working medium refrigeration cycle precooling, has complex equipment, high debugging difficulty and large occupied space, performs normal-para-hydrogen conversion at the lowest temperature of the whole refrigeration cycle, has large refrigeration load and low energy efficiency, and does not perform cold recovery of liquid hydrogen evaporation gas.
Disclosure of Invention
The invention provides a hydrogen liquefying method and device for precooling by using a refrigerator, which are convenient to start and stop, simple and easy to operate and have higher energy efficiency.
A hydrogen liquefying device precooled by a refrigerator comprises a high-pressure hydrogen source, a pressure reducing valve, a first normal-para-hydrogen conversion reactor, a second normal-para-hydrogen conversion reactor, a first throttle valve, a third normal-para-hydrogen conversion reactor, a second throttle valve and a liquid hydrogen storage tank which are connected in sequence;
the first positive para-hydrogen conversion reactor, the second positive para-hydrogen conversion reactor and the third positive para-hydrogen conversion reactor are respectively connected with a first refrigerator, a second refrigerator and a third refrigerator; wherein, the first refrigerator, the second refrigerator and the third refrigerator all adopt one or more refrigerators;
the first refrigerator is used for enabling the temperature of the outlet of the first normal-para-hydrogen conversion reactor to be 70-90K; the second refrigerator is used for enabling the temperature of the outlet of the second normal-para-hydrogen conversion reactor to be 40-60K; the third refrigerator is used for enabling the temperature of the outlet of the third normal para-hydrogen conversion reactor to be 20-35K;
the first throttle valve is used for controlling the front pressure of the valve to be 6.5-12.7 MPa absolute pressure; the second throttle valve is used for controlling the front pressure of the valve to be 1.293-4.4 MPa absolute pressure.
Preferably, the first refrigerator is used for enabling the temperature of the outlet of the first normal-para-hydrogen conversion reactor to be 77K; the second refrigerator is used for enabling the temperature of the outlet of the second normal-para-hydrogen conversion reactor to be 50K; the third refrigerator is used for enabling the temperature of the outlet of the third normal-para-hydrogen conversion reactor to be 30K; the first throttle valve is used for controlling the pre-valve pressure to be 10.05MPa absolute pressure; the second throttle valve is used for controlling the pre-valve pressure to be 1.936MPa absolute pressure.
Further, the first refrigerator, the second refrigerator and the third refrigerator are Stirling refrigerators, GM refrigerators or pulse tube refrigerators, and may be one or a combination of more. Preferably, the third refrigerator is a two-stage Stirling refrigerator.
Further, the hydrogen liquefying device also comprises a first para-ortho-hydrogen conversion reactor, a second para-ortho-hydrogen conversion reactor and a third para-ortho-hydrogen conversion reactor;
the gas phase outlet of the liquid hydrogen storage tank is sequentially connected with the third para-ortho-hydrogen conversion reactor, the second para-ortho-hydrogen conversion reactor and the first para-ortho-hydrogen conversion reactor; the first para-ortho-hydrogen conversion reactor and the first ortho-para-hydrogen conversion reactor, the second para-ortho-hydrogen conversion reactor and the second ortho-para-hydrogen conversion reactor, the third para-ortho-hydrogen conversion reactor and the third ortho-hydrogen conversion reactor respectively form thermal contact or respectively form heat exchange through heat exchangers.
The first, second, third and third para-hydrogen conversion reactors are internally provided with iron-based catalysts or chromium-based catalysts.
The first positive para-hydrogen conversion reactor, the second positive para-hydrogen conversion reactor, the third positive para-hydrogen conversion reactor, the first para-positive hydrogen conversion reactor, the second para-positive hydrogen conversion reactor and the third para-positive hydrogen conversion reactor are all positioned in a vacuum insulation cold box, wherein the third positive para-hydrogen conversion reactor and the third para-positive hydrogen conversion reactor are positioned in the vacuum insulation cold box with a liquid nitrogen temperature zone cold screen.
The shell materials of the first positive para-hydrogen conversion reactor, the second positive para-hydrogen conversion reactor, the third positive para-hydrogen conversion reactor, the first para-positive hydrogen conversion reactor, the second para-positive hydrogen conversion reactor and the third para-positive hydrogen conversion reactor are 316L stainless steel, and the supporting element between the shell and the vacuum insulation cold box is made of epoxy glass fiber reinforced plastics.
The invention also provides a hydrogen liquefying method precooled by a refrigerator, which adopts the hydrogen liquefying device and comprises the following specific process flows:
(1) Outputting hydrogen from a high-pressure hydrogen source, reducing the pressure of the hydrogen by a pressure reducing valve, and then entering a first normal para-hydrogen conversion reactor; the first normal-para-hydrogen conversion reactor is cooled by a first refrigerator; the hydrogen is subjected to normal-para-hydrogen conversion while being cooled; the temperature of the outlet of the first normal-para-hydrogen conversion reactor is 77K;
(2) The hydrogen flows out of the first normal-para-hydrogen conversion reactor and then enters a second normal-para-hydrogen conversion reactor, and the second normal-para-hydrogen conversion reactor is cooled by a second refrigerator; the hydrogen is subjected to normal-para-hydrogen conversion while being cooled; the temperature of the outlet of the second normal-para-hydrogen conversion reactor is 50K;
(3) The hydrogen flows out of the second normal-para-hydrogen conversion reactor, is throttled by the first throttle valve, and then enters the third normal-para-hydrogen conversion reactor, and the third normal-para-hydrogen conversion reactor is cooled by a third refrigerator; the hydrogen is subjected to normal-para-hydrogen conversion while being cooled; the temperature of the outlet of the third normal-para-hydrogen conversion reactor is 30K; the pre-valve pressure of the first throttle valve is 10.05MPa absolute;
(4) The hydrogen gas flows out of the third normal-para-hydrogen conversion reactor, is throttled by a second throttle valve and enters a liquid hydrogen storage tank, and the pre-valve pressure of the second throttle valve is 1.936MPa absolute pressure;
(5) The gas-phase hydrogen in the liquid hydrogen storage tank flows out from a gas-phase outlet of the liquid hydrogen storage tank, enters the third para-hydrogen conversion reactor, absorbs the heat of the third para-hydrogen conversion reactor, and carries out para-hydrogen conversion while heating;
(6) The hydrogen flows out of the third para-ortho-hydrogen conversion reactor and then enters the second para-ortho-hydrogen conversion reactor to absorb the heat of the second para-ortho-hydrogen conversion reactor, and para-ortho-hydrogen conversion is carried out when the temperature of the hydrogen is raised;
(7) The hydrogen flows out of the second para-ortho-hydrogen conversion reactor and then enters the first para-ortho-hydrogen conversion reactor to absorb the heat of the first para-ortho-hydrogen conversion reactor, and para-ortho-hydrogen conversion is carried out when the temperature of the hydrogen is raised;
(8) The hydrogen exits the first para-normal hydrogen conversion reactor.
Compared with the prior art, the invention has the following beneficial effects:
1. the start and stop are convenient, and the operation is simple: the invention adopts the Stirling refrigerator, the no-load cooling time can reach 10min, and the start and stop are rapid.
2. The energy efficiency of the whole device is higher: according to the invention, the hydrogen cooling is firstly reduced to 77K from normal temperature, then reduced to 50K and finally reduced to 30K, and the optimal throttling pressure and throttling temperature are selected by matching the throttling pressure reduction of each stage of cooling; the Stirling refrigerator with the theoretical cycle efficiency capable of reaching the Kano efficiency is selected, so that the energy efficiency is high; the gas of the liquid hydrogen storage tank is utilized for carrying out heat recovery, and the cold energy converted by Zhong Zhengqing of the evaporation gas is effectively utilized.
3. Miniaturization: compared with large-scale equipment for large-scale hydrogen production, the device only needs to be provided with a plurality of Stirling refrigerators, occupies small area, is quick to start, and is particularly suitable for occasions of small-scale liquid hydrogen use.
Drawings
FIG. 1 is a process flow diagram of the present invention;
fig. 2 is a flow chart of the inventive strip heat recovery process.
Detailed Description
The invention will be described in further detail with reference to the drawings and examples, it being noted that the examples described below are intended to facilitate the understanding of the invention and are not intended to limit the invention in any way.
As shown in fig. 1, a hydrogen liquefaction apparatus precooled by a refrigerator includes a high-pressure hydrogen source 1, a pressure reducing valve 2, a first normal-para-hydrogen conversion reactor 31, a second normal-para-hydrogen conversion reactor 32, a first throttle valve 41, a third normal-para-hydrogen conversion reactor 33, a second throttle valve 42, a liquid hydrogen storage tank 5, a first refrigerator 61, a second refrigerator 62, and a third refrigerator 63.
The high-pressure hydrogen source 1, the pressure reducing valve 2, the first normal-para-hydrogen conversion reactor 31, the second normal-para-hydrogen conversion reactor 32, the first throttle valve 41, the third normal-para-hydrogen conversion reactor 33, the second throttle valve 42, and the liquid hydrogen storage tank 5 are connected in this order. The first refrigerator 61 is connected to the first normal-para-hydrogen reactor 31, the second refrigerator 62 is connected to the second normal-para-hydrogen conversion reactor 32, and the third refrigerator 63 is connected to the third normal-para-hydrogen conversion reactor 33. The first refrigerator 61, the second refrigerator 62, and the third refrigerator 63 each employ one or more refrigerators.
In the present embodiment, the first refrigerator 61 and the second refrigerator 62 are one or more single-stage stirling refrigerators, and the third refrigerator 63 is one or more two-stage stirling refrigerators.
In the present invention, the temperature of the outlet of the first normal-para-hydrogen conversion reactor is controlled to 77K, the temperature of the outlet of the second normal-para-hydrogen conversion reactor is controlled to 50K, and the temperature of the outlet of the third normal-para-hydrogen conversion reactor is controlled to 30K under the cooling action provided by the first refrigerator 61, the second refrigerator 62, and the third refrigerator 63. Meanwhile, the pre-valve pressure of the first throttle valve 41 is controlled to be 10.05MPa absolute; the pre-valve pressure of the second throttle valve 42 is controlled to be 1.936MPa absolute.
The higher the temperature, the lower the refrigeration cost, and therefore, the reasonable distribution of the heat of each part in the hydrogen liquefaction process is the key for improving the energy efficiency. 77K is the nitrogen liquefaction temperature, and the model of a more mature low-temperature refrigerator can be optimized according to the refrigerating capacity of the temperature area so as to adapt to the applications of nitrogen liquefaction, oxygen liquefaction, air separation and the like. Taking Stirling refrigerator as an example, the single machine refrigerating capacity under 77K can reach 1000W. In addition, at this temperature, the equilibrium concentration of para-hydrogen is 0.5, and more ortho-hydrogen can be converted to para-hydrogen than at normal temperature, the equilibrium concentration of para-hydrogen is 0.25. Similarly, the 50K para-hydrogen equilibrium concentration is 0.777, and the 30K is 0.97, so that compared with other existing schemes, the method has obvious energy efficiency benefit when performing all normal para-hydrogen conversion under 30K and converting by dividing the temperature bits. The invention selects the absolute pressure of 10.05MPa before the first throttle valve and the absolute pressure of 1.936MPa before the second throttle valve as the optimal throttle pressure of the hydrogen at the corresponding temperatures of 50K and 30K, and can obtain the maximum throttle refrigerating capacity.
As shown in fig. 2, a hydrogen liquefying apparatus precooled by a refrigerator further includes a first para-ortho-hydrogen shift reactor 71, a second para-ortho-hydrogen shift reactor 72, a third para-ortho-hydrogen shift reactor 73; the gas phase outlet of the liquid hydrogen tank 5 is connected to the third para-ortho-hydrogen conversion reactor 73, the second para-ortho-hydrogen conversion reactor 72, and the first para-ortho-hydrogen conversion reactor 71 in this order. The first para-ortho-hydrogen shift reactor 71 is in thermal contact with the first ortho-para-hydrogen shift reactor 31, the second para-ortho-hydrogen shift reactor 72 is in thermal contact with the second ortho-para-hydrogen shift reactor 32, the third para-ortho-hydrogen shift reactor 73 is in thermal contact with the third ortho-para-hydrogen shift reactor 33, or heat exchange is performed by a heat exchanger, respectively.
The first, second, third, and fourth normal hydrogen conversion reactors 31, 32, 33, 71, 72, and 73 have an iron-based catalyst or a chromium-based catalyst therein.
The first, second, third and fourth para-hydrogen conversion reactors 31, 32, 33, 71, 72, 73 are all in a vacuum insulation cold box and are wrapped with vacuum multi-layer insulation materials; wherein the third para-hydrogen conversion reactor 73 and the third para-hydrogen conversion reactor 33 are in a vacuum insulation cold box with a cold screen of a liquid nitrogen temperature zone.
The first, second, third and fourth para-hydrogen conversion reactors 31, 32, 33, 71, 72 and 73 are made of 316L stainless steel, and the support members between the vacuum insulation cooling boxes are made of epoxy glass fiber reinforced plastics.
As shown in fig. 2, the process flow of hydrogen liquefaction using the hydrogen liquefaction apparatus of the present invention is as follows:
(1) Hydrogen is output from a high-pressure hydrogen source 1, depressurized by a pressure reducing valve 2 and enters a first para-hydrogen conversion reactor 31; the first normal-para-hydrogen conversion reactor 31 is cooled by a first refrigerator 61; the hydrogen is subjected to normal-para-hydrogen conversion while being cooled; the temperature at the outlet of the first normal-para-hydrogen conversion reactor 31 was 77K.
(2) The hydrogen flows out of the first normal-para-hydrogen conversion reactor 31 and then enters the second normal-para-hydrogen conversion reactor 32, and the second normal-para-hydrogen conversion reactor 32 is cooled by the second refrigerator 62; the hydrogen is subjected to normal-para-hydrogen conversion while being cooled; the temperature at the outlet of the second normal-para-hydrogen conversion reactor 32 was 50K.
(3) The hydrogen gas flows out of the second normal-para-hydrogen conversion reactor 32, throttled by the first throttle valve 41 and enters the third normal-para-hydrogen conversion reactor 33, and the third normal-para-hydrogen conversion reactor 33 is cooled by the third refrigerator 63; the hydrogen is subjected to normal-para-hydrogen conversion while being cooled; the temperature at the outlet of the third normal-para-hydrogen conversion reactor 33 is 30K; the pre-valve pressure of the first throttle 41 is 10.05MPa absolute.
(4) The hydrogen gas flows out of the third normal-para-hydrogen conversion reactor 33, throttled by the second throttle valve 42, and then enters the liquid hydrogen storage tank 5, and the pre-valve pressure of the second throttle valve 42 is 1.936MPa absolute.
(5) The gas-phase hydrogen in the liquid hydrogen storage tank 5 flows out from the gas-phase outlet of the liquid hydrogen storage tank 5, enters the third para-hydrogen conversion reactor 73, absorbs the heat of the third para-hydrogen conversion reactor 73, and performs para-hydrogen conversion while the temperature is raised.
(6) The hydrogen gas flows out of the third para-ortho-hydrogen conversion reactor 73, then enters the second para-ortho-hydrogen conversion reactor 72, absorbs the heat of the second para-ortho-hydrogen conversion reactor 72, and undergoes para-ortho-hydrogen conversion while the temperature is raised.
(7) The hydrogen gas flows out of the second para-ortho-hydrogen conversion reactor 72, then enters the first para-ortho-hydrogen conversion reactor 71, absorbs the heat of the first para-ortho-hydrogen conversion reactor 71, and undergoes para-ortho-hydrogen conversion while the temperature is raised.
(8) The hydrogen gas flows out of the first para-normal hydrogen conversion reactor 71.
The foregoing embodiments have described in detail the technical solution and the advantages of the present invention, it should be understood that the foregoing embodiments are merely illustrative of the present invention and are not intended to limit the invention, and any modifications, additions and equivalents made within the scope of the principles of the present invention should be included in the scope of the invention.
Claims (7)
1. The hydrogen liquefying device precooled by the refrigerator is characterized by comprising a high-pressure hydrogen source, a pressure reducing valve, a first normal-para-hydrogen conversion reactor, a second normal-para-hydrogen conversion reactor, a first throttle valve, a third normal-para-hydrogen conversion reactor, a second throttle valve and a liquid hydrogen storage tank which are connected in sequence;
the first positive para-hydrogen conversion reactor, the second positive para-hydrogen conversion reactor and the third positive para-hydrogen conversion reactor are respectively connected with a first refrigerator, a second refrigerator and a third refrigerator; the first refrigerator, the second refrigerator and the third refrigerator are Stirling refrigerators, GM refrigerators or pulse tube refrigerators; the first refrigerator, the second refrigerator and the third refrigerator adopt one or more refrigerators;
the first refrigerator is used for enabling the temperature of the outlet of the first normal-para-hydrogen conversion reactor to be 77K; the second refrigerator is used for enabling the temperature of the outlet of the second normal-para-hydrogen conversion reactor to be 50K; the third refrigerator is used for enabling the temperature of the outlet of the third normal-para-hydrogen conversion reactor to be 30K;
the first throttle valve is used for controlling the pre-valve pressure to be 10.05MPa absolute pressure; the second throttle valve is used for controlling the pre-valve pressure to be 1.936MPa absolute pressure.
2. The hydrogen liquefaction device precooled by a refrigerator according to claim 1, wherein the third refrigerator is a two-stage stirling refrigerator.
3. The refrigerator pre-cooled hydrogen liquefaction plant of claim 1, further comprising a first para-ortho-hydrogen shift reactor, a second para-ortho-hydrogen shift reactor, and a third para-ortho-hydrogen shift reactor;
the gas phase outlet of the liquid hydrogen storage tank is sequentially connected with the third para-ortho-hydrogen conversion reactor, the second para-ortho-hydrogen conversion reactor and the first para-ortho-hydrogen conversion reactor; the first para-ortho-hydrogen conversion reactor and the first ortho-para-hydrogen conversion reactor, the second para-ortho-hydrogen conversion reactor and the second ortho-para-hydrogen conversion reactor, the third para-ortho-hydrogen conversion reactor and the third ortho-hydrogen conversion reactor respectively form thermal contact or respectively form heat exchange through heat exchangers.
4. The refrigerator precooled hydrogen liquefaction device according to claim 3, wherein an iron-based catalyst or a chromium-based catalyst is disposed in the first, second, third, first, second, and third para-hydrogen conversion reactors.
5. The refrigerator pre-cooled hydrogen liquefaction plant of claim 3, wherein the first, second, third, first, second, and third para-hydrogen conversion reactors are all in a vacuum insulated cold box, wherein the third, and third para-hydrogen conversion reactors are in a vacuum insulated cold box with a cold screen in a liquid nitrogen temperature zone.
6. The refrigerator precooled hydrogen liquefaction device according to claim 5, wherein the first, second, third, first, second, third and third para-hydrogen conversion reactors are made of 316L stainless steel, and the support member between the shell and the vacuum insulation cooling box is made of epoxy glass fiber reinforced plastic.
7. A hydrogen liquefying method precooled by a refrigerator, which is characterized in that a hydrogen liquefying device as claimed in any one of claims 1 to 6 is adopted, and the specific process flow is as follows:
(1) Outputting hydrogen from a high-pressure hydrogen source, reducing the pressure of the hydrogen by a pressure reducing valve, and then entering a first normal para-hydrogen conversion reactor; the first normal-para-hydrogen conversion reactor is cooled by a first refrigerator; the hydrogen is subjected to normal-para-hydrogen conversion while being cooled; the temperature of the outlet of the first normal-para-hydrogen conversion reactor is 77K;
(2) The hydrogen flows out of the first normal-para-hydrogen conversion reactor and then enters a second normal-para-hydrogen conversion reactor, and the second normal-para-hydrogen conversion reactor is cooled by a second refrigerator; the hydrogen is subjected to normal-para-hydrogen conversion while being cooled; the temperature of the outlet of the second normal-para-hydrogen conversion reactor is 50K;
(3) The hydrogen flows out of the second normal-para-hydrogen conversion reactor, is throttled by the first throttle valve, and then enters the third normal-para-hydrogen conversion reactor, and the third normal-para-hydrogen conversion reactor is cooled by a third refrigerator; the hydrogen is subjected to normal-para-hydrogen conversion while being cooled; the temperature of the outlet of the third normal-para-hydrogen conversion reactor is 30K; the pre-valve pressure of the first throttle valve is 10.05MPa absolute;
(4) The hydrogen gas flows out of the third normal-para-hydrogen conversion reactor, is throttled by a second throttle valve and enters a liquid hydrogen storage tank, and the pre-valve pressure of the second throttle valve is 1.936MPa absolute pressure;
(5) The gas-phase hydrogen in the liquid hydrogen storage tank flows out from a gas-phase outlet of the liquid hydrogen storage tank, enters the third para-hydrogen conversion reactor, absorbs the heat of the third para-hydrogen conversion reactor, and carries out para-hydrogen conversion while heating;
(6) The hydrogen flows out of the third para-ortho-hydrogen conversion reactor and then enters the second para-ortho-hydrogen conversion reactor to absorb the heat of the second para-ortho-hydrogen conversion reactor, and para-ortho-hydrogen conversion is carried out when the temperature of the hydrogen is raised;
(7) The hydrogen flows out of the second para-ortho-hydrogen conversion reactor and then enters the first para-ortho-hydrogen conversion reactor to absorb the heat of the first para-ortho-hydrogen conversion reactor, and para-ortho-hydrogen conversion is carried out when the temperature of the hydrogen is raised;
(8) The hydrogen exits the first para-normal hydrogen conversion reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211490038.2A CN115854651B (en) | 2022-11-25 | 2022-11-25 | Hydrogen liquefaction method and device for precooling by utilizing refrigerator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211490038.2A CN115854651B (en) | 2022-11-25 | 2022-11-25 | Hydrogen liquefaction method and device for precooling by utilizing refrigerator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115854651A CN115854651A (en) | 2023-03-28 |
| CN115854651B true CN115854651B (en) | 2023-09-15 |
Family
ID=85666460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211490038.2A Active CN115854651B (en) | 2022-11-25 | 2022-11-25 | Hydrogen liquefaction method and device for precooling by utilizing refrigerator |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115854651B (en) |
Citations (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1001938A (en) * | 1963-09-06 | 1965-08-18 | Sulzer Ag | Process for the production of liquid hydrogen |
| US3396784A (en) * | 1965-04-17 | 1968-08-13 | Sulzer Ag | Honeycomed restricted tube heat exchanger |
| JPH08159654A (en) * | 1994-12-02 | 1996-06-21 | Nippon Sanso Kk | Method and device for manufacturing liquid hydrogen |
| EP1562013A1 (en) * | 2004-02-03 | 2005-08-10 | Linde Aktiengesellschaft | Method of gas reliquefaction |
| CN102080919A (en) * | 2011-01-18 | 2011-06-01 | 四川亚联高科技股份有限公司 | Hydrogen liquefaction process |
| CN103062951A (en) * | 2013-01-25 | 2013-04-24 | 浙江大学 | Low-temperature J-T (Joule-Thomson) throttling cooler precooled by Stirling/pulse tube composite type cooler |
| CN104654648A (en) * | 2013-11-22 | 2015-05-27 | 同济大学 | Multistage Stirling type pulse tube refrigerator |
| CN108413705A (en) * | 2018-05-09 | 2018-08-17 | 上海理工大学 | Use the cascade back-heating type natural gas liquefaction system of pulse type sterlin refrigerator |
| CN108562111A (en) * | 2018-05-28 | 2018-09-21 | 张家港富瑞氢能装备有限公司 | Liquefaction of hydrogen pre-cooler |
| CN109028755A (en) * | 2018-05-28 | 2018-12-18 | 张家港富瑞氢能装备有限公司 | A kind of n- parahydrogen conversion process when producing liquid hydrogen |
| CN208332857U (en) * | 2018-05-28 | 2019-01-04 | 张家港富瑞氢能装备有限公司 | Liquefaction of hydrogen device |
| CN112361712A (en) * | 2020-10-30 | 2021-02-12 | 北京航天试验技术研究所 | Hydrogen liquefaction equipment adopting helium refrigeration cycle system |
| 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 |
| 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 |
| KR20210122922A (en) * | 2020-03-31 | 2021-10-13 | 주식회사 패리티 | Hydrogen reliquefaction system |
| CN114001273A (en) * | 2021-11-30 | 2022-02-01 | 中船动力研究院有限公司 | Hydrogen liquefaction and hydrogen storage system |
| EP3945274A1 (en) * | 2020-07-30 | 2022-02-02 | Linde Kryotechnik AG | Method for liquefying hydrogen |
| CN114034158A (en) * | 2021-07-26 | 2022-02-11 | 中国科学院理化技术研究所 | Hydrogen liquefaction device |
| CN114087845A (en) * | 2021-11-19 | 2022-02-25 | 北京大臻科技有限公司 | Liquid hydrogen production device, system and method based on parahydrogen circulation |
| CN216204684U (en) * | 2021-10-28 | 2022-04-05 | 上海交通大学 | Hydrogen liquefaction system based on refrigeration of two return circuits circulation hydrogen |
| EP4001462A1 (en) * | 2020-11-23 | 2022-05-25 | Linde GmbH | A liquid hydrogen product and method and system for producing a liquid oxygen product |
| CN114739114A (en) * | 2022-04-02 | 2022-07-12 | 北京中电丰业技术开发有限公司 | Hydrogen liquefaction device |
| CN114963688A (en) * | 2021-02-27 | 2022-08-30 | 河南中科清能科技有限公司 | Hydrogen liquefaction system adopting low-temperature turbine compression cycle |
| CN115325774A (en) * | 2022-06-23 | 2022-11-11 | 北京航天试验技术研究所 | Small-sized hydrogen liquefying device and method for segmented conversion of orthohydrogen and parahydrogen by adopting low-temperature cooler |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10612841B2 (en) * | 2016-01-20 | 2020-04-07 | Hylium Industries, Inc | Small-scale hydrogen liquefaction system equipped with cryocooler |
-
2022
- 2022-11-25 CN CN202211490038.2A patent/CN115854651B/en active Active
Patent Citations (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1001938A (en) * | 1963-09-06 | 1965-08-18 | Sulzer Ag | Process for the production of liquid hydrogen |
| US3396784A (en) * | 1965-04-17 | 1968-08-13 | Sulzer Ag | Honeycomed restricted tube heat exchanger |
| JPH08159654A (en) * | 1994-12-02 | 1996-06-21 | Nippon Sanso Kk | Method and device for manufacturing liquid hydrogen |
| EP1562013A1 (en) * | 2004-02-03 | 2005-08-10 | Linde Aktiengesellschaft | Method of gas reliquefaction |
| CN102080919A (en) * | 2011-01-18 | 2011-06-01 | 四川亚联高科技股份有限公司 | Hydrogen liquefaction process |
| CN103062951A (en) * | 2013-01-25 | 2013-04-24 | 浙江大学 | Low-temperature J-T (Joule-Thomson) throttling cooler precooled by Stirling/pulse tube composite type cooler |
| CN104654648A (en) * | 2013-11-22 | 2015-05-27 | 同济大学 | Multistage Stirling type pulse tube refrigerator |
| CN108413705A (en) * | 2018-05-09 | 2018-08-17 | 上海理工大学 | Use the cascade back-heating type natural gas liquefaction system of pulse type sterlin refrigerator |
| CN108562111A (en) * | 2018-05-28 | 2018-09-21 | 张家港富瑞氢能装备有限公司 | Liquefaction of hydrogen pre-cooler |
| CN109028755A (en) * | 2018-05-28 | 2018-12-18 | 张家港富瑞氢能装备有限公司 | A kind of n- parahydrogen conversion process when producing liquid hydrogen |
| CN208332857U (en) * | 2018-05-28 | 2019-01-04 | 张家港富瑞氢能装备有限公司 | Liquefaction of hydrogen device |
| KR20210122922A (en) * | 2020-03-31 | 2021-10-13 | 주식회사 패리티 | Hydrogen reliquefaction system |
| EP3945274A1 (en) * | 2020-07-30 | 2022-02-02 | Linde Kryotechnik AG | Method for liquefying hydrogen |
| 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 |
| 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 |
| CN112361712A (en) * | 2020-10-30 | 2021-02-12 | 北京航天试验技术研究所 | Hydrogen liquefaction equipment adopting helium refrigeration cycle system |
| EP4001462A1 (en) * | 2020-11-23 | 2022-05-25 | Linde GmbH | A liquid hydrogen product and method and system for producing a liquid oxygen product |
| CN114963688A (en) * | 2021-02-27 | 2022-08-30 | 河南中科清能科技有限公司 | Hydrogen liquefaction system adopting low-temperature turbine compression cycle |
| CN114034158A (en) * | 2021-07-26 | 2022-02-11 | 中国科学院理化技术研究所 | Hydrogen liquefaction device |
| CN216204684U (en) * | 2021-10-28 | 2022-04-05 | 上海交通大学 | Hydrogen liquefaction system based on refrigeration of two return circuits circulation hydrogen |
| CN114087845A (en) * | 2021-11-19 | 2022-02-25 | 北京大臻科技有限公司 | Liquid hydrogen production device, system and method based on parahydrogen circulation |
| CN114001273A (en) * | 2021-11-30 | 2022-02-01 | 中船动力研究院有限公司 | Hydrogen liquefaction and hydrogen storage system |
| CN114739114A (en) * | 2022-04-02 | 2022-07-12 | 北京中电丰业技术开发有限公司 | Hydrogen liquefaction device |
| CN115325774A (en) * | 2022-06-23 | 2022-11-11 | 北京航天试验技术研究所 | Small-sized hydrogen liquefying device and method for segmented conversion of orthohydrogen and parahydrogen by adopting low-temperature cooler |
Non-Patent Citations (1)
| Title |
|---|
| "基于G-M 制冷机的小型氢液化装置开发";谢福寿;夏斯琦;朱宇豪;马原;王磊;《低温工程》(第第246期期);第2-6页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115854651A (en) | 2023-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112361712B (en) | Hydrogen liquefying equipment adopting helium refrigerating circulation system | |
| Yang et al. | Optimization and analysis of a hydrogen liquefaction process integrated with the liquefied natural gas gasification and organic Rankine cycle | |
| CN114087845B (en) | Liquid hydrogen production device, system and method based on parahydrogen circulation | |
| EP4365526A1 (en) | Hydrogen liquefaction system | |
| Wang et al. | Thermodynamic analysis of low-temperature and high-pressure (cryo-compressed) hydrogen storage processes cooled by mixed-refrigerants | |
| CN114353432B (en) | Hydrogen liquefying device adopting magnetic refrigeration | |
| CN114704765B (en) | Hydrogen liquefaction and boil-off gas recondensation system based on cryocooler | |
| CN214095167U (en) | Hydrogen liquefaction equipment adopting helium refrigeration cycle system | |
| CN115451647B (en) | Hydrogen liquefaction system integrated with liquefied air energy storage system | |
| CN216620451U (en) | LNG reforming hydrogen production and LNG cold energy liquefied hydrogen integrated system | |
| CN115854651B (en) | Hydrogen liquefaction method and device for precooling by utilizing refrigerator | |
| CN203310202U (en) | Dual-mixed-refrigerant liquefying system applied to base load type natural gas liquefaction factory | |
| CN216204684U (en) | Hydrogen liquefaction system based on refrigeration of two return circuits circulation hydrogen | |
| CN103776237A (en) | Multi-refrigerator precooling in-band purification redundancy helium liquefying device | |
| CN216384787U (en) | Hydrogen liquefaction equipment and system | |
| CN114518015B (en) | Hydrogen liquefaction process adopting nitrogen turbine expansion precooling | |
| CN113701388B (en) | Multi-element mixed working medium throttling-supersonic speed two-phase expansion composite low-temperature hydrogen liquefying system | |
| CN117168087A (en) | Modular hydrogen liquefaction system | |
| CN115325774A (en) | Small-sized hydrogen liquefying device and method for segmented conversion of orthohydrogen and parahydrogen by adopting low-temperature cooler | |
| CN116972597A (en) | Hydrogen liquefying device | |
| US20240263871A1 (en) | A hydrogen or helium throttling liquefaction system using direct current flow from the cold and hot ends of the regenerative cryocoolers | |
| CN115751755B (en) | Multi-combination low-temperature propellant deep supercooling integrated system and method thereof | |
| CN221724699U (en) | Low-cost air separation device with power generation function | |
| CN216868943U (en) | Hydrogen liquefaction device | |
| CN115342596B (en) | Hydrogen open-cycle refrigeration system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |