CN112539601A - Throttling hydrogen liquefying device with precooling function - Google Patents
Throttling hydrogen liquefying device with precooling function Download PDFInfo
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- CN112539601A CN112539601A CN201910901434.1A CN201910901434A CN112539601A CN 112539601 A CN112539601 A CN 112539601A CN 201910901434 A CN201910901434 A CN 201910901434A CN 112539601 A CN112539601 A CN 112539601A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 145
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 145
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 140
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000007788 liquid Substances 0.000 claims abstract description 86
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000004781 supercooling Methods 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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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
- F25J1/0002—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
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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
- F25J1/003—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
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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
- F25J1/003—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"
- F25J1/0045—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 vaporising a liquid return stream
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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
- F25J1/0221—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 the cold stored in an external cryogenic component in an open refrigeration loop
- F25J1/0224—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 the cold stored in an external cryogenic component in an open refrigeration loop in combination with an internal quasi-closed refrigeration loop
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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
- F25J1/0243—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
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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
- 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
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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
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/42—Nitrogen
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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
- F25J2215/00—Processes characterised by the type or other details of the product stream
- F25J2215/10—Hydrogen
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- Engineering & Computer Science (AREA)
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- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Separation By Low-Temperature Treatments (AREA)
Abstract
The invention belongs to the technical field of hydrogen production equipment, and particularly relates to a throttling hydrogen liquefying device with precooling, which comprises a hydrogen liquefying route for conveying raw material hydrogen and a hydrogen circulating route for conveying circulating hydrogen, wherein the two routes respectively pass through a primary precooling section, a secondary precooling section and a liquefying section in sequence; the primary precooling section is provided with a first heat exchanger and a normal-pressure liquid nitrogen precooler, and the secondary precooling section is provided with a second heat exchanger and a negative-pressure liquid nitrogen precooler; and after being precooled by the first heat exchanger and the normal-pressure liquid nitrogen precooler, the hydrogen liquefaction route enters the second heat exchanger and the negative-pressure liquid nitrogen precooler to be continuously cooled. The hydrogen liquefying device with precooling and throttling functions provided by the invention adopts a two-stage precooling structure of a normal-pressure liquid nitrogen precooler and a negative-pressure liquid nitrogen precooler, so that the liquefying effect is better.
Description
Technical Field
The invention belongs to the technical field of hydrogen production equipment, and particularly relates to a throttling hydrogen liquefying device with precooling.
Background
The pre-cooling of the existing hydrogen liquefaction equipment usually adopts a single liquid nitrogen pre-cooling device, such as the invention patent application with the publication number of CN 108469150A. The liquefaction effect of the raw material hydrogen of a single precooled liquefaction system is poor, and the hydrogen production efficiency is influenced.
Disclosure of Invention
The invention aims to provide a precooling throttling hydrogen liquefaction device, which adopts a two-stage precooling structure of a normal-pressure liquid nitrogen precooler and a negative-pressure liquid nitrogen precooler and has a better liquefaction effect.
The purpose of the invention is realized as follows: a precooling throttling hydrogen liquefying device comprises a hydrogen liquefying route for conveying raw material hydrogen and a hydrogen circulating route for conveying circulating hydrogen, wherein the two routes respectively pass through a primary precooling section, a secondary precooling section and a liquefying section in sequence; the primary precooling section is provided with a first heat exchanger and a normal-pressure liquid nitrogen precooler, the secondary precooling section is provided with a second heat exchanger and a negative-pressure liquid nitrogen precooler, and the liquefaction section is provided with a third heat exchanger and a liquid hydrogen subcooler; the hydrogen liquefaction route is precooled by a heat exchanger I and a normal-pressure liquid nitrogen precooler, then enters a heat exchanger II and a negative-pressure liquid nitrogen precooler for continuous cooling, then enters a liquid hydrogen subcooler for supercooling by a heat exchanger III, and finally enters a gas-liquid separation tank after being throttled by a throttle valve; after being precooled by a heat exchanger I and a normal-pressure liquid nitrogen precooler, a hydrogen circulation route enters a heat exchanger II and a negative-pressure liquid nitrogen precooler to be continuously cooled; the hydrogen circulation route after the two-stage precooling is divided into two branches, the first branch is throttled by the throttle valve I and then used as backflow hydrogen to pass through the heat exchanger II and the heat exchanger I again, and finally the backflow hydrogen is converged to the hydrogen circulation route; and the second branch is cooled continuously by the third heat exchanger, and then is converged into the liquid hydrogen subcooler by the second throttle valve for subcooling the raw material hydrogen.
Furthermore, the primary precooling section is also provided with a first adsorber, a second adsorber and a first normal-secondary hydrogen conversion, and a hydrogen liquefaction route is precooled by the first heat exchanger and the normal-pressure liquid nitrogen precooler, then passes through the first adsorber to adsorb impurities, then passes through the first normal-secondary hydrogen conversion to be subjected to catalytic conversion, returns to the normal-pressure liquid nitrogen precooler to perform heat exchange again, and then enters the second heat exchanger; and the hydrogen circulation line is precooled, passes through the second adsorber to adsorb impurities and then enters the second heat exchanger.
And furthermore, the liquefaction section also comprises a second positive-secondary hydrogen conversion, the hydrogen liquefaction route passes through a third heat exchanger, enters a liquid hydrogen subcooler for supercooling, then passes through the second positive-secondary hydrogen conversion for catalytic conversion, returns to the liquid hydrogen subcooler for supercooling, and finally enters a gas-liquid separation tank after being throttled by a throttle valve.
Furthermore, the hydrogen gas gasified in the gas-liquid separation tank and the liquid hydrogen subcooler is converged into the hydrogen circulation route through the third heat exchanger, the second heat exchanger and the first heat exchanger.
Furthermore, the first adsorber and the second adsorber are molecular sieve adsorbers.
Further, an atmospheric pipeline of the atmospheric liquid nitrogen precooler is communicated with the atmosphere after passing through the first heat exchanger; and a negative pressure pipeline of the negative pressure liquid nitrogen precooler is connected with a vacuum pump after passing through the heat exchanger II and the heat exchanger I.
Further, the first and second adsorbers are shown as operating in pairs, one for purging and the other for regeneration or on standby.
Furthermore, the hydrogen circulation line is sequentially pressurized by a first compressor and a second compressor, the first compressor is connected with a circulating hydrogen supplementing port, the first branch is pressurized by the second compressor and then converged into the hydrogen circulation line, and the hydrogen gasified in the gas-liquid separation tank and the liquid hydrogen subcooler is finally pressurized by the first compressor and the second compressor and then converged into the hydrogen circulation line.
Compared with the prior art, the invention has the outstanding and beneficial technical effects that: the liquefaction device carries out two-stage precooling firstly, then carries out liquefaction again, guarantees the hydrogen liquefaction effect. And realizing a cooling and purifying step through a molecular sieve adsorber in a precooling stage to remove impurities (carbon monoxide, carbon dioxide, methane, inert gases and the like); two times of catalytic conversion are carried out in the pre-cooling section and the liquefaction section to convert the ortho-hydrogen into the para-hydrogen, thereby reducing the irreversibility of the process and enhancing the thermal efficiency.
Drawings
FIG. 1 is an overall schematic diagram of a hydrogen liquefaction plant with precooling throttling according to an embodiment of the invention.
FIG. 2 is a hydrogen liquefaction scheme in an example of the present invention.
FIG. 3 is a hydrogen circulation route diagram in an example of the present invention.
Reference numerals: e1, a first heat exchanger; e2, a second heat exchanger; e3, heat exchanger III; e4, a normal-pressure liquid nitrogen precooler; e5, a negative pressure liquid nitrogen precooler; e6, a liquid hydrogen subcooler; a1, adsorber one; a2 and an absorber II; k1, para-hydrogen conversion one; k2, para-hydrogen conversion II; v1, a gas-liquid separation tank; v2, a liquid hydrogen storage tank; j1, a first throttle valve; j2, a second throttle valve; j3, throttle valve III; y1, compressor one; y2 and a second compressor.
Detailed Description
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
A hydrogen liquefying device with precooling and throttling functions is shown in figure 1 and comprises a hydrogen liquefying route for conveying raw material hydrogen and a hydrogen circulating route for conveying circulating hydrogen, wherein the two routes respectively sequentially pass through a primary precooling section, a secondary precooling section and a liquefying section.
The primary precooling section is provided with a heat exchanger I E1, an atmospheric liquid nitrogen precooler E4, an adsorber I A1 and an adsorber II A2 for adsorbing impurities in hydrogen, the normal-secondary hydrogen filled with a catalyst is converted into K1, the atmospheric liquid nitrogen precooler E4 is communicated with the atmosphere through an atmospheric pipeline, and the atmospheric pipeline passes through the heat exchanger I E1. Among them, in order to improve and ensure the conversion efficiency of orthohydrogen to parahydrogen, more than two orthohydrogen-to-parahydrogen-K1 may be connected in series.
The secondary pre-cooling section is provided with a second heat exchanger E2 and a negative pressure liquid nitrogen pre-cooler E5, the negative pressure liquid nitrogen pre-cooler E5 is connected with a vacuum pump through a negative pressure pipeline, so that the inside of the negative pressure liquid nitrogen pre-cooler E5 is kept in vacuum or negative pressure, and the negative pressure pipeline passes through the second heat exchanger E2 and the first heat exchanger E1.
The liquefaction section is provided with a heat exchanger III E3, a liquid hydrogen subcooler E6, an ortho-para hydrogen conversion II K2 for carrying out secondary catalytic conversion on the raw material hydrogen, and a gas-liquid separation tank V1 for carrying out gas-liquid separation. Among them, in order to improve and ensure the conversion efficiency of orthohydrogen to parahydrogen, two or more of orthoparahydrogen-converted dik 2 may be connected in series.
With reference to fig. 1 and 2, the pipeline layout of the hydrogen liquefaction route is specifically as follows: raw material hydrogen → first heat exchanger E1 → atmospheric liquid nitrogen precooler E4 → first adsorber A1 → first conversion of normal and secondary hydrogen K1 → atmospheric liquid nitrogen precooler E4 → second heat exchanger E2 → negative pressure liquid nitrogen precooler E5 → third heat exchanger E3 → liquid hydrogen subcooler E6 → second conversion of normal and secondary hydrogen K2 → liquid hydrogen subcooler E63 6 → third throttle J3 → gas-liquid separation tank V1 → liquid hydrogen storage tank V2
With reference to fig. 1 and 3, the layout of the hydrogen circulation lines is specifically: circulating hydrogen → compressor one Y1 → compressor two Y2 → heat exchanger one E1 → atmospheric liquid nitrogen precooler E4 → adsorber two A2 → heat exchanger two E2 → negative pressure liquid nitrogen precooler E5 → two branches
Wherein the first branch → the throttle valve I J1 → the heat exchanger II E2 → the heat exchanger I E1 → the compressor II Y2
Wherein: second branch → heat exchanger III E3 → liquid hydrogen subcooler E6
Hydrogen gas vaporized in the liquid hydrogen subcooler E6 → heat exchanger three E3 → heat exchanger two E2 → heat exchanger one E1 → compressor one Y1 → compressor two Y2
Gasified hydrogen in the gas-liquid separation tank V1 → heat exchanger E5 → heat exchanger E3 → heat exchanger E1 → circulating hydrogen
In summary, the liquefaction apparatus in this embodiment mainly includes two cooling steps: two-stage precooling is carried out, and then liquefaction is carried out. In the pre-cooling stage there is a cooling purge step to remove impurities (carbon monoxide, carbon dioxide, methane, inerts, etc.) that might otherwise freeze at the temperature of the hydrogen liquefier and clog the heat exchangers, and carbon monoxide and nitrogen must be removed before entering the liquefaction stage. The removal of carbon monoxide and nitrogen is realized by adsorption through an adsorber arranged in a primary pre-cooling area.
To achieve a satisfactory level of purification, we use molecular sieves as adsorbents. Adsorber one a1 and adsorber two a2 both run side-by-side using two vessels: one of which treats the hydrogen to be purified and the other of which is regenerated or on standby. The switching period was designed to be approximately 8 days of adsorption and 1.5 days of regeneration. According to the set sequence, the switching of the adsorbers is realized through a group of valves, and the stable operation of hydrogen liquefaction is kept.
A first-stage precooling stage: the raw material hydrogen and the circulating hydrogen are firstly cooled in a first heat exchanger E1 together with the nitrogen and the hydrogen which flow back, and then enter an atmospheric liquid nitrogen precooler E4 to be precooled to about 80K.
A secondary precooling stage: the hydrogen gas after primary precooling enters a negative pressure liquid nitrogen precooler E5 in a vacuum or negative pressure state, and is continuously cooled to about 65K-75K by liquid nitrogen. The circulating hydrogen after the secondary precooling is divided into 2 strands, and one strand of the circulating hydrogen is throttled by a throttle valve I J1 and then is used as backflow hydrogen to cool the forward flow hydrogen; and the other strand and the raw material hydrogen enter a heat exchanger of the low-temperature liquefaction section to be continuously cooled.
A liquefaction section: and (3) cooling the 65K-75K hydrogen to be close to 20K-25K for liquefaction through a liquefaction section. And the cooled circulating hydrogen is throttled to normal pressure by a throttling valve II J2 and enters a liquid hydrogen subcooler E6, and the raw material hydrogen is liquefied and subcooled. The liquefied raw material hydrogen is throttled to normal pressure and enters a gas-liquid separation tank V1, and a liquid hydrogen product is provided for a user through the gas-liquid separation tank V1; the hydrogen gasified by the gas-liquid separation tank V1 is converged with the normal-pressure circulating hydrogen returned by the liquid hydrogen subcooler E6, is subjected to heat exchange with the positive-flow hydrogen through the heat exchanger and reheated to normal temperature, and enters the inlet of the compressor Y1 again.
Catalytic conversion of para-hydrogen: for hydrogen liquefaction to occur, it is important to convert ortho-hydrogen to para-hydrogen. These two forms of hydrogen coexist and are distinguished by their electron spin directions. The ratio of these two hydrogen gases has corresponding equilibrium values at various temperatures. The equilibrium ratio of the positive and secondary hydrogen gases is about 75/25 at normal temperature and about 2/98 at low temperature. At low temperatures, orthohydrogen is in an unstable state and gradually becomes more stable parahydrogen, releasing heat and causing the hydrogen gas to vaporize in the storage vessel. Since normal hydrogen accounts for 75% of normal temperature hydrogen, its endothermic vaporization greatly increases the storage difficulty and cost of liquid hydrogen. This conversion process is relatively slow and therefore requires a catalyst to accelerate and some additional cold to compensate for the heat released by the exothermic reaction. On the process pipeline, a first-stage precooling section heat exchanger and a liquefaction section heat exchanger or a special container are filled with a catalyst for carrying out catalytic conversion twice. Thereby dispersing the heat of conversion throughout the flow path, thereby reducing flow irreversibility and thereby enhancing thermal efficiency.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and substitutions can be made without departing from the technical principle of the present invention, and these modifications and substitutions should also be regarded as the protection scope of the present invention.
Claims (8)
1. The utility model provides a take precooling throttle hydrogen liquefying plant which characterized in that:
the hydrogen liquefaction line for conveying the raw material hydrogen and the hydrogen circulation line for conveying the circulating hydrogen respectively pass through a primary precooling section, a secondary precooling section and a liquefaction section in sequence;
the primary precooling section is provided with a heat exchanger I (E1) and a normal-pressure liquid nitrogen precooler (E4), the secondary precooling section is provided with a heat exchanger II (E2) and a negative-pressure liquid nitrogen precooler (E5), and the liquefaction section is provided with a heat exchanger III (E3) and a liquid hydrogen subcooler (E6);
the hydrogen liquefaction route is precooled by a first heat exchanger (E1) and a normal-pressure liquid nitrogen precooler (E4), then enters a second heat exchanger (E2) and a negative-pressure liquid nitrogen precooler (E5) for continuous cooling, then passes through a third heat exchanger (E3), enters a liquid hydrogen subcooler (E6) for subcooling, finally is throttled by a third throttle valve (J3) and then enters a gas-liquid separation tank (V1);
after being precooled by a first heat exchanger (E1) and a normal-pressure liquid nitrogen precooler (E4), the hydrogen circulation route enters a second heat exchanger (E2) and a negative-pressure liquid nitrogen precooler (E5) to be continuously cooled; the hydrogen circulation route after the two-stage precooling is divided into two branches, the first branch is throttled by a throttle valve I (J1) and then used as the return hydrogen to pass through a heat exchanger II (E2) and a heat exchanger I (E1) again, and finally the return hydrogen is converged to the hydrogen circulation route; and the second branch is continuously cooled by a third heat exchanger (E3), passes through a second throttle valve (J2) and then is converged into a liquid hydrogen subcooler (E6) for subcooling the raw material hydrogen.
2. The pre-cooled throttling hydrogen liquefaction device according to claim 1, wherein: the primary pre-cooling section is further provided with a first adsorber (A1), a second adsorber (A2) and a first normal-secondary hydrogen conversion (K1), a hydrogen liquefaction route is pre-cooled through a first heat exchanger (E1) and an atmospheric liquid nitrogen pre-cooler (E4), impurities are adsorbed through the first adsorber (A1), catalytic conversion is carried out through the first normal-secondary hydrogen conversion (K1), the obtained product returns to the atmospheric liquid nitrogen pre-cooler (E4) to be subjected to heat exchange again, and then the obtained product enters a second heat exchanger (E2); and after precooling, the hydrogen circulation line passes through the second adsorber (A2) to adsorb impurities and then enters the second heat exchanger (E2).
3. The pre-cooling throttling hydrogen liquefying apparatus according to claim 1 or 2, wherein: the liquefaction section also comprises a secondary-positive hydrogen conversion unit II (K2), the hydrogen liquefaction route passes through a heat exchanger III (E3), enters a liquid hydrogen subcooler (E6) for subcooling, then passes through the secondary-positive hydrogen conversion unit II (K2) for catalytic conversion, returns to the liquid hydrogen subcooler (E6) for subcooling, finally passes through a throttle valve III (J3) for throttling, and then enters a gas-liquid separation tank (V1).
4. The pre-cooled throttling hydrogen liquefaction device according to claim 1, wherein: and the hydrogen gas gasified in the gas-liquid separation tank (V1) and the liquid hydrogen subcooler (E6) is converged into a hydrogen circulation route through a third heat exchanger (E3), a second heat exchanger (E2) and a first heat exchanger (E1).
5. The pre-cooling throttling hydrogen liquefying device according to claim 2, wherein: the first adsorber (A1) and the second adsorber (A2) are molecular sieve adsorbers.
6. The pre-cooled throttling hydrogen liquefaction device according to claim 1, wherein: an atmospheric pipeline of the atmospheric liquid nitrogen precooler (E4) is communicated with the atmosphere after passing through a first heat exchanger (E1); and a negative pressure pipeline of the negative pressure liquid nitrogen precooler (E5) is connected with a vacuum pump after passing through a second heat exchanger (E2) and a first heat exchanger (E1).
7. The pre-cooling throttling hydrogen liquefying device according to claim 2, wherein: adsorber one (a1) and adsorber two (a2) are shown operating in pairs, one for purging and the other for regeneration or stand-by.
8. The pre-cooled throttling hydrogen liquefaction device according to claim 4, wherein: the hydrogen circulation line is sequentially pressurized by a first compressor (Y1) and a second compressor (Y2), the first compressor (Y1) is connected with a circulating hydrogen supplementing port, the first branch is pressurized by the second compressor (Y2) and then converged into the hydrogen circulation line, and the gasified hydrogen in the gas-liquid separation tank (V1) and the liquid hydrogen subcooler (E6) is finally pressurized by the first compressor (Y1) and the second compressor (Y2) and then converged into the hydrogen circulation line.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113446815A (en) * | 2021-09-01 | 2021-09-28 | 杭州制氧机集团股份有限公司 | Hydrogen liquefaction equipment adopting mixed refrigeration and using method thereof |
| 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 |
| CN114322451A (en) * | 2021-12-20 | 2022-04-12 | 江苏国富氢能技术装备股份有限公司 | Hydrogen liquefaction device for hydrogen production |
| CN115264380A (en) * | 2022-05-26 | 2022-11-01 | 合肥通用机械研究院有限公司 | Liquid hydrogen station with hidden high-pressure precooling/cold accumulation unit and operation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113446815A (en) * | 2021-09-01 | 2021-09-28 | 杭州制氧机集团股份有限公司 | Hydrogen liquefaction equipment adopting mixed refrigeration and using method thereof |
| 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 |
| CN114322451A (en) * | 2021-12-20 | 2022-04-12 | 江苏国富氢能技术装备股份有限公司 | Hydrogen liquefaction device for hydrogen production |
| CN114322451B (en) * | 2021-12-20 | 2024-04-30 | 江苏国富氢能技术装备股份有限公司 | Hydrogen liquefying device for hydrogen production |
| CN115264380A (en) * | 2022-05-26 | 2022-11-01 | 合肥通用机械研究院有限公司 | Liquid hydrogen station with hidden high-pressure precooling/cold accumulation unit and operation method |
| CN115264380B (en) * | 2022-05-26 | 2024-01-26 | 合肥通用机械研究院有限公司 | Liquid hydrogen station with hidden high-pressure precooling/cold accumulation unit and operation method |
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