EP3163235A1 - Nouveau procédé en cascade de refroidissement et de liquéfaction d'hydrogène à grande échelle - Google Patents

Nouveau procédé en cascade de refroidissement et de liquéfaction d'hydrogène à grande échelle Download PDF

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Publication number
EP3163235A1
EP3163235A1 EP15003068.2A EP15003068A EP3163235A1 EP 3163235 A1 EP3163235 A1 EP 3163235A1 EP 15003068 A EP15003068 A EP 15003068A EP 3163235 A1 EP3163235 A1 EP 3163235A1
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EP
European Patent Office
Prior art keywords
stream
expanded
refrigerant
hydrogen
feed gas
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.)
Withdrawn
Application number
EP15003068.2A
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German (de)
English (en)
Inventor
Lutz Decker
Harald Klein
Umberto Cardella
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linde GmbH
Technische Universitaet Muenchen
Original Assignee
Linde GmbH
Technische Universitaet Muenchen
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Linde GmbH, Technische Universitaet Muenchen filed Critical Linde GmbH
Priority to EP15003068.2A priority Critical patent/EP3163235A1/fr
Priority to PCT/EP2016/075205 priority patent/WO2017072018A1/fr
Priority to EP16784202.0A priority patent/EP3368844A1/fr
Publication of EP3163235A1 publication Critical patent/EP3163235A1/fr
Withdrawn legal-status Critical Current

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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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    • 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"
    • F25J1/0042—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 liquid expansion with extraction of work
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    • 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
    • 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.
    • F25J1/0291—Refrigerant compression by combined gas compression and liquid pumping
    • 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.
    • F25J1/0292—Refrigerant compression by cold or cryogenic suction of the refrigerant 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
    • F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0294—Multiple compressor casings/strings in parallel, e.g. split arrangement
    • 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
    • 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
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/08—Cold compressor, i.e. suction of the gas at cryogenic temperature and generally without afterstage-cooler
    • 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
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/30—Compression of 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
    • F25J2240/40—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
    • F25J2270/14—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

Definitions

  • the present invention relates to a method for liquefying hydrogen in large-scale.
  • the method comprises the steps of: providing a feed gas stream comprising hydrogen, wherein the feed gas stream is characterized by an initial temperature and a pressure of at least 15 bar(a), precooling the feed gas stream to an intermediate temperature in a precooling step yielding a precooled feed gas stream, wherein particularly the intermediate temperature is in the range of 70 K to 150 K, and cooling the precooled feed gas stream to a temperature below the critical temperature of hydrogen, particularly below 24 K, more particular below 21.15 K, yielding a liquid product stream comprising hydrogen.
  • the known technology of hydrogen liquefaction is primarily based on process technology for small-scale industrial hydrogen liquefaction plants with a production capacity typically up to 10 tpd (tons per day) LH2 (for example, the Linde Leuna plant, a hydrogen liquefier with 5 tpd capacity).
  • the hydrogen feed is produced outside the battery limit of the plant from a methane steam reformer or an electrolyser and fed to the liquefaction plant with a typical feed pressure between 15 bar(a) and 30 bar(a).
  • the evaporation of a liquid nitrogen stream at typically 78 K, the nitrogen saturation temperature for 1.1 bar(a) is used to precool the hydrogen feed from ambient temperature to about 80 K in an aluminum-brazed plate-fin heat exchanger.
  • the hydrogen feed is conducted through a purifier to remove residual impurities, mainly nitrogen, in an absorber vessel.
  • the hydrogen feed is allowed to pass through additional plate-fin heat exchanger passages filled with catalyst, typically hydrous ferric oxide, for the ortho to para hydrogen conversion.
  • the feed is then again cooled down to about 80 K by the means of liquid nitrogen.
  • the final cooling and liquefaction of the hydrogen feed is provided by the means of a closed hydrogen Claude loop with typically between one and three cooling strings with turbines expanding the gas from a high pressure (HP) to medium pressure (MP) to provide refrigeration at different temperature levels.
  • HP high pressure
  • MP medium pressure
  • a third or the coldest high-pressure refrigeration stream is expanded in a Joule-Thomson valve to a low pressure level (LP) as two-phase gas-liquid stream at the cold end to provide cooling at temperatures below the liquid hydrogen feed stream.
  • the hydrogen feed stream is expanded in a Joule-Thomson valve from supercritical pressure to the desired storage pressure e.g. 1.1 bar(a) (20.5 K), before being stored in a storage tank.
  • the entire refrigeration and liquefaction process is installed within one vacuum insulated cold box.
  • One, two or more hydrogen compressors, particularly reciprocating pistons, are employed at ambient temperature to compress the respective LP and MP hydrogen refrigerant to the HP level before entering the cold-box and being precooled by the warming LP and MP hydrogen in a closed cycle.
  • an open nitrogen stream is used as additional precooling, wherein hydrogen is expanded into the two-phase region with a dense-fluid expander (piston).
  • the hydrogen feed is only cooled via a closed neon cycle.
  • Ortho-para catalytic conversion is carried out as described above and additionally in two isothermal converters within a liquid nitrogen and a liquid neon bath, respectively.
  • the final expansion of the hydrogen feed results in a two-phase fluid.
  • the saturated liquid product is separated in a phase separator while the produced flash gas is warmed up to ambient temperature and compressed together with the feed hydrogen.
  • Turbo-compressors allow for higher volumetric suction flows. However, at suction temperatures close to ambient, stage pressure ratios for light gases such as helium and hydrogen are low for blade tip speeds that are feasible today. Multi-stage turbo-compressors are designed with up to 6 or 8 stages. Thus, the pressure ratios in cold refrigeration cycles containing pure helium or hydrogen require turbo-compressors with an unfavourable or even not viable high number of compressor stages.
  • turbo-expanders with high isentropic efficiencies which are designed with energy recovery, e.g. via turbo-generators or booster compressors, are crucial to increase the overall process efficiency.
  • energy and cost efficient turbo-expanders are currently limited by feasible rotational speeds and available frame-sizes.
  • known mixed-refrigerant cycles for natural gas or hydrogen liquefaction applications can increase precooling efficiency but are typically designed for relatively high precooling temperatures ( ⁇ 120 K), thus shifting the generation of the required cooling duty to the colder, more inefficient refrigeration cycle in a hydrogen liquefier.
  • common refrigerant mixtures have been designed with a high number of fluid components e.g. 5 to 7. These have to be regularly imported to the hydrogen liquefier plant for inventory make-up and require additional storage tanks for each component, thus increasing operational complexity and handling.
  • refrigeration fluids providing cooling down to temperatures below approximately 60 K and close to the liquid hydrogen product are limited to hydrogen, helium and neon as well as to mixtures of these. Both normal boiling point (27.1 K) and melting point (24.6 K) of neon are higher than the normal boiling point of hydrogen (20.3 K). Hence, in order to avoid freeze-out within the process equipment, cold refrigeration cycles with pure neon or mixtures with neon are not designed to reach cooling temperatures close or lower than 24.6 K.
  • the precooled feed gas stream is cooled to a first temperature in a first cooling step, particularly in a first cooling zone, by a first closed cooling cycle with a first refrigerant stream consisting of or comprising neon and/or hydrogen, wherein the first refrigerant stream is expanded, thereby producing cold
  • the cooled feed gas stream is further cooled from the first temperature to a temperature below the critical temperature of hydrogen, particularly below 24 K, more particular below 21.15 K, in a second cooling step, particularly in a second cooling zone, by a second closed cooling cycle with a second refrigerant stream comprising or consisting of hydrogen and/or helium, wherein the second refrigerant stream is expanded, thereby producing cold.
  • the method of the invention enables a thermodynamically and economically efficient liquefaction of hydrogen on a large-scale, with production capacities of up to 10 to 20 times above conventional liquefiers e.g. 150 tpd per liquefier train.
  • Specific energy consumption, and thus operational costs, is significantly reduced compared to prior concepts described above, while utilizing process equipment and frame sizes that are commercially available today.
  • the method of the invention requires significantly reduced rotating equipment count and a lower number of imported refrigerant fluids, thus reducing the plant operational complexity and capital costs, as well as increasing plant availability and maintainability.
  • the feed gas stream is characterized by hydrogen concentration of at least 99.99 Vol.%
  • ortho hydrogen comprised within the feed gas stream (about 75%) is converted to higher para hydrogen fractions preferably before liquefaction of the feed gas stream to avoid that the exothermic ortho to para reaction takes place in the liquid product possibly resulting in an undesired partial vaporization of the liquid hydrogen product during storage and transport.
  • the feed gas stream is precooled to the intermediate temperature in a precooling zone.
  • the first refrigerant stream and/or the second refrigerant stream is precooled to the intermediate temperature, particularly in the above-mentioned precooling zone.
  • the first temperature lies in the range of 24.6 K to 44.5 K, particularly in the range of 26 K to 33 K.
  • the first refrigerant stream comprises neon in the range of 0 mol. % to 100 mol. %. In certain embodiments, the first refrigerant stream comprises neon in the range of 80 mol. % to 100 mol. %. In certain embodiments, the first refrigerant stream consists of neon. In certain embodiments, the first refrigerant stream comprises or consists of 50 mol. % to 100 mol. % neon, and optionally hydrogen, particularly in a concentration up to 50 mol. %. In certain embodiments, the first refrigerant stream comprises or consists of 20 mol. % to 100 mol. % neon, and optionally hydrogen, particularly up to 80 mol. %.
  • the first refrigerant stream comprises 30 mol. % to 70 mol. % neon, and optionally hydrogen, particularly up to 70 mol. %. In certain embodiments, the first refrigerant stream consists of 30 mol. % to 70 mol. % neon and hydrogen. In certain embodiments, the first refrigerant stream comprises 40 mol. % to 60 mol. % neon, and optionally hydrogen, particularly up to 60 mol. %. In certain embodiments, the first refrigerant stream consists of 40 mol. % to 60 mol. % neon and hydrogen. In certain embodiments, the first refrigerant stream comprises 80 mol. % to 100 mol. % hydrogen and neon, particularly up to 20 mol. %.
  • the first refrigerant stream comprises 80 mol. % to 90 mol. % hydrogen and 10 mol. % to 20 mol. % neon. In certain embodiments, the first refrigerant stream consists of 80 mol. % to 90 mol. % hydrogen and neon.
  • the intermediate temperature is in the range of 70 K to 120 K. In certain embodiments, the intermediate temperature is in the range of 80 K to 120 K. In certain embodiments, the intermediate temperature is in the range of 85 K to 120 K. In certain embodiments, the intermediate is in the range of 90 K to 120 K. In certain embodiments, the intermediate temperature is around 100 K. In certain embodiments, the intermediate temperature is in the range of 120 K to 140 K.
  • the precooling zone is located within an at least one precooling heat exchanger or a precooling block of a heat exchanger. In certain embodiments, the at least one precooling heat exchanger is a plate fin heat exchanger.
  • the feed gas stream is precooled to an intermediate temperature in the range of 80 K to 120 K, particularly 100 K, yielding the precooled feed gas stream, and the precooled feed gas stream is brought into contact with a catalyst being able to catalyse the ortho to para conversion of hydrogen, particularly before the first cooling step.
  • the catalyst is or comprises hydrous ferric oxide.
  • the catalyst is arranged within a heat exchanger, particularly within the at least one precooling heat exchanger or the precooling block, in which the feed gas stream is precooled.
  • the feed gas stream is precooled in the precooling step by a closed precooling cycle with a third refrigerant stream, wherein the third refrigerant stream is expanded, thereby producing cold, and the third refrigerant stream comprises or consists of nitrogen, a mixture of C 1 -C 5 hydrocarbons, or a mixture of nitrogen and at least one C 1 -C 5 hydrocarbons.
  • the third refrigerant stream consist of a liquid nitrogen stream, wherein the liquid nitrogen stream is expanded or evaporated, thereby cooled, particularly to a temperature in the range of 70 K to 80K, and the cool expanded or evaporated nitrogen stream and the feed gas stream, the first refrigerant stream and/or the second refrigerant stream are guided such that heat can indirectly be transferred between the expanded or evaporated nitrogen stream and any one or all of the aforementioned streams, thereby particularly cooling the feed gas stream, the first refrigerant stream and/or the second refrigerant stream, particularly in the above mentioned at least one precooling heat exchanger or precooling block.
  • the expanded or evaporated nitrogen refrigerant stream is released into the environment after cooling the above-mentioned stream.
  • the liquid nitrogen stream is expanded or evaporated, particularly in a turbo expander and a throttle valve, and compressed in a closed cycle.
  • the expanded or evaporated nitrogen stream is guided against the feed gas stream and/or the first refrigerant stream in the precooling zone.
  • the third refrigerant stream consists of a liquid natural gas stream, wherein the liquid natural gas stream is expanded or evaporated, thereby cooled, particularly to a temperature in the range of 110 K to 150 K, and the expanded or evaporated natural gas stream and the feed gas stream, the first refrigerant stream and/or the second refrigerant stream are guided such that heat can indirectly be transferred between the expanded natural gas stream and any one or all of the aforementioned streams, thereby particularly cooling the feed gas stream, the first refrigerant stream and/or the second refrigerant stream, particularly in the above mentioned at least one precooling heat exchanger or precooling block.
  • the expanded or evaporated natural gas stream can be guided into a supply line or to a process consuming natural gas.
  • the expanded or evaporated natural gas stream is guided against the feed gas stream and/or the first refrigerant stream in the precooling zone.
  • the C 1 -C 5 hydrocarbon is selected from the group comprised of methane, ethane, ethylene, n-butane, isobutane, propane, propylene, n-pentane, isopentane and 1-butene.
  • the third refrigerant is a single-mixed refrigerant comprising or consisting of four components, wherein a first component is nitrogen, or optionally nitrogen in a mixture with neon and/or argon, a second component is methane, a third component is ethane or ethylene, and a fourth component is n-butane, isobutane, 1-butene, propane, propylene, n-pentane or isopentane.
  • the third refrigerant comprises a fifth component, wherein the fifth component is n-butane, isobutane, 1-butene, propane, propylene, n-pentane or isopentane provided the fifth component is different from the fourth component, e.g. the fifth component can be n-butane, isobutane, propane, propylene or n-pentane if the fourth component is isopentane.
  • the third refrigerant comprises a sixth component, wherein the sixth component is n-butane, isobutane, propane, propylene, n-pentane or isopentane provided the sixth component differs from the fourth component and fifth component, e.g. the sixth component can be isobutane, propane, propylene or n-pentane if the fourth component is isopentane and the fifth component is n-butane.
  • the third component is ethane. Such composition of the third refrigerant is particularly useful if the intermediate temperature to be achieved in the precooling step is below or equal to 100 K. In certain embodiments, third component is ethylene. Such composition of the third refrigerant is particularly useful if the intermediate temperature to be achieved in the precooling step is above 100 K.
  • the fourth component and optionally the fifth component is, isobutane, 1-butene, propane, propylene or isopentane, provided that the fifth component is different from the fourth component.
  • Such composition of the third refrigerant is particularly useful if the intermediate temperature to be achieved in the precooling step is below 100 K.
  • the first component is nitrogen in a mixture with neon and/or argon
  • a second component is methane
  • a third component is ethane or ethylene
  • a fourth component is n-butane, isobutane, 1-butene propane, propylene, n-pentane or isopentane.
  • Such composition of the third refrigerant is particularly useful if the intermediate temperature to be achieved in the precooling step is below 100 K
  • the third refrigerant comprises 18 mol. % to 23 mol. % nitrogen, and/or 27 mol. % to 29 mol. % methane, and/or 24 mol. % to 37 mol. % ethane, and/or 18 mol. % to 24 mol. % isopentane or isobutane, provided that the sum of the concentrations of the above-mentioned components does not exceed 100 mol %.
  • Such composition of the third refrigerant is particularly useful if the intermediate temperature to be achieved in the precooling step is around 100 K.
  • the third refrigerant consists of 18 mol. % nitrogen, 27 mol. % methane, 37 mol. % ethane and 18 mol. % isopentane.
  • Such composition of the third refrigerant is particularly useful if the intermediate temperature to be achieved in the precooling step is around 100 K.
  • the third refrigerant consists of 23 mol. % nitrogen, 29 mol. % methane, 24 mol. % ethane, and to 24 mol. % isobutane.
  • Such composition of the third refrigerant stream is particularly useful if the intermediate temperature to be achieved in the precooling step is around 100 K.
  • residual impurities, particularly nitrogen, and/or oxygen are removed from the precooled feed gas stream before contacting the precooled feed stream with the above-mentioned catalyst and/or before the intermediate temperature is below 80 K, particularly by means of an adsorber.
  • an adiabatic or isothermal ortho-para catalytic converter vessel is placed directly downstream or within the adsorber, wherein normal-hydrogen comprised within the feed gas stream is converted in a first step to a para-content near the equilibrium at the intermediate temperature, e.g. 39 % at 100 K.
  • the first cooling cycle comprises the steps of:
  • directly heat transfer in the context of the present invention refers to the heat transfer between at least two fluid streams that are spatially separated such that the at least two fluid streams do not merge or mix but are in thermal contact, e.g. two fluid streams are guided through two cavities, for example of a plate heat exchanger, wherein the cavities are separated from each other by a wall or plate, and both streams do not mix, but heat can be transferred via the wall or the plate.
  • the expanded second partial stream is compressed to a pressure close or equal to the first intermediate pressure, and the partially expanded first partial stream is guided into or unified with the second partial stream after compression to the pressure close or equal to the first intermediate pressure yielding a partially expanded first refrigerant stream, which is then particularly compressed to the first pressure yielding the first refrigerant stream.
  • a first pressure is close to a second pressure if both pressures do not differ more the 10 % or not more than 5 bar(a), 4 bar(a), 3 bar(a), 2 bar(a) or 1 bar(a) from each other.
  • the first refrigerant stream is precooled by the third refrigerant stream.
  • the expanded first refrigerant stream and the precooled feed gas stream are guided such that heat can indirectly be transferred between the streams, thereby particularly cooling the precooled feed gas stream, particularly in the first cooling zone.
  • the expanded first refrigerant and the second partial stream and/or the first refrigerant stream are guided such that heat can be transferred between the expanded first refrigerant stream and the second partial stream and/or the first refrigerant stream, thereby particularly cooling the second partial stream and/or the first refrigerant stream, particularly in the first cooling zone.
  • the partially expanded first partial stream or the expanded first partial stream within the expanded first refrigerant stream provides additional cooling duty to cool the aforementioned streams.
  • the expanded first refrigerant stream is guided against the second partial stream, the precooled feed gas stream and/or the first refrigerant stream in the first cooling zone such that heat can indirectly be transferred between the expanded first refrigerant stream and the precooled feed gas stream and/or the first refrigerant stream.
  • the first expansion device comprises at least one turbo-expander. In certain embodiments, the first expansion device comprises at least two turbo-expanders, wherein particularly the first partial stream is expanded in a first turbo-expander to the first intermediate pressure yielding the partially expanded first partial stream, and the partially expanded first partial stream is expanded in a second turbo-expander to the second pressure.
  • the partially expanded first partial stream and the second partial stream are guided such that heat can be indirectly transferred between the partially expanded first partial stream and the second partial stream, wherein particularly the second partial stream is cooled.
  • the partially expanded first partial stream is guided against the second partial stream in the first cooling zone such that heat can indirectly be transferred between the partially expanded first partial stream and the second partial stream, thereby particularly cooling the second partial stream.
  • the second partial stream is expanded in a second expansion device to a second intermediate pressure yielding a partially expanded second partial stream
  • the partially expanded second partial stream and the second refrigerant stream and/or the precooled feed gas stream are guided such that heat can be transferred between the partially expanded second partial stream and the second refrigerant stream and/or the precooled feed gas stream, thereby particularly cooling the second refrigerant stream and/or the precooled feed gas stream
  • the partially expanded second partial stream is expanded to the second pressure yielding the expanded partial stream.
  • the partially expanded second partial stream is guided against the second refrigerant stream and/or the precooled feed gas stream in the first cooling zone such that heat can indirectly be transferred between the partially expanded second partial stream and the second refrigerant stream and/or the precooled feed gas stream.
  • the second expansion device comprises at least one turbo-expander. In certain embodiments, the second expansion device comprises at least two turbo-expanders, wherein particularly the second partial stream is expanded in a third turbo-expander to the second intermediate pressure yielding the partially expanded second partial stream, the partially expanded second partial stream is expanded in a fourth turbo-expander to the third pressure.
  • the first cooling zone is located within at least one cooling heat exchanger or a cooling block of a heat exchanger, through which particularly the expanded second partial and the precooled feed stream, the first partial stream, the second partial stream, the first refrigerant stream and/or the second refrigerant stream are guided.
  • the at least one heat exchanger comprises a catalyst being able to catalyse the ortho to para conversion of hydrogen, wherein the precooled feed gas stream is guided through the at least one heat exchanger such that the precooled feed gas stream contacts the catalyst.
  • the at least one cooling heat exchanger is a plate heat exchanger.
  • the first refrigerant stream consists of neon
  • the first pressure is in the range of 5 bar(a) to 40 bar(a) and, particularly in the range of 10 bar(a) to 30 bar(a)
  • the second pressure and/or third pressure is in the range of 1.013 bar(a) to 10 bar(a), particularly in the range of range of 1.3 bar(a) and 4 bar(a), particularly provided that the first refrigerant is precooled to a precooling temperature in the range of 70 K to 120 K, particularly 100 K.
  • the first refrigerant stream consists of neon
  • the first pressure is in the range of 4 bar(a) to 10 bar(a)
  • the second pressure and/or third pressure is in the range of 0.7 bar(a) to 1.013 bar(a), particularly provided that the first refrigerant is precooled to a precooling temperature in the range of 70 K to 120 K, particularly 100 K.
  • the first refrigerant stream comprises or consists of 20 mol. % to 100 mol. % neon, particularly 50 mol.% to 100 mol.% neon, more particular 30 mol.% to 70 mol. % neon, even more particular 40 mol.% to 60 mol.% neon, and optionally hydrogen
  • the first pressure is in the range of 5 bar(a) and 75 bar(a), particularly 10 bar(a) to 60 bar(a)
  • the first intermediate pressure is between the first pressure and third pressure
  • the second and/or third pressure is in the range of 0.7 bar(a) and 13 bar(a), particularly provided that the first refrigerant is precooled to a precooling temperature in the range of 70 K to 120 K, particularly 100 K.
  • the first refrigerant stream comprises or consists of 80 mol. % to 100 mol. % hydrogen, particularly 80 mol. % to 90 mol. % hydrogen, and optionally neon, particularly 10 mol. % to 20 mol. % neon, the first pressure is in the range of 20 bar(a) and 75 bar(a), and the second and/or the third pressure is in the range of 0.7 bar(a) to 13 bar(a), particularly provided that the first refrigerant is precooled to a precooling temperature in the range of 70 K to 120 K, particularly 100 K.
  • a higher hydrogen mole fraction in present in the first refrigerant stream (lower molecular weight)
  • a higher low pressure level is feasible at the discharge of the coldest turbine for the same cooling temperature.
  • a hydrogen is characterized by a significantly lower heat capacity ratio compared to neon (and helium), resulting in lower compressor discharge temperatures. Higher energy-efficiency can be realized
  • the expanded second partial stream is characterized by a temperature in the range of 26 K to 33 K, wherein particularly the precooled feed gas stream and/or the second refrigerant stream is cooled by the expanded second partial stream close to those temperatures.
  • the expanded first refrigerant stream is compressed with a suction temperature close to ambient temperature, or in the range of 230 K to 313 K, or in cold-compressors at a temperature in the range of 80 K to 120 K, or in the range of 120 K to 230 K, particularly above the precooling or intermediate temperature, e.g. 150 K.
  • the expanded first refrigerant stream is compressed in a multi stage compressor comprising at least three compressor stages with intercooling.
  • the partially expanded first refrigerant stream and/or the expanded first refrigerant stream is compressed in at least one multi-stage reciprocating compressors, particularly in two or three multi-stage reciprocating compressors running in parallel configuration e.g. 2 x 100% (capacity) or 2 x 100% (capacity) plus 1 x 50% (capacity), or in two 100 % (capacity) multi-stage reciprocating compressors and one 50 % (capacity) reciprocating compressor.
  • the first refrigerant stream is separated in the first partial and the second partial stream as described above, and additionally in a third partial stream and optionally in a fourth partial stream, wherein the third partial stream is expanded in a sixth expansion device to a third intermediate pressure yielding a partially expanded third partial stream or to the second pressure yielding an expanded third partial stream, and optionally the fourth partial stream is expanded in a seventh expansion device to a fourth intermediate pressure yielding a partially expanded fourth partial stream or to the second pressure yielding an expanded fourth partial stream, and the partially expanded third partial stream or the expanded third partial stream is guided into or unified with the partially expanded second partial stream, the expanded second partial stream or the partially expanded first refrigerant stream, and optionally the partially expanded fourth partial stream or the expanded fourth partial stream is guided into or unified with the partially expanded second partial stream, the expanded second partial stream or the partially expanded first refrigerant stream.
  • the partially or fully expanded third and/or fourth partial stream within the expanded second partial stream provides additional cooling duty to cool the aforementioned streams to be cooled.
  • the expanded second partial stream is compressed from the third pressure to the pressure close or equal to the first intermediate pressure by means of at least one reciprocating piston compressor, particularly two or three reciprocating piston compressors, particularly at any suction temperature.
  • at least one reciprocating piston compressor particularly two or three reciprocating piston compressors, particularly at any suction temperature.
  • one or two multi stage turbo-compressor are preferred.
  • the first refrigerant stream comprises 5 mol. % to 100 mol. % neon
  • the expanded first refrigerant stream and/or the expanded second partial stream is compressed with a suction temperature close to ambient temperature, or in the range of 230 K to 313 K in one or two multi-stage turbo compressors in series.
  • the first refrigerant stream comprises 20 mol. % to 100 mol. % neon, and the partially expanded first refrigerant stream, the expanded first refrigerant stream and/or the partially expanded second partial stream is compressed with a suction temperature close to ambient temperature, or in the range of 230 K to 313 K in one multi-stage turbo compressor.
  • the sixth and/or the seventh expansion device comprise at least one turbo-expander.
  • compressing an expanded refrigerant stream such as the above mentioned expanded first refrigerant stream, at a temperature below the ambient temperature, particularly at temperature in the range of 80 K to 230 K, has the advantage that the volume of the stream to be compressed is reduced, thereby smaller compressors and smaller capital costs are required. Further, advantageously, less compressor stages are required.
  • the second cooling cycle comprises the steps of:
  • the second refrigerant stream is precooled by the third refrigerant stream.
  • the third expansion device is a turbo-expander or piston-expander, a throttle valve or a combination of a turbo-expander or piston-expander and a throttle valve.
  • the expanded second refrigerant and the second refrigerant stream are guided in the second cooling zone such that heat can indirectly be transferred between the expanded second refrigerant and the second refrigerant stream, thereby particularly cooling the second refrigerant stream.
  • the expanded second refrigerant stream and the first refrigerant stream and/or the second partial stream are guided in the second cooling zone such that heat can indirectly be transferred between the expanded second refrigerant stream and the first refrigerant stream and/or the second partial stream, thereby particularly cooling the first refrigerant stream and/or warming the second partial stream.
  • the expanded second refrigerant stream is guided against the cooled feed gas stream, the first refrigerant stream, the second refrigerant stream and/or the second partial stream such that heat can indirectly be transferred between the expanded second refrigerant stream and the cooled feed gas stream, the first refrigerant stream, the second refrigerant stream and/or the second partial stream, thereby particularly liquefying the cooled feed gas stream and/or cooling the first refrigerant stream and/or the second refrigerant stream and/or warming the second partial stream, particularly in the second cooling zone.
  • the second refrigerant comprises essentially hydrogen
  • the fourth pressure is equal or above 15 bar(a), preferably between 15 bar(a) and 30 bar(a) and the fifth pressure (particularly after expansion device and throttle valve) is below the critical pressure of hydrogen, preferably between 1.0.bar(a) and 2 bar(a), wherein particularly the expanded second refrigerant is characterized by a temperature in the range of 18 K and 30 K, particularly after expansion in a turbo-expander or piston expander and a throttle valve, particularly in the range of 20 K and 24 K.
  • the second refrigerant comprises essentially helium
  • the fourth pressure is above 20 bar(a), preferably between 20 bar(a) and 100 bar(a), more preferably between 50 bar(a) and 70 bar(a)
  • the fifth pressure is above 5 bar(a)), preferably in the range of 12 bar(a) and 25 bar(a).
  • such second refrigerant can directly be expanded to the fifth pressure in a single turbo-expander without formation of a two-phase fluid, whereby additionally a phase separator can be saved.
  • a low hydrogen feed storage temperature can be reached, particularly below 20 K.
  • the second refrigerant stream comprises essentially helium
  • the expanded second refrigerant stream is compressed in an ionic liquid piston compressor.
  • An ionic liquid piston compressor in the context of the present specification particularly refers to a compressor, in which at least one or all conventional metal pistons are replaced by a nearly incompressible ionic liquid, wherein particularly the gas is compressed in the cylinder of the compressor by the up-and-down motion of the liquid column, similar to the reciprocating motion of an ordinary piston.
  • the second refrigerant stream comprises essentially hydrogen and is expanded to an intermediate pressure, at which a two-phase flow within a turbo-expander is avoided, e.g. in the range of 5 bar(a) to 15 bar(a), and the partially expanded second refrigerant stream is further expanded in a throttle valve to the fifth pressure.
  • the throttle valve isenthalpic expansion
  • the expansion device is designed to allow a two-phase fluid at the expander outlet, e.g. wet turbine / piston-expander, then throttle valve might not be required.
  • the expanded second refrigerant is separated into a vapour phase and a liquid phase, wherein both phases are separately or together guided with the above mentioned streams.
  • the second refrigerant is separated into at least two partial streams, wherein a first partial stream is expanded to the fourth pressure as described above, and a second partial stream is expanded to an intermediate pressure, the expanded first partial stream is compressed to a pressure close or equal to the intermediate pressure, the partially expanded second partial stream is guided into or unified with the first partial stream after compression to the pressure close or equal to the intermediate pressure yielding a partially expanded second refrigerant stream, which is then compressed to the fourth pressure yielding the second refrigerant stream.
  • the second cooling zone is located within at least one heat exchanger or a block of the at least on cooling heat exchanger, through which particularly the expanded second partial stream and the hydrogen feed stream are guided.
  • the at least one heat exchanger or the block of the at least on cooling heat exchanger comprises a catalyst being able to catalyse the ortho to para conversion of hydrogen, wherein the feed gas stream is guided through the at least one heat exchanger or the block of the at least on cooling heat exchanger such that the feed gas stream contact the catalyst.
  • the second refrigerant is directly replenished by the feed gas stream, particularly after residual impurities have been removed from the feed gas stream as described above.
  • the second refrigerant stream is separated at least into a first partial stream and a second partial stream, wherein the first partial stream of the second refrigerant stream is expanded to the fifth pressure yielding an expanded first partial stream of the second refrigerant stream, and the second partial stream of the second refrigerant stream is expanded to an intermediate pressure yielding a partially expanded second partial stream of the second refrigerant stream or to the fifth pressure yielding an expanded second partial stream of the second refrigerant stream, the expanded first partial stream of the second refrigerant stream and the cooled feed gas stream are guided such that heat can indirectly be transferred between the expanded first partial stream of the second refrigerant stream and the cooled feed gas stream, particularly in the second cooling zone, thereby particularly cooling the cooled feed gas stream to a temperature below the critical temperature of hydrogen, particularly below 24 K, and the partially expanded second partial stream or the expanded second partial stream of the second refrigerant is guided into or unified with the expanded first partial stream of the second refrigerant stream.
  • the first partial stream of the second refrigerant stream is guided against the cooled feed gas stream in the second cooling zone such that heat can indirectly be transferred between the first partial stream of the second refrigerant stream and the cooled feed gas stream, thereby particularly cooling the cooled feed gas stream.
  • the second refrigerant stream is further separated into a third and optionally a fourth partial stream, wherein the third, and optionally the fourth partial stream of the second refrigerant stream, is expanded and guided in the same manner as the above-mentioned partially expanded second partial stream or expanded second partial stream of the second refrigerant stream.
  • the expanded first partial stream of the second refrigerant stream is compressed to a pressure close to the intermediate pressure of the partially expanded second, third or fourth partial stream of the second refrigerant stream yielding a partially expanded first partial stream, and the partially expanded second, third and/or fourth partial stream of the second refrigerant stream are guided into or unified with the partially expanded first partial stream yielding a partially expanded second refrigerant stream, which is then particularly compressed to the fourth pressure yielding the second refrigerant stream.
  • the expanded second refrigerant stream, the partially expanded second refrigerant stream and/or the expanded first partial stream of the second refrigerant stream is compressed with a compressor suction temperature close to the ambient temperature, or at a temperature in the range of 230 K to 313 K, or at a temperature in the range of 120 K to 230 K, particularly 150 K, or at a temperature in the range of 80 K to 120 K, or a temperature in the range of 30 K to 80 K, particularly after being warmed to the temperature in a heat exchanger.
  • the expanded second refrigerant stream, the partially expanded second refrigerant stream and/or the expanded first partial stream of the second refrigerant stream is compressed in a multi stage reciprocating piston compressor with at least two compressor stages, preferably at least three compressor stages, optionally with intercooling, or in an ionic liquid piston compressor.
  • an ionic liquid piston compressor can be employed for compressing the expanded second refrigerant stream if the second refrigerant stream essentially comprises helium.
  • the partially expanded second refrigerant stream and/or the expanded first partial stream of the second refrigerant stream particularly at a suction temperature in the range of 80 K to 120 K, or in the range of 120 K to 230 K, one or two multi stage turbo-compressor are preferred.
  • the precooling step comprises the steps of:
  • the expanded third refrigerant stream is guided against the feed gas stream in the precooling zone such that heat can indirectly be transferred between the expanded third refrigerant stream and the feed gas stream, thereby precooling the feed gas stream, particularly to the intermediate temperature.
  • the sixth pressure is above 20 bar(a). In certain embodiments, sixth pressure is in the range of 20 bar(a) to 75 bar(a). In certain embodiments, the sixth pressure is in the range 30 bar(a) to 60 bar(a). In certain embodiments, the seventh pressure is in the range of 1.1 bar(a) to 8 bar(a). In certain embodiments, the expanded third refrigerant stream is characterized by a temperature in the range of 70 K to 150 K, preferably in the range of 70 k to 120 K, more preferable in the range of 80 K to 120 K, most preferable in the range of 90 K to 120 K.
  • the expanded third refrigerant stream and the first refrigerant stream and/or the second refrigerant stream and/or the third refrigerant stream are guided such that heat can indirectly be transferred between the expanded third refrigerant stream and the first refrigerant stream and/or the second refrigerant stream and/or the third refrigerant stream, thereby particularly precooling the first refrigerant stream and/or the second refrigerant stream and/or the third refrigerant, particularly in the precooling zone.
  • the fourth expansion device is a throttle valve.
  • the expanded third refrigerant stream is guided against the first refrigerant stream and/or the second refrigerant stream and/or the third refrigerant stream in the precooling zone such that heat can indirectly be transferred between the expanded third refrigerant stream and the first refrigerant stream and/or the second refrigerant stream and/or the third refrigerant stream, thereby particularly cooling the first refrigerant stream and/or the second refrigerant stream and/or the third refrigerant stream.
  • compressing the expanded third refrigerant stream comprises the steps of:
  • the expanded third refrigerant stream is compressed in at least 2 compressor stages or compressors, optionally with intercooling, or if the third refrigerant is compressed in the two phase region with a pump and a phase separator between the compressor stages or the compressor stages, wherein as described above liquid phases and vapour phases of the third refrigerant stream are separately compressed. Alternatively, all liquid phases are unified and pumped together.
  • the intermediate pressure is in the range of 10 bar(a) and 30 bar(a).
  • the third refrigerant stream is additionally separated into a mainly gaseous phase and a mainly liquid phase, wherein the mainly gaseous phase and the mainly liquid phase are separately expanded, particularly at different temperature levels, and separately guided with the feed gas stream, particularly in separate heat exchangers or in separate heat exchanger blocks.
  • the mainly gaseous phase and/or the mainly liquid phase are expanded in a throttle valve.
  • the cooled feed gas stream is expanded in a sixth expansion device, thereby cooled.
  • the fifth expansion device is a turbo-expander or a throttle valve.
  • the fifth expansion device is a combination of a turbo-expander and a throttle valve.
  • At least one or all of above mentioned expansion devices comprise, particularly of the first, second, third and fifth expansion device, comprises at least one turbo-expander, wherein particularly the at least one turbo-expander is capable or designed to generate mechanical or electrical energy upon expansion of said respective streams, e.g. by means of a brake wheel, wherein particularly the at least one turbo-expander drives a compressor that partially or fully compresses the expanded first refrigerant stream and/or a compressor that compresses the expanded second refrigerant stream and or a compressor that compresses the third refrigerant stream.
  • the generated electrical energy may be supplied to the power grid or may be used elsewhere.
  • the generated mechanical energy may used to compress any other as the above-mentioned streams.
  • the feed gas stream is precooled from the initial temperature to a temperature in the range of 278K to 313K in a second precooling step.
  • the second precooling step is performed by means of water cooling.
  • at least one or all of the above-mentioned feed gas stream, first refrigerant stream, second refrigerant stream and third refrigerant stream are additionally precooled before the precooling step by chilled water or cold devices using refrigerants as propane, propylene or carbon dioxide, particularly to temperature in the range of 230 K to 278 K.
  • the feed gas stream is provided with a pressure in the range of 15 bar(a) to 75 bar(a). In certain embodiments, the feed gas stream is provided with a pressure in the range of 25 bar(a) to 50 bar(a).
  • the feed gas stream is provided by compressing a feed gas stream comprising hydrogen at ambient temperature to a pressure of at least 15 bar(a), particularly in the range of 15 bar(a) to 75 bar(a), more particular in the range of 25 bar(a) to 60 bar(a), with at least one compressor, wherein particularly the compressor is a reciprocating piston compressor with at least one compressor stage, or an ionic liquid piston compressor.
  • the precooled stream is further compressed by cold compression, particularly up to 90 bar, more particular up to 75 bar, even more particular to a pressure in the range of 25 bar(a) to 60 bar(a).
  • any one of all of the above-mentioned heat exchangers are plate-fin heat exchangers, particularly aluminium-brazed plate-fin heat exchangers.
  • the precooling heat exchanger is a coil-wound heat exchanger.
  • the herein presented invention consists of a novel process design for hydrogen liquefaction on a large-scale, combining several process features to a new technically feasible and thermodynamically efficient configuration.
  • the novel process includes the design of three efficient closed-loop refrigeration cycles providing cooling duty at different temperature levels between ambient temperature and liquid hydrogen temperature. This helps to match more closely the enthalpy-temperature curve within the plate-fin heat exchangers, significantly reducing refrigerant mass flow rates and energy consumption. Compared to aforementioned prior technologies with only one closed refrigeration cycle, the new invention can reduce specific energy consumption by as much as 30%, thus enabling an economical production of liquid hydrogen on a large-scale for e.g. clean energy applications.
  • the hydrogen feed stream can be directly cooled and liquefied to the state of saturated or even subcooled liquid, with a final para-hydrogen that can be catalytically converted in the coldest plate-fin heat exchanger to contents above 99.9 % para.
  • the hydrogen feed gas cooling and liquefaction as well as the closed-loop refrigeration cycles are installed in at least one cold-box, preferably in two separate cold-box vessels 78,79 or more, for large-scale liquefaction capacities.
  • the precooling cold box 78 contains the process equipment for the hydrogen feed gas cooling and part of the single-mixed refrigerant cycle, namely the aluminium-brazed plate-fin heat exchanger 81 and the feed gas purification units 76,77 (adsorber vessels).
  • the feed gas cooling from the lower precooling temperature to liquid hydrogen state is installed in the liquefier cold box 79.
  • the cooling duty is provided by a configuration that is new to hydrogen liquefaction: a double closed-loop cold refrigeration cycle consisting of a main new Neon Brayton cycle (Cold-Cycle 1) and a low-temperature Hydrogen Claude cycle (Cold-Cycle 2) or Helium Brayton cycle for the cold-end liquefaction.
  • a double closed-loop cold refrigeration cycle consisting of a main new Neon Brayton cycle (Cold-Cycle 1) and a low-temperature Hydrogen Claude cycle (Cold-Cycle 2) or Helium Brayton cycle for the cold-end liquefaction.
  • Cold-cycle 1 and cold-cycle 2 designs are optimized in pressure level and respective cooling temperature range. This allows an appropriate shifting of the respective refrigerant cooling duty and total mass flow rate of the two cycles in order to obtain optimal compressor and expander frame-sizes, in terms of energy-efficiency and technical feasibility.
  • a normal hydrogen (25% para) feed gas stream 11 from a hydrogen production plant is fed to the liquefaction plant 100 with a feed pressure above 15 bar(a), particularly 25 bar(a), and a feed temperature near ambient temperature, particularly 303 K.
  • the feed stream 11 with a mass flow rate above 15 tpd, particularly 100 tpd is cooled down between 278 K and 308 K, particularly 298 K, with cooling water 75 before entering the precooling cold box 78 through plate-fin heat exchanger 81.
  • a valve can be used to fill the refrigerant inventory for the hydrogen Cold-Cycle 2 directly from the purified feed stream downstream of 76,77.
  • the hydrogen feed 11 is cooled in the heat exchanger 81 to the temperature T-PC, particularly 100 K, by the warming-up low pressure streams 42 of the single mixed-refrigerant cycle, the neon cold-cycle 1 cold stream 28 and the hydrogen cold-cycle 2 cold stream 32.
  • T-PC temperature of the heat exchanger 81
  • residual impurities are removed from the hydrogen feed gas 12 to achieve a purity of ⁇ 99.99% in the adsorber vessels 76, 77 by physisorption.
  • the precooled feed gas 12 enters the adsorber unit at the temperature T-PC, particularly 100 K, which is about 20 K higher than in prior known hydrogen liquefier applications.
  • the catalytic ortho-para conversion at this temperature runs thermodynamically more favourable.
  • the stream 12 is routed back to the exchanger 81 through the catalyst filled passages of the plate-fin heat exchanger 81, where hydrogen naturally occurring with a para content of 25% is catalytically converted to hydrogen with a para content of about 39% and cooled to the temperature T-PC while the exothermic heat of conversion is being removed by the warming up refrigerants stream 28, 32 and/or 42 in the heat exchanger 81.
  • the precooled hydrogen feed stream 12 then enters the liquefier cold-box 78 with T - PC e.g. 100 K (between 90 K and 120 K).
  • T - PC e.g. 100 K (between 90 K and 120 K).
  • the feed stream 12 is subsequently cooled and liquefied as well as being catalytically converted to higher hydrogen para-fractions in one plate-fin heat exchanger 82 to 90.
  • the hydrogen gas feed stream 11 from battery-limits can be further compressed e.g. from 25 bar(a) to higher pressures, e.g. 75 bar(a), to increase process efficiency and to reduce volumetric flows and equipment sizes by means of a one or two stage reciprocating piston compressor at ambient temperature, a one stage reciprocating piston compressor with cold-suction temperatures after precooling in the heat exchanger 81 or an ionic liquid piston compressor.
  • an adiabatic ortho-para catalytic converter vessel may be used in the precooling cold box 78 to pre-convert normal-hydrogen (25%) para to a para-fraction near equilibrium in the feed gas stream 12 at the outlet of adsorber 76,77, before routing the feed gas stream 12 back to the heat exchanger 81.
  • the precooling duty is provided by a new designed highly efficient single mixed-refrigerant (MR) cycle.
  • the new MR composition in this invention has been optimized for hydrogen precooling to temperatures between 90 K and 120 K, thus differentiating itself from warmer cooling temperature applications as in natural gas liquefaction.
  • the MR mixture precooling is carried out down to a temperature T -PC of about 100 K.
  • a low pressure mixed-refrigerant stream 42 is routed through suction drum 71 to avoid that entrained liquid droplets from the warmed-up refrigerant stream 41 arrive at the suction side of stage one 63a of compressor 63.
  • the MR composition and the discharge pressure of the first compression stage are optimized to produce an intercooled stream 43 with a relatively high liquid fraction. This reduces the mass-flow of refrigerant 43 that has to be compressed in stage two 63b of the compressor 63.
  • the intercooled refrigerant stream 43 is separated into a first liquid mixed refrigerant stream 45 that is pumped to the high pressure (particularly in the range of 25 bar(a) to 60 bar(a)) and into a first vapour refrigerant stream 44, which is compressed to high pressure (particularly in the range of 25 bar(a) to 60 bar(a)) by the second stage 63b of compressor 63.
  • Both the vapour 44 and the liquid stream 45 are mixed to a two-phase high pressure mixed-refrigerant stream 41 after compression 63.
  • the first vapour stream 44 may be additionally separated into a second liquid phase and a second vapour phase, wherein preferably the first liquid phase 45 and the second liquid phase are unified, pumped together to high pressure and afterwards unified with the second vapour phase before entering the precooling cold box 78.
  • the low pressure mixed refrigerant stream may be compressed by more than two stages. If compression and after-cooling results in the formation of a liquid phase, additionally phase separators may be arranged between the compressor stages.
  • the two-phase high pressure mixed-refrigerant stream 41 enters the precooling cold-box 78 passing through the heat exchanger 81, where it is precooled to the lower precooling temperature of 100 K.
  • a Joule-Thomson valve 59 expands the precooled mixed-refrigerant stream 41 to an expanded mixed refrigerant stream 42 that is characterized by an optimized low pressure level, particularly between 2 bar(a) and 8 bar(a).
  • the refrigerant mixture of the high pressure mixed refrigerant stream 41 is designed to cool down from the temperature T-PC by more than 2.5 K, e.g. from 96 K to 100 K, through the Joule-Thomson expansion.
  • the mixture temperature decrease is designed to maintain a feasible temperature difference between warming up and cooling down streams in the heat exchanger 81 as well as to assure that no component freeze-out occurs in the refrigerant mixture.
  • the two-phase high pressure mixed-refrigerant stream may be additionally separated into a vapour and a liquid phase, wherein the liquid phase may be additionally pumped to high pressure and unified with the vapour phase before entering the precooling cold box 78.
  • the vapour stream of the above mentioned additional separation is guided through the heat exchanger 81 and an additional heat exchanger or through two separate blocks of heat exchanger 81 in the precooling cold box 78, expanded in a throttle valve and guided again through both exchangers or blocks, whereby the liquid stream of the additional separation is guided through the additional heat exchanger or block, expanded in a throttle valve and guided again through the additional exchanger or block.
  • the MR composition can be regulated and controlled by the make-up system to adapt to ambient conditions and changed process conditions.
  • the mixed-refrigerant is compressed in a turbo-compressor with at least two stages and inter-stage water cooling to decrease power requirement.
  • the low pressure refrigerant stream can be compressed within an at least two-stage compression 63 with inter-stage cooling without liquid fraction after the first compression stage 63a.
  • no liquid pumps and no phase separator are required.
  • Low temperature precooling is efficiently achieved with a refrigerant mixture optimized specifically for hydrogen liquefaction, wherein the refrigerant preferably contains only four refrigerant components to maintain a manageable plant makeup system.
  • a preferred mixture composition for a precooling temperature in the range of 90 K to 100 K consists of 23 mol. % nitrogen, 29 mol. % methane, 24 mol. % ethane and 0.24 mol. % isobutane.
  • Ethylene may replace the ethane component for precooling temperature above 100 K.
  • iso-butane may be replaced by 1-butene, isopentane, propane or propylene (due to lower melting points).
  • the mixture of the mixed-refrigerant may be adapted depending on the precooling temperatures. Accordingly, the mixture may contain nitrogen, methane, ethylene, and n-butane, isobutane, propane, propylene isopentane, isobutane and/or n-pentane for temperatures between 100 K and 120 K (or higher).
  • the mixture may contain nitrogen, argon, neon, methane, ethane, propane, propylene, 1-butene.
  • the hydrogen feed stream 11 may be precooled to temperatures above 120 K, wherein in this case the mixed-refrigerant preferably contains nitrogen, methane, ethylene, n-pentane
  • a fifth or more refrigerant mixture components can be added to the refrigerant mixture: iso-butane, iso-pentane, 1-butane, argon, neon, propane or propylene for precooling temperatures between 90 K and 100 K, or n-butane, iso-butane, iso-pentane, propane, propylene or pentane for precooling temperature T-PC particularly above 100 K, and additionally n-pentane, for precooling temperatures above 110 K.
  • a high pressure neon stream 21 enters the precooling cold-box 78 and is precooled by the warming up streams 28, 32, 42 in the heat exchanger 81 to the precooling temperature T-PC, particularly 100 K.
  • the precooled neon stream 21 is separated in at least two neon turbine-strings 22, 23 to generate cooling work by nearly isentropic expansions (polytropic) in at least four turbine-expanders (51, 52, 53, 54).
  • two separate turbine-strings 22 and 23 are shown.
  • One or maximal two additional separate turbine-strings with respectively one turbine can be added to this configuration at a higher temperature level to match more closely the temperature-enthalpy curve of cooling down and warming up streams in the heat exchangers.
  • All said turbo-expanders 51, 52, 53, 54 are designed to partially recover energy by the means of turbine brakes coupled with a turbo-generator to produce electricity or via at least one compressor stage of Neon compressor 61 (Neon compander) to increase the total plant energy-efficiency.
  • the main cooling (neon) cold cycle 1 is unique to hydrogen liquefaction as it is combined with the Single-Mixed Refrigerant Precooling Cycle at the precooling temperature T-PC.
  • the HP neon stream is cooled down in the heat exchanger 82 further from T-PC by the warming streams of the Cold-cycle 1 and Cold-cycle 2, namely by the low pressure hydrogen stream 32 and the low pressure neon stream 28.
  • the high pressure neon stream 21 is separated in two fractions: one fraction 22 is routed to turbine string 1, where the stream 22 is expanded in turbo-expander 51 to a medium-pressure level MP2 (medium pressure first partial neon stream 24).
  • MP2 medium pressure first partial neon stream 24
  • the MP2 stream 24 provides cooling duty to the cooling the down streams 11, 21, 31 in heat exchanger 84 as it is partially re-warmed before being expanded again in turbo-expander 52 to the low pressure level (to low pressure first partial neon stream 25). In this way, cooling with turbine string 1 is generated at two different pressure (low pressure and medium pressure) and temperature levels.
  • the second high pressure fraction 23 is subsequently cooled in the heat exchanger(s) 83, 84, 85, and 86 to the temperature of the second turbine string before being expanded in the turbine expander 53 to an intermediate pressure level MP1 (medium pressure second partial stream 26).
  • This stream 26 is then re-warmed providing cooling to the cooling down streams 21,31,12 in heat exchanger 88 before finally being expanded to low pressure level (to the low pressure second partial neon stream 27) in the turbine expander 54.
  • This new process configuration is particularly beneficial for hydrogen feed cooling for two reasons: the specific isobaric heat capacity of the hydrogen feed stream possesses steep gradients or even a peak close to its critical temperature (around 33 K).
  • the low pressure second partial stream 27 provides cooling duty to the cooling down streams 23, 31 up to the temperature of turbine outlet 52, where it is mixed to the low pressure first partial neon stream 25.
  • the mixed stream 28 is warmed up close to ambient temperature as suction stream 28 for neon compressor 61, which is particularly a multi-stage (min. 3) turbo-compressor with stage intercooling.
  • the hot compressor discharge stream 21 is cooled by a water-after-cooler before entering the precooling cold-box 78.
  • the outlet temperature and pressure of neon turbo-expander 54 are optimized in combination with the Hydrogen Cold-cycle 2.
  • the temperature of stream 27 is the cold-end temperature T-CE.
  • T-CE is limited to about 26 K at the outlet of turbine expander 54, to maintain a safe margin from the neon melting point.
  • Optimal cold-end temperatures T-CE are set between 26 K and 33 K (e.g. 28 K.) in order to design the compressor with a beneficial suction pressure above 1 bar(a).
  • the fraction 22 is expanded only to a medium pressure level MP2 (medium pressure partially expanded first partial stream 24), and mixed to the expanded second partial stream 27 ( Figs. 2 and 3 ).
  • the second high pressure fraction 23 is directly expanded to low pressure level (low pressure second partial stream 27) ( Figs. 2 and 4 ).
  • a third high pressure fraction is separated from the neon high pressure fraction 21 and routed to a third turbine string 23 after being further cooled down by the warming up streams 28,32 and expanded to an intermediate pressure.
  • This intermediate pressure stream is then re-warmed slightly before being expanded again in a turbo-expander 52 to the medium pressure level. In this way, cooling with the third turbine string is generated at two different pressure (medium and intermediate pressure) and temperature levels.
  • This new process configuration is particularly beneficial for hydrogen feed cooling since: depending on the pressure, the specific isobaric heat capacity of the hydrogen feed stream possesses steep gradients in the region close to its critical temperature (particularly between 30 K and 50 K).
  • the third turbine string can be designed analogous to first and second turbine strings as described above, with no intermediate warming-up after the first turbine, or with a slight cooling down between the expanders.
  • the low pressure neon stream 28 may be alternatively compressed at low temperature e.g. 150 K particularly by means of a turbo-compressor Advantageously, thereby the volumetric flow of the neon stream and thus the required equipment size for compression can be reduced, as well as the number of required compression stages resulting in a reduced frame-size and reduced capital costs.
  • the above mentioned medium pressure partial neon stream 24 and 26 may be cooled or warmed in the heat exchangers 84 and 88, respectively.
  • the above mentioned partial stream may be directly guided into the respective turbine expanders 52 and 54, without passing any heat exchanger.
  • Hydrogen is used as a refrigerant; in particular normal hydrogen with an approximate 25% para-fraction is used as a preferred refrigerant.
  • the high pressure hydrogen refrigerant 31 is precooled in the heat exchanger 81 (stream 31) to T-PC, particularly 100 K.
  • the high pressure hydrogen refrigerant 31 is then subsequently cooled down to a temperature around 28 K.
  • the hydrogen cold-cycle provides the cooling for the final liquefaction and final ortho-para conversion and subcooling of the hydrogen feed stream 13, 14.
  • the high pressure hydrogen refrigerant 31 is expanded from high pressure to low pressure in at least one turbine string though at least one turbo-expander 55, wherein particularly a second turbine string with an additional turbo-expander or more turbine strings may be added. If this turbo-expander 55 is to be designed with a dry-gas discharge, the high pressure hydrogen refrigerant 31 is expanded from high pressure to an intermediate pressure, above the critical pressure or to a pressure in the range of 5 bar(a) to 13 bar(a) if no two-phase is generated within the turbine 57 or at the outlet of the turbine 57. Subsequently, the cooled stream is expanded to low pressure 32 through a Joule-Thomson throttle valve 56 into a gas-liquid separator 74.
  • the high pressure hydrogen refrigerant 31 can be expanded directly to low pressure level 32.
  • a cold liquid piston expander can be employed to expand the high pressure stream 31 directly to low pressure level 32 into the two-phase region.
  • the low pressure level 32 is fixed to provide a cooling temperature below the feed temperature for saturated or even subcooled liquid (between 20 K and 24 K).
  • the low pressure hydrogen refrigerant 32 is warmed-up to near ambient temperature providing cooling duty to the cooling down streams in the precooling 78 and liquefier cold-box 79.
  • the warmed low pressure hydrogen refrigerant 32 is compressed in one multi-stage reciprocating piston compressor 62 with inter-stage cooling.
  • the piston compressor 62 is designed with at least three intercooled stages.
  • the low pressure hydrogen refrigerant 32 may be compressed in an ionic liquid piston compressor.
  • the low pressure hydrogen refrigerant is warmed up to a temperature below the ambient temperature e.g. to 150 K in the precooling heat exchanger 81 before compression.
  • the high pressure refrigerant 31 is separated into at least two partial streams, wherein the first partial stream is expanded to low pressure level as described above, and the second partial stream is expanded in an additional turbo-expander to a medium pressure level (between high and low pressure) and guided into the expanded first partial stream between two compressor stages, in which the expanded first partial stream is compressed from low pressure level to high pressure level, particularly after a compressor stage, in which the expanded first partial stream is compressed to a pressure level close to the medium pressure level of the partially expanded second partial stream.
  • T-CE provided by the main cooling cycle
  • the feed stream After cooling the hydrogen feed stream 13 to a temperature equal to the cooled high pressure hydrogen refrigerant 31, e.g. 28 K, the feed stream is catalytically converted to a para-fraction slightly below the equilibrium para-fraction at T-CE or as required.
  • the stream 13 is then expanded by the means of at least one turbo-expander from feed pressure to an intermediate pressure above the critical pressure or to a pressure in the range of 5 bar(a) to 13 bar(a) if no two-phase is generated within the turbine 57 or at the outlet of the turbine 57.
  • the expanded and cooled feed stream 14 is further expanded through the Joule-Thomson throttle valve 58 to the low pressure level near the final product storage pressure e.g. 2 bar(a).
  • the cooled hydrogen feed stream 13 can be directly expanded into the two-phase region to the final product storage pressure e.g. 2 bar(a).
  • the final product storage pressure e.g. 2 bar(a).
  • a turbo-expander with energy-recovery via a turbo-generator can be employed to raise energy-efficiency.
  • a cold liquid piston expander can be employed to directly expand the feed stream from the intermediate pressure level, e.g. 13 bara, to the low pressure level near the final product storage pressure.
  • the two-phase hydrogen feed stream 14 is finally cooled and catalytically converted in the last part of the plate-fin heat exchanger 91 against the warming up Cold-cycle 2 refrigerant stream 32.
  • a high pressure Helium Brayton cycle is employed as a separate closed-loop refrigerant cycle, instead of the above described hydrogen cold cycle 2, to provide the cooling duty at temperatures below the cold-end T-CE.
  • compressor 62 is a helium compressor.
  • the high pressure helium stream is expanded and is routed back to the cold-box 79 in a separate closed-loop cycle.
  • the high pressure helium Brayton refrigeration cycle is capable of providing refrigeration at temperatures significantly below the normal boiling point of the hydrogen feed, due to the low melting point of helium.
  • Helium is expanded in a turbo-expander from high pressure in range of 50 bar(a) to 70 bar(a) to low pressure in the range of 5 bar(a) to 25 bar(a) to provide cooling duty for the cooling and liquefaction of the hydrogen feed stream.
  • the helium compression from low pressure to high pressure at near ambient temperature can be implemented through highly-efficient new ionic liquid piston compressor technology (Linde Ionic Compressor). This feature is new to the hydrogen liquefaction process.
  • a liquid hydrogen product stream 15 at the outlet can be generated as saturated liquid or even subcooled liquid, a final para-fraction of F-LH2-01 above 99.5% can be reached, depending on temperature of the liquid hydrogen product.

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  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation By Low-Temperature Treatments (AREA)
EP15003068.2A 2015-10-27 2015-10-27 Nouveau procédé en cascade de refroidissement et de liquéfaction d'hydrogène à grande échelle Withdrawn EP3163235A1 (fr)

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EP15003068.2A EP3163235A1 (fr) 2015-10-27 2015-10-27 Nouveau procédé en cascade de refroidissement et de liquéfaction d'hydrogène à grande échelle
PCT/EP2016/075205 WO2017072018A1 (fr) 2015-10-27 2016-10-20 Nouveau procédé en cascade destiné à refroidir et à liquéfier de l'hydrogène à grande échelle
EP16784202.0A EP3368844A1 (fr) 2015-10-27 2016-10-20 Nouveau procédé en cascade destiné à refroidir et à liquéfier de l'hydrogène à grande échelle

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US20200400371A1 (en) * 2018-03-02 2020-12-24 Linde Gmbh Cooling system
FR3098574A1 (fr) * 2019-07-10 2021-01-15 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Dispositif de réfrigération et/ou de liquéfaction

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US11391511B1 (en) 2021-01-10 2022-07-19 JTurbo Engineering & Technology, LLC Methods and systems for hydrogen liquefaction
FR3119883B1 (fr) 2021-02-18 2023-03-31 Air Liquide Procédé et appareil de liquéfaction d’hydrogène
CN113959175B (zh) * 2021-10-20 2023-01-31 北京石油化工工程有限公司 一种用于大规模制备液氢的方法与系统

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US20200400371A1 (en) * 2018-03-02 2020-12-24 Linde Gmbh Cooling system
FR3098574A1 (fr) * 2019-07-10 2021-01-15 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Dispositif de réfrigération et/ou de liquéfaction

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