Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
  • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
  • F25J1/0005—Light or noble gases
  • F25J1/001—Hydrogen
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
  • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
  • F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
  • F25J1/004—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by flash gas recovery
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
  • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
  • F25J1/0201—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 only internal refrigeration means, i.e. without external refrigeration
  • F25J1/0202—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 only internal refrigeration means, i.e. without external refrigeration in a quasi-closed internal refrigeration loop
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
  • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
  • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
  • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
  • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
  • F25J1/0229—Integration with a unit for using hydrocarbons, e.g. consuming hydrocarbons as feed stock
  • F25J1/023—Integration with a unit for using hydrocarbons, e.g. consuming hydrocarbons as feed stock for the combustion as fuels, i.e. integration with the fuel gas system
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
  • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
  • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
  • F25J1/0257—Construction and layout of liquefaction equipments, e.g. valves, machines
  • F25J1/0275—Construction and layout of liquefaction equipments, e.g. valves, machines adapted for special use of the liquefaction unit, e.g. portable or transportable devices
  • F25J1/0277—Offshore use, e.g. during shipping
• • 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
  • F25J2210/00—Processes characterised by the type or other details of the feed stream
  • F25J2210/90—Boil-off gas from storage

Definitions

• the present invention relates to the field of floating structures or terrestrial structures of which at least one consumer is powered by dihydrogen. These structures make it possible to store and/or transport dihydrogen in the liquid state. It relates more particularly to a device for the liquefaction of gaseous dihydrogen used as fuel for at least one consumer of a structure, in particular floating or terrestrial.
• the dihydrogen In order to transport and/or store dihydrogen more easily, the dihydrogen is generally in the liquid state by cooling it to cryogenic temperatures below the vaporization temperature of the dihydrogen at atmospheric pressure.
• Dihydrogen is, for example, cooled to -253°C at atmospheric pressure to pass to the liquid state. This liquefied hydrogen is then loaded into dedicated tanks in the structure.
• Part of the dihydrogen present in the tank in gaseous form can be used to supply a consumer, such as a fuel cell, intended to meet the energy needs for the operation of the structure, in particular for its propulsion and/or the production of electricity for on-board equipment.
• Another part of the dihydrogen in gaseous form can be reliquefied in order to limit the increase in pressure inside the tank instead of using the vent and thus losing dihydrogen.
• These liquefaction devices have the drawback of being complex and difficult to implement, in particular because of the properties of dihydrogen. The liquefaction yield is low so that the transport of dihydrogen in the liquid state remains expensive and not very profitable.
• the object of the present invention is to overcome at least one of the aforementioned drawbacks and also to lead to other advantages by proposing a new device for the liquefaction of gaseous dihydrogen resulting from the evaporation of dihydrogen in the liquid state.
• the present invention proposes a device for the liquefaction of gaseous dihydrogen resulting from the evaporation of dihydrogen in the liquid state stored in at least one tank, the liquefaction device comprising at least one heat exchanger with several passes, at least one branch of feed configured to supply at least a portion of the hydrogen gas from the vessel to a consumer of the hydrogen gas, a part of the feed branch passing through the heat exchanger via a first pass inside which is disposed a catalyst involved in the conversion of the para isomer of dihydrogen into the ortho isomer of dihydrogen, the liquefaction device comprising at least one cooling branch configured to liquefy at least a portion of the gaseous dihydrogen, the cooling branch comprising at least one compression member , a portion of the cooling branch passing through the heat exchanger via a second pass available dared after the compression unit, the second pass exchanging calories with the first pass in order to liquefy at least part of the dihydrogen circulating in the cooling branch.
• the liquefaction device is configured to implement, within a heat exchanger, calorie exchanges between gaseous dihydrogen at cryogenic temperatures intended to be used as fuel by a consumer and gaseous dihydrogen at temperatures cryogenic intended to be liquefied at least in part, the dihydrogen gas at cryogenic temperatures being issued from one or more tanks.
• cryogenic means a temperature below -40°C, or even below -90°C, and preferably below -150°C.
• Dihydrogen occurs in two forms called nuclear spin isomers, otherwise known as orthohydrogen and parahydrogen.
• Orthohydrogen is dihydrogen composed of molecules in which the two protons, one in each atom of the molecule, have spins that are parallel and in the same direction with each other.
• Parahydrogen is dihydrogen composed of molecules in which the two protons, one in each atom of the molecule, have antiparallel spins.
• Dihydrogen in the liquid state that is to say for a temperature less than or equal to - 253°C at atmospheric pressure, is made up of 99.8% parahydrogen.
• dihydrogen consists of about 75% orthohydrogen and 25% parahydrogen.
• the enthalpy of the isomerization reaction of parahydrogen to orthohydrogen is equal to +525 kj/kg indicating an endothermic reaction.
• the enthalpy of vaporization of dihydrogen is only 476 kj/kg.
• the isomerization reaction of parahydrogen to orthohydrogen is of the order of a few days. It is understood in this context that even if the dihydrogen is gaseous and at 25° C., the proportion of parahydrogen can still be very largely predominant.
• the gaseous dihydrogen resulting from the evaporation of dihydrogen stored in the liquid state in the tank is intended to be used as fuel by the consumer and circulates in a first pass of the heat exchanger.
• the first pass includes a catalyst which makes it possible to accelerate the reaction of isomerization of parahydrogen into orthohydrogen and therefore makes it possible to take advantage of the energy absorption capacity of the isomerization reaction during the exchange of calories with the second pass. pass from the heat exchanger.
• the dihydrogen gas at cryogenic temperatures intended to be liquefied passes through a compression device then into the second pass of the heat exchanger to be liquefied there, at least in part.
• the compressed hydrogen gas gives up its calories to the gaseous hydrogen present in the first pass.
• the gaseous dihydrogen which circulates in the first pass isomerizes rapidly in the presence of the catalyst, in addition to warm up, with the absorption of calories received from the second pass.
• the compressed dihydrogen gas circulating in the second pass cools until it condenses.
• the liquefaction device thus makes it possible to recover the evaporation of the nominal cargo of dihydrogen in the liquid state stored in one or more tanks.
• the catalyst is chosen from nickel, copper, iron or metal hydride gels, nickel, copper or iron films, hydroxides of iron, cobalt, nickel, chromium, manganese, iron oxides, nickel-silicon complexes, an activated carbon and/or at least one of their combinations.
• the supply branch comprises at least one compression device arranged after an output of the first pass.
• the compression device is placed between an outlet of the first pass and the dihydrogen consumer. Therefore, when the hydrogen gas circulates in the supply leg, it passes through the compression device after leaving the first pass of the heat exchanger and before reaching the consumer.
• the compression device makes it possible in particular to put the gaseous dihydrogen into forced circulation in the supply branch, the pressure of the dihydrogen possibly also being high.
• another portion of the cooling branch passes through the heat exchanger via a third pass, an outlet of the third pass being connected to an inlet of the second pass by a connecting portion of the cooling branch, the connecting portion comprising the compression member.
• the second pass of the heat exchanger is arranged so as to exchange calories with the first pass and the third pass of the heat exchanger.
• the liquefaction device comprises a gas-liquid separator arranged on the cooling branch after an outlet from the second pass.
• the dihydrogen When the dihydrogen circulates in the cooling branch after leaving successively the third pass and then the second pass of the heat exchanger, the dihydrogen may not be completely liquefied.
• it can be in the form of a two-phase fluid, that is to say that part of the dihydrogen is in liquid form and part in gaseous form after having gone through the second pass, the two phases then being mixed.
• the gas-liquid separator will in particular make it possible to separate the liquid form of dihydrogen from the gaseous form of dihydrogen.
• the cooling branch comprises an expansion device arranged between an outlet of the second pass of the heat exchanger and an inlet of the gas-liquid separator.
• the liquefaction device is configured to place a liquid outlet of the gas-liquid separator in fluid communication with a tank.
• the fluid communication between the liquid outlet of the gas-liquid separator and a tank can be ensured by a third portion of the cooling pipe.
• the liquefied hydrogen can be returned to the tank where the gaseous hydrogen was taken or it can be sent to a storage tank for hydrogen gas in the liquid state different from the tank where the gaseous hydrogen was taken.
• a gas outlet of the gas-liquid separator is in fluid communication with the cooling branch before an inlet of the third pass of the heat exchanger. More specifically, fluid communication between the gas outlet of the gas-liquid separator is ensured by a connection branch connecting the gas outlet of the gas-liquid separator and a junction point arranged on the cooling branch. The junction point is before an inlet of the third pass of the heat exchanger. Consequently, the gaseous phase of the dihydrogen in the gas-liquid separator can be sent to the cooling branch in order to be upgraded there.
• the liquefaction device comprises a bypass branch connecting a convergence point arranged on the supply branch before an inlet of the first pass of the heat exchanger and a junction point arranged on the cooling branch before the compression member (25).
• the junction point is arranged on the cooling branch before an inlet of the third pass of the heat exchanger.
• the point of convergence is between a gas outlet of a tank from which the gaseous dihydrogen is taken and the heat exchanger, when the dihydrogen circulates in the cooling branch.
• this makes it possible to use dihydrogen from the same tank as that circulating in the supply branch.
• the junction point is arranged on the cooling branch between an outlet of the third pass of the heat exchanger and an inlet of the compression member.
• a fourth pass of the heat exchanger constitutes the bypass branch.
• the fourth pass of the heat exchanger is arranged so as to exchange calories with the second pass and the third pass of the heat exchanger.
• the second pass of the heat exchanger is arranged to exchange calories with the first pass of the heat exchanger and the fourth pass of the heat exchanger.
• the invention also relates to a structure, in particular floating or terrestrial, comprising at least one tank intended for the transport and/or storage of dihydrogen in the liquid state, the structure comprising at least one consumer of dihydrogen as as fuel and at least one liquefaction device having at least one of the characteristics described above, the at least one consumer being configured to be supplied with fuel by the dihydrogen in the gaseous state flowing at least in part in said liquefaction device.
• the consumer may for example be an engine comprising at least one fuel cell.
• the tank can form a fuel tank for the consumer.
• a flow of dihydrogen in the first pass of the heat exchanger is oriented in a direction opposite to a flow of dihydrogen in the second pass of the heat exchanger.
• the flow of the dihydrogen in the first pass of the heat exchanger takes place countercurrent to the flow of the dihydrogen in the second pass.
• the exchanges of calories between the first pass and the second pass of the heat exchanger are increased.
• a flow of dihydrogen in the first pass of the heat exchanger is oriented in the same direction as a flow of dihydrogen in the third pass of the heat exchanger.
• the flow of dihydrogen in the first pass of the heat exchanger is co-current with the flow of dihydrogen in the third pass.
• the flow of dihydrogen in the third pass of the heat exchanger is countercurrent to the flow of dihydrogen in the second pass.
• a flow of dihydrogen in the fourth pass of the heat exchanger is oriented in the same direction as a flow of dihydrogen in the third pass.
• the flow of dihydrogen in the fourth pass of the heat exchanger is co-current with the flow of dihydrogen in the third pass.
• the flow of dihydrogen in the fourth pass of the heat exchanger is countercurrent to the flow of dihydrogen in the second pass.
• the invention also proposes a transfer system for dihydrogen in the liquid state, the system comprising a structure having at least the above characteristics, insulated pipes arranged so as to connect the tank installed on the structure, in particular in the shell of the structure, to a floating or onshore storage facility and a pump to drive a flow of cold dihydrogen product through the insulated pipes from or to the floating or onshore storage facility to or from the tank of the 'work.
• the invention also offers a method for loading or unloading a structure having at least one of the preceding characteristics, during which dihydrogen in the liquid state is conveyed through insulated pipes from or to a floating storage installation. or land to or from the structure tank.
• the invention also proposes a process for the liquefaction of gaseous dihydrogen resulting from the evaporation of dihydrogen in the liquid state stored in at least one tank by a liquefaction device having at least one of the characteristics described above, the process comprising at least a step of compressing the dihydrogen gas, a step of exchanging calories between the compressed dihydrogen gas and the dihydrogen gas withdrawn from the tank so that the compressed dihydrogen gas liquefies, the conversion, in the presence of the catalyst, of the para isomer into the ortho isomer for the dihydrogen gas withdrawn taking place during the calorie exchange step.
• the liquefaction process comprises a step of compressing the hydrogen gas withdrawn from the tank after the calorie exchange step in order to supply a consumer with hydrogen.
• Figure 1 is a schematic representation of a first embodiment of a liquefaction device according to the invention, the liquefaction device being configured to liquefy gaseous dihydrogen resulting from the evaporation of dihydrogen in the liquid state stored in at least one tank of a floating structure;
• FIG. 2 is a schematic representation of a second embodiment of a liquefaction device according to the invention, the liquefaction device being configured to liquefy gaseous dihydrogen resulting from the evaporation of dihydrogen at the liquid state stored in at least one tank of a floating structure;
• FIG. 3 is a cutaway schematic representation of the floating structure for transporting liquid dihydrogen in figure 1 and of a terminal for loading/unloading the tanks of the floating structure.
• FIG. 1 represents a device 11 for liquefying liquid dihydrogen stored in at least one tank 3, 5 of a floating structure for transporting and/or storing dihydrogen.
• the liquefaction device 11 is configured to cooperate with the tanks 3, 5 and with at least one consumer 7 of the floating structure.
• the tank or tanks 3, 5 contain dihydrogen in liquid form 9, that is to say dihydrogen in the liquid state. As the thermal insulation of the tanks is not perfect, part of the hydrogen in the liquid state 9 evaporates naturally. Consequently, the tanks 3, 5 of the floating structure comprise both dihydrogen in liquid form 9 and dihydrogen in gaseous form 10.
• the liquefaction device 11 supplies the consumer 7 with dihydrogen coming from at least one of the tanks 3, 5.
• the consumer 7 comprises at least one fuel cell, but it can also be of a combustion engine or a turbine.
• the liquefaction device 11 comprises at least one heat exchanger 13 with several passes 15, 17, 19, at least one supply branch 21 configured to bring at least a portion of the gaseous dihydrogen 10 from one of the tanks 3, 5 to the gaseous dihydrogen consumer 7 and at least one cooling branch 23 configured to liquefy at least a part of the gaseous dihydrogen 10 from one of the tanks 3, 5.
• a first part of the supply branch 21 crosses the heat exchanger 13 via a first pass 15 inside which is placed a catalyst 151 involved in the conversion of the para isomer of dihydrogen into the ortho isomer of dihydrogen.
• Catalyst 151 is chosen from gels of nickel, copper, iron or metal hydride, films of nickel, copper or iron, hydroxides of iron, cobalt, nickel, chromium, manganese, iron oxides, nickel-silicon complexes, activated carbon and/or at least one of their combinations.
• the supply branch 21 comprises at least one compression device 27 arranged on a second part of the supply branch 21 which connects an output of the first pass 15 of the heat exchanger 13 to the consumer 7 of dihydrogen.
• the compression device 27 is therefore arranged on the supply branch after an outlet 155 of the first pass 15, that is to say downstream of the latter, according to the direction of circulation of the dihydrogen in the branch of food 21.
• the supply branch 21 comprises a third part which connects at least one dihydrogen storage tank 3, 5 to an inlet 153 of the first pass 15 so that the gaseous dihydrogen 10 retained in at least one of the tanks 3, 5 can flow in the supply branch 21 to the consumer 7.
• the third part of the supply branch 21 comprises a first sub-branch 211 connected to a first tank 3 and a second sub-branch 213 connected to a second tank 5.
• the first sub-branch 211 and the second sub-branch 213 meet at a point of convergence 33 of the supply branch 21 which is connected to the inlet 153 of the first pass 15 of the heat exchanger 13 by a connecting pipe.
• the supply branch 21 may include a valve placed at the point of convergence 33 in order to be able to choose the origin of the gaseous dihydrogen, that is to say select the dihydrogen gas 10 from the first tank 3 and/or the dihydrogen gas 10 from the second tank 5.
• the dihydrogen gas 10 from at least one of these tanks 3, 5 is forced into circulation in the supply branch 21 by the compression device 27.
• the gaseous dihydrogen then flows from the tank to the entry 153 of the first pass 15 of the heat exchanger 13, then passes through the first pass 15 of the heat exchanger 13.
• the dihydrogen By flowing from the inlet 153 of the first pass 15 to the outlet 155 of the first pass, the dihydrogen will exchange calories with a second pass 17 of the heat exchanger 13. The gaseous dihydrogen flowing in the first pass 15 will then be warmed up.
• the dihydrogen gas has a temperature of -240° C. at 1.1 bar absolute at the inlet 153 of the first pass 15 and a temperature of +25° C. at 1.1 bar at the outlet 155 of the first pass 15.
• the presence of the catalyst 151 inside the first pass 15 of the heat exchanger 13 makes it possible to accelerate the reaction of isomerization of parahydrogen into orthohydrogen, such a reaction being endothermic.
• the dihydrogen gas circulating in the first pass 15 can absorb even more calories coming from the second pass 17 of the heat exchanger 13. The heat transfer from the second pass 17 to the first pass 15 is greatly increased.
• the cooling branch 23 comprises at least one compression member 25 of dihydrogen.
• a first portion of the cooling branch 23 passes through the heat exchanger 13 via a second pass 17 arranged after the compression member 25.
• the gaseous dihydrogen which circulates in the cooling branch 23 is thus compressed by the compression member 25 , before its cooling within the second pass 17, as explained above. This rise in pressure promotes the liquefaction of the dihydrogen within the second pass 17, and subsequent thereto.
• a second portion of the cooling branch 23 passes through the heat exchanger 13 via a third pass 19.
• An outlet 195 of the third pass 19 is connected to the inlet 173 of the second pass 17 by a connecting portion 231 of the cooling branch 23.
• the connecting portion 231 carries the compression member 25.
• the second pass 17 of the heat exchanger 13 is arranged so as to exchange calories with the first pass 15 and the third pass 19 of the heat exchanger 13.
• the liquefaction device 11 further comprises a bypass branch 31 connecting the point of convergence 33 of the supply branch 21 and a junction point 35 arranged on the cooling branch 23. the same tank in the supply branch 21 and in the cooling branch 23.
• the junction point 35 is arranged before the compression member 25. More specifically, in the first embodiment shown in Figure 1, the junction point is arranged before the inlet 193 of the third pass 19 of the heat exchanger 13.
• the dihydrogen gas 10 from at least one of the tanks flows from one of the tanks 3, 5 to the inlet 193 of the third pass 15 of the heat exchanger 13 then crosses the third pass 19 of the heat exchanger thermal 13.
• the dihydrogen is compressed by the compression member 25 and sent to the inlet 173 of the second pass of the heat exchanger 13.
• the pressure of the dihydrogen after passing through the compression member 25 is greater than the pressure of the dihydrogen before it passes through the compression member 25.
• the compression member 25 due to its function allows the forced circulation of gaseous dihydrogen 10 from at least one of the tanks 3,
• the compressed dihydrogen flows into the second pass 17 of the heat exchanger 13 where it yields calories to the dihydrogen flowing in the third pass 19 of the heat exchanger 13 and to the dihydrogen flowing in the first pass 15 of the heat exchanger 13.
• the dihydrogen circulating in the second pass 17 will therefore change state, to at least partly pass to the liquid state.
• at the outlet 175 of the second pass 17 of the heat exchanger 13 at least part of the dihydrogen is liquefied, preferably all the dihydrogen is liquefied.
• the flow of dihydrogen in the second pass 17 takes place countercurrent to the flow of dihydrogen in the first pass 15.
• the flow of dihydrogen in the second pass 17 takes place countercurrent to the flow of dihydrogen in the third pass 19. that the dihydrogen in the first pass 15 flows in the same direction as the direction of circulation of the dihydrogen within the third pass 19.
• dihydrogen has a temperature of -250° C. at the inlet 193 of the third pass 19 of the heat exchanger 13 and a temperature of +25° C. at the outlet 195 of the third pass 19 of the heat exchanger 13.
• the compression member 25 compresses the dihydrogen to a pressure of between 35 and 45 bars for a temperature of +43°C.
• the dihydrogen has a temperature of +43°C at the inlet 173 of the second pass 17 of the heat exchanger 13 and a temperature of -240°C at the outlet 175 of the second pass 17 of the heat exchanger 13.
• the dihydrogen is at least partly liquefied.
• the dihydrogen can present a liquid phase and a gaseous phase after having traveled through the second pass 17 of the heat exchanger 13. The two phases are then mixed.
• the liquefaction device 11 comprises a gas-liquid separator 29 arranged on the cooling branch 23.
• the separator is arranged after the outlet 175 of the second pass 17.
• the at least partially liquefied hydrogen flows to an inlet 293 of the gas-liquid separator 29.
• An expansion device can be arranged between the outlet 175 of the second pass 17 and the inlet 293 of the gas-liquid separator 29 so as to reduce the pressure of the fluid entering the gas separator. - liquid 29.
• a liquid outlet 295 from the gas-liquid separator 29 is in fluid communication with at least one of the tanks 3, 5, such fluid communication being ensured by a third portion 41 of the cooling pipe 23.
• a gas outlet 297 of the gas-liquid separator 29 is in fluid communication with the cooling branch 23 before an inlet 193 of the third pass 19 of the heat exchanger 13.
• dihydrogen has a temperature of - 254°C at the gas outlet 297 of the gas-liquid separator 29.
• the fluidic communication of the gas outlet 297 of the gas-liquid separator 29 with the cooling branch 23 is provided by a connecting branch 299 connecting the gas outlet 297 of the gas-liquid separator 29 with the junction point 35 arranged on the cooling branch 23.
• the dihydrogen circulates in the liquefaction device 11, after leaving the second pass 17 of the heat exchanger 13, the dihydrogen is sent to the gas-liquid separator 29 so that the liquid phase of the dihydrogen is separated from the gaseous phase. .
• the liquid phase of dihydrogen contained in the gas-liquid separator 29 can be sent into the liquid phase 9 of the dihydrogen stored in one of the tanks 3, 5 via the third portion 41 of the cooling pipe 23.
• the gaseous phase of dihydrogen contained in the gas-liquid separator 29 can be introduced into the cooling branch 23 at the junction point 35 via the connecting branch 299 to be liquefied there.
• Figure 2 illustrates a second embodiment of the liquefaction device according to the invention.
• the second embodiment differs from the first embodiment in that the junction point 35 is between the output 195 of the third pass 19 and the member compression 25 on the cooling branch 23, and in that the bypass branch 31 passes through the heat exchanger 13 via a fourth pass 20.
• Identical elements are designated by the same references. Reference will be made to the description above for more details on these identical elements.
• the fourth pass 20 of the heat exchanger 13 is constitutive of the bypass branch 31 which connects the point of convergence 33 and the junction point 35.
• the point of convergence 31 is on the branch of supply 21 before input 153 of the first pass 15.
• the junction point 35 is on the cooling branch 23.
• the junction point 35 is arranged between the front of the compression member 25. As shown in Figure 2, the junction point 35 is arranged between the outlet 195 of the third pass 19 and the inlet 173 of the second pass 17, more precisely before an inlet of the compression member 25.
• the gas outlet 297 of the gas-liquid separator 29 is in fluid communication with the inlet 193 of the third pass 19 via the connecting branch 299.
• the connecting branch 299 is, in this second embodiment constituting the second portion of the cooling branch 23.
• the dihydrogen entering the third pass 19 has a temperature identical to the gaseous phase of dihydrogen leaving the gas-liquid separator 29, that is to say ⁇ 254° C. in this second embodiment.
• the fourth pass 20 of the heat exchanger 13 is constitutive of the bypass branch 31.
• the fourth pass 20 is arranged so as to exchange calories with the second pass 17 and the third pass 19 of the heat exchanger 13. Consequently , the second pass 17 of the heat exchanger 13 is arranged so as to exchange calories with the first pass 15 of the heat exchanger 13 and the fourth pass 20 of the heat exchanger 13.
• a flow of gaseous dihydrogen in the fourth pass 20 of the heat exchanger 13 is oriented in the same direction as a flow of gaseous dihydrogen in the third pass 19.
• the flow of dihydrogen in the fourth pass 20 of the heat exchanger 13 is co-current with the flow of dihydrogen in the third pass 19.
• the flow of gaseous dihydrogen in the fourth pass 20 of the heat exchanger 13 is countercurrent to the flow of dihydrogen in the third pass 19. flow of dihydrogen in the second pass 17.
• the dihydrogen comes out compressed and cooled from the second pass 17 of the heat exchanger 13.
• the dihydrogen from the pipe cooling 23 enters the gas-liquid separator 29, it undergoes an expansion which has the effect of creating a liquid phase of dihydrogen and a gaseous phase of dihydrogen in the gas-liquid separator 29.
• An expansion device 28 can, optionally, be arranged between the outlet 175 of the second pass 17 and the inlet 293 of the gas-liquid separator 29 so as to reduce the pressure of the fluid entering the gas-liquid separator 29.
• the liquid phase of dihydrogen in the gas-liquid separator 29 can be returned to one of the tanks 3, 5. More specifically, the liquid phase of dihydrogen is directly delivered into the liquid phase 9 contained in the tank 5 via the third portion 41 of the cooling pipe 23 which extends from the liquid outlet 295 of the gas-liquid separator 29 into the tank 5 so that one end of the third portion 41 is immersed in the liquid dihydrogen contained in the tank 5.
• the gaseous phase of dihydrogen in the gas-liquid separator 29 is, for its part, sent to the cooling branch 23 passing through the third pass 19 of the heat exchanger 13.
• the dihydrogen at the inlet 193 of the third pass 19 of the heat exchanger 13, which is in the gaseous state coming from the gas-liquid separator 29, is colder than the dihydrogen at the inlet 203 of the fourth pass 20.
• the second embodiment then makes it possible to take advantage of the calorie absorption capacity of the gaseous phase coming from the gas-liquid separator 29 thanks to the fourth pass 20 of the heat exchanger 13.
• the dihydrogen at the outlet 195 of the third pass 19 is colder than in the case of the first embodiment where the liquefaction device 1 has no fourth pass.
• the dihydrogen at the inlet 173 of the second pass 17 in this second embodiment is therefore colder and will therefore be even more cooled at the outlet 175 of the second pass 17 than in the first embodiment.
• the dihydrogen being colder at the outlet 175 of the second pass 17 than in the first embodiment, it creates less gas phase in the gas-liquid separator 29. Consequently, the quantity of dihydrogen to be recycled via the connecting branch 299 is less and the energy consumption of the liquefaction device is reduced compared to the first embodiment.
• a cutaway view of a floating structure 70 shows a sealed and thermally insulated tank 3, 5 of generally prismatic shape mounted in a double hull 72 of the floating structure 70, which can be a ship or a floating platform.
• a wall of the tank 3, 5 comprises a primary tight barrier intended to be in contact with the dihydrogen in the liquid state contained in the tank 3, 5, a secondary tight barrier arranged between the primary tight barrier and the double shell 72 of the ship, and two thermally insulating barriers arranged respectively between the primary waterproof barrier and the secondary waterproof barrier and between the secondary waterproof barrier and the double hull 72.
• the floating structure 70 comprises a single hull.
• the dihydrogen tanks are spherical tanks insulated under vacuum.
• Loading/unloading pipes 73 arranged on an upper deck of the floating structure 70 can be connected, by means of appropriate connectors, to a maritime or port terminal to transfer a cargo of dihydrogen in the liquid state from or to the tank. 3, 5.
• FIG. 3 represents an example of a maritime terminal comprising a loading and/or unloading station 75, an underwater pipeline 76 and a shore installation 77.
• the loading and/or unloading station 75 is a fixed installation off- shore comprising a movable arm 74 and a tower 78 which supports the movable arm 74.
• the movable arm 74 carries a bundle of insulated flexible pipes 79 which can be connected to the loading/unloading pipes 73.
• the movable arm 74 is orientable and adapts to all the templates of floating structures 70.
• a connecting pipe, not shown, is extends inside the tower 78.
• the loading and/or unloading station 75 allows the loading and/or unloading of the floating structure 70 from or to the shore installation 77.
• This comprises dihydrogen storage tanks in the liquid state 80 and connecting pipes 81 connected by the underwater pipe 76 to the loading and/or unloading station 75.
• the underwater pipe 76 allows the transfer of the dihydrogen to the liquid state between the loading and/or unloading station 75 and the shore installation 77 over a great distance, for example 5 km, which makes it possible to keep the floating structure 70 at a great distance from the coast during the operations of loading and/or unloading.
• pumps on board the floating structure 70 and/or pumps fitted to the shore installation 77 and/or pumps fitted to the loading and unloading station 75 are used.
• the dihydrogen can be discharged by pressure effect, i.e. by increasing the pressure in tank 3.5.
• the unloading of dihydrogen can be carried out without a pump.
• the invention is not limited to the examples which have just been described and many adjustments can be made to these examples without departing from the scope of the invention.
• the two embodiments of the liquefaction device according to the invention have been described in the context of a floating structure. However, they can be implemented in a land structure.

Landscapes

• Engineering & Computer Science (AREA)
• General Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Mechanical Engineering (AREA)
• Thermal Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Ocean & Marine Engineering (AREA)
• Combustion & Propulsion (AREA)
• Separation By Low-Temperature Treatments (AREA)
• Filling Or Discharging Of Gas Storage Vessels (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Hydrogen, Water And Hydrids (AREA)
• Catalysts (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=76283974

Family Applications (1)

Country Status (11)

Families Citing this family (3)

Family Cites Families (14)

• 2021
  • 2021-04-21 FR FR2104153A patent/FR3122250B1/fr active Active
• 2022
  • 2022-04-14 JP JP2023564572A patent/JP2024516170A/ja active Pending
  • 2022-04-14 CA CA3214186A patent/CA3214186A1/fr active Pending
  • 2022-04-14 EP EP22722310.4A patent/EP4327037A1/fr active Pending
  • 2022-04-14 CN CN202280030097.3A patent/CN117295921A/zh active Pending
  • 2022-04-14 US US18/555,975 patent/US20240200866A1/en active Pending
  • 2022-04-14 KR KR1020237037984A patent/KR20230175223A/ko active Pending
  • 2022-04-14 WO PCT/FR2022/050701 patent/WO2022223909A1/fr not_active Ceased
  • 2022-04-14 AU AU2022262269A patent/AU2022262269A1/en active Pending
• 2023
  • 2023-10-18 CL CL2023003101A patent/CL2023003101A1/es unknown
  • 2023-10-19 ZA ZA2023/09762A patent/ZA202309762B/en unknown

Also Published As

Similar Documents

Legal Events