EP0125980B1 - Procédé et appareil de refroidissement et liquéfaction d'au moins un gaz à bas point d'ébullition, tel que par exemple du gaz naturel - Google Patents
Procédé et appareil de refroidissement et liquéfaction d'au moins un gaz à bas point d'ébullition, tel que par exemple du gaz naturel Download PDFInfo
- Publication number
- EP0125980B1 EP0125980B1 EP84400906A EP84400906A EP0125980B1 EP 0125980 B1 EP0125980 B1 EP 0125980B1 EP 84400906 A EP84400906 A EP 84400906A EP 84400906 A EP84400906 A EP 84400906A EP 0125980 B1 EP0125980 B1 EP 0125980B1
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- European Patent Office
- Prior art keywords
- aforesaid
- cooling medium
- exchanger
- pressure
- vapor
- Prior art date
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- 239000007789 gas Substances 0.000 title claims description 48
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 38
- 238000000034 method Methods 0.000 title claims description 34
- 238000001816 cooling Methods 0.000 title claims description 23
- 239000003345 natural gas Substances 0.000 title claims description 18
- 238000009835 boiling Methods 0.000 title claims description 7
- 239000003507 refrigerant Substances 0.000 claims description 89
- 239000007791 liquid phase Substances 0.000 claims description 44
- 239000002826 coolant Substances 0.000 claims description 42
- 239000012808 vapor phase Substances 0.000 claims description 39
- 239000012530 fluid Substances 0.000 claims description 37
- 238000005057 refrigeration Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 238000009834 vaporization Methods 0.000 claims description 15
- 230000008016 vaporization Effects 0.000 claims description 14
- 238000011144 upstream manufacturing Methods 0.000 claims description 10
- 230000006835 compression Effects 0.000 claims description 8
- 238000007906 compression Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000110 cooling liquid Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 239000012809 cooling fluid Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007792 gaseous phase Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IDRGFNPZDVBSSE-UHFFFAOYSA-N OCCN1CCN(CC1)c1ccc(Nc2ncc3cccc(-c4cccc(NC(=O)C=C)c4)c3n2)c(F)c1F Chemical compound OCCN1CCN(CC1)c1ccc(Nc2ncc3cccc(-c4cccc(NC(=O)C=C)c4)c3n2)c(F)c1F IDRGFNPZDVBSSE-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
- F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
- F25J1/0257—Construction and layout of liquefaction equipments, e.g. valves, machines
- F25J1/0262—Details of the cold heat exchange system
- F25J1/0264—Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams
-
- 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
- F25J1/0022—Hydrocarbons, e.g. natural gas
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
- F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
- F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
- F25J1/0055—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream originating from an incorporated cascade
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
- F25J1/0211—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a multi-component refrigerant [MCR] fluid in a closed vapor compression cycle
- F25J1/0214—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a multi-component refrigerant [MCR] fluid in a closed vapor compression cycle as a dual level refrigeration cascade with at least one MCR cycle
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
- F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
- F25J1/0279—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.
- F25J1/0295—Shifting of the compression load between different cooling stages within a refrigerant cycle or within a cascade refrigeration 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
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/06—Splitting of the feed stream, e.g. for treating or cooling in different ways
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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
- F25J2220/00—Processes or apparatus involving steps for the removal of impurities
- F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
- F25J2220/62—Separating low boiling components, e.g. He, H2, N2, Air
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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
- F25J2220/00—Processes or apparatus involving steps for the removal of impurities
- F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
- F25J2220/64—Separating heavy hydrocarbons, e.g. NGL, LPG, C4+ hydrocarbons or heavy condensates in general
Definitions
- the subject of the present invention is a method and an apparatus for cooling and liquefying water minus a gas with low boiling point, such as for example natural gas, or possibly any mixture of gases comprising at least one component with low boiling point.
- a gas with low boiling point such as for example natural gas, or possibly any mixture of gases comprising at least one component with low boiling point.
- the condensed part (s) of said refrigeration fluid also constitutes a refrigeration fluid with several components.
- the cooling curve of the multi-component refrigeration fluid is in this case close to the cooling curve of natural gas.
- the installation is simplified requiring only one compressor unit since there is only one refrigeration fluid (complex) in the installation.
- the object of the present invention is to avoid the drawbacks of the processes of the prior art indicated above, by creating a method of cooling and liquefying natural gas for example, making it possible in particular to obtain a better yield at a lower cost. low.
- the present invention relates to a process for liquefying a gas with low boiling point, such as for example natural gas, by heat exchange with at least part of a main refrigerant fluid with several components, which is previously cooled to at least partial liquefaction by heat exchange with a multi-component auxiliary refrigerant, said main and auxiliary refrigerants forming a refrigeration cascade, and the main refrigerant evolving in a closed circuit in which it undergoes successively: at least one compression in the gaseous state; at least one preliminary cooling with at least partial condensation by heat exchange with the auxiliary refrigerant; separation of the liquid and vapor phases thus obtained; the vapor phase undergoing at least refrigeration with total liquefaction, the vapor phase thus liquefied and the liquid phase being sub-cooled and then expanded for subsequent heat exchange, and resulting vaporization, against the current, with themselves and with the gas to at least partially liquefy it, the vapor thus heated of the main refrigerant being finally recycled and recompressed,
- the first aforementioned parts of the aforementioned vapor and liquid phases are mixed, before recompression and the aforementioned second parts of said vapor and liquid phases are mixed before recompression.
- the first aforementioned parts of the vapor and liquid phases are mixed, and the aforementioned second parts of said vapor and liquid phases are mixed.
- the first aforementioned pressure is a low pressure less than about 1 effective bar and the second aforementioned pressure is an average pressure between about 1.5 effective bar and about 3 effective bar.
- At least a portion of the aforementioned liquefied gas is precooled by heat exchange with at least a portion of the aforementioned reheated steam at the first or second pressure mentioned above.
- At least a part of the aforementioned main refrigerant is precooled by heat exchange with at least a part of the aforementioned heated vapor at the first or the second pressure.
- the invention also relates to a method in which the aforementioned auxiliary refrigerating fluid evolves according to a closed cycle cooling cycle by undergoing successively: at least one compression in the gaseous state; at least one preliminary cooling with possibly at least partial condensation by heat exchange with a cooling agent preferably of external origin; at least one self-refrigeration with total liquefaction then sub-cooling and then expansion for subsequent heat exchange and concomitant resulting vaporization against the current with itself before its expansion and with the main refrigerant, and possibly the gas to be liquefied, the steam thus reheated being recycled and recompressed, characterized in that the expansion of the auxiliary refrigerant, before vaporization, takes place at at least two pressure levels, in particular at three pressure levels.
- the above-mentioned main refrigerant has the following molar composition:
- the aforementioned auxiliary refrigerant has the following molar composition:
- the invention also relates to an apparatus for implementing the above process, and of the type comprising an open circuit of liquefied gas, a closed circuit of main refrigerant in heat exchange relationship with the gas circuit by means a cryogenic plate heat exchanger, and a closed auxiliary refrigerant circuit in heat exchange relation with the main refrigerant circuit by means of a cryogenic heat exchanger, said closed main refrigerant circuit successively comprising at least one compression stage, at least one heat exchanger or cooler connected to a flow path of the main refrigerant which passes through the cryogenic heat exchanger, a separator of the vapor and liquid phases obtained, the above-mentioned cryogenic heat exchanger, and a expansion device on the flow path of each separate and sub-cooled fraction of the main coolant, characterized in that the flow paths ge of the gaseous and liquid fractions of the main refrigerant passing through the cryogenic plate exchanger are, at the outlet of this exchanger, respectively divided into at least two pipes each equipped with an expansion member and each extending by passages
- This device is further characterized by a heat exchanger crossed against the current, on the one hand by the main refrigerant vaporized after expansion in said cryogenic heat exchanger and, on the other hand, by at least part of the gas to be liquefied and / or the main refrigerant, this exchanger being located downstream of the cryogenic plate exchanger with respect to the direction of flow of the vaporized main refrigerant.
- the aforementioned liquefied gas circuit comprises a flow path to and through the aforementioned heat exchanger of the main coolant circuit, and comprises, downstream of said exchanger, an expansion member, a bypass of said path passing through the above-mentioned heat exchanger of the auxiliary refrigerant circuit before joining said flow path before said cryogenic heat exchanger of the main refrigerant circuit.
- the apparatus according to this invention is of the type in which the auxiliary refrigerant circuit successively comprises: at least one compressor, at least one exchanger-cooler, with refrigerant preferably of external origin; the aforementioned cryogenic heat exchanger being traversed by a flow path of the aforesaid auxiliary refrigerant fluid comprising at least one expansion member and by at least one flow path, against the current, of said refrigerant fluid after expansion, and is characterized in that said flow path of the auxiliary refrigerant in said cryogenic exchanger has at least two branches, for example three each comprising a expansion member, the part of each branch downstream of said expansion member passing through the corresponding part of said exchanger cryogenic substantially parallel to said flow path, and against the current.
- a vapor and liquid phase separator is provided downstream of the above-mentioned expansion member, the part of the above-mentioned branch, downstream of said separator, being divided into a flow path of the vapor phase and a liquid phase flow path.
- the aforementioned flow paths of the liquid phase pass through the corresponding part of the above-mentioned cryogenic exchanger before joining the aforementioned flow paths of the vapor phase which have not passed through said exchanger.
- the open circuit of gas for example natural gas, to be liquefied
- the closed circuit of main refrigerant fluid is generally designated by the reference numeral 2
- the closed auxiliary refrigerant circuit is designated by the reference numeral 3.
- the closed main and auxiliary refrigerant circuits are symbolically delimited and contained within a rectangular frame drawn in broken lines in broken lines, and the path gas to be liquefied is indicated by a solid solid line.
- the liquefied gas circuit 1 and the main refrigerant circuit 2 are thermally combined or interconnected by means of common cryogenic heat exchangers respectively for liquefaction and gas sub-cooling 4, on the one hand, and preliminary gas cooling 5, on the other hand.
- the main 2 and auxiliary 3 refrigerant circuits respectively are combined by means of at least one common cryogenic heat exchanger 6 for precooling and at least partial liquefaction of the main refrigerant.
- the open circuit 1 of gas to be liquefied comprises a pipe 7 for arrival at the pre-cooling heat exchanger 5 connected to at least one internal flow path 8 of this exchanger, the outlet of which is connected by a pipe 9 to a optional gas treatment apparatus 10, in particular for the extraction of ethane.
- a gas treatment apparatus 10 in particular for the extraction of ethane.
- gas treatment devices in particular a nitrogen extraction device can for example be provided at the level of the cryogenic heat exchanger 4.
- the outlet of this device 10 is connected by a line 11 at the inlet of the heat exchanger 4.
- a bypass 12 of the pipe 7 can optionally be provided, a bypass 12 which is connected to a flow path 13 of part of the gas to be liquefied in the cryogenic heat exchanger 6 of the auxiliary refrigerant circuit, the outlet of which is connected by a flow path 14 to the pipe 11 before the inlet of the heat exchanger 4.
- the pipe 11 is connected to an internal flow path 15 passing through the cryogenic heat exchanger 4 and are the downstream end is connected, at the outlet of the heat exchanger 4 to a pipe 16 of liquefied natural gas through at least one expansion member 17 such as for example an expansion valve.
- the closed circuit 2 contains a main refrigerant consisting of a mixture of several components, at least the major part of which is advantageously formed of hydrocarbons.
- the relative composition in moles of this refrigerant fluid can be for example the following:
- This circuit 2 successively comprises in the direction of flow of coolant: a first compressor 18 and a second compressor sor 19 of refrigerant in the gaseous state, each driven either separately by an individual drive machine or else together jointly by a common drive machine while then having their respective shafts mechanically coupled.
- These two compressors 18, 19 are connected in series to an exchanger-cooler 20, the coolant of which is advantageously of external origin and constituted for example by water or air.
- the outlet of the exchanger-cooler 20 is connected by a line 21 to a third compressor 22 and a fourth compressor 23 connected in series through at least one intermediate cooler 24, the coolant of which is advantageously of external origin and constituted for example by water or air.
- the compressors 22, 23 can be driven jointly or even jointly with at least one of the compressors 18, 19 or separately each.
- the outlet and discharge port of the compressor 23 is connected by a line 25, through an exchanger-cooler 26 (the coolant of which is advantageously of external origin, such as for example water or air ), at the inlet of the heat exchanger 6 and more precisely at the upstream end of at least one internal flow path 27 extending therein.
- the cryogenic heat exchanger 6 of the auxiliary refrigerant circuit is advantageously a plate exchanger.
- the downstream end of the flow path 27 is connected by a pipe 28 to at least one phase separator 29.
- the liquid collecting space of this phase separator is connected by a pipe 30 at the inlet of the heat exchanger 4 and more precisely at the upstream end of at least one flow path 31 extending inside the heat exchanger 4 in substantially the same direction as the internal flow path 15 of the gas to be liquefied.
- the downstream end of the internal flow path 31 is divided, after the exit from the heat exchanger 4, into two flow paths 33, 32 respectively, connected to the inlet of expansion members 34, 35 respectively.
- At the outlet of each expansion member 34, 35 is connected a flow path 36, 37 extending inside the cryogenic heat exchanger 4 in substantially the same direction as the internal flow path 15 of the gas to liquefy and to flow path 31, and against the current.
- the vapor collector space of the phase separator 29 is connected by a pipe 38 to the inlet of the cryogenic heat exchanger 4 and more precisely to the upstream end of at least one other internal flow path 39 s extending substantially parallel to the flow paths 15 and 31.
- the downstream end of this flow path 39 is divided, after the exit from the heat exchanger 4, into two flow paths 40, 41 connected to the inlet of expansion members 42, 43, respectively, the outlet of expansion members 42, 43 is connected to flow paths 44, 45, respectively, extending inside the cryogenic heat exchanger 4 in substantially the same direction as the other flow paths 15, 31, 36, 37 and 39.
- the cryogenic heat exchanger 4 of the main coolant circuit 2 is a plate exchanger comprising, as we have seen above, different passageways for each of the fluids present during the heat exchange, namely the gas to be liquefied, the liquid or vapor phases or fractions of the partially condensed main refrigerant, as well as the fractions from the previous ones, expanded at different pressure levels.
- the flow paths 36 and 44 of the fractions of the main coolant expanded at the same pressure for example an average pressure, in particular between approximately 1.5 and 3 bars, meet in one single flow path 46 which can optionally pass through the heat exchanger 5 for precooling the gas to be liquefied, in particular against the current, the downstream end of this flow path 46 being connected to the suction port of the compressor 19.
- the flow paths 37 and 45 of the fractions of the main coolant expanded at the same pressure in particular a low pressure, for example less than about 1 bar effective meet in a single flow path 47 whose downstream end opens into the suction port of the compressor 18.
- Circuit 3 contains an auxiliary refrigerant consisting of a mixture preferably only based on hydrocarbons, for example having the following relative molar composition:
- the closed circuit 3 of the auxiliary refrigerant fluid successively comprises the following elements in the direction of flow of the fluid: first 48, second 49 and third 51 compressors connected in series with each other and driven are respectively by individual power machines or else by at least one drive machine common to at least two compressors which are then directly mechanically coupled by their respective shafts.
- the outlet or discharge port of the second compressor 49 is connected to the inlet or suction port of the third compressor 51 by a pipe 54 through a heat exchanger-cooler 50 with cooling agent preferably of external origin such as such as water or air.
- the outlet or discharge port of the third compressor 51 is connected by a line 55 to a condenser 52, the outlet of which is connected by a line 56 to a sub-cooler 53.
- the outlet of the sub-cooler 53 is connected by a pipe 57 to the cryogenic heat exchanger 6, which may in particular be constituted by a plate exchanger, and more particularly to the upstream end of a flow path 58 passing through the heat exchanger 6 in a direction substantially parallel to the flow paths 13 and 27 of the gas to be liquefied and the main refrigerant, respectively.
- the cryogenic heat exchanger 6 which may in particular be constituted by a plate exchanger, and more particularly to the upstream end of a flow path 58 passing through the heat exchanger 6 in a direction substantially parallel to the flow paths 13 and 27 of the gas to be liquefied and the main refrigerant, respectively.
- the flow path 58 of the auxiliary refrigerant in the cryogenic heat exchanger 6 has, for example, three branches 59, 60 and 61 provided at three different levels in the exchanger 6.
- the three branches 59, 60 and 61 are each connected to an expansion member 62, 63 and 64, respectively, the outlet of which is connected to a vapor and liquid phase separator 65, 66 and 67, respectively.
- the liquid collecting space of the phase separators 65, 66 and 67 is connected by a line 68, 69 and 70, respectively, to an inlet of the cryogenic heat exchanger 6 and more precisely to the upstream end of a flow path 71, 72 and 73, respectively, the major part of which extends inside the cryogenic heat exchanger 6 in a direction at least approximately parallel to the flow paths 13 of the gas to be liquefied, 27 of the main refrigerant and 58 of the auxiliary refrigerant before expansion.
- each phase separator 65, 66, 67 are connected by a pipe 74, 75 and 76, respectively, to an inlet of the cryogenic heat exchanger 6 and more particularly at the upstream end a flow path 77, 78, 79 the major part of which extends inside the cryogenic heat exchanger 6 in substantially the same direction as the other internal flow paths 13, 27 and 58.
- the flow path 82 is connected to the suction port of the compressor 48, the flow path 81 is connected to the suction port of the compressor 49 and the flow path 80 is connected to the port compressor 51.
- Circuit 1 operates in the following manner: the gas to be liquefied, for example natural gas, arriving via line 7 at a temperature, for example, of approximately + 20 ° C. and at a pressure, for example, of approximately 42.5 bars, crosses the passageway 8 of the heat exchanger 5 to be cooled there preliminary by heat exchange with the main refrigerant vaporized after expansion in the cryogenic heat exchanger 4 and circulating in the flow path 46 in the opposite direction to direction of flow of the gas in the passageway 8. Leaving the heat exchanger 5 via line 9, the gas is then at a temperature for example of approximately -45 ° C. and at a pressure for example of around 42 bars.
- the gas to be liquefied for example natural gas
- the treatment apparatus 10 passes through the treatment apparatus 10 to reach via the pipe 11 the entry of the flow path 15 into the plate exchanger 4 to be entirely liquefied there and then sub-cooled by heat exchange with the main refrigerant. .
- the liquefied gas is at a temperature, for example, of approximately -154 ° C. and at a pressure, for example, of approximately 41.5 bars. It is then expanded in the expansion valve 17 and then transferred to the place of conservation or storage of liquefied natural gas or to a place of treatment or use thereof.
- Part of the gas to be liquefied can also be previously cooled by heat exchange with the auxiliary refrigerant in the cryogenic heat exchanger 6, this part then being combined with the rest of the gas to be liquefied before it enters the cryogenic heat exchanger 4 .
- the main refrigerant cycle 2 operates in the following manner: the part of the main refrigerant expanded at low pressure is sucked in the gaseous state, at a temperature for example of approximately -52 ° C. and at a pressure for example d '' about 0.08 bar by the first presser wedge 18 from which it is discharged at an average pressure of about for example 2 bars and at a temperature of about for example 10 ° C, then it is sucked by the second compressor 19, at the same time as the part of the main coolant expanded to an average pressure equal for example to about 2 bars and whose temperature is for example about 10 ° C.
- the assembly is discharged from the compressor 19 at a temperature equal for example to approximately 71 ° C.
- the exchanger-cooler 20 in which the temperature of the main refrigerant is lowered at about, for example, 15 ° C. Via the flow path 21, it then enters the suction port of the compressor 22, passes through the exchanger-cooler 24 then is compressed in the compressor 23 and, via the flow path 25, passes through the exchanger of heat 26.
- the main refrigerant is for example at a temperature of approximately 15 ° C. and at a pressure of approximately 27.4 bars. It then enters the flow path 27 of the cryogenic heat exchanger 6 where the main refrigerant is cooled by heat exchange with the auxiliary refrigerant so as to at least partially liquefy.
- the main refrigerant thus at least partially condensed at a temperature for example of around -50 ° C. and at a pressure for example of around 26.5 bars, then leaves the heat exchanger 6 in the form of a mixture of gaseous and liquid phases respectively which are then separated in the phase separator 29.
- the gaseous phase is brought by the pipe 38 into the segment of the flow path 39 located in the cryogenic heat exchanger 4 to be liquefied there and then sub-cooled to a temperature, for example, of approximately -154 ° C.
- Part of this liquefied and sub-cooled gaseous phase flows in the channel 41 and is expanded in the expansion member 43 to a pressure for example of approximately 0.3 bar, its temperature being for example of approximately - 156 ° C.
- the temperature and pressure conditions are for example around -52 ° C and around 0.08 bar, respectively .
- the other part of the liquefied and sub-cooled gas phase flows through the channel 40 and is expanded in the expansion member 42 to a pressure for example of about 2.3 bars, its temperature being about -153 ° C.
- the temperature and pressure conditions are for example as follows: -52 ° C. and 2.10 bars.
- the liquid phase of the main refrigerant coming from the phase separator 29 is brought via line 30 into the flow path 31 of the cryogenic heat exchanger 4 to be sub-cooled there to a temperature by example of approximately -154 ° C, at a pressure for example of approximately 26 bars.
- Part of the sub-cooled liquid phase of the main cooling fluid passes through the expansion member 35 where its pressure is reduced to, for example, approximately 0.3 bar; while another part of the sub-cooled liquid phase flowing in the channel 33 is expanded in the expansion member 34 to a pressure of about 2.3 bars, its temperature being approximately for example-153 ° C.
- the first and second abovementioned parts of the liquid phase of the main refrigerant have the following temperature and pressure conditions: -52 ° C and 0.08 bar, and -52 ° C and 2.10 bars, respectively.
- a first part of the vapor phase of the main refrigerant, condensed and sub-cooled is expanded at a first pressure, a second part being expanded at a second pressure, and a first part of the aforementioned liquid phase.
- main, sub-cooled refrigerant is expanded at said first pressure, a second portion being expanded at said second pressure.
- the vapor and liquid phases can be divided into a desired number of parts, for example three or more, the pressure at which a part of the liquid phase being expanded corresponds to the pressure at which a corresponding portion of the vapor phase.
- the first parts of the vapor and liquid phases are mixed, and the second parts of said vapor and liquid phases are mixed.
- Another possibility consists in mixing the first parts of the vapor and liquid phases, and in mixing the second parts of the vapor and liquid phases after expansion but before vaporization (embodiment illustrated in fig. 2).
- the part of the main coolant vaporized at low pressure is admitted by the flow path 47 into the suction port of the compressor 18, while the part of the main coolant vaporized at medium pressure is admitted by the way flow 46, and possibly after passing through the heat exchanger 5 for precooling the gas to be liquefied, in the suction orifice of the compressor 19.
- the auxiliary refrigerant cycle 3 is as follows: the auxiliary refrigerant, in the gaseous state, leaving the compressor group 48, 49, 51 is for example at a temperature of around +46 ° C. and at a pressure for example around 16 bars. After passing through the cooler exchangers 52 and 53, the temperature of the auxiliary refrigerant is approximately +13 ° C., while its pressure is approximately 15.1 bars. The part of the auxiliary refrigerating fluid diverted in the flow path 59 is at a temperature for example of approximately 0 ° C. and at a pressure for example of approximately 15 bars. After expansion in the expansion member 62, the temperature drops to, for example, approximately -6.5 ° C and the pressure to, for example, approximately 8.5 bars.
- the temperature and pressure conditions of the second part of the auxiliary refrigerant flowing through the bypass 60 are as follows: for example approximately -25 ° C. and for example approximately 14.5 bars. After expansion in the expansion member 63, the temperature is lowered to, for example, approximately -29 ° C and the pressure to, for example, approximately 4 bars.
- the vapor and liquid phases thus obtained flow in the flow paths 78 and 72, respectively, in the exchanger 6 so as to participate in the heat exchange with the other fluids flowing in said exchanger 6, then are gathered after the exit of said exchanger 6 in the flow path 81.
- the temperature and pressure conditions of this part of the auxiliary refrigerant are then as follows: for example around -3 ° C. and for example around 3.9 bars. This part of the auxiliary refrigerant is introduced into the suction port of the compressor 49.
- a third part of the auxiliary cooling fluid flows in the flow path 61 at a temperature for example of around -50 ° C. and a pressure for example of around 14.2 bars.
- these temperature and pressure conditions change as follows: for example around -54 ° C. and for example around 1.1 bars.
- the vapor and liquid phases thus obtained are separated in the phase separator 67 and then flow through the flow paths 73 and 79 in the heat exchanger 6 to participate in the heat exchange with the other fluids which circulate there.
- These phases vapor and liquid once combined, after leaving the exchanger 6, are at a temperature for example of about -28 ° C and a pressure for example of about 0.90 bar.
- This third part of the auxiliary refrigerant is introduced into the suction port of the compressor 48 by the flow path 82.
- Fig. 3 illustrates a variant of the auxiliary refrigeration circuit.
- the conduits 74, 75, 76 coming from the vapor collecting space of the separators 65, 66, 67 are connected directly to the flow paths 80, 81, 82 without passing through the exchanger 6.
- fig. 2 illustrates an alternative embodiment in which the first parts of the vapor and liquid phases are mixed and the second parts of said vapor and liquid phases are mixed, after expansion, in the valves 83, 84 '; 83 ', 84, respectively, but before recirculation against the current, in the exchanger 4.
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation By Low-Temperature Treatments (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8307620 | 1983-05-06 | ||
FR8307620A FR2545589B1 (fr) | 1983-05-06 | 1983-05-06 | Procede et appareil de refroidissement et liquefaction d'au moins un gaz a bas point d'ebullition, tel que par exemple du gaz naturel |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0125980A2 EP0125980A2 (fr) | 1984-11-21 |
EP0125980A3 EP0125980A3 (en) | 1984-12-27 |
EP0125980B1 true EP0125980B1 (fr) | 1987-04-01 |
Family
ID=9288670
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84400906A Expired EP0125980B1 (fr) | 1983-05-06 | 1984-05-03 | Procédé et appareil de refroidissement et liquéfaction d'au moins un gaz à bas point d'ébullition, tel que par exemple du gaz naturel |
Country Status (13)
Country | Link |
---|---|
US (1) | US4539028A (es) |
EP (1) | EP0125980B1 (es) |
JP (1) | JPH0627618B2 (es) |
AU (1) | AU560904B2 (es) |
CA (1) | CA1226206A (es) |
DE (1) | DE3462945D1 (es) |
ES (1) | ES8502536A1 (es) |
FR (1) | FR2545589B1 (es) |
IN (1) | IN161272B (es) |
MY (1) | MY101481A (es) |
NO (1) | NO159683C (es) |
OA (1) | OA07764A (es) |
SU (1) | SU1627097A3 (es) |
Families Citing this family (36)
Publication number | Priority date | Publication date | Assignee | Title |
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GB2180921B (en) * | 1985-09-25 | 1990-01-24 | Sanyo Electric Co | Refrigeration system |
US4911741A (en) * | 1988-09-23 | 1990-03-27 | Davis Robert N | Natural gas liquefaction process using low level high level and absorption refrigeration cycles |
FR2681859B1 (fr) * | 1991-09-30 | 1994-02-11 | Technip Cie Fse Etudes Const | Procede de liquefaction de gaz naturel. |
US5271231A (en) * | 1992-08-10 | 1993-12-21 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method and apparatus for gas liquefaction with plural work expansion of feed as refrigerant and air separation cycle embodying the same |
US5615561A (en) * | 1994-11-08 | 1997-04-01 | Williams Field Services Company | LNG production in cryogenic natural gas processing plants |
FR2743140B1 (fr) * | 1995-12-28 | 1998-01-23 | Inst Francais Du Petrole | Procede et dispositif de liquefaction en deux etapes d'un melange gazeux tel qu'un gaz naturel |
US5657643A (en) * | 1996-02-28 | 1997-08-19 | The Pritchard Corporation | Closed loop single mixed refrigerant process |
US5746066A (en) * | 1996-09-17 | 1998-05-05 | Manley; David B. | Pre-fractionation of cracked gas or olefins fractionation by one or two mixed refrigerant loops and cooling water |
US6659730B2 (en) * | 1997-11-07 | 2003-12-09 | Westport Research Inc. | High pressure pump system for supplying a cryogenic fluid from a storage tank |
US6446465B1 (en) * | 1997-12-11 | 2002-09-10 | Bhp Petroleum Pty, Ltd. | Liquefaction process and apparatus |
US6119479A (en) | 1998-12-09 | 2000-09-19 | Air Products And Chemicals, Inc. | Dual mixed refrigerant cycle for gas liquefaction |
MY117548A (en) | 1998-12-18 | 2004-07-31 | Exxon Production Research Co | Dual multi-component refrigeration cycles for liquefaction of natural gas |
US6471694B1 (en) | 2000-08-09 | 2002-10-29 | Cryogen, Inc. | Control system for cryosurgery |
US7004936B2 (en) * | 2000-08-09 | 2006-02-28 | Cryocor, Inc. | Refrigeration source for a cryoablation catheter |
US6347532B1 (en) | 1999-10-12 | 2002-02-19 | Air Products And Chemicals, Inc. | Gas liquefaction process with partial condensation of mixed refrigerant at intermediate temperatures |
FR2821351B1 (fr) * | 2001-02-26 | 2003-05-16 | Technip Cie | Procede de recuperation d'ethane, mettant en oeuvre un cycle de refrigeration utilisant un melange d'au moins deux fluides refrigerants, gaz obtenus par ce procede, et installation de mise en oeuvre |
US6640586B1 (en) * | 2002-11-01 | 2003-11-04 | Conocophillips Company | Motor driven compressor system for natural gas liquefaction |
RU2352877C2 (ru) * | 2003-09-23 | 2009-04-20 | Статойл Аса | Способ сжижения природного газа |
DE102004011481A1 (de) * | 2004-03-09 | 2005-09-29 | Linde Ag | Verfahren zum Verflüssigen eines Kohlenwasserstoff-reichen Stromes |
US8491636B2 (en) | 2004-03-23 | 2013-07-23 | Medtronic Cryopath LP | Method and apparatus for inflating and deflating balloon catheters |
US7727228B2 (en) | 2004-03-23 | 2010-06-01 | Medtronic Cryocath Lp | Method and apparatus for inflating and deflating balloon catheters |
CN100344872C (zh) * | 2004-06-11 | 2007-10-24 | 中国科学院理化技术研究所 | 高真空深冷水汽捕集器 |
BRPI0511785B8 (pt) * | 2004-06-23 | 2018-04-24 | Exxonmobil Upstream Res Co | métodos para a liquefação de uma corrente de gás natural |
US8206345B2 (en) | 2005-03-07 | 2012-06-26 | Medtronic Cryocath Lp | Fluid control system for a medical device |
WO2008049821A2 (en) * | 2006-10-23 | 2008-05-02 | Shell Internationale Research Maatschappij B.V. | Method and apparatus for liquefying hydrocarbon streams |
RU2464510C2 (ru) * | 2006-11-14 | 2012-10-20 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Способ и устройство для охлаждения потока углеводородов |
DE102007006370A1 (de) * | 2007-02-08 | 2008-08-14 | Linde Ag | Verfahren zum Verflüssigen eines Kohlenwasserstoff-reichen Stromes |
AU2009316236B2 (en) * | 2008-11-17 | 2013-05-02 | Woodside Energy Limited | Power matched mixed refrigerant compression circuit |
FR2957407B1 (fr) * | 2010-03-15 | 2012-08-17 | Inst Francais Du Petrole | Procede de liquefaction d'un gaz naturel avec des melanges refrigerants contenant au moins un hydrocarbure insature |
EA026653B1 (ru) | 2010-03-25 | 2017-05-31 | Дзе Юниверсити Оф Манчестер | Способ охлаждения |
RU2620310C2 (ru) * | 2011-12-20 | 2017-05-24 | Конокофиллипс Компани | Сжижение природного газа в движущейся окружающей среде |
CN103322769B (zh) * | 2012-03-20 | 2015-07-08 | 中国海洋石油总公司 | 一种基荷型天然气液化工厂的级联式液化系统 |
DE102013016695A1 (de) * | 2013-10-08 | 2015-04-09 | Linde Aktiengesellschaft | Verfahren zum Verflüssigen einer Kohlenwasserstoff-reichen Fraktion |
JP6689277B2 (ja) * | 2014-12-12 | 2020-04-28 | ドレッサー ランド カンパニーDresser−Rand Company | 天然ガスを液化するシステムおよび方法 |
RU2601670C1 (ru) * | 2015-07-22 | 2016-11-10 | Федеральное Государственное Автономное Образовательное Учреждение Высшего Профессионального Образования "Дальневосточный Федеральный Университет" (Двфу) | Холодильная машина |
US10976103B2 (en) * | 2017-12-15 | 2021-04-13 | Saudi Arabian Oil Company | Process integration for natural gas liquid recovery |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2292203A1 (fr) * | 1974-11-21 | 1976-06-18 | Technip Cie | Procede et installation pour la liquefaction d'un gaz a bas point d'ebullition |
FR2471566B1 (fr) * | 1979-12-12 | 1986-09-05 | Technip Cie | Procede et systeme de liquefaction d'un gaz a bas point d'ebullition |
FR2499226B1 (fr) * | 1981-02-05 | 1985-09-27 | Air Liquide | Procede et installation de liquefaction d'un gaz |
-
1983
- 1983-05-06 FR FR8307620A patent/FR2545589B1/fr not_active Expired
-
1984
- 1984-04-24 IN IN347/DEL/84A patent/IN161272B/en unknown
- 1984-04-26 US US06/604,049 patent/US4539028A/en not_active Expired - Lifetime
- 1984-04-27 AU AU27460/84A patent/AU560904B2/en not_active Ceased
- 1984-05-02 CA CA000453353A patent/CA1226206A/en not_active Expired
- 1984-05-03 EP EP84400906A patent/EP0125980B1/fr not_active Expired
- 1984-05-03 DE DE8484400906T patent/DE3462945D1/de not_active Expired
- 1984-05-04 ES ES532222A patent/ES8502536A1/es not_active Expired
- 1984-05-04 OA OA58289A patent/OA07764A/xx unknown
- 1984-05-04 SU SU843737939A patent/SU1627097A3/ru active
- 1984-05-04 NO NO841803A patent/NO159683C/no not_active IP Right Cessation
- 1984-05-07 JP JP59090837A patent/JPH0627618B2/ja not_active Expired - Fee Related
-
1987
- 1987-09-30 MY MYPI87002502A patent/MY101481A/en unknown
Also Published As
Publication number | Publication date |
---|---|
NO159683C (no) | 1989-01-25 |
EP0125980A3 (en) | 1984-12-27 |
DE3462945D1 (en) | 1987-05-07 |
CA1226206A (en) | 1987-09-01 |
ES532222A0 (es) | 1985-01-01 |
AU560904B2 (en) | 1987-04-16 |
ES8502536A1 (es) | 1985-01-01 |
AU2746084A (en) | 1984-11-08 |
NO841803L (no) | 1984-11-07 |
MY101481A (en) | 1991-11-18 |
JPH0627618B2 (ja) | 1994-04-13 |
OA07764A (fr) | 1985-08-30 |
SU1627097A3 (ru) | 1991-02-07 |
JPS6099982A (ja) | 1985-06-03 |
EP0125980A2 (fr) | 1984-11-21 |
FR2545589B1 (fr) | 1985-08-30 |
IN161272B (es) | 1987-11-07 |
US4539028A (en) | 1985-09-03 |
FR2545589A1 (fr) | 1984-11-09 |
NO159683B (no) | 1988-10-17 |
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