EP1939564A1 - Procédé d'obtention de gaz naturel liquéfié - Google Patents
Procédé d'obtention de gaz naturel liquéfié Download PDFInfo
- Publication number
- EP1939564A1 EP1939564A1 EP06127190A EP06127190A EP1939564A1 EP 1939564 A1 EP1939564 A1 EP 1939564A1 EP 06127190 A EP06127190 A EP 06127190A EP 06127190 A EP06127190 A EP 06127190A EP 1939564 A1 EP1939564 A1 EP 1939564A1
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- EP
- European Patent Office
- Prior art keywords
- natural gas
- stream
- air
- process according
- cooling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000003949 liquefied natural gas Substances 0.000 title claims abstract description 31
- 239000003507 refrigerant Substances 0.000 claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 186
- 239000003345 natural gas Substances 0.000 claims description 90
- 239000007789 gas Substances 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 19
- 238000000605 extraction Methods 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 239000002737 fuel gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 238000005057 refrigeration Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000001273 butane Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- IOYQOOUTHXXDIC-UHFFFAOYSA-N CSc1cccc(CC(C)N)c1 Chemical compound CSc1cccc(CC(C)N)c1 IOYQOOUTHXXDIC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000926 separation method Methods 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
- F25J1/0269—Arrangement of liquefaction units or equipments fulfilling the same process step, e.g. multiple "trains" concept
- F25J1/0271—Inter-connecting multiple cold equipments within or downstream of the cold box
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B35/00—Vessels or similar floating structures specially adapted for specific purposes and not otherwise provided for
- B63B35/28—Barges or lighters
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
- F25J1/0022—Hydrocarbons, e.g. natural gas
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
- F25J1/004—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by flash gas recovery
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0047—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
- F25J1/005—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 expansion of a gaseous refrigerant stream with extraction of work
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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
- F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
- F25J1/007—Primary atmospheric gases, mixtures thereof
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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
- F25J1/0203—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 single-component refrigerant [SCR] fluid in a closed vapor compression cycle
- F25J1/0204—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 single-component refrigerant [SCR] fluid in a closed vapor compression cycle as a single flow SCR 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
- F25J1/0221—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using the cold stored in an external cryogenic component in an open refrigeration loop
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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
- F25J1/0265—Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams comprising cores associated exclusively with the cooling of a refrigerant stream, e.g. for auto-refrigeration or economizer
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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
- F25J1/0275—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
- F25J1/0278—Unit being stationary, e.g. on floating barge or fixed platform
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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.
- F25J1/0285—Combination of different types of drivers mechanically coupled to the same refrigerant compressor, possibly split on multiple compressor casings
- F25J1/0288—Combination of different types of drivers mechanically coupled to the same refrigerant compressor, possibly split on multiple compressor casings using work extraction by mechanical coupling of compression and expansion of the refrigerant, so-called companders
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/40—Air or oxygen enriched air, i.e. generally less than 30mol% of O2
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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
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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
- F25J2240/00—Processes or apparatus involving steps for expanding of process streams
- F25J2240/02—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
- F25J2240/04—Multiple expansion turbines in parallel
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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
- F25J2270/00—Refrigeration techniques used
- F25J2270/14—External refrigeration with work-producing gas expansion loop
- F25J2270/16—External refrigeration with work-producing gas expansion loop with mutliple gas expansion loops of the same refrigerant
Definitions
- the invention relates to a process to obtain Liquefied Natural Gas (LNG) using air as refrigerant. This process can be performed by using an open or close air refrigerant cycle.
- LNG Liquefied Natural Gas
- Natural gas is often available in areas remote from where it will be ultimately used. When carrying it, natural gas is cooled to a temperature of approximately -260 °F (-160 °C) at atmospheric pressure so that it condenses to a liquid called liquefied natural gas (LNG). This LNG is normally transported overseas in appropriate carrier vessels.
- LNG liquefied natural gas
- the present invention refers to a novel process, system or plant capable of liquefying natural gas from any kind of natural gas fields, and particularly from "offshore” fields, and more particularly from stranded natural gas fields, wherein this process comprises air used as refrigerant.
- the system of the present invention comprises a simple and easily reproducible process in all possible locations, preferably "offshore" natural gas fields. This system is particularly advantageous when located in barges for liquefying gas from small natural gas fields located in distant areas, far away from the coast.
- a first aspect of this invention refers to a process to obtain liquefied natural gas which comprises the air used as refrigerant.
- This process can be developed as an air refrigeration cycle independent from the natural gas stream.
- an air refrigeration cycle comprising the following steps:
- the process can also comprise the further step:
- the air make-up may be treated to remove the CO 2 and water that can be carried using treating facilities known in the art.
- step (a) of the process is carried out in at least one stage, preferably more than one.
- the air refrigerant cycle of the invention can be open or closed.
- the air refrigeration cycle When the air refrigeration cycle is open, the air is continuously taken from the environment, at atmospheric conditions, treated to remove CO 2 and water, used to cool natural gas according to the above steps, and given back to the atmosphere.
- step (a) When the air refrigeration cycle is closed, the air used to cool natural gas goes back to the beginning of the process (step (a)).
- the natural gas stream passes through the following steps:
- the natural gas can be liquefied completely (LNG), without letting any vapor phase, or not obtaining two phases, liquid and vapor.
- the natural gas stream comprises the further step:
- the natural gas stream may further comprise the stage of separating their natural gas liquids (NGL), before liquefaction.
- NNL natural gas liquids
- Natural gas liquids refers to less volatile components of the natural gas, from ethane to higher hydrocarbons (ethane, propane, butane, isobutane and natural gasoline, the latter sometimes called condensate), with minor content of methane.
- the natural gas stream can be pre-treated, if required, before cooling it.
- pretreatment arrangements are known in the art. The appropriate pretreatment depends on the location, the type, the precise composition and the level and nature of undesirable contaminants or impurities present in the natural gas feed. It usually could comprise the removal, but are not limited to, Hg, H 2 O, CO 2 or H 2 S.
- This natural gas stream is often passed to the process with a pressure of at least 1 bar, and preferably above 10 bar; it also depends on the location, and the type of the natural gas in the gas-field.
- the feed of natural gas can be poor in heavier hydrocarbons and it needs no separation of the natural gas liquids; alternately, should the natural gas is partially rich in heavier hydrocarbons, the natural gas liquids can be kept in the final LNG and separated by fractionation after its transportation to the final destination. In both cases the natural gas is liquefied as such and this is realized using a single heat exchanger.
- a natural gas stream particularly rich in heavier hydrocarbons is cooled in two stages:
- the natural gas is cooled with air, until a suitable temperature that allows condensing as a liquid the required quantity of natural gas liquids (NGL).
- NNL natural gas liquids
- This stage is carried out through a first heat exchanger.
- This temperature could depend on the natural gas feed composition, LNG specifications, or on particular requirements in heavier components recoveries and/or purities. This temperature will not be lower than -100°C.
- lean natural gas refers to a stream which contains almost all the methane and the nitrogen of the initial feed, the desired quantity of ethane and small residual quantities of the less volatile components (propane and higher).
- the lean natural gas goes through a second heat exchanger where it is cooled with the air, until the gas is almost totally or fully liquefied.
- the temperature at which the NG exits this heat exchanger will not be lower than -163°C.
- the cooling and liquefaction of a natural gas stream particularly rich in heavier hydrocarbons can be carried out in only one heat exchanger.
- the NGL extraction is done after the gas pretreatment and before the cooling and liquefaction.
- the endflash gas stream obtained as subproduct in the liquefying of natural gas, is used to cool natural gas and air streams in the process in order to recover its cryogenic energy, and as fuel gas.
- This fuel could feed gas turbines and it will typically need to be pressurized by a compressor before being introduced to them.
- the amount of endflash gas obtained can match the quantity of required fuel gas or it can be part of it or it can be in excess and be used partly for other purposes.
- a second aspect of the present invention refers to a system to carry out the previously described process which comprises a continuous stream of natural gas, gas treatment facilities and an air refrigerant cycle.
- Air is used as refrigerant in the refrigerant cycle of this system in order to obtain liquefied natural gas.
- This cycle can preferably be closed loop or open cycle.
- system comprises the following pieces of equipment:
- system comprises further equipment:
- system comprises further equipment:
- this system may be located on a fixed structure such as a platform or a movable structure such as a barge or a ship. Both structures may be used in all types of natural gas fields, including onshore and offshore gas fields. This allows the exploitation in any kind of deposit, even for exploitation of stranded gas (small volume and remote area fields).
- onshore refers to something that is on land.
- offshore refers to something that is in the sea away from the shore; not on the shoreline but out to the sea.
- the system can be located on two separate areas (two different fixed structures, two different movable structures or one fixed structure and one movable structure).
- One area may be dedicated to the gas pretreatment unit and the NGL extraction facilities, while the other area may be dedicated to the liquefaction unit.
- a third aspect of this invention refers to the use of the system previously described for natural gas fields, and preferably for stranded natural gas fields.
- stranded natural gas field refers to a natural gas field that has been discovered, but remains unusable for either physical or economic reasons. Economically, because the reserve is too remote from a market for natural gas; or physically, if the gas field is too deep to drill for, or is beneath an obstruction.
- Another aspect of this invention relates to the use of the previously described system for producing at least 0.1 MTA (million tonnes per year) of LNG, and preferably, the production of LNG is within the range of 0.5 to 3 MTA.
- Fig.1 shows one example of the present invention as applied to liquefaction of a natural gas feed stream using air as refrigerant.
- the natural gas feed stream 1 is treated in a conventional pretreatment plant A to remove CO 2 , H 2 S, water and mercury contaminants.
- the treated gas, stream 2 corresponds to a sweet, dry natural gas stream at 15°C, 30 bar.
- Stream 2 has a molar composition as given in Table 1 below.
- Table 1 Treated gas composition example Component Mole Fraction Nitrogen 0.0020 Methane 0.8387 Ethane 0.1204 Propane 0.0274 n-Butane 0.0081 n-Pentane 0.0034
- Stream 2 enters the liquefaction plant, passing through two heat exchangers 100, 101 in order to obtain a subcooled high pressure liquid, stream 6.
- the natural gas is precooled to an intermediate temperature of about -69°C (stream 3), in order to condense the natural gas liquids.
- Stream 3 enters a column B where the natural gas liquids are extracted as stream 4 at the bottom, while the lean gas, stream 5, exits the column at the top.
- Stream 4 will be directed to a fractionation zone, if specific products like propane and butane are required.
- the lean natural gas (stream 5) enters the second heat exchanger 101, and it is cooled to a temperature of about -130°C, obtaining a subcooled high pressure liquid stream (stream 6), which is directed to a JT-valve 102, through which the stream 6 is expanded adiabatically to 1.1 bar and finally directed to an endflash vessel 103, which separates liquid and vapor, producing LNG to storage (stream 8) and endflash gas (stream 9), both at about -160°C and 1.1 bar.
- stream 9 is passed back to both heat exchangers 101 and 100, respectively, where the cryogenic energy of this stream is recovered.
- stream 9 exits the heat exchanger 101 at -91°C, obtaining stream 10, which is further heated by heat exchanger 100 to the temperature of 15°C (stream 11).
- This vapor stream 11 can be used as fuel within the plant. In case this fuel feeds gas turbines, stream 11 will typically need to be pressurized by a compressor before being introduced to them.
- the heat exchangers in the natural gas side are plate-fin heat exchangers.
- the air refrigeration cycle which transforms gas stream 2 to liquid stream 6 will now be described, starting with air stream 12 which has been exhausted of all or most of its cooling properties by absorbing heat from the feed gas.
- Stream 12 at about 34°C, is at the lowest pressure of the cycle (about 2 bar) and is fed to and recompressed in a multistage compressor unit 104 provided with intercooling and aftercooling stages to produce compressed stream 18.
- the compressor zone comprises three compressors 105, 107 and 109, with one heat exchanger 106 between compressors 105 and 107, one heat exchanger 108 between compressors 107 and 109 and one heat exchanger 110 after the last compressor 109.
- the intercoolers 106 and 108, and the aftercooler 110 use water as coolant medium.
- Compressed stream 18 exits the compressor unit 104 at 40°C, 30 bar and is directed to heat exchanger 100, where is precooled to -24°C by the countercurrent passage of air refrigerant stream 21 and of endflash gas 10.
- Stream 18 emerges as stream 19 from heat exchanger 100 and is passed to an expander zone 111 to reduce the pressure and temperature of the air stream 19, resulting in the stream 24.
- the expander zone comprises two turboexpanders 112 and 113 in parallel and is used to provide part of the power for the compressors of the compressor unit 104.
- the air stream 24 (which has been expanded in the expander zone 111) is at 2.1 bar and at a temperature of about -135°C. It passes through both heat exchangers 101 and 100, respectively.
- the stream 24 provides enough cooling to liquefy the natural gas stream 5 to form liquid natural gas (stream 6).
- Stream 24 emerges as stream 25 from heat exchanger 101 at a temperature of -73°C and it enters heat exchanger 100, where it precools both the natural gas (stream 2) and the compressed air (stream 18).
- Stream 25 leaves the heat exchanger 100 as stream 12 and it starts the cycle again.
- the air cycle will have a point for make up in order to compensate for air losses in the air cycle.
- the air make-up will have to be treated in treating facilities to eliminate the CO 2 and water that it can carry.
- Table 2 shows the operating conditions of the main streams of FIG. 1 .
- Table 2 Stream P (bar) T (°C) 2 30 15 3 29.8 -68.6 5 29.8 -68.6 6 29.6 -130.4 7 1.1 -159.4 8 1.1 -159.4 9 1.1 -159.4 10 1.05 -90.8 11 1 15 12 1.95 34.5 18 30 40 19 29.9 -24.1 24 2.15 -134.6 25 2.05 -73.4
- FIG. 2 shows another example of the present invention.
- the example shown in FIG. 2 has, as modification in relation to FIG. 1 , that the air used as refrigerant flows in an open loop.
- the natural gas 1 is treated in the pretreatment plant A to remove CO 2 , H 2 S, water and mercury contaminants (the treated gas, stream 2, has the composition shown in Table 1) and then liquefied by exchange with cold air in two steps.
- the heat exchanger 100 precooled in the heat exchanger 100 to a temperature of about -69°C (stream 3). It passes through a column B where the liquids are extracted as the bottom stream 4; the lean natural gas exits the column B at the top (stream 5) and enters the second heat exchanger 101.
- the liquid stream emerging from heat exchanger 101 at about -130°C (stream 6) is directed to an expansion zone, where is expanded adiabatically in a JT-valve 102 to 1.1 bar (stream 7).
- stream 7 is directed to an endflash vessel 103, which separates liquid and vapor, producing LNG to storage (stream 8) and endflash gas (stream 9), both at about -160°C and 1.1 bar.
- Stream 9 is passed back to both heat exchangers 101 and 100, respectively, where the cryogenic energy of this stream is recovered, in an identical way as in Example 1.
- endflash gas exits heat exchanger 100 as stream 11 at 15°C, 1 bar.
- This vapor stream 11 can be used as fuel within the plant.
- the air refrigeration cycle in FIG. 2 , is an open loop. In this cycle, the air is continuously taken from the atmosphere at ambient conditions (stream 12*). Stream 12* enters the treating plant C, which is in charge of removing the CO 2 and water that can carry the air and leaves the plant as stream 12 (15°C, 1 bar). Stream 12 is compressed in a multistage compressor unit 104 provided with intercooling and aftercooling stages to produce compressed stream 18, which exits the compressor unit 104 at 40°C and 16 bar. It is directed to heat exchanger 100, where is precooled to about -27°C by the countercurrent passage of air refrigerant stream 21 and of endflash gas 10.
- Stream 18 emerges as stream 19 from heat exchanger 100 and is passed to an expander zone 111, where the pressure and the temperature is reduced to about 1.2 bar and -133°C, respectively (stream 24).
- Stream 24 passes through both heat exchangers 101 and 100, respectively.
- the stream 24 provides enough cooling to liquefy the natural gas stream 5 to form liquid natural gas (stream 6).
- Stream 24 emerges as stream 25 from heat exchanger 101 at a temperature of about -74°C and it enters heat exchanger 100, where it precools both the natural gas (stream 2) and the compressed air (stream 18).
- Stream 25 leaves the heat exchanger 100 as stream 26 at about 33°C and 1 bar, and it is released directly to the atmosphere.
- Table 3 shows the operating conditions of the main streams of FIG. 2 .
- Table 3 Stream P (bar) T (°C) 2 30 15 3 29.8 -68.6 5 29.8 -68.6 6 29.6 -130.4 7 1.1 -159.4 8 1.1 -159.4 9 1.1 -159.4 10 1.05 -90.8 11 1 15 12 1 15 18 16 40 19 15.9 -26.7 24 1.2 -133.1 25 1.1 -74.1 26 1 33.3
- FIG. 3 shows another example of the present invention.
- the natural gas 1 is treated in the pretreatment plant A (the treated gas, stream 2, has the composition shown in Table 1) and then liquefied by exchanging heat with cold air in two steps.
- the heat exchanger 100 precooled in the heat exchanger 100 to a temperature of about -69°C (stream 3). It passes through a column B where the liquids are extracted as the bottom stream 4; the lean natural gas exits the column B at the top (stream 5) and enters the second heat exchanger 101.
- the liquid stream emerging from heat exchanger 101 at about -131°C (stream 6) is directed to an expansion zone, where is expanded adiabatically in a JT-valve 102 to 1.1 bar (stream 7).
- stream 7 is directed to an endflash vessel 103, which separates liquid and vapor, producing LNG to storage (stream 8) and endflash gas (stream 9), both at about -160°C and 1.1 bar.
- Stream 9 is passed back to both heat exchangers 101 and 100, respectively, where the cryogenic energy of this stream is recovered, in an identical way as in Examples 1 and 2.
- endflash gas exits heat exchanger 100 as stream 11 at 15°C, 1 bar. This vapor stream 11 can be used as fuel within the plant.
- the stream 24 provides enough cooling to liquefy the natural gas stream 5 to form liquid natural gas (stream 6).
- Stream 24 emerges as stream 25 from heat exchanger 101 at a temperature of about -81°C and it enters heat exchanger 100, where it precools the natural gas (stream 2).
- Stream 25 leaves the heat exchanger 100 as stream 26 at about -43°C and 3.7 bar, and is directed to the heat exchanger 114, where this stream precools the countercurrent air stream 18.
- Stream 26 leaves the heat exchanger 114 as stream 12 and it starts the cycle again.
- the air cycle will have a point for make up in order to compensate for air losses in the air cycle.
- the air make up will have to be treated in treating facilities to eliminate the CO 2 and water that it can carry.
- Table 4 shows the operating conditions of the main streams of FIG. 3 .
- Table 4 Stream P (bar) T (°C) 2 30 15 3 29.9 -69.1 5 29.8 -68.9 6 29.6 -130.6 7 1.1 -159.5 8 1.1 -159.5 9 1.1 -159.5 10 1.05 -80 11 1 15 12 3.6 36.4 18 43 40 19 42.9 -33.1 24 3.9 -135.4 25 3.8 -80.7 26 3.7 -43.3
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Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06127190A EP1939564A1 (fr) | 2006-12-26 | 2006-12-26 | Procédé d'obtention de gaz naturel liquéfié |
CN2007800484718A CN101606033B (zh) | 2006-12-26 | 2007-12-12 | 生产液化天然气的系统和方法 |
PCT/EP2007/063792 WO2008077788A2 (fr) | 2006-12-26 | 2007-12-12 | Système et procédé de production de gaz naturel liquéfié |
ES200990007A ES2346731B1 (es) | 2006-12-26 | 2007-12-12 | Sistema y procedimiento de produccion de gas natural licuado. |
JP2009543431A JP5547967B2 (ja) | 2006-12-26 | 2007-12-12 | 液化天然ガスの製造システムおよびその方法 |
KR1020097013479A KR101462290B1 (ko) | 2006-12-26 | 2007-12-12 | 액화 천연가스(lng)의 생산 시스템 및 생산 방법 |
BRPI0719617-2A2A BRPI0719617A2 (pt) | 2006-12-26 | 2007-12-12 | "sistema e método de produção de gás natural liquifeito (gnl) " |
DE112007003171T DE112007003171T5 (de) | 2006-12-26 | 2007-12-12 | System und Verfahren zur Herstellung von Flüssigerdgas |
NO20092396A NO20092396L (no) | 2006-12-26 | 2009-06-24 | System og fremgangsmate for produksjon av flytende naturgass |
HK10106031.6A HK1139454A1 (en) | 2006-12-26 | 2010-06-17 | System and method of production of liquefied natural gas |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06127190A EP1939564A1 (fr) | 2006-12-26 | 2006-12-26 | Procédé d'obtention de gaz naturel liquéfié |
Publications (1)
Publication Number | Publication Date |
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EP1939564A1 true EP1939564A1 (fr) | 2008-07-02 |
Family
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EP06127190A Ceased EP1939564A1 (fr) | 2006-12-26 | 2006-12-26 | Procédé d'obtention de gaz naturel liquéfié |
Country Status (10)
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---|---|
EP (1) | EP1939564A1 (fr) |
JP (1) | JP5547967B2 (fr) |
KR (1) | KR101462290B1 (fr) |
CN (1) | CN101606033B (fr) |
BR (1) | BRPI0719617A2 (fr) |
DE (1) | DE112007003171T5 (fr) |
ES (1) | ES2346731B1 (fr) |
HK (1) | HK1139454A1 (fr) |
NO (1) | NO20092396L (fr) |
WO (1) | WO2008077788A2 (fr) |
Cited By (5)
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WO2010024691A2 (fr) * | 2008-08-29 | 2010-03-04 | Hamworthy Gas Systems As | Procédé et système pour une production de gnl optimisée |
ES2355467A1 (es) * | 2009-09-11 | 2011-03-28 | Repsol Ypf, S.A. | Proceso y sistema para obtener gas natural licuado. |
WO2012175887A2 (fr) | 2011-06-24 | 2012-12-27 | Saipem S.A. | Procede de liquefaction de gaz naturel avec un melange de gaz refrigerant |
CN102239377B (zh) * | 2008-08-29 | 2016-12-14 | 瓦锡兰油气系统公司 | 用于优化的液化天然气生产的方法和系统 |
WO2020205750A1 (fr) * | 2019-03-29 | 2020-10-08 | Bright Energy Storage Technologies, Llp | Système et procédé de séparation et de liquéfaction du co2 |
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US8601833B2 (en) | 2007-10-19 | 2013-12-10 | Air Products And Chemicals, Inc. | System to cold compress an air stream using natural gas refrigeration |
KR101110864B1 (ko) | 2009-02-27 | 2012-02-16 | 삼성중공업 주식회사 | 부유식 액화천연가스생산 저장설비 |
CN102115683A (zh) * | 2009-12-30 | 2011-07-06 | 中国科学院理化技术研究所 | 一种生产液化天然气的方法 |
KR101637334B1 (ko) * | 2010-04-30 | 2016-07-08 | 대우조선해양 주식회사 | 천연가스 액화방법 및 장치 |
CN102206520B (zh) * | 2011-04-21 | 2013-11-06 | 北京工业大学 | 一种天然气直接膨胀式液化方法及装置 |
CN102200370A (zh) * | 2011-04-21 | 2011-09-28 | 北京工业大学 | 一种膨胀式可燃气体液化装置及流程 |
GB2486036B (en) * | 2011-06-15 | 2012-11-07 | Anthony Dwight Maunder | Process for liquefaction of natural gas |
BR112015002174A2 (pt) * | 2012-09-07 | 2017-07-04 | Keppel Offshore & Marine Tech Ct Pte Ltd | sistema e método para a liquefação de gás natural |
KR102239826B1 (ko) * | 2014-08-14 | 2021-04-13 | 대우조선해양 주식회사 | 해상 천연가스 액화 및 저장 구조물 및 방법 |
CN104845692A (zh) * | 2015-04-03 | 2015-08-19 | 浙江大学 | 一种油田伴生气全液化回收系统及其方法 |
WO2017121042A1 (fr) * | 2016-01-15 | 2017-07-20 | 成都赛普瑞兴科技有限公司 | Procédé et appareil de liquéfaction de gaz riche en méthane par réfrigération par détente |
CN106705569A (zh) * | 2017-03-28 | 2017-05-24 | 北京工业大学 | 一种容积式压缩膨胀制冷的可燃气体液化装置及使用方法 |
KR102144193B1 (ko) * | 2018-11-15 | 2020-08-28 | 한국조선해양 주식회사 | 가스 처리 시스템 및 이를 포함하는 해양 구조물 |
KR102622554B1 (ko) * | 2021-08-18 | 2024-01-11 | 부산대학교 산학협력단 | 천연가스 액화 시스템, 이를 포함하는 선박, 천연가스 및 공기의 액화 방법 |
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- 2007-12-12 CN CN2007800484718A patent/CN101606033B/zh not_active Expired - Fee Related
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010024691A2 (fr) * | 2008-08-29 | 2010-03-04 | Hamworthy Gas Systems As | Procédé et système pour une production de gnl optimisée |
CN102239377A (zh) * | 2008-08-29 | 2011-11-09 | 海威石油天然气系统公司 | 用于优化的液化天然气生产的方法和系统 |
WO2010024691A3 (fr) * | 2008-08-29 | 2012-01-19 | Hamworthy Oil & Gas Systems As | Procédé et système pour une production de gnl optimisée |
AU2009286189B2 (en) * | 2008-08-29 | 2013-07-18 | Wartsila Oil & Gas Systems As | Method and system for optimized LNG production |
US9163873B2 (en) | 2008-08-29 | 2015-10-20 | Wärtsilä Oil & Gas Systems As | Method and system for optimized LNG production |
CN102239377B (zh) * | 2008-08-29 | 2016-12-14 | 瓦锡兰油气系统公司 | 用于优化的液化天然气生产的方法和系统 |
ES2355467A1 (es) * | 2009-09-11 | 2011-03-28 | Repsol Ypf, S.A. | Proceso y sistema para obtener gas natural licuado. |
WO2012175887A2 (fr) | 2011-06-24 | 2012-12-27 | Saipem S.A. | Procede de liquefaction de gaz naturel avec un melange de gaz refrigerant |
FR2977014A1 (fr) * | 2011-06-24 | 2012-12-28 | Saipem Sa | Procede de liquefaction de gaz naturel avec un melange de gaz refrigerant. |
US9777959B2 (en) | 2011-06-24 | 2017-10-03 | Saipem S.A. | Method for liquefying natural gas with a mixture of coolant gas |
WO2020205750A1 (fr) * | 2019-03-29 | 2020-10-08 | Bright Energy Storage Technologies, Llp | Système et procédé de séparation et de liquéfaction du co2 |
US11486638B2 (en) | 2019-03-29 | 2022-11-01 | Carbon Capture America, Inc. | CO2 separation and liquefaction system and method |
Also Published As
Publication number | Publication date |
---|---|
KR101462290B1 (ko) | 2014-11-14 |
JP5547967B2 (ja) | 2014-07-16 |
CN101606033A (zh) | 2009-12-16 |
BRPI0719617A2 (pt) | 2014-04-08 |
HK1139454A1 (en) | 2010-09-17 |
ES2346731A1 (es) | 2010-10-19 |
CN101606033B (zh) | 2011-10-26 |
DE112007003171T5 (de) | 2009-11-26 |
WO2008077788A2 (fr) | 2008-07-03 |
JP2010514871A (ja) | 2010-05-06 |
ES2346731B1 (es) | 2011-08-10 |
WO2008077788A3 (fr) | 2008-11-27 |
NO20092396L (no) | 2009-09-04 |
KR20090105919A (ko) | 2009-10-07 |
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