DK174634B1 - Forbedret fremgangsmåde til fortætning af naturgas - Google Patents
Forbedret fremgangsmåde til fortætning af naturgas Download PDFInfo
- Publication number
- DK174634B1 DK174634B1 DK199901813A DKPA199901813A DK174634B1 DK 174634 B1 DK174634 B1 DK 174634B1 DK 199901813 A DK199901813 A DK 199901813A DK PA199901813 A DKPA199901813 A DK PA199901813A DK 174634 B1 DK174634 B1 DK 174634B1
- Authority
- DK
- Denmark
- Prior art keywords
- stream
- gas
- methane
- rich
- vapor
- Prior art date
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 149
- 238000000034 method Methods 0.000 title claims description 84
- 239000003345 natural gas Substances 0.000 title claims description 48
- 238000000280 densification Methods 0.000 title description 17
- 239000007789 gas Substances 0.000 claims description 89
- 230000008569 process Effects 0.000 claims description 59
- 238000001816 cooling Methods 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 32
- 239000012071 phase Substances 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims description 16
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 239000012263 liquid product Substances 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 11
- 238000005194 fractionation Methods 0.000 claims description 10
- 239000003507 refrigerant Substances 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 7
- 239000001294 propane Substances 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims 5
- 239000003949 liquefied natural gas Substances 0.000 description 41
- 241000196324 Embryophyta Species 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000006835 compression Effects 0.000 description 10
- 238000007906 compression Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DTAFLBZLAZYRDX-UHFFFAOYSA-N OOOOOO Chemical compound OOOOOO DTAFLBZLAZYRDX-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 235000010044 Hernandia moerenhoutiana Nutrition 0.000 description 1
- 244000084296 Hernandia moerenhoutiana Species 0.000 description 1
- RSPISYXLHRIGJD-UHFFFAOYSA-N OOOO Chemical compound OOOO RSPISYXLHRIGJD-UHFFFAOYSA-N 0.000 description 1
- JLNTWVDSQRNWFU-UHFFFAOYSA-N OOOOOOO Chemical compound OOOOOOO JLNTWVDSQRNWFU-UHFFFAOYSA-N 0.000 description 1
- OZBZONOEYUBXTD-UHFFFAOYSA-N OOOOOOOOO Chemical compound OOOOOOOOO OZBZONOEYUBXTD-UHFFFAOYSA-N 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- -1 benzene Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011555 saturated liquid Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0247—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 4 carbon atoms or more
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C13/00—Details of vessels or of the filling or discharging of vessels
- F17C13/001—Thermal insulation specially adapted for cryogenic vessels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3053—Fe as the principal constituent
- B23K35/3066—Fe as the principal constituent with Ni as next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K9/00—Arc welding or cutting
- B23K9/16—Arc welding or cutting making use of shielding gas
- B23K9/173—Arc welding or cutting making use of shielding gas and of a consumable electrode
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
- B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
- B60K15/03—Fuel tanks
- B60K15/03006—Gas tanks
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- C—CHEMISTRY; METALLURGY
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C—CHEMISTRY; METALLURGY
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
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- F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
- F17C1/002—Storage in barges or on ships
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
- F17C1/14—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of aluminium; constructed of non-magnetic steel
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C3/00—Vessels not under pressure
- F17C3/02—Vessels not under pressure with provision for thermal insulation
- F17C3/025—Bulk storage in barges or on ships
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C7/00—Methods or apparatus for discharging liquefied, solidified, or compressed gases from pressure vessels, not covered by another subclass
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C7/00—Methods or apparatus for discharging liquefied, solidified, or compressed gases from pressure vessels, not covered by another subclass
- F17C7/02—Discharging liquefied gases
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- F17D1/00—Pipe-line systems
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- F17D1/082—Pipe-line systems for liquids or viscous products for cold fluids, e.g. liquefied gas
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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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"
- F25J1/0035—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 gas expansion 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
- F25J1/003—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"
- F25J1/0035—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 gas expansion with extraction of work
- F25J1/0037—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 gas expansion with extraction of work of a return stream
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/003—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
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- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
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- F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
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Description
FORBEDRET FREMGANGSMÅDE TIL FORTÆTNING AF NATURGAS
OPFINDELSENS OMRÅDE
DK 174634 B1 5 Den foreliggende opfindelse angår en naturgasfortætningsproces og mere specifikt en fremgangsmåde til fremstilling af flydende naturgas under tryk (PLNG).
OPFINDELSENS BAGGRUND
10 På grund af sine rene brændegenskaber og bekvemmelighed er naturgas blevet vidt anvendt i de senere år. Mange naturgaskilder er beliggende i fjerntliggende områder i store afstande fra eventuelle kommercielle markeder for gassen. Sommetider er en rørledning tilgængelig til at transportere produceret naturgas til et kommercielt marked. Når rørledningstransport ikke er mulig, bliver produceret naturgas ofte forarbejdet til fortættet 15 eller flydendegjort naturgas (som kaldes "LNG") til transport til markedet.
Ét af de typiske kendetegn for et LNG-anlæg er den store kapitalinvestering, der er nødvendig for anlægget. Det udstyr, der anvendes til at gøre naturgas flydende, er generelt temmeligt dyrt. Fortætningsanlægget består af flere basale systemer, herunder gasbe-20 handling for at fjerne urenheder, fortætning, nedkøling, energifaciliteter og lagrings- og skibslastningsfaciliteter. Om end prisen for et LNG-anlæg kan variere meget afhængigt af anlæggets beliggenhed, kan et typisk konventionelt LNG-projekt koste fra US $ 5 milliarder til US $ 10 milliarder, inklusive feltudviklingsomkostninger. Anlæggets nedkølingssystemer kan udgøre op til 30% af omkostningerne.
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Ved konstruktion af et LNG-anlæg er tre af de vigtigste hensyn (1) valg af fortætningscyklus, (2) de anvendte materialer i beholdere, rør og andet udstyr og (3) procestrinnene til at omdanne naturgas-f ødestrøm til LNG.
30 LNG-kølesystemer er dyre, fordi der kræves så meget køling til at fortætte naturgas. En typisk naturgasstrøm kommer ind i et LNG-anlæg ved tryk på fra ca. 4830 kPa (700 psia) til ca. 7600 kPa (1100 psia) og temperaturer fra ca. 20°C (68°F) til ca. 40°C (104°F).
Naturgas, som hovedsagelig er methan, kan ikke fortættes ved blot at øge trykket, således som det er tilfældet med tungere carbonhydrider, der anvendes til energiformål. Den 35 kritiske temperatur for methan er -82,5°C (-116,5°F). Dette betyder, at methan kun kan DK 174634 B1 2 fortættes under den temperatur, uanset det påførte tryk. Eftersom naturgas er en blanding af gasser, fortætter den over et temperaturinterval. Den kritiske temperatur for naturgas er mellem ca. -85°C (-121°F) og -62°C (-80°F). Naturgaskompositioner ved atmosfærisk tryk vil typisk fortætte i temperaturintervallet mellem ca. -165°C (-265°F) og -155°C (-247°F).
5 Eftersom køleudstyr repræsenterer en så signifikant del af LNG-anlæggets pris, er der blevet gjort en betydelig indsats på at reducere køleomkostninger.
Selv om der er blevet anvendt mange kølecykler til at fortætte naturgas, er de tre typer, der mest almindeligt anvendes i LNG-anlæg i dag: (1) "kaskadecyklen", som anvender multiple 10 enkeltkomponent-kølemidler i varmevekslere arrangeret progressivt for at reducere temperaturen af gassen til en fortætningstemperatur, (2) "multikomponent-kølecyklen", som anvender et multikomponent-kølemiddel i særligt konstruerede vekslere og (3) "ekspansionscyklen", som ekspanderer gas fra et højt tryk til et lavt tryk med en tilsvarende reduktion i temperatur. De fleste naturgas-fortætningscykler anvender variationer eller kombinationer 15 af disse tre basistyper.
Ekspansionssystemet opererer ud fra det princip, at gas kan komprimeres til et udvalgt tryk, afkøles og derefter tillades at ekspandere gennem en ekspansionsturbine, hvorved der udføres arbejde, og gassens temperatur reduceres. Det er muligt at fortætte en del af 20 gassen i en sådan ekspansion. Lavtemperaturgassen varmeveksles derefter for at bevirke fortætning af fødematerialet. Den fra ekspansionen opnåede energi anvendes sædvanligvis til at levere en del af den hovedkompressionsenergi, der anvendes i kølecyklen. Eksempler på ekspansionsprocesser til fremstilling af LNG er beskrevet i US-patent nr. 3.724.226; 4.456.459; 4.698.081; og WO 9713109.
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Materialer anvendt i konventionelle LNG-anlæg bidrager også til anlæggets pris. Beholdere, rørføringer og andet udstyr anvendt i LNG-anlæg er typisk konstrueret i hvert fald delvist af aluminium, rustfrit stål eller stål med højt nikkelindhold for at give den nødvendige styrke og brud-sejhed ved lave temperaturer.
30 I konventionelle LNG-anlæg skal vand, carbondioxid, svovlholdige forbindelser såsom hydrogensulfid og andre sure gasser, n-pentan og tungere carbonhydrider, herunder benzen, i det væsentlige fjernes fra naturgasforarbejdningen ned til niveauer på milliontedele (ppm). Nogle af disse forbindelser vil fryse, hvilket forårsager tilstopningsproblemer i procesudsty-35 ret. Andre forbindelser såsom dem, der indeholder svovl, fjernes typisk for at overholde 3 DK 174634 B1 salgsspecifikationer. I et konventionelt LNG-anlæg kræves der gasbehandlingsudstyr for at fjerne carbondioxidet og de sure gasser. Gasbehandlingsudstyret anvender typisk en kemisk og/eller fysisk solvent-regenereringsproces og kræver en betydelig kapitalinvestering. Driftsomkostningerne er også høje. Dry-bed-dehydratorer såsom molekylsier er 5 nødvendige for at fjerne vanddampen. En scrubber-kolonne og fraktioneringsudstyr anvendes typisk til at fjerne de carbonhydrider, der har tendens til at forårsage tilstopningsproblemer. Kviksølv fjernes også i et konventionelt LNG-anlæg, eftersom det kan forårsage svigt i udstyr konstrueret af aluminium. Endvidere bliver en stor del af det nitrogen, der kan være til stede i naturgas, fjernet efter forarbejdning, eftersom nitrogen 10 ikke vil forblive i væskefasen under transport af konventionel LNG, og det er uønsket at have nitrogendamp i LNG-beholdere på leveringsstedet.
Der er et fortsat behov inden for industrien for en forbedret proces til fortætning af naturgas, hvilken proces minimerer den nødvendige mængde behandlingsudstyr.
15
OPSUMMERING
Den foreliggende opfindelse angår en forbedret fremgangsmåde til fortætning af en føde-gasstrøm, der er rig på methan ifølge Krav 1. Fødegasstrømmen har et tryk på over ca.
20 3100 kPa (450 psia). Hvis trykket er for lavt, kan gassen først blive komprimeret. Fremgangsmåden er yderligere beskrevet ved træk som angivet i krav 2-18.
Dersom fødegassen indeholder komponenter tungere end methan, fjernes den overvejende del af de tungere carbonhydrider i en anden udførelsesform for opfindelsen 25 ved en fraktioneringsproces før fortætningen ved trykekspansion. 1 endnu en udførelsesform af opfindelsen kan en afkogningsgas, der resulterer fra fordampning af fortættet naturgas, tilsættes til fødegassen til fortætning ved trykekspansion til fremstilling af flydende naturgas undertryk (PLNG).
30
Fremgangsmåden ifølge den foreliggende opfindelse kan anvendes både til den indledende fortætning af en naturgas ved forsyningskilden for til lagring eller transport og til at genfortætte naturgasdamp, der afgives under opbevaring og skibslastning. Et formål med denne opfindelse er følgelig at tilvejebringe et forbedret fortætningssystem til fortætning 35 eller genfortætning af naturgas. Et andet formål med denne opfindelse er at tilvejebringe et DK 174634 B1 4 forbedret fortætningssystem, hvor der kræves væsentligt mindre kompressionsenergi end i kendte systemer. Endnu et formål med opfindelsen er at tilvejebringe en forbedret fortætningsproces, der er økonomisk og effektiv i drift. Konventionelle LNG-processers nedkøling til meget lave temperaturer er meget dyr sammenlignet med den relativt milde nedkøling, 5 der er nødvendig ved fremstilling af PLNG i overensstemmelse med den foreliggende opfindelses praksis.
KORT BESKRIVELSE AF TEGNINGERNE
10 Den foreliggende opfindelse og dens fordele vil blive bedre forstået ved henvisning til den følgende detaljerede beskrivelse og de vedhæftede figurer, som er skematiske flowdia-grammer af repræsentative udførelsesformer af denne opfindelse.
Fig. 1 er et skematisk flowdiagram af én udførelsesform af denne opfindelse til fremstilling 15 af PLNG.
Fig. 2 er et skematisk flowdiagram af en anden udførelsesform af denne opfindelse, i hvilken naturgassen for-køles ved hjælp af et kølesystem med lukket cyklus inden fortætning af naturgassen ved trykekspansion.
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Fig. 3 er et skematisk flowdiagram af en tredje udførelsesform af denne opfindelse, i hvilken fødenaturgas fraktioneres inden fortætning til PLNG.
Fig. 4 er et skematisk flowdiagram af en fjerde udførelsesform af denne opfindelse, der lig-25 ner fremgangsmåden illustreret i fig. 3, og i hvilken et kølesystem med lukket cyklus og trykekspansion anvendes til at fremstille PLNG.
5 DK 174634 B1
Flowdiagrammerne illustreret i figurerne præsenterer forskellige udførelsesformer for udøvelse af fremgangsmåden ifølge opfindelsen. Figurerne er ikke tænkt at skulle udelukke fra opfindelsens omfang andre udførelsesformer, som er resultatet af normale og forventede modifikationer af disse specifikke udførelsesformer. Forskellige nødvendige 5 undersystemer såsom pumper, ventiler, flowstrømblandere, styresystemer og følere er blevet fjernet fra figurerne af hensyn til præsentationens enkelthed og klarhed.
BESKRIVELSE AF DE FORETRUKNE UDFØRELSESFORMER
Den foreliggende opfindelse er en forbedret fremgangsmåde til fortætning af naturgas ved 10 trykekspansion til fremstilling af et methanrigt flydende produkt med en temperatur over ca.
-112°C (-170°F) og et tryk, der er tilstrækkeligt til, at det flydende produkt er ved eller under sit boblepunkt. Dette methanrige produkt betegnes til tider i denne beskrivelse som flydende naturgas under tryk ("PLNG"). Udtrykket "boblepunkt" er den temperatur og det tryk, ved hvilken/hvilket en væske begynder at omdannes til gas. Hvis fx et vist volumen PLNG 15 holdes ved konstant tryk, men dens temperatur øges, er boblepunktet den temperatur, ved hvilken bobler af gas begynder at dannes i PLNG'en. Hvis på samme måde et vist volumen PLNG holdes ved konstant temperatur, men trykket reduceres, defineres boblepunktet som det tryk, ved hvilket gas begynder at dannes. Ved boblepunktet er blandingen mættet væske.
20
Gasfortætningsfremgangsmåden ifølge den foreliggende opfindelse kræver mindre energi til fortætning af naturgassen end tidligere anvendte processer, og udstyret anvendt i fremgangsmåden ifølge opfindelsen kan fremstilles af mindre dyre materialer. I kontrast hertil kræver tidligere kendte processer, der fremstiller LNG ved atmosfæriske tryk med 25 temperaturer så lave som -160°C (-256°F), procesudstyr fremstillet af dyre materialer med henblik på sikker drift.
Den energi, der kræves til fortætning af naturgassen ved udøvelse af denne opfindelse, er væsentligt reduceret i forhold til energikravene i et konventionel LNG-anlæg. Reduktionen i 30 nødvendig køleenergi, der er nødvendig til fremgangsmåden ifølge den foreliggende opfindelse, resulterer i en stor reduktion i kapitalomkostninger, proportionalt lavere driftsomkostninger og øget effektivitet og driftssikkerhed og forbedrer således i høj grad økonomien ved fremstilling af fortættet naturgas.
DK 174634 B1 6
Ved den foreliggende opfindelses driftstryk og -temperaturer kan der anvendes stål med ca. 3½ vægtprocent nikkel i rørføringer og faciliteter i de koldest opererende områder af fortætningsprocessen, medens det dyrere 9 vægtprocent nikkel eller aluminium generelt er nødvendigt til det samme udstyr i en konventionel LNG-proces. Dette giver endnu en signi-5 fikant omkostningsreduktion for fremgangsmåden ifølge opfindelsen sammenlignet med kendte LNG-processer.
Det første hensyn ved kryogen forarbejdning af naturgas er kontaminering. Det rå naturgas-fødemateriale, der er egnet til fremgangsmåden ifølge opfindelsen, kan omfatte 10 naturgas, der er opnået fra en råoliebrønd (associeret gas) eller fra en gasbrønd (ikke-associeret gas). Sammensætningen af naturgas kan variere signifikant. Som anvendt heri indeholder en naturgasstrøm methan (C,) som en hovedkomponent. Naturgassen vil typisk også indeholde ethan (C2), højere carbonhydrider (C3+) og mindre mængder af forureninger såsom vand, carbondioxid, hydrogensulfid, nitrogen, butan, carbonhydrider med seks eller 15 flere carbonatomer, snavs, jernsulfid, voks og råolie. Opløselighederne af disse forureninger varierer alt efter temperatur, tryk og sammensætning. Ved kryogene temperaturer kan C02, vand og andre forureninger danne faste stoffer, som kan tilstoppe strømningspassager i kryogene varmevekslere. Disse potentielle vanskeligheder kan undgås ved at fjerne sådanne forureninger, hvis der inden for deres rene komponent 20 forventes fastfasede temperatur/tryk-fasegrænser. I den følgende beskrivelse af opfindelsen antages det, at naturgasstrømmen er blevet behandlet på passende måde for at fjerne sulfider og carbondioxid og tørret for at fjerne vand under anvendelse af konventionelle og velkendte processer til fremstilling af en "sød, tør" naturgasstrøm. Hvis naturgasstrømmen indeholder tunge carbonhydrider, som kunne fryse ud under fortætning, 25 eller hvis de tunge carbonhydrider ikke ønskes i PLNG'en, kan det tunge carbonhydrid fjernes ved en fraktioneringsproces før fremstilling af PLNG’en som beskrevet i nærmere detaljer nedenfor.
Én fordel ved den foreliggende opfindelse er, at de varmere driftstemperaturer gør det mu-30 ligt for naturgassen at have højere koncentrationsniveauer af frysbare komponenter, end hvad der ville være muligt i en konventionel LNG-proces. I et konventionelt LNG-anlæg, der fremstiller LNG ved -160°C (-256°F), skal C02 fx være under ca. 50 ppm for at undgå fryseproblemer. Ved at holde procestemperaturer over ca. -112°C (-170°F) kan naturgassen derimod indeholde C02 ved niveauer så høje som ca. 1,4 molprocent C02 7 DK 174634 B1 ved temperaturer på -112°C (-17Q°F) og ca. 4,2% ved -95°C (-139°F) uden at forårsage fryseproblemer i fortætningsprocessen ifølge opfindelsen.
Endvidere behøver moderate mængder nitrogen i naturgassen ikke fjernes ved frem-5 gangsmåden ifølge opfindelsen, fordi nitrogen vil forblive i væskefasen sammen med de fortættede carbonhydrider ved den foreliggende opfindelses driftstryk og -temperaturer.
Evnen til at reducere eller i visse tilfælde udelade det udstyr, der er nødvendigt til gasbehandling og nitrogenfjernelse, tilvejebringer, når naturgassens sammensætning tillader det, signifikante tekniske og økonomiske fordele. Disse og andre fordele ved opfindelsen vil 10 blive forstået bedre under henvisning til figurerne.
Idet der henvises til fig. 1 kommer en naturgasfødestrøm fortrinsvis ind i fortætningsprocessen ved et tryk over ca. 3100 kPa (450 psia) og især over ca. 4827 kPa (700 psia) og fortrinsvis ved temperaturer under ca. 40°C (104°F); der kan imidlertid anvendes andre tryk 15 og temperaturer, hvis det ønskes, og systemet kan på passende måde modificeres i overensstemmelse dermed af personer med almindelig viden inden for området efter kendskab til den foreliggende opfindelses lære. Hvis gasstrømmen 10 er under ca. 3102 kPa (450 psia) kan den sættes under tryk ved hjælp af et passende kompressionsorgan (ikke vist), som kan omfatte én eller flere kompressorer.
20
Trykfødestrømmen 10 afkøles af én eller flere varmevekslere 20. Den afkølede fødestrøm 11 ekspanderes derefter ved hjælp af mindst ét hensigtsmæssigt ekspansionsorgan 30. Ekspansionsorganet kan være en turboekspander af kommerciel type, som kan være akselkoblet til passende kompressorer, pumper eller generatorer, hvilket gør det muligt at 25 omdanne det arbejde, der udtages fra ekspanderen, til brugbar mekanisk og/eller elektrisk J energi, hvilket resulterer i en betydelig energibesparelse for det samlede system.
Ekspansionsorganet 30 fortætter i det mindste en del af naturgasstrømmen 11 til dannelse af en strøm 12. Strømmen 12 føres til en konventionel faseseparator 40, som fremstiller en 30 flydende produktstrøm 13, som er PLNG med en temperatur over ca. -112°C (-170°F) og et tryk, der er tilstrækkeligt til, at det flydende produkt er ved eller under boblepunktet.
PLNG’en ledes til et passende lagrings- eller transportorgan 90 (såsom en rørledning, en stationær opbevaringstank eller en transportør såsom et PLNG-skib, en PLNG-lastbil eller en PLNG-jernbanevogn) til opbevaring ved en temperatur over ca. -112® ('-170°F). For at 35 det flydende produkt skal forblive i en flydende fase, skal temperaturen være under pro- DK 174634 B1 8 duktets kritiske temperatur, som typisk vil være under -62°C (-80°F). Separatoren 40 fremstiller også en dampstrøm 14, som ledes gennem varmevekslere 20, hvor dampstrømmen 14 afkøler fødestrømmen 10. Én eller flere kompressorer komprimerer derefter dampstrømmen 15. Fig. 1 illustrerer en foretrukken anvendelse af én kompressor 50 til at gen-5 komprimere recirkulationsdampen til omtrent trykket af den indkommende fødestrøm 10. imidlertid kan der anvendes yderligere kompressorer ved udøvelse af den foreliggende opfindelse. Den komprimerede gasstrøm 16 afkøles ved hjælp af en varmeveksler 60 for at genvinde varmeværdier til anvendelse andetsteds, eller sådan afkøling kan bevirkes under anvendelse af luft eller vand. Efter at have forladt varmeveksleren 60 forenes den afkølede 10 dampstrøm 17 med fødestrømmen 10 til recirkulering. I denne udførelsesform kan fødestrømmen fortættes uden behov for et kølesystem med lukket sløjfe.
Ved opbevaring, transport og håndtering af fortættet naturgas kan der være en betydelig mængde "afkogning”, dvs. den damp, der resulterer fra fordampning af en fortættet natur-15 gas. Denne opfindelse er særligt velegnet til at fortætte afkogningsdamp dannet af PLNG.
Idet der henvises til fig. 1, kan afkogningsdamp indføres i fortætningsprocessen gennem ledning 18 til kombination med dampstrømmen 14, som recirkuleres som beskrevet ovenfor. Afkogningsdampens tryk bør fortrinsvis være ved eller nær trykket af gasstrøm 14. Hvis afkogningsdampen er under trykket af strømmen 14, kan afkogningsdampen komprimeres 20 ved hjælp af konventionelle kompressionsorganer (ikke vist i fig. 1).
En mindre del af dampstrømmen 15 kan eventuelt fjernes fra processen som brændstof (strøm 19) til at tilføre en del af den energi, der er nødvendig til at drive kompressorer og pumper i fortætningsprocessen. Selv om denne mindre del kan udtages fra processen på 25 et hvilket som helst punkt efter udløb fra separatoren 40, fjernes brændstoffet fortrinsvis fra processen efter at være blevet opvarmet af varmeveksleren 20.
Fig. 2 illustrerer en anden udførelsesform af fremgangsmåden ifølge opfindelsen, og i denne udførelsesform har dele med de samme henvisningstal som delene i fig. 1 de 30 samme procesfunktioner. Fagfolk inden for området vil imidlertid indse, at procesudstyret fra én udførelsesform til en anden kan variere i størrelse og kapacitet til at håndtere forskellige væskestrømningshastighedsmængder, -temperaturer og -sammensætninger. Udførelsesformen illustreret i fig. 2 ligner udførelsesformen beskrevet i fig. 1 med undtagelse af, at der ved hjælp af varmeveksleren 70 tilvejebringes yderligere køling af 35 fødestrømmen 10. Denne udførelsesform i fig. 2 reducerer mængden af 9 DK 174634 B1 recirkulationsstrøm 14 og kræver mindre energi end udførelsesformen i fig. 1. Køling til varmeveksleren 70 tilvejebringes af et konventionelt kølesystem 80 med lukket sløjfe.
Kølemidlet til kølesystemet kan være propan, propylen, ethan, carbondioxid eller et hvilket som helst andet egnet kølemiddel.
5
Fig. 3 illustrerer endnu en yderligere udførelsesform af den foreliggende opfindelse. Denne udførelsesform inkluderer et system til at fjerne tunge carbonhydrider og et strømdelingsarrangement for trykgassen umiddelbart opstrøms i forhold til de endelige fortætningstrin. Dette strømdelingsarrangement kan reducere de samlede energikrav sammen-10 lignet med udførelsesformen i fig. 2 ved at tillade tættere tilnærmninger i hovedfortætningsveksleren 142. Strømdelingsarrangementet tillader også mere operationel fleksibilitet ved håndtering af varierende mængder afkogningsgas fra LNG- eller PLNG-lastnings- og -losningsoperationer. Idet der henvises til fig. 3 kommer fødestrøm 100 ind i separator 130, hvor strømmen deles i to separate strømme, nemlig dampstrøm 101 og væskestrøm 102.
15 Om end det ikke er vist i fig. 3, kan fødestrømmen 100 afkøles ved hjælp af et hvilket som helst egnet kølesystem, inden den fødes til separatoren 130. Væskestrømmen 102 ledes til en konventionel demethanisator 131. Dampstrøm 101 passerer gennem to eller flere kompressorer og kølere for at booste trykket af dampstrømmen 101 fra fødegastrykket til ca.
10.343 kPa (1500 psia). Fig. 3 viser en sekvens af to kompressorer 132 og 133 til at kom-20 primere gassen og konventionelle varmevekslere 134 og 135 efter hvert kompressionstrin til at afkøle den komprimerede gas. Efter at dampstrømmen 101 forlader varmeveksleren 135, afkøler genkoger 136 den yderligere under anvendelse af væske fra demethanisatoren 131. Fra genkogeren 136 ledes den afkølede strøm 101 til en konventionel faseseparator 137. En dampstrøm 103 fra separatoren 137 ekspanderes ved 25 hjælp af en konventionel turboekspander 138, hvorved gastrømmens tryk reduceres, før den kommer ind i den øvre sektion af demethanisatoren 131. Turboekspanderen 138 leverer fortrinsvis i det mindste en del af den energi, der er nødvendig til at drive kompressoren 132. Væsker fra separatoren 137 ledes via ledning 104 til den midterste del af demethanisatoren 131.
30
Efterhånden som væske fødes til demethanisatorkolonnen 131, løber den nedad under tyngdekraftens indvirkning. Under sin vej møder væsken opstigende dampe, som stripper methanen fra væsken, efterhånden som den stiger opad. Stripningsoperationen frembringer et i det væsentlige demethaniseret flydende produkt, som fjernes fra bunden af de-35 methanisatorkolonnen 131 som strøm 105.
DK 174634 B1 10
Den øvre dampstrøm 106, der forlader demethanisatorkolonnen, ledes til en varmeveksler 139. Efter opvarmning i varmeveksleren 139 kan en første del af den opvarmede dampstrøm (strøm 107) eventuelt udtages (strøm 108) til anvendelse som et brændstof til 5 gasfortætningsanlægget. En anden del af strømmen 107 ledes derefter gennem en serie kompressorer 140 og 141 og varmevekslere 142 og 143 for at øge dampstrømmens tryk og tilvejebringe afkøling efter hvert kompressionstrin. Antallet af kompressionstrin ligger fortrinsvis fra 2 til 4. En del af den strøm, der forlader varmeveksleren 42, udtages og leds som strøm 110 til varmeveksler 139 for yderligere at afkøle strøm 110. Den optimale 10 fraktion af strøm 109, der skilles fra som strøm 110, vil afhænge af temperaturen, trykket og sammensætningen af strøm 109. Denne optimering kan foretages af personer med almindelig fagviden inden for området baseret på den heri beskrevne lære. Efter at have forlagt varmeveksleren 139 ledes strømmen 110 til et ekspansionsorgan såsom en turbo-ekspander 144, som i det mindste delvis fortætter strømmen 110 til dannelse af strømmen 15 111. Strømmen 111 ledes derefter til en konventionel faseseparator 145. Faseseparatoren 145 fremstiller PLNG (strøm 121) ved en temperatur over ca. -112°C (-170°F) og et tryk, der er tilstrækkeligt til, at det flydende produkt er ved eller under sit boblepunkt. PLNG'en ledes til et hensigtsmæssigt lagringsorgan 153 til opbevaring af PLNG’en ved en temperatur over -112°C (-170°F). Separatoren 145 producerer også en gasdampstrøm 115 under 20 tryk, som kombineres med strømmen 106 til recirkulering.
Strømmen 112, som er den afkølede strøm, der forlader varmeveksleren 143, ledes til et passende ekspansionsorgan såsom turboekspander 146 for at reducere trykket og yderligere afkøle strømmen 112. Turboekspanderen 146 fortætter i det mindste delvist natur-25 gasstrømmen 112. Efter at have forladt turboekspanderen 146 ledes den delvist fortættede strøm til en faseseparator 147 til dannelse af en væskestrøm 113 og en dampstrøm 114. Dampstrømmen 114 ledes tilbage til og kombineres med demethanisator-dampstrømmen 106 til recirkulering. Væskestrøm 113, der forlader separator 147, kombineres med strøm 111.
30 Væskestrøm 105, der forlader demethanisatoren 131, ledes til en konventionel kondensatstabilisator 150, som frembringer en øvre strøm 116, der er rig på ethan og andre lette carbonhydrider, primært methan. Den øvre strøm 16 ledes gennem varmeveksler 151, som afkøler den øvre damp 116. En del af strømmen 116 returneres derefter til 35 kondensatstabilisatoren 150 som refluksstrøm 114. Den resterende del af strøm 116 ledes 11 DK 174634 B1 gennem en kompressor 152 for at øge trykket af strøm 116 til omtrent trykket af strøm 107.
Efter at være blevet komprimeret afkøles den øvre strøm 116, og den afkølede gas (strøm 118) sammenblandes med strøm 107. Væske, der forlader bunden af kondensatstabilisatoren 150, er tilgængelig som et kondensatprodukt (strøm 119).
5
Fremgangsmåden ifølge den foreliggende opfindelse som illustreret i fig. 3 kan eventuelt genfortætte afkogningsdamp. Afkogningsdamp kan indføres i processen illustreret i fig. 3 gennem ledning 120, som forenes med den øvre dampstrøm 106.
10 Idet der henvises til fig. 4 kommer fødestrøm 201 ind i separator 230, hvor strømmen deles i to separate strømme, dampstrøm 202 og væskestrøm 203. Denne udførelsesform illustrerer en ekstern kølesløjfe til at minimere energikravene og størrelsen af procesudstyr og en fraktioneringssevens til at tilvejebringe kølekomplettering for kølesløjfen. Væskestrøm 203 ledes til demethanisatorkolonne 231. Dampstrøm 202 komprimeres i ét eller to kompres-15 sionstrin, fortrinsvis to trin. Af simplificeringshensyn viser fig. 3 kun én kompressor 232.
Efter hvert kompressionstrin køles den komprimerede damp fortrinsvis ved hjælp af en konventionel luft- eller vandkøler såsom køler 234. Gasstrøm 202 bliver efter at have forladt køler 234 afkølet af genkoger 235, gennem hvilken demethanisatorvæsken strømmer fra demethanisatorkolonnen 231. Fra genkogeren 235 bliver den afkølede strøm 202 20 afkølet yderligere ved hjælp af varmevekslere 236 og 237, som køles ved hjælp af et konventionelt kølesystem 238 med lukket sløjfe, i hvilket kølemidlet fortrinsvis er propan.
Fra vekslerne 236 og 237 skilles den afkølede naturgas igen i en konventionel faseseparator 238. En dampstrøm 204 fra separator 238 ekspanderes ved hjælp af en turboekspander 239, hvorved gasstrømmens tryk reduceres, før den kommer ind i den 25 øvre del af demethanisatoren 231. Turboekspanderen 239 tilvejebringer fortrinsvis energi til kompressoren 232. Væsker fra separatoren 238 ledes via ledning 205 til den midterste del af demethanisatoren 231.
Den øvre gasstrøm 207, der forlader demethanisatoren 231, ledes til en varmeveksler 240.
30 En del af den strøm 208, der forlader varmeveksleren 240, kan eventuelt udtages (strøm 209) til anvendelse som et brændstof til gasfortætningsanlægget. Den resterende del af strømmen 208 komprimeres af én eller flere kompressorer 241 til et tryk, fortrinsvis mellem ca. 5516 kPa (800 psia) og 13.790 kPa (2000 psia). Den komprimerede gas ledes derefter gennem en serie varmevekslere 242, 243 og 244 for at afkøle gassen til dannelse af strøm DK 174634 B1 12 210. Varmeveksler 242 køles fortrinsvis med luft eller vand. Varmevekslere 243 og 244 køles fortrinsvis ved hjælp af kølesystem 238, som er det samme system, der anvendes til køling af varmevekslerne 236 og 237. En del af strømmen 210 ledes som strøm 211 til varmeveksleren 240 for at tilvejebringe køleevne til yderligere afkøling af dampstrømmen 5 211. Strømmen 211, der forlader varmeveksleren 240, ledes til et ekspansionsorgan såsom en turboekspander 245, som i det mindste delvist fortætter strømmen 211 til dannelse af strømmen 212. Strømmen 212 ledes derefter til en konventionel faseseparator 246.
Den del af strømmen 210, der er tilbage efter at strømmen 211 er blevet udtaget, ledes til 10 et passende ekspansionsorgan såsom turboekspander 248 for at reducere gastrykket og for at afkøle gasstrømmen yderligere. Turboekspanderen 248 frembringer en strøm 213, der i det mindste delvist er flydende naturgas. Strømmen 213 ledes til en konventionel faseseparator 249 til dannelse af en væskestrøm 214 og en dampstrøm 215. Strømmen 215 recirkuleres ved at blive forenet med demethanisatorens øvre dampstrøm 207.
15 Væskestrømmen 214 forenes med strømmen strømmen 212 og ledes til separatoren 246, som separerer gassen i en dampstrøm 216 og en væskestrøm 217. Dampstrømmen 216 bliver, ligesom dampstrømmen 215, forenet med demethanisatorens øvre strøm 207 til recirkulering. Væskestrømmen 217 er PLNG, der har en temperatur over ca. -112°C (-170°F) og et tryk, der er tilstrækkeligt til, at væsken er ved eller under sit boblepunkt, og 20 sendes til en passende oplagringsbeholder 258 til oplagring ved en temperatur over ca.
-112°C (-170°F).
Væskestrømmen 206, der forlader demethanisatoren 231, ledes til et fraktioneringssystem, der omfatter en serie fraktioneringskolonner 250, 251 og 251. Fraktioneringskolonne 250 er 25 en konventionel de-ethanisator, som frembringer en øvre strøm, der er rig på ethan og andre lette carbonhydrider, primært methan. Den øvre dampstrøm 218 ledes gennem varmeveksler 253 for at opvarme brændstofstrøm 209. Efter at have passeret gennem varmeveksleren 253 ledes dampstrømmen 218 til en konventionel faseseparator 254, som fremstiller en dampstrøm 220 og en væskestrøm 221. Væskestrømmen 221 returneres til de-30 ethanisatorkolonnen 250 som refluks. Dampstrømmen 220 forenes med strømmen 208.
Væsker, der forlader bunden af de-ethanisatoren 250, afkøles ved hjælp af varmeveksler 257 og ledes til depropanisator 251. Den øvre damp fra depropanisatoren 251 er rig på propan og kan eventuelt anvendes som propansupplement til kølesystemet 238. Væsker, 35 der forlader bunden af depropanisatoren 251, ledes derefter til débutanisatoren 252.
13 DK 174634 B1 Væsker, der forlader bunden af debutanisatoren tages ud af processen som flydende kondensat (strøm 222). I det mindste en del af den øvre damp fra debutanisatoren 252 ledes via ledning 223 gennem en varmeveksler 255 for at afkøle dampstrømmen. Denne dampstrøm 223 ledes derefter gennem en kompressor 256 for at øge trykket af strømmen 223 til 5 omtrent trykket af strømmen 208. Efter at have forladt kompressoren 256 forenes den komprimerede strøm med strøm 220.
Afkogningsdamp kan eventuelt introduceres til processen ifølge opfindelsen gennem ledning 224, som forenes med den øvre dampstrøm 207.
10
Eksempel
Der blev foretaget en simuleret masse- og energibalance for at illustrere udførelsesformerne illustreret i figurerne, og resultaterne er angivet i tabellerne 1, 3, 4 og 5 nedenfor. De 15 i tabellerne viste data præsenteres for at tilvejebringe en bedre forståelse af udførelsesformerne vist i figurerne, men opfindelsen bør ikke betragtes som unødvendigt begrænset dertil. De i tabellerne angivne temperaturer og strømningshastigheder bør ikke betragtes som begrænsninger af opfindelsen, som kan have mange variationer i temperaturer og strømningshastigheder i lyset af den heri angivne lære.
20
Dataene blev opnået under anvendelse af et kommercielt tilgængeligt processimuleringsprogram ved navn HYSYS™, om end andre kommercielt tilgængelige processimuleringsprogrammer kan anvendes til at udvikle dataene, herunder fx HYSIM™, PROII™ og ASPEN PLUS™, som vil være velkendte for fagfolk.
25
Den energi, der er nødvendig til at fremstille PLNG i overensstemmelse med opfindelsen, er signifikant mindre end den energi, der er nødvendig til at fremstille LNG ved næsten atmosfæriske betingelser og ved en temperatur på -164,5°C (-264°F) under anvendelse af en ekspansionsproces. Sammenligning af tabel 2 med tabel 1 illustrerer denne energifor-30 skel. Tabel 2 viser resultater af en simuleret masse- og energibalance under anvendelse af flowprocessen i fig. 1 til fremstilling af LNG ved næsten atmosfæriske tryk. Resultaterne i tabel 2 var baseret på at fremstille flydende produkt med næsten atmosfærisk tryk, signifikant reduceret mængde afkogningsdamp, der indføres til processen, og behovet for recirkulationskompression i flere trin (fire recirkulationskompressorer i stedet for én kompressor 35 50 vist i fig. 1). I disse to simulationer var den samlede tilførte energi, der var nødvendig til DK 174634 B1 14 at fremstilte konventionel LNG (data fra tabel 2), over to gange mere end det, der er nødvendigt til at fremstille PLNG (data fra tabel 1). Forbedringer i PLNG-ekspansionspro-cessen såsom den, der afbildet i fig. 2, kunne også forbedre den konventionelle LNG-pro-ces. Imidlertid ville forholdet mellem tilført energi for den konventionelle LNG-proces og .
5 den tilførte energi for PLNG-processen i overensstemmelse med den foreliggende opfindelse ikke ændres signifikant. PLNG-processen ifølge den foreliggende opfindelse kræver ca. halvdelen af energien ved at anvende en konventionel ekspansionsproces til fremstilling af LNG ved atmosfærisk tryk.
10 De i tabel 3 præsenterede data er vist for at tilvejebringe en bedre forståelse af udførelsesformen vist i fig. 2. Sammenlignet med udførelsesformen vist i fig. 1 kan de totale krav til tilført energi for udførelsesformen i fig. 2 reduceres fra 198.359 kW (266.000 hk) til 111.857 kW (150.000 hk) ved at tilføje et propanafkølingssystem. Fagfolk ville være i stand til yderligere at reducere den nødvendige energi ved at optimere processen.
15
De i tabel 4 præsenterede data er vist for at tilvejebringe en bedre forståelse af udførelsesformen vist i fig. 3. Fødegassen i fig. 3 og 4 har en anden sammensætning og er ved anderledes betingelser end fødegassen i fig. 1 og 2.
20 De i tabel præsenterede data er vist for at tilvejebringe en bedre forståelse af udførelsesformen vist i fig. 4. Denne proces påviser atter en gang fordelen ved propanafkølingssystemet ved signifikant at sænke den nødvendige tilførte energi sammenlignet med den i udførelsesformen vist i fig. 3.
25 En fagmand, især én som har fordelen af det foreliggende patents lære, vil indse mange modifikationer og variationer på de ovenfor beskrevne specifikke processer. Fx kan der i overensstemmelse med opfindelsen anvendes en række temperaturer og tryk, afhængigt af systemets samlede design og sammensætningen af fødegassen. Endvidere kan føde-gas-afkølingssekvensen suppleres eller rekonfigureres afhængigt af de samlede design- 30 krav for at opnå optimale og effektive varmevekslingskrav. Som diskuteret ovenfor bør de specifikt beskrevne udførelsesformer og eksempler ikke anvendes til at begrænse opfindelsens omfang, som skal fastlægges af kravene nedenfor og deres ækvivalenter.
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Energi Energi __hk__kW,
Kompressorer 132 22.000 16.406 133 24,000 17,897 140vTrin1 58.000 43.251 140, Trin 2 55.000 41.014 141, Trin 1 4,000 2.983 141. Trin 2 27.000 20.134 152 1.000 746
Ekspandere 138 -22.000 -16.406 144 —4.000 -2.983 146 -27.000 -20,134
Nettoenergi 138.000 102.908
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o r n —’ —' —'p~' ρΤ’ρ-'οο 00' oo'p'~'r-'vo'pf pT pT mN~ m-Γ p'pT2 ^ h-ip N PI N n ro 1 pnpnpipiOnOnOnOn On l I Π On
0 II I I I I I I I I I I
ΟΟΟ^τρΟΟΡιΡΝΟΟΟΟΟΟ OPOPPOOOOO ro ooonpno — — oor-p- — — — — — oooono-nj-o "K OOOOOO^ — NpNTNpNpNrNpNpNpNp'P ΤΡ'^ΤΓ'ΝΡ'^Ρ — — ·ΝΡ jc °* — — --
t— nOONDP'P'PP-On On n in P P P P POnMOnOnnPOPI
-1 ^-MininNplPPMnpiN(St^ ριρ-όρρρρι —
p\ in in <n On On M CO P P p - CO DO 00 00 M P P P P O O M
3 in in mi p' p (S pi pi N O O pi P pi pi pi pi pi pi pi — — pi Ψ—4 1-m
Si £ Si > > p — pirovrimopMONO^ ριρ-ντόΌΡ'ΟΟΟνο — pi pi nt
s OOOOOOOOO — — — — — — — — — — PIPIPIPIPI i; NMPIPIPICSMPIPINPIPIMPINPIPIPIMNPINNPI
(Λ 21 DK 174634 B1
Tabel 5, fortsat
Energi
Energi Energi’
__hk__kW
Kompressorer 232>Trin1 11.000 8.203 232. Trin 2 4.000 2.983 238. Trim 9.000 6.711 238. Trin 2 26.000 19.389 241 Trin 1 43.000 32.066 241 i Trin 2 45.000 33.557 56 1.000 746
Ekspandere 239 11.000 8.203 245 4.000 2^83 248 11.000 8,203
Nettoenergi 113.000 84 265
Totalt tilført_ 165.000 123 043
Claims (18)
1. Fremgangsmåde til fortætning af en gasstrøm, der er rig på methan, hvori gasstrømmen tilvejebringes ved et tryk på over 3100 kPa; 5 KENDETEGNET VED AT (a) ekspandere gasstrømmen (11) til et lavere tryk til dannelse af en gasfase og et flydende methanrigt produkt, der har en temperatur over -112°C og et 10 tryk, der er tilstrækkeligt til, at det flydende produkt er ved eller under sit boblepunkt; (b) faseseparere (40) gasfasen og det methanrige flydende produkt; og (c) indføre det methanrige flydende produkt i et opbevaringsorgan (90) til opbevaring ved en temperatur på over -112°C. 15
2. Fremgangsmåde ifølge krav 1, som yderligere omfatter at afkøle gasstrømmen inden trin (a).
3. Fremgangsmåde ifølge krav 2, som yderligere omfatter at afkøle gasstrømmen i en var-20 meveksler, der er afkølet ved hjælp af et kølesystem med lukket sløjfe.
4. Fremgangsmåde ifølge krav 3, hvor kølesystemet med lukket sløjfe har propan som det fremherskende kølemiddel.
5. Fremgangsmåde ifølge krav 3, hvor kølesystemet med lukket sløjfe har carbondioxid som det fremherskende kølemiddel.
6. Fremgangsmåde ifølge krav 2, som endvidere omfatter det trin at afkøle gasstrømmen ved varmevekslingsforhold med gasfasen fra trin (b) i krav 1, hvorved gasfasen opvarmes. 30
7. Fremgangsmåde ifølge krav 6, som endvidere omfatter at komprimere den opvarmede gasfase, afkøle den komprimerede gasfase, og returnere den afkølede, komprimerede gasfase til gasstrømmen for recirkulering i processen.
8. Fremgangsmåde ifølge krav 6, som endvidere omfatter, inden køletrinnet i krav 6, at afkøle gasstrømmen i en varmeveksler, der er afkølet ved hjælp af et kølesystem med lukket sløjfe.
9. Fremgangsmåde ifølge krav 1, som, inden fortætning af gasstrømmen, endvidere om-40 fatter, at en afkogningsgas, der resulterer fra fordampning af fortættet naturgas, kombineres med gasstrømmen.
10. Fremgangsmåde ifølge krav 1, hvor gasstrømmen indeholder methan og carbonhydrid-komponenter, der er tungere end methan, hvilken fremgangsmåde endvidere omfatter, at DK 174634 B1 en overvejende andel af de tungere carbonhydrider fjernes ved fraktionering til dannelse af en dampstrøm, der er rig på methan, og en væskestrøm, der er rig på de tungere carbonhydrider, og at dampstrømmen derefter fortættes ved ekspansion ifølge trin (a) i krav 1.
11. Fremgangsmåde ifølge krav 10, som endvidere omfatter at afkøle gasstrømmen inden fraktionering af gasstrømmen.
12. Fremgangsmåde ifølge krav 1, hvor fortætningen af gasstrømmen foretages uden et kølesystem med lukket sløjfe. 10
13. Fremgangsmåde til fortætning af en gasstrøm (201), der er rig på methan, og tilvejebringes ved et tryk større end 3100 kPa til en demethaniseringskolonne (231) som giver en methanrig dampstrøm (207) og en væskestrøm (206), der er demethaniseret,
14. Fremgangsmåde ifølge krav 13, som endvidere omfatter at kombinere dampfasen (215) fra trin (g) med dampstrømmen (207) fra trin (a) og lede den kombinerede gasstrøm gennem varmeveksleren (240) i trin (a). 40
15. Fremgangsmåde ifølge krav 13, som endvidere omfatter at kombinere dampfasen (216) fra trin (e) med dampfasen (215) fra trin (g) og lede den kombinerede gasstrøm gennem varmeveksleren (240). DK 174634 B1
15 KENDETEGNET VED AT (a) lede den methanrige dampstrøm (207) gennem en varmeveksler (240) for at opvarme dampstrømmen, og komprimere (241) den opvarmede dampstrøm for at sætte dampstrømmen under yderligere tryk, 20 (b) afkøle (242) den komprimerede gasstrøm fra (a), (c) dele den afkølede komprimerede strøm fra trin (b) i en første afkølet strøm (211) og en anden afkølet strøm (213) og lede den første afkølede strøm gennem varmeveksleren (240) for yderligere at afkøle den første strøm; (d) ekspandere (245) den første afkølede strøm til dannelse af gas- og 25 væskefaser; (e) faseseparere (246) gas- og væskefaserne fra trin (d) og derved danne en første dampfase (216) og en methanrig fortættet gas (217) ved en temperatur over -112°C og et tryk, der er tilstrækkeligt til, at den methanrige fortættede gas er ved eller under sit boblepunkt; 30 (f) ekspandere (248) den anden afkølede strøm fra trin (c) til et lavere tryk, hvorved den afkøles yderligere og danner gas- og væskefaser; (g) faseseparere (249) de i trin (f) dannede gas- og væskefaser, og derved danne en dampfase (215) og en methanrig fortættet gas (214) ved en temperatur over -112°C og et tryk, der er tilstrækkeligt til, at den 35 methanrige fortættede gas er ved eller under sit boblepunkt;
16. Fremgangsmåde ifølge krav 14, hvor afkølingen i trin {b) er ved indirekte varmeveksling (243) med kølemiddel fra et kølesystem med lukket sløjfe (238).
17. Fremgangsmåde ifølge krav 13, hvor processen endvidere omfatter at lede vaeskestrøm, der er demathaniseret, (206) til mindst én fraktioneringskolonne (250), der frembringer en øvre dampstrøm (218), og kombinere den øvre dampstrøm (218) dannet i fraktioneringskolonnen med den opvarmede dampstrøm (208) fra trin (a).
18. Fremgangsmåde ifølge krav 13, hvor processen endvidere omfatter at introducere en afkogningsgas (224), der resulterer fra fordampningen af en fortættet gas, ind i den methanrige dampstrøm (207) og lede den kombinerede gasstrøm gennem varmeveksleren (240) i trin (a).
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Application Number | Priority Date | Filing Date | Title |
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US5028097P | 1997-06-20 | 1997-06-20 | |
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US7961298P | 1998-03-27 | 1998-03-27 | |
US7961298 | 1998-03-27 | ||
US9812742 | 1998-06-18 | ||
PCT/US1998/012742 WO1998059205A2 (en) | 1997-06-20 | 1998-06-18 | Improved process for liquefaction of natural gas |
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DK174634B1 true DK174634B1 (da) | 2003-07-28 |
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