EP0535752A1 - Verfahren zur Verflüssigung von Erdgas - Google Patents
Verfahren zur Verflüssigung von Erdgas Download PDFInfo
- Publication number
- EP0535752A1 EP0535752A1 EP92203009A EP92203009A EP0535752A1 EP 0535752 A1 EP0535752 A1 EP 0535752A1 EP 92203009 A EP92203009 A EP 92203009A EP 92203009 A EP92203009 A EP 92203009A EP 0535752 A1 EP0535752 A1 EP 0535752A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gas
- pressure
- phase
- methane
- fractionation zone
- 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.)
- Granted
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000003345 natural gas Substances 0.000 title claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 48
- 239000007791 liquid phase Substances 0.000 claims abstract description 24
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 238000005194 fractionation Methods 0.000 claims description 31
- 239000012071 phase Substances 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 16
- 239000012530 fluid Substances 0.000 claims description 8
- 239000002912 waste gas Substances 0.000 claims description 8
- 238000009834 vaporization Methods 0.000 claims description 4
- 230000008016 vaporization Effects 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 230000000295 complement effect Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000007792 gaseous phase Substances 0.000 abstract description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 8
- 239000001294 propane Substances 0.000 description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005057 refrigeration 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
- F25J1/003—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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- 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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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
- F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
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- 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
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- F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
- F25J1/0055—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream originating from an incorporated cascade
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- F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
- F25J1/0235—Heat exchange integration
- F25J1/0237—Heat exchange integration integrating refrigeration provided for liquefaction and purification/treatment of the gas to be liquefied, e.g. heavy hydrocarbon removal from natural gas
- F25J1/0239—Purification or treatment step being integrated between two refrigeration cycles of a refrigeration cascade, i.e. first cycle providing feed gas cooling and second cycle providing overhead gas cooling
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- F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
- F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
- F25J1/0292—Refrigerant compression by cold or cryogenic suction of the refrigerant gas
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- F25J3/0204—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 feed stream
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Definitions
- the invention relates to a process for liquefying natural gas comprising the separation of hydrocarbons heavier than methane.
- Natural gas and other methane-rich gas streams are commonly available at sites away from places of use, and it is therefore common to liquefy natural gas for transportation by land or sea. Liquefaction is widely practiced in the present time and the literature and the patents describe many processes and apparatuses of liquefaction. US-A-3945 214, 4251 247, 4274 849, 4339 253 and 4539 028 are examples of such methods.
- US Pat. No. 4,690,702 describes a process in which the charge of hydrocarbons under high pressure (P1) is cooled so as to cause the liquefaction of part of the hydrocarbons, a gas phase (G1) is separated from a liquid phase (L1), the gas phase is relaxed (G1) to lower its pressure to a value (P2) lower than (P1), the liquid phase (L1) and the gas phase (G1) are sent under pressure (P2) in a first fractionation zone, for example a purification column - contact refrigeration, a residual gas (G2) rich in methane is drawn off at the head, the pressure of which is then raised to a value (P3), it is withdrawn in melts a liquid phase (L2), the phase (L2) is sent to a second fractionation zone, for example a fractionation column, a liquid phase is drawn off at the bottom (L3), enriched in higher hydrocarbons, for example C3 +, a gas phase (G3) is drawn off at the head, at least part of the gas phase
- the expansion of G1 takes place in a turboexpander which transmits at least part of the energy collected to a turbocharger which raises the pressure of G2 up to the value P3.
- the advantage of such a process is to collect, with a high yield, condensates such as C3, C4, gasoline, etc. which are valuable products.
- the process of the invention differs, for its fractionation part, from the process of US-A-4 690 702, in that the pressures used in the fractionation zones are higher than those previously used and in that the second fractionation zone operates under a lower pressure than the first fractionation zone.
- the gaseous charge of hydrocarbons containing methane and at least one hydrocarbon heavier than methane, under pressure P1 is cooled in one or more stages so as to form at least one gaseous phase G on, the gas phase G1 to lower its pressure from the value P1 to a value P2 lower than P1, the pressure reduction product P la is sent to a first contact fractionation zone, a residual gas G2 enriched in methane is drawn off at the head , a liquid phase L2 is drawn off at the bottom, the liquid phase L2 is sent to a second fractionation zone by distillation, at least one liquid phase L3 is drawn off at the bottom, enriched in hydrocarbons heavier than methane, an gas phase G3, at least part of the gas phase G3 is condensed to produce a condensed phase L4 and the pressure of at least part of the condensed phase L4 q is raised that is sent to the first fractionation zone as reflux and then the residual gas G2 is further cooled under a pressure at least equal to P2, in
- the gas is initially available under a pressure P1 of at least 5 MPa, preferably at least 6 MPa.
- P2 0.3 to 0.8 P1
- P2 being chosen for example between 3.5 and 7 MPa, preferably between 4.5 and 6 MPa.
- the expansion of G1 is done in one or more turboexpanders coupled (s) to one or more turbocharger (s) which recompresses (s) the waste gas G2 of the pressure
- At least one liquid phase L1 is formed in addition to the gas phase G1, and the liquid phase L1 is sent, after expansion, to said first fractionation zone by contact .
- the gas phase G3 is completely condensed and a portion is sent to the second fractionation zone as internal reflux and the complement to the first fractionation zone as reflux.
- the condensation can be completed by further compressing, with subsequent cooling of the said G3 phase.
- Natural gas from line 1 passes through one or more exchangers 2, for example of the propane or C ou / C3 liquid mixture type, and advantageously one or more exchangers using cold process fluids.
- the cold fluid comes from line 5 of the first contact column 7.
- the gas which here is partially liquefied, is fractionated in the flask 4 into liquid conveyed to column 7 via line 6 equipped with a valve.
- the expansion causes partial liquefaction of the gas and the product of the expansion is sent by line 10 to column 7.
- This column is of a conventional type, for example at trays or filled. It comprises a reboiling circuit 11.
- the liquid effluent from the bottom of the column is expanded by the valve 12 and sent by line 13 to the column read.
- This column which operates at a higher pressure than column 7, has a reboiler 15.
- the vapors are condensed into part or all in the capacitor 17.
- the phase resulting liquid is returned at least in part to column 14 as reflux via line 18.
- the gas phase (line 19 and valve V2) is then condensed, preferably entirely, by cooling preferably in the exchanger 20 supplied by minus part of the overhead waste gas from column 7 (lines 21 and 22).
- valve V2 is closed if all of the vapor phase has been condensed in 17.
- the valve V3 is open and it is then the liquid phase which is sent to column 7 via line 19a. You can also open the 2 valves V2 and V3 and thus send a mixed phase.
- the liquid phase resulting from cooling in the exchanger 20 passes into the balloon 23, the recompression pump 24 and returns to column 7 via line 25 as reflux. If the condensation in the exchanger 20 is not total, which is less preferred, the residual gas can be evacuated by line 26.
- the waste gas coming from the head of column 7 by line 21, in the form of the aforementioned embodiment, passes through the exchanger 20 before being sent to the turbocharger 27 via the lines 28 and 29.
- the turbocharger is driven by the turboexpander 9.
- At least part of the waste gas from line 21 is sent by line 30 to the exchanger 3 to cool the natural gas. It then joins the turbocharger 27 via lines 5 and 29.
- the waste gas (line 21) passes successively through the exchangers 20 and 3, or vice versa, before joining the turbocharger 27.
- the gas is sent via line 32, which may include one or more exchangers, not shown, to a conventional methane liquefaction unit, shown here in a simplified manner. It passes through a first cooling exchanger 33, then the expansion valve V4 and a second cooling exchanger 34 where the liquefaction and sub-cooling are completed.
- the refrigerant circuit of conventional or improved type (one can for example use the circuit of US-A-4 274 849) is shown here by the use of a multi-component fluid for example a mixture of nitrogen, methane , ethane and propane, initially in the gaseous state (line 35), which is compressed by one or more compressors such as 36, cooled by the external medium, air or water, in one or more exchangers such as 37, further cooled in exchanger 38, for example with propane or a C2 / C3 liquid mixture.
- a multi-component fluid for example a mixture of nitrogen, methane , ethane and propane, initially in the gaseous state (line 35), which is compressed by one or more compressors such as 36, cooled by the external medium, air or water, in one or more exchangers such as 37, further cooled in exchanger 38, for example with propane or a C2 / C3 liquid mixture.
- the partially condensed mixture reaches the flask 40 via line 39.
- the liquid phase passes through line 41 in the exchanger 33, is expanded by the valve 42 and returns to line 35 through the exchanger 33 where it heats up in cooling the streams 32 and 41.
- the vapor phase of the tank 40 (line 43) passes through the exchangers 33 and 34, where it is condensed, then is expanded in the valve 44 and passes through the exchangers 34 and 33 via the lines 45 and 35.
- the methane liquefaction is carried out by indirect contact with one or more fractions of a multicomponent fluid in the course of vaporization and circulating in a closed circuit comprising compression, cooling with liquefaction giving one or more condensates and vaporization said condensates constituting said multicomponent fluid.
- a natural gas having the following composition is treated, in mol%: Methane 90.03 Ethane 5.50 Propane 2.10 C4 - C6 2.34 Mercaptans 0.03 100.00 ⁇ under a pressure of 8 MPa.
- Reductory gas leaves column 7 at -63 ° C and it is directed partly towards the exchanger 3 and partly towards the exchanger 20. After recompression in 27 using only the energy of the turboexpander 9, the gas pressure is 5.93 MPa.
- This gas the temperature of which is -28 ° C., has the following% molar composition: Methane 93.90 Ethane 5.51 Propane 0.53 C4 - C6 Mercaptans less than 10 ppm 0.06 100.00 ⁇
- This current represents 95.88 mol% of the load current of the installation.
- Liquefaction takes place as follows: The gas is cooled and condensed to -126 ° C in a first bundle of the heat exchanger 33 then expanded to 1.4 MPa and sub-cooled in a second bundle of the heat exchanger 34 to at -160 ° C. From there it is sent to storage.
- the refrigerant has the following molar composition: N2 7% Methane 38% Ethane 41% Propane 14%
- This fluid is compressed to 4.97 MPa, cooled to 40 ° C in a water exchanger 37, then cooled to -25 ° C in the exchangers represented diagrammatically by 38 in indirect contact with a liquid mixture C2 / C3, then fractionated in the separator 40 giving the liquid 41 and gaseous phases 43.
- the gaseous phase is condensed and cooled to -126 ° C in a second bundle of the exchanger 33 then sub-cooled to -160 ° C in a bundle of the exchanger 34.
- the pressure is 0.3 MPa and the temperature is -28 ° C.
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- Engineering & Computer Science (AREA)
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- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9112007A FR2681859B1 (fr) | 1991-09-30 | 1991-09-30 | Procede de liquefaction de gaz naturel. |
FR9112007 | 1991-09-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0535752A1 true EP0535752A1 (de) | 1993-04-07 |
EP0535752B1 EP0535752B1 (de) | 1995-11-22 |
Family
ID=9417426
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92203009A Expired - Lifetime EP0535752B1 (de) | 1991-09-30 | 1992-09-30 | Verfahren zur Verflüssigung von Erdgas |
Country Status (16)
Country | Link |
---|---|
US (1) | US5291736A (de) |
EP (1) | EP0535752B1 (de) |
JP (1) | JP3187160B2 (de) |
AR (1) | AR247945A1 (de) |
AU (1) | AU648695B2 (de) |
CA (1) | CA2079407C (de) |
DE (1) | DE69206232T2 (de) |
DZ (1) | DZ1625A1 (de) |
EG (1) | EG20248A (de) |
ES (1) | ES2089373T3 (de) |
FR (1) | FR2681859B1 (de) |
MY (1) | MY107837A (de) |
NO (1) | NO177840C (de) |
NZ (1) | NZ244542A (de) |
RU (1) | RU2093765C1 (de) |
SA (1) | SA92130161B1 (de) |
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- 1992-09-29 RU SU925052813A patent/RU2093765C1/ru active
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- 1992-09-29 NO NO923783A patent/NO177840C/no unknown
- 1992-09-30 EP EP92203009A patent/EP0535752B1/de not_active Expired - Lifetime
- 1992-09-30 ES ES92203009T patent/ES2089373T3/es not_active Expired - Lifetime
- 1992-09-30 AU AU26127/92A patent/AU648695B2/en not_active Expired
- 1992-09-30 JP JP26196992A patent/JP3187160B2/ja not_active Expired - Lifetime
- 1992-09-30 DE DE69206232T patent/DE69206232T2/de not_active Expired - Fee Related
- 1992-09-30 US US07/954,318 patent/US5291736A/en not_active Expired - Lifetime
- 1992-09-30 AR AR92323310A patent/AR247945A1/es active
- 1992-10-10 SA SA92130161A patent/SA92130161B1/ar unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2128674A1 (de) * | 1971-03-04 | 1972-10-20 | Linde Ag | |
US4657571A (en) * | 1984-06-29 | 1987-04-14 | Snamprogetti S.P.A. | Process for the recovery of heavy constituents from hydrocarbon gaseous mixtures |
EP0178207A1 (de) * | 1984-09-28 | 1986-04-16 | Compagnie Francaise D'etudes Et De Construction "Technip" | Verfahren und Anlage zur kryogenischen Fraktionierung gasförmiger Massen |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0988497A4 (de) * | 1997-06-20 | 2002-05-15 | Exxonmobil Upstream Res Co | Verbessertes mehrkomponentenkühlsverfahren für erdgasverflüssigung |
EP0988497A1 (de) * | 1997-06-20 | 2000-03-29 | Exxon Production Research Company | Verbessertes mehrkomponentenkühlsverfahren für erdgasverflüssigung |
US10352499B2 (en) | 2007-02-12 | 2019-07-16 | Daewoo Shipbuilding & Marine Engineering Co., Ltd. | LNG tank and operation of the same |
US11168837B2 (en) | 2007-02-12 | 2021-11-09 | Daewoo Shipbuilding & Marine Engineering Co., Ltd. | LNG tank and operation of the same |
US8028724B2 (en) | 2007-02-12 | 2011-10-04 | Daewoo Shipbuilding & Marine Engineering Co., Ltd. | LNG tank and unloading of LNG from the tank |
US8820096B2 (en) | 2007-02-12 | 2014-09-02 | Daewoo Shipbuilding & Marine Engineering Co., Ltd. | LNG tank and operation of the same |
US8943841B2 (en) | 2007-02-12 | 2015-02-03 | Daewoo Shipbuilding & Marine Engineering Co., Ltd. | LNG tank ship having LNG circulating device |
US10508769B2 (en) | 2007-02-12 | 2019-12-17 | Daewoo Shipbuilding & Marine Engineering Co., Ltd. | LNG tank and operation of the same |
US7841288B2 (en) | 2008-02-11 | 2010-11-30 | Daewoo Shipbuilding & Marine Engineering Co., Ltd. | Storage tank containing liquefied natural gas with butane |
US7644676B2 (en) | 2008-02-11 | 2010-01-12 | Daewoo Shipbuilding & Marine Engineering Co., Ltd. | Storage tank containing liquefied natural gas with butane |
US9086188B2 (en) | 2008-04-10 | 2015-07-21 | Daewoo Shipbuilding & Marine Engineering Co., Ltd. | Method and system for reducing heating value of natural gas |
WO2018055264A1 (fr) * | 2016-09-20 | 2018-03-29 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Procédé de purification de gaz naturel à liquéfier |
FR3056223A1 (fr) * | 2016-09-20 | 2018-03-23 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Procede de purification de gaz naturel a liquefier |
EP4045859A4 (de) * | 2019-10-17 | 2023-11-15 | ConocoPhillips Company | Eigenständige hochdruck-einheit zur entfernung von schweren bestandteilen in der lng-verarbeitung |
Also Published As
Publication number | Publication date |
---|---|
NO923783L (no) | 1993-03-31 |
CA2079407C (en) | 2001-05-15 |
RU2093765C1 (ru) | 1997-10-20 |
FR2681859A1 (fr) | 1993-04-02 |
MY107837A (en) | 1996-06-29 |
NO177840B (no) | 1995-08-21 |
AU648695B2 (en) | 1994-04-28 |
JP3187160B2 (ja) | 2001-07-11 |
AU2612792A (en) | 1993-04-01 |
AR247945A1 (es) | 1995-04-28 |
SA92130161B1 (ar) | 2004-05-29 |
EP0535752B1 (de) | 1995-11-22 |
US5291736A (en) | 1994-03-08 |
JPH05240576A (ja) | 1993-09-17 |
NO923783D0 (no) | 1992-09-29 |
CA2079407A1 (en) | 1993-03-31 |
ES2089373T3 (es) | 1996-10-01 |
DZ1625A1 (fr) | 2002-02-17 |
NZ244542A (en) | 1994-07-26 |
EG20248A (en) | 1998-05-31 |
FR2681859B1 (fr) | 1994-02-11 |
DE69206232T2 (de) | 1996-07-18 |
DE69206232D1 (de) | 1996-01-04 |
NO177840C (no) | 1995-11-29 |
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