EP0768502B1 - Verfahren und Vorrichtung zur Verflüssigung und Behandlung von Erdgas - Google Patents
Verfahren und Vorrichtung zur Verflüssigung und Behandlung von Erdgas Download PDFInfo
- Publication number
- EP0768502B1 EP0768502B1 EP96402006A EP96402006A EP0768502B1 EP 0768502 B1 EP0768502 B1 EP 0768502B1 EP 96402006 A EP96402006 A EP 96402006A EP 96402006 A EP96402006 A EP 96402006A EP 0768502 B1 EP0768502 B1 EP 0768502B1
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- EP
- European Patent Office
- Prior art keywords
- hydrocarbons
- gas
- exchanger
- liquid
- mixture
- 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 60
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 120
- 239000003345 natural gas Substances 0.000 title claims description 37
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 92
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 88
- 239000012071 phase Substances 0.000 claims abstract description 75
- 239000000203 mixture Substances 0.000 claims abstract description 70
- 239000007788 liquid Substances 0.000 claims abstract description 55
- 239000007791 liquid phase Substances 0.000 claims abstract description 32
- 239000012530 fluid Substances 0.000 claims abstract description 30
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims description 88
- 239000002904 solvent Substances 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 30
- 230000006641 stabilisation Effects 0.000 claims description 15
- 238000011105 stabilization Methods 0.000 claims description 13
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- 230000001174 ascending effect Effects 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 6
- 230000008016 vaporization Effects 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000009834 vaporization Methods 0.000 claims description 4
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims 1
- 238000005057 refrigeration Methods 0.000 abstract description 65
- 239000003507 refrigerant Substances 0.000 description 28
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000000470 constituent Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000005194 fractionation Methods 0.000 description 11
- 239000001294 propane Substances 0.000 description 11
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 10
- 208000003173 lipoprotein glomerulopathy Diseases 0.000 description 10
- 239000003949 liquefied natural gas Substances 0.000 description 10
- 238000009434 installation Methods 0.000 description 9
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- 239000008346 aqueous phase Substances 0.000 description 8
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- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 235000013844 butane Nutrition 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000001273 butane Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- -1 LPG and gasoline Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003466 welding 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
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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
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
- F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
- F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
- F25J1/0292—Refrigerant compression by cold or cryogenic suction of the refrigerant gas
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- F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25J2220/00—Processes or apparatus involving steps for the removal of impurities
- F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
- F25J2220/68—Separating water or hydrates
-
- 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
- F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
- F25J2230/60—Processes or apparatus involving steps for increasing the pressure of gaseous process streams the fluid being hydrocarbons or a mixture of hydrocarbons
-
- 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
- F25J2245/00—Processes or apparatus involving steps for recycling of process streams
- F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
-
- 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
- F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
- F25J2290/44—Particular materials used, e.g. copper, steel or alloys thereof or surface treatments used, e.g. enhanced surface
Definitions
- the present invention relates to a process and an installation for liquefaction and fractionation of a fluid or a gaseous mixture formed at least in part hydrocarbons, including natural gas.
- Natural gas is commonly produced at sites far from places of use and it is common to liquefy it in order to transport it over long distances by LNG carrier or store it in liquid form.
- a gaseous phase rich in methane and depleted in heavy hydrocarbons and one or more liquid hydrocarbon or aqueous phases is provided.
- the method according to the invention makes it possible to increase the production yield of separate constituents, for example hydrocarbons in C3 +.
- the pre-cooling stage can be ensured by an indirect heat exchange over at least part of the contact area.
- At least two samples are taken, for example liquid fractions having different compositions at different levels.
- the pre-refrigeration step and the final liquefaction step are for example carried out by means of two different refrigeration cycles, each cycle operating with its own refrigerant mixture, the refrigerant mixture used during the final stage of liquefaction being, for example, partially condensed during the pre-cooling step.
- the pre-refrigeration step and the final liquefaction step are refrigerated for example by means of a unique refrigeration operating with a refrigerant mixture.
- the pre-refrigeration step can be carried out in the presence of a solvent.
- the solvent is for example injected into the gas.
- the process according to the invention applies particularly well to the liquefaction of a natural gas, or to obtain a cooling mixture ensuring liquefaction of a natural gas obtained at least in part by vaporization of at least a fraction liquid from a mixture of hydrocarbons resulting from the implementation of the process according to the invention.
- the main circuit includes for example at least one sampling means said liquid hydrocarbon fractions.
- the installation comprises, for example, means for stabilizing said fractions liquid hydrocarbons, said stabilization means being connected to said means of sample.
- the pre-cooling means may include at least one injection means, allowing the injection of a fluid other than gas.
- the fluid can be a solvent sent in the gas to treat it, the solvent can also be chosen to be used as an agent of seperation.
- the pre-cooling means comprises, for example, a plate exchanger vertical in which contact is made between the fluid or gas to be treated in circulation ascending and a liquid fraction descending by gravity.
- the installation may include a precooling means comprising a brazed aluminum plate heat exchanger and a final liquefaction device including a stainless steel plate exchanger.
- the invention also relates to an installation suitable for the liquefaction of a gas natural.
- the liquefaction process includes a pre-refrigeration cycle which allows partially condense the heaviest hydrocarbons contained in the gas natural and in the mixture used in the main refrigeration cycle. These two cycles use a mixture of fluid as a coolant which upon vaporizing liquefies natural gas under pressure. After vaporization, the mixture is compressed, condensed by exchanging heat with the surrounding environment, such as water or available and recycled air.
- the two-phase mixture is introduced into a unit of separation from which on the one hand a gaseous fraction depleted in hydrocarbons heavy, i.e. composed mainly of methane and / or nitrogen and other share one or more liquid sections of higher molecular weight. These cuts or liquid fractions can be made as narrow as necessary by making them pass in a series of fractionation columns.
- the gas fraction is sent towards a final refrigeration stage to be liquefied.
- the principle implemented in the invention described below consists in carrying out the pre-refrigeration of natural gas by simultaneously causing condensation of a liquid fraction of hydrocarbons and contacting preferably against the current liquid fractions of hydrocarbons with gas.
- condensation of hydrocarbons and their contact are advantageously carried out during an operation indirect heat exchange.
- FIG. 2A The principle of the process is illustrated in FIG. 2A and applied by way of example to a natural gas containing hydrocarbons other than methane and in particular C 3 + hydrocarbons.
- the gas to be treated is introduced into an enclosure EC1, such as a heat exchanger heat, through conduit 2 located in its lower part.
- Refrigeration of natural gas causes condensation of hydrocarbons heavy contained in the gas.
- the liquid phase (s) of condensed hydrocarbons descend into the gravity exchanger, against the flow of the depleted treated gas gradually into propane, butane and heavy hydrocarbons due to the exchange of material.
- the condensed hydrocarbon liquid phase is enriched as and when measure in heavier constituents.
- the gas phase rich in methane and depleted in propane, butane and heavy oil is evacuated through a pipe 5 at the head of the exchanger, and sent towards a second refrigeration stage or schematic final liquefaction stage in FIG. 2A by the reference L2.
- the temperature variation or the temperature gradient caused in the exchanger are for example chosen according to the nature of the gas and the quantity condensed hydrocarbons, such as LPG and gasoline, to be recovered.
- the reduction in temperature of the gas to be treated is preferably produced to obtain a temperature gradient over the entire exchanger.
- the two refrigeration steps are carried out by means of two independent refrigeration cycles.
- the final liquefaction stage is carried out, for example as follows: the natural gas which leaves the exchanger EC1 via the conduit 5 is sent to the exchanger E2 in which it is liquefied and then to the exchanger E3 in which it is sub-cooled. It emerges from the exchanger E3 through the conduit 50 and it is expanded through the expansion valve V100 to form the LNG produced. Refrigeration in the exchangers E2 and E3 is ensured, for example, by means of a refrigerant mixture which is compressed by means of the compressor K2, cooled by means of water or cooling air in the exchangers C2 and C3.
- the refrigerant mixture is sent to the exchanger EC 1 through the line 100 and comes out partially condensed through the line 101.
- the liquid and vapor phases are separated in the phase separator S100.
- the liquid refrigerant mixture from the separator S100 is sent through the conduit 102 into the exchanger E2 in which it is sub-cooled, and expanded through the expansion valve V300.
- the vapor refrigerant mixture from the separator S100 is sent through the pipe 103 in the exchanger E2 in which it is liquefied.
- the liquid refrigerant mixture as well obtained is sent via conduit 104 from exchanger E2 to exchanger E3 in which it is sub-cooled before being expanded through the expansion valve V200 and re-sent, after expansion, through the conduit 105 in the exchanger E3.
- At least partial vaporization in the E3 exchanger ensures the sub-cooling of the LNG before expansion and the subcooling of the cooling mixture.
- the refrigeration cycle used during the pre-cooling step can implement different arrangements while remaining within the scope of the invention.
- FIG. 2B shows a first example of an arrangement where the refrigerant mixture used during the pre-cooling step is condensed using water or cooling air in the exchanger C1.
- the liquid refrigerant mixture thus obtained is sent via line 3 to the exchanger EC 1 in which it is sub-cooled. It is expanded at lower and lower pressure levels through the expansion valves V12, V11 and V10, the steam fractions obtained after each spraying being sent to the compressor K1 by the conduits 40, 41 and 42.
- the compressor K1 is cooled by the exchanger C20 using water or cooling air. This arrangement makes it possible to reduce the compression power required, the maximum compression ratio of the compressor K1 applying only to the fraction of mixture which provides refrigeration in the lowest temperature zone in the exchanger EC 1 .
- the exchanger EC 1 comprises at least one means of recovery, for example a plate 7 delimiting, for example, two zones Z 1 and Z 2 .
- This plateau communicates with the natural gas flow circuit (s) in each of the zones and with an evacuation duct 8 for the hydrocarbon fraction separated and recovered at the level of the plateau 7.
- This hydrocarbon fraction enriched in propane and butane corresponds to the hydrocarbons which have condensed in zone Z2.
- the liquid hydrocarbon phase not recovered at the level of the plate 7 is redistributed in the zone Z1 in order to flow downwards towards the bottom of the exchanger.
- the latter is for example provided with a conduit 9 located in its lower part for evacuate the gasoline fraction.
- the exchanger can be equipped with several distributed recovery trays according to, for example, the nature of the cuts or hydrocarbons to be recovered, their volatility and / or the temperature prevailing at different places in the exchanger.
- the hydrocarbon phases liquids thus recovered are stabilized according to methods described in FIGS. 4A, 4B and 4C.
- a first embodiment consists in using a means of heating of the liquid volume collected at the bottom, for example an integrated reboiler B1 not shown in the figures in the lower part of the exchanger.
- a means of heating of the liquid volume collected at the bottom for example an integrated reboiler B1 not shown in the figures in the lower part of the exchanger.
- the evacuation duct 8 communicating with the tray recovery 7 of the condensed LPGs of FIG. 3 is connected to a device 10 allowing their stabilization.
- the additional stabilization process consists in sending, into the stabilization device 10, the fraction of condensate comprising methane and ethane in small quantity and formed mainly by an LPG fraction, recovered at the level of the plate 7.
- the gaseous fraction rich in methane and ethane produced during stabilization is discharged through a conduit 11 and recycled to the exchanger EC 1 at the level of the plate 7 to be recovered and mixed with the gas to be treated.
- the stabilized LPG fraction is discharged to the bottom of the stabilization device at reboiler level 13 through a conduit 12.
- Such a procedure advantageously makes it possible to stabilize the fraction rich in LPG before its recovery by the producer and thus increasing the yield methane and ethane production.
- FIG. 4B the installation described in FIG. 4A integrates a second device for stabilization 14, of the gasoline discharged through the pipe 9.
- the operating diagram is identical to that described in relation to the FIG. 4A, the condensate discharged through line 9 comprising mainly gasoline is sent to the stabilization device 14.
- the stabilized gasoline essentially composed of the C 5 + fraction, is evacuated through line 16 at the reboiler 17.
- the gaseous fraction composed essentially of methane, ethane, propane and butane is evacuated from the device via line 15 to be recycled and remixed with the gas to be treated arriving via line 2.
- FIG. 4C differs from that of FIG. 4A by the addition of two expansion valves V 1 and V 2 located respectively on the evacuation conduits 8 and 9.
- the gas fractions from the stabilization devices 10 and 14 are recompressed through means such as compressors K 1 and K 2 before being returned by a pipe 16 to the gas to be treated at the pipe 2.
- the stabilization of the different fractions advantageously makes it possible to increase the production yield of recoverable compounds such as the LPG fraction and the gasoline and secondly to be able to use them as constituents of a refrigerant in the liquefaction process.
- Natural gas is cooled to 15 ° C in the exchanger E1. It is then sent to the exchanger EC 1 through the conduit 3 'from which it emerges through the conduit 101 at -55 ° C. A liquid fraction is drawn off at the bottom through line 6 and an intermediate fraction richer in LPG is drawn off at -45 ° C through the line.
- the content of heavy hydrocarbons entrained in the gas would be much higher than in the process according to the invention.
- the content of isopentane would be of the order of 100 ppm instead of about 1 ppm with the method according to the invention.
- Refrigeration of the first and second liquefaction stages of natural gas can be carried out independently or depending on examples given below by way of illustration only in FIGS. 5A, 5B and 5C.
- FIG. 5A shows an alternative implementation of the method described previously in FIG. 2A comprising an intermediate separation step and for which, the two process refrigeration steps are carried out with independent refrigerant mixtures.
- the gas is pre-refrigerated in the exchanger EC 1 and that of the final liquefaction stage producing liquefied natural gas (or LNG) with the same mixture of refrigerants .
- the refrigerant mixture circulating in the cycle (K1, C1) is sent to a separator F in which it is separated into a vapor fraction containing the fractions light of the mixture and in a liquid fraction containing the heavy fractions.
- the heavy fractions condensed by refrigeration using for example water or cooling air, are evacuated at the bottom of the separator F and sent through the conduits 51 and 3 to the exchanger EC 1 , to form a first fluid refrigerant, after passing for example through the exchanger E1.
- this first fluid ensures the precooling of the gas according to the method described for example in FIG. 2A in order to obtain at the head of the exchanger a gas purified mainly of heavy hydrocarbons and rich in methane . This gas is then sent to the final liquefaction stage.
- the light fractions, coming from the separator F through the conduit 52 and forming a second refrigerant fluid are sent via the conduit 100 into the exchanger EC 1 .
- This second fluid is at least partially condensed in the exchanger by heat exchange with the first fluid consisting of the heavy fractions previously described.
- This second fluid is then sent via line 101 to the final liquefaction stage to obtain Liquefied Natural Gas (or LNG).
- the second fluid is sent through line 4 "of the exchanger E2 of the final liquefaction cycle to line 4, to be mixed with the first fluid before being returned to the cycle (K1, C1) via line 4 ', after passing through the exchanger EC1.
- FIG. 5C describes another embodiment according to the invention in which the gas pre-refrigeration is ensured at least in part by recycling a fraction of the gas purified from the heavy constituents, as well as by a first refrigerant mixture such as described in Figure 2A.
- the gas purified from the heavy fractions is sent via line 5 to the final liquefaction stage L2 where it is first expanded in a turbine T1 according to a process for example described in detail in application FR 94/02 024 of requestor before being sent to an F2 separator.
- the vapor fraction obtained is sent via a pipe 53 to a pipe 54 for introduction into the exchanger EC 1 .
- the liquid fraction Issue at the bottom of the separator F2 via the conduit 56 is expanded in one or more turbines T6 before being sent to a second separator F3.
- the mixture of the two fractions is then introduced at the head of the exchanger EC 1 through the conduit 54. It emerges at the bottom of the exchanger EC1, after having warmed up and thus having provided part of the pre-refrigeration of natural gas. It is sent through line 57, for example, in exchanger E1 where it is used as a refrigeration agent, and sent from this exchanger through line 59 to compressor K3 before being cooled in a condenser. At the outlet of the condenser, it is sent through the conduit 58 to be recycled with the gas to be treated.
- the tightness of the refrigeration circuits turns out to be imperfect, for example when the compression devices used are not completely waterproof. It then becomes necessary to compensate for these losses of mixture, by example by adding a coolant mixture.
- this top-up is carried out using at least in part fractioned and recovered hydrocarbon cuts according to the process described in the figure 3, for example.
- These cups can be advantageously stabilized before use as constituents of a mixture of refrigerants for example in the pre-refrigeration stage and / or in another stage of the liquefaction process.
- the device of FIG. 2A is provided with at least one conduit introduction 20 preferably located at the head of the exchanger.
- the condensed hydrocarbon liquid phase is gradually enriched by heavier constituents going down and the condensed aqueous phase rich in solvent at the top of the exchanger loses solvent by contact with the gas.
- the aqueous phase is evacuated via line 7 and the phase liquid hydrocarbon through line 9.
- the solvent vaporized and entrained in the gas phase makes it possible to avoid hydrate formation problems related to cooling.
- a solvent at least partially miscible with water is used.
- II has a boiling temperature lower than that of water or forms with water a azeotrope whose boiling point is lower than that of water so as to be able to be driven by uncondensed gas.
- This solvent is for example an alcohol and preferably methanol. He can too be chosen from the following solvents: methylpropylether, ethylpropylether, dipropyl ether, methyltertiobutylether, dimethoxymethane, dimethoxyethane, ethanol, methoxyethanol, propanol or even be chosen from different classes of solvents such as for example amines or ketones or a mixture formed from one or more of these products.
- the amount of solvent to be injected is usually adjusted according to the temperature, pressure and / or composition of the gas to avoid formation hydrates and ice crystal formation due to the presence of water.
- the mole ratio of solvent flow to gas flow treated is between 1/1000 and 1/10.
- the treatment process is optimized by adapting the quantity of solvent injected as a function of a parameter relating to the gas, for example its temperature and / or its variation in temperature and / or its composition and / or its pressure and / or operating conditions.
- a parameter relating to the gas for example its temperature and / or its variation in temperature and / or its composition and / or its pressure and / or operating conditions.
- account is also taken of the operations then carried out on the treated gas from the enclosure.
- the gas By flow against the current, the gas entrains the solvent contained in the liquid phases which descend by gravity. These liquid phases are collected at the bottom, substantially purified from solvent.
- the solvent injected at the head is therefore mainly evacuated in the gas phase leaving the head. The amount of solvent injected can thus be adjusted in order to obtain the level of concentration in this phase gas required to avoid the formation of hydrates, taking into account the conditions of temperature and pressure.
- the solvent injected at the head is not necessarily pure and can be, for example example, mixed with water, provided however that the concentration of solvent in the aqueous phase makes it possible to avoid the formation of hydrates.
- the injection of a solvent through line 20 also makes it possible to eliminate constituents other than water.
- the solvent can be in this case for example a polar solvent such as for example an ether, an alcohol, or a ketone.
- FIG. 6B describes an embodiment allowing the injection of a separation, for example a solvent via line 20.
- the gas is initially refrigerated in an E1 exchanger before being sent to the EC1 exchanger.
- the line 20 for injecting the separating agent is located in the figure at the top exchanger but can also without departing from the scope of the invention be positioned at any level of the EC1 exchanger.
- FIGS. 6C and 6D describe two other modes of implementing the method according to the invention where the refrigeration at least in one stage of the liquefaction cycle is carried out using a refrigerating agent obtained by using at least two stages of the method according to the invention.
- FIG. 6C describes a first example of implementation of the method according to the invention in which natural gas is refrigerated by means of two cycles of independent refrigeration.
- the refrigerant mixture used during the second stage of refrigeration is made up of methane, ethane, propane and nitrogen and sent under pressure in vapor phase via conduit 100 in exchanger EC1 where it is partially and cooled condensed.
- the liquid phase thus obtained descends by gravity and is simultaneously contacted against the current by the gas phase which circulates in an ascending direction.
- a first fraction is collected via the conduit 206 liquid enriched with propane. This liquid fraction is then refrigerated in the exchanger EC1 and sent via the conduit 204 in the exchanger E2 where it is cooled, relaxed and vaporized to provide the refrigeration required in the exchanger E2.
- a vapor fraction is collected via line 205 enriched in methane and nitrogen which is then sent to the exchanger E2 in which it is liquefied by forming a second liquid fraction.
- This second liquid fraction is sub-cooled in the exchanger E3, expanded and vaporized to provide the required refrigeration in exchanger E3.
- the natural gas arriving through line 2 is cooled during a first step in the EC1 exchanger. At the end of this first stage of refrigeration, a first liquid fraction is evacuated through line 8.
- the gaseous fraction produced during this first step and leaving the exchanger EC1 via the conduit 5 is sent to the exchangers E2 and E3. She stands out liquefied from the exchanger E3 by the conduit 50 and after expansion through the valve V100, forms the LNG produced.
- Refrigeration during the first stage is ensured for example by a refrigeration cycle operating with a mixture of fluids similar to that described in Figure 2B.
- FIG. 6D schematizes an example of implementation according to the invention where the Natural gas refrigeration is provided by a unique refrigeration cycle.
- the refrigerant mixture consisting of methane, ethane, propane, butane, pentane and nitrogen is sent under pressure in vapor phase in the condenser C1 from which it emerges partially condensed.
- the two phases thus produced are separated in the separator S200.
- the liquid fraction from the bottom of the separator is then sent through the pipe 3 in the exchanger EC1 where it is sub-cooled, then expanded and vaporized to provide the required refrigeration in the EC1 exchanger.
- the steam fraction from the head of the S200 separator is sent via line 207 to the EC1 exchanger.
- a depleted liquid fraction is collected in methane and nitrogen which is sent to the exchanger E2 via line 5, in which it is sub-cooled, then expanded and vaporized to provide the required refrigeration in the E2 exchanger.
- a vapor fraction enriched in methane is collected and in nitrogen which is sent to the exchanger E2 in which it is liquefied. Then she is sub-cooled in the exchanger E3, then expanded and vaporized to produce the refrigeration required in exchanger E3.
- the exchanger EC 1 is for example a tube and shell type exchanger such as that which is shown diagrammatically in FIG. 7.
- the gas to be treated arriving via line 2 circulates in an ascending direction at the interior of vertical tubes 30.
- These tubes are preferably provided with a lining, for example a structured packing making it possible to improve the contact between the gas which goes up and the liquid fractions go down.
- the treated gas is evacuated at the head by the conduit 5.
- the solvent introduced through line 20 (FIG. 6A) is sent to the different tubes 30 by a feed ramp 31 and a distribution plate 32.
- the liquid hydrocarbon phase stabilized by heating using a reboiler B 2 located in the lower part of the exchanger EC 1 , for example, is discharged under level control, via line 9, and the aqueous phase is evacuated under level control via line 6.
- Refrigeration is provided by a heat transfer fluid introduced into the exchanger via line 33 and removed after heat exchange via line 34.
- the exchanger EC 1 is a plate exchanger, for example of brazed aluminum, such as that which is shown diagrammatically in FIG. 8.
- Such an exchanger consists of an assembly of flat plates 35 between which are corrugated intermediate plates 36 which allow to maintain mechanically assembling and improving heat transfer.
- These plates delimit channels 37 in which the fluids circulate participating in the heat exchange process.
- the gas to be treated introduced into the exchanger through line 2 circulates in the channels 37 in an upward direction being cooled progressively by the fluid coolant.
- the corrugated intermediate plates 36 playing the role of a lining structured, favor the contact between the rising gas and the liquid fractions which down.
- the solvent sent through line 20 in the case of simultaneous methods of dehydration and fractionation, is distributed evenly over the canals 37 in which the gas to be treated circulates.
- the refrigeration fluid is introduced into the exchanger at its part upper by the conduit 38 which arrives substantially perpendicular to the plane of the section shown in FIG. 8 in an enclosure for supplying the channels not shown in the figure. It is evacuated after heat exchange through line 39 which spring perpendicular to the plane of the section shown in Figure 8, the conduit being connected to a channel evacuation enclosure not shown in the figure.
- the supply and discharge chambers are devices known to those skilled in the art loom allowing the passage of the fluids circulating in each of the channels in the discharge pipe and vice versa to distribute the fluid coming from a pipe in the different channels.
- the liquid hydrocarbon phase is removed under level control (LC, V) via line 9 and the aqueous phase is removed under level control via line 6.
- plate heat exchangers can also be used, for example example of exchangers with stainless steel plates welded together, either on the edge on board, or over their entire surface using a diffusion welding technique.
- Figure 9 shows schematically an embodiment of a tray for sample phases according to their nature according to a process described in Figure 3, by example.
- the plate 7 includes chimneys 40 allowing the gas to rise towards the upper part of the exchanger.
- the liquid phase which is collected on this tray can be evacuated through line 8 with a controlled flow, but can also flow by overflow towards the lower part of the exchanger. It is thus possible not to collect only a fraction of the liquid phase arriving from the upper part of the exchanger.
- two liquid phases are taken from the pan, for example one phase liquid hydrocarbon and an aqueous phase, it is possible to evacuate them at least by part separately.
- the heavier aqueous phase tends to accumulate at the bottom of the tray and it is possible to evacuate it for example through perforations 41 arranged in the plateau.
- the liquefaction plant may include plate heat exchangers different.
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Claims (15)
- Verfahren zur Verflüssigung eines wenigstens zum Teil aus einem Kohlenwasserstoffgemisch gebildeten Fluids, wobei das Verfahren die folgenden Stufen umfasst:eine Stufe zur Vorkühlung dieses Fluids durch indirekten Wärmeaustausch, bei dem man dieses Gemisch unter Druck derart kühlt, dass es wenigstens partiell kondensiert, um eine flüssige Phase und eine gasförmige nichtkondensierte Phase zu erzeugen und wobei man gleichzeitig zu dieser Kühlung im Gegenstrom die gasförmige aufsteigende Phase sowie eine Fraktion wenigstens der flüssigen absteigenden Phase kontaktiert, um durch Stoffübergang eine gasförmige an leichten Kohlenwasserstoffen angereicherte Phase und eine erste flüssige an schweren Kohlenwasserstoffen angereicherte Phase zu erhalten undeine Stufe der Trennung der beiden so erhaltenen Phasen und ein Leiten der an leichten Kohlenwasserstoffen angereicherten gasförmigen Phase zu einer zweiten Kühlstufe, um eine zweite flüssige an leichten Kohlenwasserstoffen angereicherte Phase zu erhalten.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Vorkühlstufe durch einen indirekten Wärmeaustausch an wenigstens einem Teil der Kontaktzone sichergestellt wird.
- Verfahren nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, dass man während der Vorkühlstufe wenigstens zwei flüssige unterschiedliche Fraktionen auf unterschiedlichen Niveaus abtrennt.
- Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Vorkühlstufe und die abschließende Verflüssigungsstufe mittels zweier unterschiedlicher Kühlzyklen realisiert werden, die je mit einem Kühlgemisch arbeiten.
- Verfahren zur Verflüssigung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Vorkühlstufe und die abschließende Verflüssigungsstufe vermittels eines einzigen Kühlzyklus gekühlt werden, der mit einem Kühlgemisch arbeitet.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Vorkühlstufe in Anwesenheit eines Lösungsmittels betrieben wird.
- Verfahren zur Verflüssigung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Fluid ein Erdgas ist.
- Verfahren zur Verflüssigung nach Anspruch 7, dadurch gekennzeichnet, dass diese für die Verflüssigung des Erdgases notwendige Kühlung wenigstens zum Teil durch Verdampfung wenigstens einer flüssigen Fraktion eines Kohlenwasserstoffgemisches erhalten wird, das aus einer Verflüssigungsstufe gemäß diesem Verfahren resultiert.
- Anlage zur Verflüssigung eines Fluids, das wenigstens zum Teil aus einem Kohlenwasserstoffgemisch gebildet ist, umfassend:wenigstens einen Hauptkreis mit einer Einführungsleitung (2) für dieses Gemisch, wenigstens eine Abzugsleitung (5) für eine gasförmige Phase und wenigstens eine Abzugsleitung (6,9) für eine flüssige Phase, wobei dieser Hauptkreis so ausgelegt ist, dass er die direkte Kontaktierung wenigstens zum Teil und im Gegenstrom der kondensierten flüssigen Phase mit der gasförmigen Phase ermöglicht, um eine an leichten Kohlenwasserstoffen reiche gasförmige Phase zu erhalten, die durch diese Abzugsleitung (5) extrahiert wurde sowie eine flüssige an schweren Kohlenwasserstoffen reiche Phase, die durch diese Abzugsleitung (6,9) extrahiert wurde;ein Mittel zur Vorkühlung dieses Hauptkreises zur Kondensierung durch indirekten Wärmeaustausch wenigstens eines Teils der schweren in diesem Gemisch enthaltenen Kohlenwasserstoffe, um die flüssige Fraktion und die gasförmige Fraktion zu erhalten, undein Kühlmittel, um eine zweite an leichten Kohlenwasserstoffen angereicherte flüssige Phase ausgehend von der gasförmigen Phase zu erhalten, die über diese Abzugsleitung (5) extrahiert wurde.
- Anlage zur Verflüssigung gemäß Anspruch 9, dadurch gekennzeichnet, dass dieser Hauptkreis wenigstens ein Entnahmemittel (7, 8) für diese flüssigen Kohlenwasserstofffraktionen umfasst.
- Anlage zur Verflüssigung gemäß Anspruch 10, dadurch gekennzeichnet, dass sie Mittel zur Stabilisierung dieser kondensierten flüssigen Kohlenwasserstofffraktionen umfasst, wobei diese Stabilisierungsmittel mit diesem Entnahmemittel verbunden sind.
- Anlage nach einem der Ansprüche 9 bis 11, dadurch gekennzeichnet, dass dieses Vorkühlmittel wenigstens ein Injektionsmittel umfasst, das die Injektion wenigstens eines Fluids außer dem Fluid, das wenigstens zum Teil Kohlenwasserstoffe umfasst, ermöglicht.
- Anlage nach einem der Ansprüche 9 bis 12, dadurch gekennzeichnet, dass das Vorkühlmittel einen vertikalen Plattenaustauscher umfasst, in dem der Kontakt zwischen dem zu behandelnden Gas in ansteigender Zirkulation und einer flüssigen in Folge der Schwerkraft absteigenden Fraktion durchgeführt wird.
- Anlage nach einem der Ansprüche 9 bis 13, dadurch gekennzeichnet, dass das Vorkühlmittel einen Plattenwärmeaustauscher aus gelötetem Aluminium und das Kühlmittel einen Plattenwärmeaustauscher aus rostfreiem Stahl umfasst.
- Anlage nach einem der Ansprüche 9 bis 14 eingerichtet für die Verflüssigung eines Erdgases.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9512002A FR2739916B1 (fr) | 1995-10-11 | 1995-10-11 | Procede et dispositif de liquefaction et de traitement d'un gaz naturel |
FR9512002 | 1995-10-11 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0768502A1 EP0768502A1 (de) | 1997-04-16 |
EP0768502B1 true EP0768502B1 (de) | 2002-01-23 |
Family
ID=9483480
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96402006A Expired - Lifetime EP0768502B1 (de) | 1995-10-11 | 1996-09-20 | Verfahren und Vorrichtung zur Verflüssigung und Behandlung von Erdgas |
Country Status (8)
Country | Link |
---|---|
US (1) | US5718126A (de) |
EP (1) | EP0768502B1 (de) |
JP (1) | JP3988840B2 (de) |
KR (1) | KR100441039B1 (de) |
DE (1) | DE69618736T2 (de) |
ES (1) | ES2171630T3 (de) |
FR (1) | FR2739916B1 (de) |
SA (1) | SA96170420B1 (de) |
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US7385357B2 (en) * | 1999-06-21 | 2008-06-10 | Access Business Group International Llc | Inductively coupled ballast circuit |
US6357257B1 (en) * | 2001-01-25 | 2002-03-19 | Praxair Technology, Inc. | Cryogenic industrial gas liquefaction with azeotropic fluid forecooling |
US6526777B1 (en) * | 2001-04-20 | 2003-03-04 | Elcor Corporation | LNG production in cryogenic natural gas processing plants |
US7637122B2 (en) | 2001-05-04 | 2009-12-29 | Battelle Energy Alliance, Llc | Apparatus for the liquefaction of a gas and methods relating to same |
US20070137246A1 (en) * | 2001-05-04 | 2007-06-21 | Battelle Energy Alliance, Llc | Systems and methods for delivering hydrogen and separation of hydrogen from a carrier medium |
US7594414B2 (en) * | 2001-05-04 | 2009-09-29 | Battelle Energy Alliance, Llc | Apparatus for the liquefaction of natural gas and methods relating to same |
US7591150B2 (en) * | 2001-05-04 | 2009-09-22 | Battelle Energy Alliance, Llc | Apparatus for the liquefaction of natural gas and methods relating to same |
US6581409B2 (en) | 2001-05-04 | 2003-06-24 | Bechtel Bwxt Idaho, Llc | Apparatus for the liquefaction of natural gas and methods related to same |
US7219512B1 (en) | 2001-05-04 | 2007-05-22 | Battelle Energy Alliance, Llc | Apparatus for the liquefaction of natural gas and methods relating to same |
US6564578B1 (en) | 2002-01-18 | 2003-05-20 | Bp Corporation North America Inc. | Self-refrigerated LNG process |
BRPI0418780B1 (pt) * | 2004-04-26 | 2015-12-29 | Ortloff Engineers Ltd | processos para liquefazer uma corrente de gás natural contendo metano e componentes hidrocarbonetos mais pesados e aparelhos para a realização dos processos |
US8899074B2 (en) | 2009-10-22 | 2014-12-02 | Battelle Energy Alliance, Llc | Methods of natural gas liquefaction and natural gas liquefaction plants utilizing multiple and varying gas streams |
US8061413B2 (en) | 2007-09-13 | 2011-11-22 | Battelle Energy Alliance, Llc | Heat exchangers comprising at least one porous member positioned within a casing |
US9574713B2 (en) | 2007-09-13 | 2017-02-21 | Battelle Energy Alliance, Llc | Vaporization chambers and associated methods |
US9254448B2 (en) | 2007-09-13 | 2016-02-09 | Battelle Energy Alliance, Llc | Sublimation systems and associated methods |
US9217603B2 (en) | 2007-09-13 | 2015-12-22 | Battelle Energy Alliance, Llc | Heat exchanger and related methods |
US8555672B2 (en) * | 2009-10-22 | 2013-10-15 | Battelle Energy Alliance, Llc | Complete liquefaction methods and apparatus |
US20090145167A1 (en) * | 2007-12-06 | 2009-06-11 | Battelle Energy Alliance, Llc | Methods, apparatuses and systems for processing fluid streams having multiple constituents |
US9441877B2 (en) | 2010-03-17 | 2016-09-13 | Chart Inc. | Integrated pre-cooled mixed refrigerant system and method |
KR101064576B1 (ko) * | 2010-10-22 | 2011-09-15 | 대우조선해양 주식회사 | 열교환기 분리형 천연가스 액화 장치 |
US10655911B2 (en) | 2012-06-20 | 2020-05-19 | Battelle Energy Alliance, Llc | Natural gas liquefaction employing independent refrigerant path |
KR101392750B1 (ko) * | 2012-06-29 | 2014-05-09 | 한국에너지기술연구원 | 천연가스 액화시스템 및 액화 방법 |
FR2993350B1 (fr) * | 2012-07-13 | 2018-06-15 | Air Liquide | Procede et appareil de refroidissement d'un debit contenant au moins 35% de dioxyde de carbone et du mercure |
US11408673B2 (en) | 2013-03-15 | 2022-08-09 | Chart Energy & Chemicals, Inc. | Mixed refrigerant system and method |
US11428463B2 (en) | 2013-03-15 | 2022-08-30 | Chart Energy & Chemicals, Inc. | Mixed refrigerant system and method |
CN108955084B (zh) | 2013-03-15 | 2020-10-30 | 查特能源化工公司 | 混合制冷剂系统和方法 |
TWI707115B (zh) | 2015-04-10 | 2020-10-11 | 美商圖表能源與化學有限公司 | 混合製冷劑液化系統和方法 |
US10619918B2 (en) | 2015-04-10 | 2020-04-14 | Chart Energy & Chemicals, Inc. | System and method for removing freezing components from a feed gas |
US10072889B2 (en) * | 2015-06-24 | 2018-09-11 | General Electric Company | Liquefaction system using a turboexpander |
AR105277A1 (es) | 2015-07-08 | 2017-09-20 | Chart Energy & Chemicals Inc | Sistema y método de refrigeración mixta |
WO2020223325A1 (en) | 2019-04-29 | 2020-11-05 | Conocophillips Company | Solvent injection and recovery in a lng plant |
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FR2292203A1 (fr) * | 1974-11-21 | 1976-06-18 | Technip Cie | Procede et installation pour la liquefaction d'un gaz a bas point d'ebullition |
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US5450728A (en) * | 1993-11-30 | 1995-09-19 | Air Products And Chemicals, Inc. | Recovery of volatile organic compounds from gas streams |
US5361589A (en) * | 1994-02-04 | 1994-11-08 | Air Products And Chemicals, Inc. | Precooling for ethylene recovery in dual demethanizer fractionation systems |
-
1995
- 1995-10-11 FR FR9512002A patent/FR2739916B1/fr not_active Expired - Lifetime
-
1996
- 1996-09-20 DE DE69618736T patent/DE69618736T2/de not_active Expired - Lifetime
- 1996-09-20 ES ES96402006T patent/ES2171630T3/es not_active Expired - Lifetime
- 1996-09-20 EP EP96402006A patent/EP0768502B1/de not_active Expired - Lifetime
- 1996-10-08 US US08/727,778 patent/US5718126A/en not_active Expired - Lifetime
- 1996-10-11 JP JP27019196A patent/JP3988840B2/ja not_active Expired - Lifetime
- 1996-10-11 KR KR1019960046115A patent/KR100441039B1/ko not_active IP Right Cessation
- 1996-11-11 SA SA96170420A patent/SA96170420B1/ar unknown
Also Published As
Publication number | Publication date |
---|---|
JPH09113129A (ja) | 1997-05-02 |
JP3988840B2 (ja) | 2007-10-10 |
EP0768502A1 (de) | 1997-04-16 |
DE69618736T2 (de) | 2002-09-05 |
FR2739916B1 (fr) | 1997-11-21 |
KR100441039B1 (ko) | 2004-10-02 |
KR970021263A (ko) | 1997-05-28 |
SA96170420B1 (ar) | 2006-04-22 |
ES2171630T3 (es) | 2002-09-16 |
FR2739916A1 (fr) | 1997-04-18 |
DE69618736D1 (de) | 2002-03-14 |
US5718126A (en) | 1998-02-17 |
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