US3747359A - Gas liquefaction by a fractionally condensed refrigerant - Google Patents
Gas liquefaction by a fractionally condensed refrigerant Download PDFInfo
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- US3747359A US3747359A US00054478A US3747359DA US3747359A US 3747359 A US3747359 A US 3747359A US 00054478 A US00054478 A US 00054478A US 3747359D A US3747359D A US 3747359DA US 3747359 A US3747359 A US 3747359A
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- 239000003507 refrigerant Substances 0.000 title claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 50
- 238000009835 boiling Methods 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 21
- 239000003345 natural gas Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000007789 gas Substances 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 239000000203 mixture Substances 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000002826 coolant Substances 0.000 description 6
- 239000007792 gaseous phase Substances 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 238000005057 refrigeration Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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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
- F25J3/0204—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
- F25J3/0209—Natural gas or substitute 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
- F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
- F25J1/0022—Hydrocarbons, e.g. natural gas
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
- F25J1/004—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by flash gas recovery
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
- F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
- F25J1/0055—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream originating from an incorporated cascade
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
- F25J1/0211—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a multi-component refrigerant [MCR] fluid in a closed vapor compression cycle
- F25J1/0212—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a multi-component refrigerant [MCR] fluid in a closed vapor compression cycle as a single flow MCR cycle
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- 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
- F25J3/0233—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 1 carbon atom or more
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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
- F25J3/0257—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 nitrogen
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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
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/02—Processes or apparatus using separation by rectification in a single pressure main column system
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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
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
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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
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
- F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2220/00—Processes or apparatus involving steps for the removal of impurities
- F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
- F25J2220/64—Separating heavy hydrocarbons, e.g. NGL, LPG, C4+ hydrocarbons or heavy condensates in general
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2250/00—Details related to the use of reboiler-condensers
- F25J2250/20—Boiler-condenser with multiple exchanger cores in parallel or with multiple re-boiling or condensing streams
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/18—External refrigeration with incorporated cascade loop
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/66—Closed external refrigeration cycle with multi component refrigerant [MCR], e.g. mixture of hydrocarbons
Definitions
- the refrigerant is fractionally condensed and the UNITED STATES PATENTS fractions are separately evaporated in the closed cycle to cool and llquefy the gas stream.
- This invention relates to a process for the liquefaction of gases or gas mixtures by means of a cooling cycle in which is circulated a cooling medium or refrigerant composed of several components that are subjected to fractional condensation and in which the condensed fractions are separately evaporated.
- the process is especially-suitable for the liquefaction of natural gas.
- condensate fractions are separately evaporated and reheated to about ambient temperature and are again mixed together during recompression.
- the process of this invention is especially advantageous for the liquefaction of natural gas since only two partial refrigerant streams fromm a single separator suffice for the liquefaction. Since the entropy increase by the mixing of cooling medium and natural gas is avoided, the energy requirement is relatively low.
- the one with the higher boiling fraction is decompressed to a medium absolute pressure, preferably five to 10 ats. (atmospheres), and the one with the lower boiling fraction is decompressed to a low absolute pressure, preferably one to five ats.
- the refrigerant or cooling medium is preferably a hydrocarbon mixture.
- natural gas is preferably subjected, in the course of the I cooling thereof, to a preseparation before being further cooled and fractionated in a nitrogen rectification column.
- the natural gas to be liquefied which has the following composition:
- purification plant 2 it is freed from impurities, especially from water and carbon dioxide, and then passed via pipe 3 successively through heat exchangers 4, 5 and 6. It is thereby cooled to a temperature of about -l00 C. and the heavy hydrocarbons condense out. These are separated in separator 7 and withdrawn through pipe 8.
- the liquid phase is separated from the gaseous phase in separator 12.
- the gaseous phase is enriched in nitrogen, whereas the liquid phase is depleted in nitrogen.
- the liquid and gaseous phases pass via pipes 13 and 14, respectively, into heat exchanger 15 where they are cooled to about l 40 C. and then used to heat the sump liquid of nitrogen column 11 by means of coils l7 and 16; respectively, whereby they are further cooled.
- the liquid phase is then decompressed via expansion valve 18 into the middle portion of nitrogen column 11, whereas the gaseous phase is first still further cooled in heat exchanger 19 to about 1 83 C. and thus liquefied before it is decompressed via expansion valve 20 into the top portion of nitrogen column 11.
- nitrogen column 11 which is at an absolute pressure of four ats., the nitrogen contained in the natural gas is completely separated and withdrawn via pipe 21 from the top of column 11 at a temperature of l83 C. It successively gives up its refrigeration in heat exchangers 19, l5, l0, 6, 5 and 4 and is then available at ambient temperature. It can also previously be decompressed to atmospheric pressure. Liquefied methane is withdrawn via pipe 22 from nitrogen column 11. It is then, in known manner, decompressed into a reservoir which is not illustrated in the drawing; the resulting flash and evaporation gases can also be utilized for recovering refrigeration therefrom.
- the refrigeration necessary for cooling and liquefying the natural gas is produced in a closed cooling cycle in which a multicomponent refrigerant is circulated and subjected to fractional condensation.
- the refrigerant or cooling medium is preponderantly composed of methane, ethane, propane and butane.
- one fraction of the refrigerant enters compressor 24 at an absolute pressure of two ats. and the other fraction enters compressor 24 at an absolute pressure of seven ats.
- the fractions thus recombined are compressed to about 25 ats. absolute and cooled in water cooler 25 to about 30 C.
- the refrigerant is then further cooled in heat exchanger 4 to about C., whereby it is partially liquefied.
- the partial refrigerant stream formed from the liquid phase and containing only a little methane and the heavier hydrocarbons, ethane, propane and butane in about equal parts, is first passed by means of pipe 28 through heat exchanger to effect further cooling of the partial stream and then is decompressed by expansion valve 29 to an absolute pressure of about 7.5 ats. This partial stream then evaporates at this pressure while giving up refrigeration in heat exchangers 5 and 4 and is returned to an intermediate stage of compressor 24.
- the partial refrigerant stream obtained from the gaseous phase leaving separator 26 consists preponderantly of methane and has a modest content of ethane and propane, whereas the content of butane is small.
- This second partial stream in pipe 30 is first cooled in heat exchangers 5, 6, and to about l40 C. and thus liquefied and then, according to this invention, is decompressed by expansion valve 31 to an absolute pressure of about 2.5 ats. Thereafter, this second stream evaporates, successively gives up refrigeration in heat exchangers l5, l0, 6, 5 and 4 and finally passes via pipe 23 back into compressor 24.
- a special advantage of the process of this invention is that it can be carried out with only a single subdivision of the closed cooling cycle.
- a process for the liquefaction of gas or a mixture of gases by indirect heat exchange with a compressed multi-component refrigerant circulated in a closed cooling cycle comprising thefollowing steps:
- a process for the liquefaction of natural gas by indirect heat exchange with a compressed multicomponent refrigerant circulated in a closed cooling cycle comprising the following steps:
Abstract
A gas stream is liquefied by indirect heat exchange with a multi-component refrigerant in a closed cooling cycle. The refrigerant is fractionally condensed and the fractions are separately evaporated in the closed cycle to cool and liquefy the gas stream.
Description
Patent: 1111 3,747,359
Streich July 24, 1973 [54] GAS LIQUEFACTION BY A FRACTIONALLY 2,823,523 2/1958 Eakin 62/40 CONDENSED REFRIGERANT 3,548,606 12/1970 Kuerston.... 62/40 3,218,816 11/1965 ,Grenier 62/28 [75] Inventor: Martin Str i h, Nl d' -Es h a h, 3,274,787 9/1966 Grenier 62/28 G FOREIGN PATENTS OR APPLICATIONS [731 8 P Aktiengmnschan, 652,208 11/1962 Canada 62 40 Wwsbaden, Germany 110,556 2/1961 Pakistan..... 62/40 Filed: J y 3, 1970 OTHER PUBLICATIONS [21] Appl. No.: 54,478 Kleemenko, One Flow Cascade Cycle, Pergamon Press 1960 Pgs. 34-39 in Prog. In Refrig. Sci. & Tech.
[30] Foreign Application Prlonty Data Primary Examiner Norman Yudkoff I Aug. 1, 1969 Germany P 19 39 114.1 Assistant Examiner Arthur R Purcell Att P 1 W. G b 52 115. CI 62/24,62/11, 62/40 at o [51 Int. Cl...., .Q F25j l/02, F25j 3/02 [58] Field of Search 62/23, 24, 27, 2s, [57] ABSTRACT 62/40 9 1 1 A gas stream is liquefied by indirect heat exchange with a multi-component refrigerant in a closed cooling cy- 5 R f ren e Cited cle. The refrigerant is fractionally condensed and the UNITED STATES PATENTS fractions are separately evaporated in the closed cycle to cool and llquefy the gas stream. 3,364,685 l/1968 Perret 62/23 3,407,052 10/1968 Huntress 62/23 4 Claims, 1 Drawing Figure PATENIEDJUI. 241m INVENTOR.
MARTIN STREICH BY m AGENT GAS LIQUEFACTION BY A FRACTIONALLY CONDENSED REFRIGERANT BACKGROUND OF THE INVENTION This invention relates to a process for the liquefaction of gases or gas mixtures by means of a cooling cycle in which is circulated a cooling medium or refrigerant composed of several components that are subjected to fractional condensation and in which the condensed fractions are separately evaporated. The process is especially-suitable for the liquefaction of natural gas.
From German Auslegeschrift 1,272,943, there is known a process of this type in which cooling media obtained by fractional condensation of components from the natural gas to be liquefied are decompressed to a common medium pressure, mixed, recompressed to the pressure of the natural gas flowing into the plant and again mixed therewith. It is characteristic of that process that the several cooling media are decompressed to a common medium pressure.
From German Offenlegungsschrift 1,501,690, it is also known to carry out the circulation of the cooling medium in a closed cycle in such process.
In comparison with the so-called classical cascade process, these processes have some advantages since only one cooling cycle with one compressor is needed. However, this single cooling cycle must be divided up into several circulation branches, with a corresponding division of the heat exchangers and with complicated connections resulting therefrom. Furthermore, the utilization of energy is higher than in the case of the classical cascade process.
'In order to avoid these disadvantages, it has been proposed to divide up a cooling medium composed of several components and obtained byfractional condensation, to decompress one partial stream to a medium pressure and the other partial stream to approximately atmospheric pressure, to combine again the decompressed partial streams, to mix the combined streams with the gas mixture to be liquefied and to compress the total gas. The process is especially suitable for comparatively small natural gas liquefaction plants since it does not require a separate natural gas compressor. In such case, it is necessary that the natural gas is supplied at low pressure. However, these prerequisites-are not always fulfilled; Thus, for example, the natural gas is frequently supplied at a pressure which is already sufficiently high. Furthermore, the mixing of light natural gas and heavy hydrocarbons always leads to an. increased use of energy because of the increased entropy whichariSes. 1
It is an object of this invention to avoid these disadvantages and to make the process of universal applicability.
SUMMARY OF THE INVENTION A process has been found for the liquefaction of gas or gas mixtures by means of a closed cooling cycle in which a circulating multi-component refrigerant is compressed by a compressor, is separated by fractional condensation into fractions with different boiling ranges and these fractions are evaported as separate streams giving up refrigeration to the refrigerant undergoing fractional condensation and to the gas or gas mixture undergoing liquefaction, are recombined and again compressed. According to this invention, the
condensate fractions are separately evaporated and reheated to about ambient temperature and are again mixed together during recompression.
The process of this invention is especially advantageous for the liquefaction of natural gas since only two partial refrigerant streams fromm a single separator suffice for the liquefaction. Since the entropy increase by the mixing of cooling medium and natural gas is avoided, the energy requirement is relatively low. When using only two partial refrigerant streams, the one with the higher boiling fraction is decompressed to a medium absolute pressure, preferably five to 10 ats. (atmospheres), and the one with the lower boiling fraction is decompressed to a low absolute pressure, preferably one to five ats. When the gas mixture to be liquefied is natural gas, the refrigerant or cooling medium is preferably a hydrocarbon mixture.
When the process of this invention is applied to natural gas and nitrogen is to be removed therefrom, the
natural gas is preferably subjected, in the course of the I cooling thereof, to a preseparation before being further cooled and fractionated in a nitrogen rectification column.
BRIEF DESCRIPTION OF THE DRAWING charged in the gaseous state.
DESCRIPTION OF A PREFERRED EMBODIMENT The natural gas to be liquefied, which has the following composition:
N 14.3% by volume CH 82.4% by volume C Hq 2.6% by volume QH, 0.4% by volume C H 0.3% by volume enters the plant through pipe 1 at an absolute pressure of 20 ats. and at a temperature of 30 C. In purification plant 2, it is freed from impurities, especially from water and carbon dioxide, and then passed via pipe 3 successively through heat exchangers 4, 5 and 6. It is thereby cooled to a temperature of about -l00 C. and the heavy hydrocarbons condense out. These are separated in separator 7 and withdrawn through pipe 8. The gaseous portion which remains, consisting preponderantly of methane and nitrogen, flows through pipe 9 into heat exchanger 10 where it is cooled to about l20 C. and partially liquefied.
In order to simplify the separation of nitrogen in this stream in nitrogen rectification column 11, the liquid phase is separated from the gaseous phase in separator 12. The gaseous phase is enriched in nitrogen, whereas the liquid phase is depleted in nitrogen. The liquid and gaseous phases pass via pipes 13 and 14, respectively, into heat exchanger 15 where they are cooled to about l 40 C. and then used to heat the sump liquid of nitrogen column 11 by means of coils l7 and 16; respectively, whereby they are further cooled. The liquid phase is then decompressed via expansion valve 18 into the middle portion of nitrogen column 11, whereas the gaseous phase is first still further cooled in heat exchanger 19 to about 1 83 C. and thus liquefied before it is decompressed via expansion valve 20 into the top portion of nitrogen column 11.
In nitrogen column 11 which is at an absolute pressure of four ats., the nitrogen contained in the natural gas is completely separated and withdrawn via pipe 21 from the top of column 11 at a temperature of l83 C. It successively gives up its refrigeration in heat exchangers 19, l5, l0, 6, 5 and 4 and is then available at ambient temperature. It can also previously be decompressed to atmospheric pressure. Liquefied methane is withdrawn via pipe 22 from nitrogen column 11. It is then, in known manner, decompressed into a reservoir which is not illustrated in the drawing; the resulting flash and evaporation gases can also be utilized for recovering refrigeration therefrom.
The refrigeration necessary for cooling and liquefying the natural gas is produced in a closed cooling cycle in which a multicomponent refrigerant is circulated and subjected to fractional condensation. The refrigerant or cooling medium is preponderantly composed of methane, ethane, propane and butane. At about ambient temperature, one fraction of the refrigerant enters compressor 24 at an absolute pressure of two ats. and the other fraction enters compressor 24 at an absolute pressure of seven ats. The fractions thus recombined are compressed to about 25 ats. absolute and cooled in water cooler 25 to about 30 C. The refrigerant is then further cooled in heat exchanger 4 to about C., whereby it is partially liquefied. lt passes via pipe 26 into separator 27 in which the liquid phase is separated from the gaseous phase. The two separated phases now provide the two fractions or partial refrigerant streams. The partial refrigerant stream formed from the liquid phase and containing only a little methane and the heavier hydrocarbons, ethane, propane and butane in about equal parts, is first passed by means of pipe 28 through heat exchanger to effect further cooling of the partial stream and then is decompressed by expansion valve 29 to an absolute pressure of about 7.5 ats. This partial stream then evaporates at this pressure while giving up refrigeration in heat exchangers 5 and 4 and is returned to an intermediate stage of compressor 24.
The partial refrigerant stream obtained from the gaseous phase leaving separator 26 consists preponderantly of methane and has a modest content of ethane and propane, whereas the content of butane is small. This second partial stream in pipe 30 is first cooled in heat exchangers 5, 6, and to about l40 C. and thus liquefied and then, according to this invention, is decompressed by expansion valve 31 to an absolute pressure of about 2.5 ats. Thereafter, this second stream evaporates, successively gives up refrigeration in heat exchangers l5, l0, 6, 5 and 4 and finally passes via pipe 23 back into compressor 24.
A special advantage of the process of this invention is that it can be carried out with only a single subdivision of the closed cooling cycle.
I claim:
1. A process for the liquefaction of gas or a mixture of gases by indirect heat exchange with a compressed multi-component refrigerant circulated in a closed cooling cycle comprising thefollowing steps:
a. cooling, fractionally condensing and separating said compressed multi-component refrigerant into higher boiling liquid and lower boiling gaseous fractions,
b. subcooling all of said higher boiling liquid fractions and further cooling, liquefying and subcooling said lower boiling gaseous fractions,
c. expanding all of said subcooled higher boiling and lower boiling liquid fractions to different pressures, said subcooled higher boiling liquid fractions being expanded to a higher pressure, and said subcooled lower boiling liquid fractions being expanded to a lower pressure,
d. separately evaporating and heating to ambient temperature said subcooled liquid fractions expanded to different pressures by indirect heat exchange with said higher boiling and lower boiling fractions of said multi-component refrigerant and with said gas or gaseous mixture to be liquefied, without mixing said higher boiling and lower boiling fractions during evaporation and heating to ambient temperature,
e. separately recycling said evaporated fractions previously expanded to different pressures to a multistage compressor and mixing said evaporated fractions only during the compression.
2. A process for the liquefaction of natural gas by indirect heat exchange with a compressed multicomponent refrigerant circulated in a closed cooling cycle comprising the following steps:
a. cooling, fractionally condensing and separating said compressed multi-component refrigerant into only a single higher boiling liquid and a single lower boiling gaseous fraction,
b. subcooling all of said higher boiling liquid fraction and further cooling, liquefying and subcooling said lower boiling gaseous fraction,
c. expanding all of said subcooled higher boiling and lower boiling liquid fractions to different pressures, said subcooled higher boiling liquid fraction being expanded to a higher pressure, and said subcooled lower boiling liquid fraction being expanded to a lower pressure,
(1. separately evaporating and heating to ambient temperature said subcooled liquid fractions expanded to different pressures by indirect heat exchange with said higher boiling and lower boiling fractions of said multi-component refrigerant and with said natural gas to be liquefied, without mixing said higher boiling and lower boiling fractions during evaporation and heating to ambient temperature,
e. separately recycling said two evaporated fractions previously expanded to different pressures to a multi-stage compressor and mixing said two evaporated fractions only during the compression.
3. The process of claim 2 wherein the subcooled higher boiling liquid fraction is expanded to an absolute pressure of not less than about 5 atmospheres and the subcooled lower boiling liquid fraction is expanded to a lower absolute pressure of'less than about 5 atmospheres.
4. The process of claim 2 wherein the subcooled boiling liquid fraction is expanded to an absolute pressure in the range of about five to 10 atmospheres and the subcooled lower boiling liquid fraction is expanded to a lower absolute pressure in the range of about one to five atmospheres.
Claims (3)
- 2. A process for the liquefaction of natural gas by indirect heat exchange with a compressed multi-component refrigerant circulated in a closed cooling cycle comprising the following steps: a. cooling, fractionally condensing and separating said compressed multi-component refrigerant into only a single higher boiling liquid and a single lower boiling gaseous fraction, b. subcooling all of said higher boiling liquid fraction and further cooling, liquefying and subcooling said lower boiling gaseous fraction, c. expanding all of said subcooled higher boiling and lower boiling liquid fractions to different pressures, said subcooled higher boiling liquid fraction being expanded to a higher pressure, and said subcooled lower boiling liquid fraction being expanded to a lower pressure, d. separately evaporating and heating to ambient temperature said subcooled liquid fractions expanded to different pressures by indirect heat exchange with said higher boiling and lower boiling fractions of said multi-component refrigerant and with said natural gas to be liquefied, without mixing said higher boiling and lower boiling fractions during evaporation and heating to ambient temperature, e. separately recycling said two evaporated fractions previously expanded to different pressures to a multi-stage compressor and mixing said two evaporated fractions only during the compression.
- 3. The process of claim 2 wherein the subcooled higher boiling liquid fraction is expanded to an absolute pressure of not less than about 5 atmospheres and the subcooled lower boiling liquid fraction is expanded to a lower absolute pressure of less than about 5 atmospheres.
- 4. The process of claim 2 wherein the subcooled boiling liquid fraction is expanded to an absolute pressure in the range of about five to 10 atmospheres and the subcooled lower boiling liquid fraction is expanded to a lower absolute pressure in the range of about one to five atmospheres.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1939114A DE1939114B2 (en) | 1969-08-01 | 1969-08-01 | Liquefaction process for gases and gas mixtures, in particular for natural gas |
Publications (1)
Publication Number | Publication Date |
---|---|
US3747359A true US3747359A (en) | 1973-07-24 |
Family
ID=5741575
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00054478A Expired - Lifetime US3747359A (en) | 1969-08-01 | 1970-07-13 | Gas liquefaction by a fractionally condensed refrigerant |
Country Status (5)
Country | Link |
---|---|
US (1) | US3747359A (en) |
DE (1) | DE1939114B2 (en) |
FR (1) | FR2056914B1 (en) |
GB (1) | GB1307640A (en) |
NL (1) | NL7010247A (en) |
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JPS5128101A (en) * | 1974-08-09 | 1976-03-09 | Linde Ag | Tennengasuno ekikahoho |
US4251247A (en) * | 1974-05-31 | 1981-02-17 | Compagnie Francaise D'etudes Et De Construction Technip | Method and apparatus for cooling a gaseous mixture |
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US4461634A (en) * | 1980-10-16 | 1984-07-24 | Petrocarbon Developments Limited | Separation of gas mixtures by partial condensation |
US4584006A (en) * | 1982-03-10 | 1986-04-22 | Flexivol, Inc. | Process for recovering propane and heavier hydrocarbons from a natural gas stream |
US4664686A (en) * | 1986-02-07 | 1987-05-12 | Union Carbide Corporation | Process to separate nitrogen and methane |
US4666483A (en) * | 1983-12-30 | 1987-05-19 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes George Claude | Method and installation for recovering the heaviest hydrocarbons from a gaseous mixture |
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US20080016910A1 (en) * | 2006-07-21 | 2008-01-24 | Adam Adrian Brostow | Integrated NGL recovery in the production of liquefied natural gas |
US20100189508A1 (en) * | 2006-06-06 | 2010-07-29 | Jose Lourenco | Method of increasing storage capacity of natural gas storage caverns |
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US9562717B2 (en) | 2010-03-25 | 2017-02-07 | The University Of Manchester | Refrigeration process |
US9945604B2 (en) | 2014-04-24 | 2018-04-17 | Air Products And Chemicals, Inc. | Integrated nitrogen removal in the production of liquefied natural gas using refrigerated heat pump |
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Families Citing this family (5)
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DE2206620B2 (en) * | 1972-02-11 | 1981-04-02 | Linde Ag, 6200 Wiesbaden | Plant for liquefying natural gas |
US3932154A (en) * | 1972-06-08 | 1976-01-13 | Chicago Bridge & Iron Company | Refrigerant apparatus and process using multicomponent refrigerant |
US4411677A (en) * | 1982-05-10 | 1983-10-25 | Air Products And Chemicals, Inc. | Nitrogen rejection from natural gas |
DE102007010032A1 (en) * | 2007-03-01 | 2008-09-04 | Linde Ag | Procedure for separating a nitrogen-rich fraction from a liquefied natural gas, comprises supplying the natural gas after its liquefaction and super cooling, to a stripping column that serves the separation of the nitrogen-rich fraction |
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Cited By (48)
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US4251247A (en) * | 1974-05-31 | 1981-02-17 | Compagnie Francaise D'etudes Et De Construction Technip | Method and apparatus for cooling a gaseous mixture |
JPS5128101A (en) * | 1974-08-09 | 1976-03-09 | Linde Ag | Tennengasuno ekikahoho |
JPS5632540B2 (en) * | 1974-08-09 | 1981-07-28 | ||
US4321795A (en) * | 1980-09-22 | 1982-03-30 | Helmut Brandt | Process for the purification of gaseous chlorine |
US4461634A (en) * | 1980-10-16 | 1984-07-24 | Petrocarbon Developments Limited | Separation of gas mixtures by partial condensation |
US4584006A (en) * | 1982-03-10 | 1986-04-22 | Flexivol, Inc. | Process for recovering propane and heavier hydrocarbons from a natural gas stream |
US4445917A (en) * | 1982-05-10 | 1984-05-01 | Air Products And Chemicals, Inc. | Process for liquefied natural gas |
US4666483A (en) * | 1983-12-30 | 1987-05-19 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes George Claude | Method and installation for recovering the heaviest hydrocarbons from a gaseous mixture |
US4664686A (en) * | 1986-02-07 | 1987-05-12 | Union Carbide Corporation | Process to separate nitrogen and methane |
US5051120A (en) * | 1990-06-12 | 1991-09-24 | Union Carbide Industrial Gases Technology Corporation | Feed processing for nitrogen rejection unit |
US5535594A (en) * | 1993-04-09 | 1996-07-16 | Gaz De France (Service National) | Process and apparatus for cooling a fluid especially for liquifying natural gas |
WO1994024500A1 (en) * | 1993-04-09 | 1994-10-27 | Gaz De France | Fluid cooling process and plant, especially for natural gas liquefaction |
FR2703762A1 (en) * | 1993-04-09 | 1994-10-14 | Grenier Maurice | Method and installation for cooling a fluid, in particular for liquefying natural gas. |
US5613373A (en) * | 1993-04-09 | 1997-03-25 | Gaz De France (Service National) | Process and apparatus for cooling a fluid especially for liquifying natural gas |
US5950453A (en) * | 1997-06-20 | 1999-09-14 | Exxon Production Research Company | Multi-component refrigeration process for liquefaction of natural gas |
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US6347531B1 (en) | 1999-10-12 | 2002-02-19 | Air Products And Chemicals, Inc. | Single mixed refrigerant gas liquefaction process |
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Also Published As
Publication number | Publication date |
---|---|
NL7010247A (en) | 1971-02-03 |
DE1939114B2 (en) | 1979-01-25 |
FR2056914A1 (en) | 1971-05-07 |
GB1307640A (en) | 1973-02-21 |
DE1939114A1 (en) | 1971-02-04 |
FR2056914B1 (en) | 1973-08-10 |
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