EP0535752B1 - Verfahren zur Verflüssigung von Erdgas - Google Patents

Verfahren zur Verflüssigung von Erdgas Download PDF

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Publication number
EP0535752B1
EP0535752B1 EP92203009A EP92203009A EP0535752B1 EP 0535752 B1 EP0535752 B1 EP 0535752B1 EP 92203009 A EP92203009 A EP 92203009A EP 92203009 A EP92203009 A EP 92203009A EP 0535752 B1 EP0535752 B1 EP 0535752B1
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EP
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Prior art keywords
pressure
zone
gas
phase
methane
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EP92203009A
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English (en)
French (fr)
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EP0535752A1 (de
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Henri Paradowski
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Francaise dEtudes et de Construction Technip SA
Technip Energies France SAS
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Francaise dEtudes et de Construction Technip SA
Technip SA
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
    • F25J1/0035—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0022—Hydrocarbons, e.g. natural gas
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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    • 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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    • F25J1/0216—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 dual level refrigeration cascade with at least one MCR cycle with one SCR cycle using a C3 pre-cooling cycle
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    • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0235—Heat exchange integration
    • F25J1/0237—Heat exchange integration integrating refrigeration provided for liquefaction and purification/treatment of the gas to be liquefied, e.g. heavy hydrocarbon removal from natural gas
    • F25J1/0239—Purification or treatment step being integrated between two refrigeration cycles of a refrigeration cascade, i.e. first cycle providing feed gas cooling and second cycle providing overhead gas cooling
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    • F25J1/02—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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    • 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
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    • 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
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    • 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
    • F25J3/0242—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 3 carbon atoms or more
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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    • F25J2200/04—Processes or apparatus using separation by rectification in a dual pressure main column system
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    • F25J2270/00—Refrigeration techniques used
    • F25J2270/66—Closed external refrigeration cycle with multi component refrigerant [MCR], e.g. mixture of hydrocarbons

Definitions

  • the invention relates to a natural gas liquefaction process comprising the separation of hydrocarbons heavier than methane.
  • Natural gas and other methane-rich gas streams are commonly available at sites away from places of use, and it is therefore common to liquefy natural gas for transportation by land or sea. Liquefaction is widely practiced in the present day and the literature and patents describe numerous processes and apparatuses for liquefaction. US-A-3945 214, 4251 247, 4274 849, 4339 253 and 4539 028 are examples of such methods.
  • US Pat. No. 4,690,702 describes a process in which the charge of hydrocarbons under high pressure (P1) is cooled so as to cause the liquefaction of part of the hydrocarbons, a gas phase (G1) is separated from a liquid phase (L1), the gas phase is relaxed (G1) to lower its pressure to a value (P2) lower than (P1), the liquid phase (L1) and the gas phase (G1) are sent under pressure (P2) in a first fractionation zone, for example a purification column - contact refrigeration, a residual gas (G2) rich in methane is drawn off at the head, the pressure of which is then raised to a value (P3), it is withdrawn in melts a liquid phase (L2), the phase (L2) is sent to a second fractionation zone, for example a fractionation column, a liquid phase is drawn off at the bottom (L3), enriched in higher hydrocarbons, for example C3 +, a gas phase (G3) is drawn off at the head, at least part of the gas phase
  • the expansion of G1 takes place in a turboexpander which transmits at least part of the energy collected to a turbocharger which raises the pressure of G2 to the value P3.
  • the process of the invention is distinguished, for its fractionation part, from the process of US-A-4 690 702, in that the pressures used in the fractionation zones are higher than those previously used and in that the second fractionation zone operates at a lower pressure than the first fractionation zone.
  • US Pat. No. 4,657,571 discloses a process corresponding to the preamble of claim 1.
  • the gaseous charge of hydrocarbons containing methane and at least one hydrocarbon heavier than methane, under pressure P1 is cooled in one or more stages so as to form at least one gaseous phase G1, the gas phase G1 to lower its pressure from the value P1 to a value P2 lower than P1, the pressure reduction product P la is sent to a first contact fractionation zone, a residual gas G2 enriched in methane is drawn off at the head , a liquid phase L2 is drawn off at the bottom, the liquid phase L2 is sent to a second fractionation zone by distillation operating under a pressure P4 lower than the pressure P2 of the first fractionation zone, it is drawn off at the bottom thereof at least one liquid phase L3, enriched in hydrocarbons heavier than methane, a gas phase G3 is drawn off at the head and it is returned to the first fractionation zone as reflux.
  • At least part of the gas phase G3 is condensed, to produce a condensed phase L4 and the pressure of at least part of the condensed phase L4 is raised, which is sent to the first zone fractionation as reflux and the residual gas G2 is then further cooled under a pressure at least equal to P2; in a methane liquefaction zone, so as to obtain a methane-rich liquid.
  • the gas is initially available under a pressure P1 of at least 5 MPa, preferably at least 6 MPa.
  • P2 0.3 to 0.8 P1
  • P2 being chosen for example between 3.5 and 7 MPa, preferably between 4.5 and 6 MPa.
  • the expansion of G1 is done in one or more turboexpanders coupled (s) to one or more turbocharger (s) which recompresses (s) the waste gas G2 from the pressure P2 to a pressure P3.
  • At least one liquid phase L1 is formed in addition to the gas phase G1, and the liquid phase L1 is sent, after expansion, to said first fractionation zone by contact.
  • the gas phase G3 is completely condensed and a portion is sent to the second fractionation zone as internal reflux and the complement to the first fractionation zone as reflux.
  • the condensation can be completed by further compressing, with subsequent cooling of the said G3 phase.
  • the invention is illustrated by the attached figure.
  • the natural gas from line 1 passes through one or more exchangers 2, for example of the propane or C connection / C3 liquid mixture type, and advantageously one or more exchangers using cold process fluids.
  • the cold fluid comes from line 5 of the first contact column 7.
  • the gas which here is partially liquefied, is fractionated in the flask 4 into liquid conveyed to column 7 via line 6 equipped with a valve.
  • the expansion causes partial liquefaction of the gas and the product of the expansion is sent by line 10 to column 7.
  • This column is of a conventional type, for example at trays or filled. It includes a reboiling circuit 11.
  • the liquid effluent from the bottom of the column is expanded by the valve 12 and sent by line 13 to column 14.
  • This column which operates at a lower pressure than column 7, has a reboiler 15.
  • the vapors are partly or completely condensed in the condenser 17.
  • the phase resulting liquid is returned at least in part to column 14 as reflux by line 18.
  • the gas phase (line 19 and valve V2) is then condensed, preferably entirely, by cooling preferably in the exchanger 20 supplied by minus part of the residual gas at the top of column 7 (lines 21 and 22).
  • valve V2 is closed if all of the vapor phase has been condensed in 17.
  • the valve V3 is open and it is then the liquid phase which is sent to column 7 via line 19a. You can also open the 2 valves V2 and V3 and thus send a mixed phase.
  • the liquid phase resulting from the cooling in the exchanger 20 passes into the balloon 23, the recompression pump 24 and returns to column 7 via line 25 as reflux. If the condensation in the exchanger 20 is not total, which is less preferred, the residual gas can be evacuated by line 26.
  • the waste gas coming from the head of column 7 by line 21, in the form of the aforementioned embodiment, passes through the exchanger 20 before being sent to the turbocharger 27 via the lines 28 and 29.
  • the turbocharger is driven by the turboexpander 9.
  • At least part of the waste gas from line 21 is sent via line 30 to the exchanger 3 to cool the natural gas. It then joins the turbocharger 27 via lines 5 and 29.
  • the waste gas (line 21) passes successively through the exchangers 20 and 3, or vice versa, before joining the turbocharger 27.
  • the gas is sent via line 32, which may include one or more exchangers, not shown, to a conventional methane liquefaction unit, shown here in a simplified manner. It passes through a first cooling exchanger 33, then the expansion valve V4 and a second cooling exchanger 34 where the liquefaction and subcooling are completed.
  • the refrigerant circuit of conventional or improved type (one can for example use the circuit of US-A-4 274 849) is shown here by the use of a multi-component fluid for example a mixture of nitrogen, methane , ethane and propane, initially in the gaseous state (line 35), which is compressed by one or more compressors such as 36, cooled by the external medium, air or water, in one or more exchangers such as 37, further cooled in exchanger 38, for example with propane or a C2 / C3 liquid mixture.
  • a multi-component fluid for example a mixture of nitrogen, methane , ethane and propane, initially in the gaseous state (line 35), which is compressed by one or more compressors such as 36, cooled by the external medium, air or water, in one or more exchangers such as 37, further cooled in exchanger 38, for example with propane or a C2 / C3 liquid mixture.
  • the partially condensed mixture reaches the flask 40 through line 39.
  • the liquid phase passes through line 41 in the exchanger 33, is expanded by the valve 42 and returns to line 35 through the exchanger 33 where it heats up in cooling the streams 32 and 41.
  • the vapor phase of the tank 40 (line 43) passes through the exchangers 33 and 34, where it is condensed, then is expanded in the valve 44 and passes through the exchangers 34 and 33 via the lines 45 and 35.
  • the liquefaction of methane is carried out by indirect contact with one or more fractions of a multicomponent fluid during vaporization and circulating in a closed circuit comprising compression, cooling with liquefaction giving one or more condensates and vaporization. said condensates constituting said multicomponent fluid.
  • a natural gas having the following composition is treated, in mol%: Methane 90.03 Ethane 5.50 Propane 2.10 C4 - C6 2.34 Mercaptans 0.03 100.00 under a pressure of 8 MPa.
  • Reductory gas leaves column 7 at -63 ° C and it is directed partly towards the exchanger 3 and partly towards the exchanger 20. After recompression in 27 using only the energy of the turboexpander 9, the gas pressure is 5.93 MPa.
  • This gas the temperature of which is -28 ° C., has the following% molar composition: Methane 93.90 Ethane 5.51 Propane 0.53 C4 - C6 Mercaptans less than 10 ppm 0.06 100.00
  • This current represents 95.88 mol% of the load current of the installation.
  • Liquefaction takes place as follows: The gas is cooled and condensed to -126 ° C in a first bundle of the heat exchanger 33 then expanded to 1.4 MPa and sub-cooled in a second bundle of the heat exchanger 34 to at -160 ° C. From there it is sent to storage.
  • the refrigerant has the following molar composition: N2 7% Methane 38% Ethane 41% Propane 14%
  • This fluid is compressed to 4.97 MPa, cooled to 40 ° C in a water exchanger 37, then cooled to -25 ° C in the exchangers represented diagrammatically by 38 in indirect contact with a liquid mixture C2 / C3, then fractionated in the separator 40 giving the liquid 41 and gas 43 phases.
  • the gas phase is condensed and cooled to -126 ° C in a second bundle of the exchanger 33 then sub-cooled to -160 ° C in a bundle of the exchanger 34.
  • the pressure is 0.3 MPa and the temperature is -28 ° C.

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Claims (9)

  1. Verfahren zur Verflüssigung von Erdgas, bei dem das genannte Gas, das Methan und Kohlenwasserstoffe, die schwerer sind als das Methan unter einem Druck P₁ enthält, abkühlt, um wenigstens eine Gasphase G₁ zu bilden, die Gasphase G₁ entspannt wird, um seinen Druck zu senken und diesen auf einen Wert P₂, der kleiner ist als P₁, zu bringen, das Produkt der Entspannung unter dem Druck P₂ in eine erste Zone zur Fraktionierung durch Kontakt gesandt wird, am Kopf ein mit Methan angereichertes Restgas G₂ abgezogen wird, am Boden eine Flüssigkeitsphase L₂ abgezogen wird, die Flüssigkeitsphase L₂ in eine zweite Zone zur Fraktionierung durch Distillation, die unter einem Druck P₄ erfolgt, der kleiner ist als der Druck P₂ der ersten Fraktionierungszone, gesandt wird, man am Boden der genannten zweiten Fraktionierungszone wenigstens eine Flüssigkeitsphase L₃ entnimmt, die an Kohlenwasserstoffen, die schwerer sind als das Methan, angereichert ist, man am Kopf der genannten zweiten Fraktionierungszone eine Gasphase G₃ entnimmt und diese in die erste Fraktionierungszone als Rückfluß zurückgesandt wird, dadurch gekennzeichnet, dass man die genannte Zurücksendung ausführt, indem wenigstens ein Teil der Gasphase G₃ kondensiert wird, um eine kondensierte Phase L₄ zu bilden, und indem der Druck wenigstens eines Teils der kondensierten Phase L₄ erhöht wird, die man als Rückfluß in die genannte erste Fraktionierungszone schickt, und dass man danach das Restgas G₂ unter einem Druck, der wenigstens gleich P₂ ist, in einer Zone zur Verflüssigung des Methans weiter abkühlt, um eine an Methan reiche Flüssigkeit zu erhalten.
  2. Verfahren nach Anspruch 1, bei dem man die Entspannung der Gasphase G₁ in einem Turboentspanner durchführt und man eine Druckerhöhung des Restgases von dem Wert P₂ auf einen Wert P₃ in einem Turbokompressor durchführt und die von der Entspannung gelieferte Energie nutzt, um den Turbokompressor anzutreiben.
  3. Verfahren nach Anspruch 1 oder 2, in dem der Druck P₁ wenigstens 5 MPa beträgt, der Druck P₂ so ist, dass P₂ = 0,3 bis 0,8 P₁ ist, mit P₂ zwischen 3,5 und 7 MPa, und der Druck P₄ so ist, dass P₄ = 0,3 bis 0,9 P₂, mit P₄ zwischen 0,5 und 4,5 MPa ist.
  4. Verfahren nach Anspruch 3, bei dem P₁ wenigstens gleich 6 MPa ist, P₂ zwischen 4,5 und 6 MPa liegt und P₄ zwischen 2,5 und 3,5 MPa liegt.
  5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem wenigstens ein Teil des Restgases G₂ vor der Erhöhung des Drucks des genannten Gases G₂ von P₂ auf P₃ Wärme mit dem Erdgas austauscht, um zu dessen Abkühlung beizutragen.
  6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem wenigstens ein Teil des Restgases G₂ Wärme mit wenigstens einem Teil der Gasphase G₃ austauscht, um diese abzukühlen und um die kondensierte Phase L₄ zu erzeugen.
  7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem die Verflüssigung des Methans durch indirektes Inberührungbringen mit einer oder mit mehreren Fraktionen eines Mehrkomponentenfluids während der Verdampfung und mit Umlauf in einem geschlossenen Kreis bewirkt wird, der eine Verdichtungszone, eine Abkühlungszone mit Verflüssigung, die ein oder mehrere Kondensate ergibt, und eine Verdampfungszone der genannten Kondensate zur Wiederherstellung des genannten Mehrkomponentenfluids besitzt.
  8. Verfahren nach einem der Ansprüche 1 bis 7, bei dem während der anfänglichen Abkühlung des Gases wenigstens eine Flüssigkeitsphase L₁ zusätzlich zu der Gasphase G₁ gebildet wird und man die Flüssigkeitsphase L₁ nach der Entspannung in die genannte erste Fraktionierungszone schickt.
  9. Verfahren nach einem der Ansprüche 1 bis 8, bei dem man die Gasphase G₃ vollständig kondensiert und man einen Teil als inneren Rückfluß in die zweite Fraktionierungszone und das Komplement als Rückfluß in die erste Fraktionierungszone geschickt wird.
EP92203009A 1991-09-30 1992-09-30 Verfahren zur Verflüssigung von Erdgas Expired - Lifetime EP0535752B1 (de)

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FR9112007A FR2681859B1 (fr) 1991-09-30 1991-09-30 Procede de liquefaction de gaz naturel.

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US4707170A (en) * 1986-07-23 1987-11-17 Air Products And Chemicals, Inc. Staged multicomponent refrigerant cycle for a process for recovery of C+ hydrocarbons

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NO177840B (no) 1995-08-21
CA2079407C (en) 2001-05-15
JP3187160B2 (ja) 2001-07-11
ES2089373T3 (es) 1996-10-01
NO177840C (no) 1995-11-29
AU2612792A (en) 1993-04-01
AU648695B2 (en) 1994-04-28
FR2681859B1 (fr) 1994-02-11
SA92130161B1 (ar) 2004-05-29
CA2079407A1 (en) 1993-03-31
NZ244542A (en) 1994-07-26
FR2681859A1 (fr) 1993-04-02
US5291736A (en) 1994-03-08
JPH05240576A (ja) 1993-09-17
DE69206232T2 (de) 1996-07-18
DZ1625A1 (fr) 2002-02-17
EP0535752A1 (de) 1993-04-07
RU2093765C1 (ru) 1997-10-20
AR247945A1 (es) 1995-04-28
NO923783D0 (no) 1992-09-29
EG20248A (en) 1998-05-31
DE69206232D1 (de) 1996-01-04
NO923783L (no) 1993-03-31
MY107837A (en) 1996-06-29

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