US20110041389A1 - Process for Separating Off Nitrogen from Natural Gas - Google Patents
Process for Separating Off Nitrogen from Natural Gas Download PDFInfo
- Publication number
- US20110041389A1 US20110041389A1 US12/860,126 US86012610A US2011041389A1 US 20110041389 A1 US20110041389 A1 US 20110041389A1 US 86012610 A US86012610 A US 86012610A US 2011041389 A1 US2011041389 A1 US 2011041389A1
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- Prior art keywords
- fraction
- nitrogen
- rich
- feed
- process according
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 59
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000003345 natural gas Substances 0.000 title claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 34
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 33
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- 230000000274 adsorptive effect Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 239000003949 liquefied natural gas Substances 0.000 description 18
- 239000002737 fuel gas Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- 238000005057 refrigeration Methods 0.000 description 7
- 150000002829 nitrogen Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000126 substance Substances 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic 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
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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
- F25J1/0032—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
- F25J1/02—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
- F25J1/0203—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 single-component refrigerant [SCR] fluid in a closed vapor compression cycle
- F25J1/0208—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 single-component refrigerant [SCR] fluid in a closed vapor compression cycle in combination with an internal quasi-closed refrigeration loop, e.g. with deep flash recycle 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
- 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
- F25J1/0219—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 in combination with an internal quasi-closed refrigeration loop, e.g. using a deep flash recycle 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
- 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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- 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
- F25J2200/72—Refluxing the column with at least a part of the totally condensed overhead 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
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/04—Mixing or blending of fluids with the feed stream
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2215/00—Processes characterised by the type or other details of the product stream
- F25J2215/04—Recovery of liquid products
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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
- 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
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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
- 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
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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
- F25J2245/00—Processes or apparatus involving steps for recycling of process streams
- F25J2245/90—Processes or apparatus involving steps for recycling of process streams the recycled stream being boil-off gas from storage
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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
- F25J2270/02—Internal refrigeration with liquid vaporising 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
- F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
- F25J2270/904—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by liquid or gaseous cryogen in an open loop
Definitions
- the invention relates to a process for liquefying a hydrocarbon-rich, nitrogen-containing feed fraction, preferably natural gas.
- Hydrocarbon-rich feed fractions or natural gases which contain nitrogen require suitable measures during their liquefaction in order to be able to limit the nitrogen concentration in the end product, liquefied natural gas (LNG), to 1% by volume.
- LNG liquefied natural gas
- customarily nitrogen is removed from the process by withdrawing a nitrogen-rich fuel gas stream at the cold end of the liquefaction process.
- This fuel gas stream compared with the feed fraction, has a significantly elevated nitrogen content. In this manner, the nitrogen content of the LNG product can be limited to a maximum of 1% by volume, even if the nitrogen concentration in the feed fraction to be liquefied is significantly greater than 1% by volume.
- Liquefaction processes frequently comprise gas turbines which can use the abovementioned fuel gas stream at least in part.
- the maximum permissible nitrogen concentration of the fuel gas stream is between 20 and 40% by volume. If the nitrogen content of the feed fraction to be liquefied is so high that the maximum permissible nitrogen content of the LNG product and also of the abovementioned fuel gas stream cannot be met, customarily a highly concentrated nitrogen fraction having a methane content of less than 1% by volume is withdrawn from the liquefaction process; this highly concentrated nitrogen fraction can be released directly to the atmosphere.
- This nitrogen fraction can be generated by the separation of the fuel gas stream proceeding in what is termed a nitrogen-rejection unit, or generation of the nitrogen fraction can be integrated into the liquefaction process—in this case still before withdrawal of the fuel gas stream.
- FIG. 1 shows a process of the prior art for liquefying a hydrocarbon-rich, nitrogen-containing feed fraction, in which the production of a highly concentrated nitrogen fraction is integrated into the liquefaction process.
- a hydrocarbon-rich, nitrogen-containing feed fraction is fed to a liquefaction process shown by the heat exchangers or heat exchange zones E 1 to E 3 .
- the circuit 120 drawn in dashed lines is in this case an arbitrary refrigeration process or an arbitrary refrigeration unit as can be used in the liquefaction and subcooling of the feed fraction.
- the feed fraction is first cooled. Then, it is fed via line 102 to a second heat exchanger or heat exchange zone E 2 where the feed fraction is completely liquefied. Via line 103 and expansion valve a, the then liquefied feed fraction is delivered to a separation column T 1 . From the bottom of separation column T 1 , a hydrocarbon-rich, nitrogen-depleted fraction is withdrawn via line 104 and subcooled in the heat exchanger or heat exchange zone E 3 .
- this subcooled fraction is withdrawn from the actual liquefaction process, expanded in valve b and fed to a separator D 1 .
- the liquid LNG product fraction is withdrawn and fed to an LNG storage tank (not shown).
- a highly concentrated nitrogen fraction is withdrawn; the nitrogen content thereof is customarily between 90 and 100% by volume.
- One part of this nitrogen fraction is released directly to the atmosphere via line 109 , while a further substream of this nitrogen fraction, after passage through the reflux condenser E 4 arranged in the separator D 1 , is applied via line 110 as reflux to the separation column T 1 .
- an aspect of the present invention is to provide a process of the type mentioned above for liquefying a hydrocarbon-rich, nitrogen-containing feed fraction, preferably natural gas, which avoids the described disadvantages and makes it possible, in particular, to release the total amount of the nitrogen contained in the feed fraction either together with the LNG product stream or together with the highly concentrated nitrogen fraction.
- FIG. 1 schematically illustrates an exemplary embodiment of the prior art
- FIG. 2 illustrates an exemplary embodiment of the process according to the invention.
- the fuel gas stream which occurs at the end of the liquefaction process and after the liquefied and subcooled feed fraction has been expanded is now no longer sent to a fuel gas consumer, such as a gas turbine for example, but instead is added to the feed fraction to be liquefied before it is fed into the cooling and liquefaction process.
- the hydrocarbon-rich, nitrogen-containing feed fraction is fed via the lines 1 and 1 ′ to a first heat exchanger E 1 and cooled therein.
- the feed fraction is then fed via the line 2 to a second heat exchanger E 2 in which it is liquefied.
- the liquefied feed fraction is applied to the separation column T 1 .
- a substream 2 ′ of the cooled feed fraction 2 is applied as stripping gas to the separation column T 1 via the expansion valve c, whereby the rectification action of the separation column T 1 is supported.
- the circuit 20 which is drawn as dashed lines is an arbitrary refrigeration process or an arbitrary refrigeration unit as can be used, for example, in the liquefaction and subcooling of the feed fraction.
- this subcooled fraction is withdrawn from the actual liquefaction process, expanded in valve b and fed to a separator D 1 .
- the liquid LNG product fraction is withdrawn and fed to an LNG storage tank (not shown).
- a highly concentrated nitrogen fraction is withdrawn; the nitrogen content thereof is customarily between 90 and 100% by volume.
- One part of this nitrogen fraction is released directly into the atmosphere via line 10 , while a further substream of this nitrogen fraction, after passage through the reflux condenser E 4 arranged in the separator D 1 , is applied as reflux to the separation column T 1 via line 11 .
- the reflux condenser E 4 and also the separator D 1 are arranged to be high enough that the reflux 11 can proceed to the separation column T 1 by gravity without the use of a pump.
- the pressure in the separator D 1 is at least 2 bar (absolute pressure), preferably 3 bar (absolute pressure), in order to make possible pump-free transfer of the LNG product fraction into an atmospheric LNG storage tank.
- At least one substream of the nitrogen-enriched fraction 10 before it is released into the atmosphere, can be used for precooling the feed fraction 1 . If the feed fraction 1 —as described hereinafter—is subjected to a drying process, the precooling is advantageously connected upstream of this drying process.
- the boil-off gas occurring in the tank is added to the nitrogen-rich fraction 7 and/or the feed fraction 1 .
- the boil-off gas from the atmospheric LNG storage tank is preferably first compressed to the pressure of the separator D 1 and then, together with the nitrogen-rich fraction 7 withdrawn from the separator D 1 , compressed to the pressure of the feed fraction 1 .
- the nitrogen-rich fraction or fuel gas fraction withdrawn at the top of the separator D 1 via line 7 is compressed C 1 according to the invention in a single stage or multiple stages, cooled in the aftercooler E 5 and then added via line 8 to the hydrocarbon-rich, nitrogen-containing feed fraction in the line 1 .
- the nitrogen-rich fraction 7 can first be mixed with the feed fraction 1 and then subjected together therewith to a compression.
- the feed fraction 1 before it is fed into the liquefaction process, is subjected to a drying A, preferably an adsorptive drying process.
- a drying A preferably an adsorptive drying process.
- the nitrogen-rich fraction can be used as a regeneration gas in the adsorptive drying process A. After regeneration has been performed, the nitrogen-rich fraction can then instead be added to the feed fraction in the line 1 .
- Recycling the nitrogen-rich fraction 7 into the feed fraction 1 has the consequence that, advantageously, an open mixed cycle is superimposed on the liquefaction process.
- This open mixed cycle consists essentially of the components nitrogen and methane, and also small amounts of higher hydrocarbons and possibly oxygen and traces of helium.
- This open mixed cycle is precooled in the heat exchanger E 1 , completely liquefied in the heat exchanger E 2 and in the separation column T 1 is fractionated into a pure nitrogen fraction, the methane content of which is less than 1% by volume, and a methane-rich bottom fraction.
- the methane fraction of the open mixed cycle and the remaining amount of nitrogen which is not released at the top of the separation column T 1 are subcooled together with the LNG in the heat exchanger E 3 , vaporized in the heat exchanger E 4 for the reflux condensation of the separation column T 1 and fed together with the gas phase from the separator D 1 again to the feed fraction 1 .
- refrigeration cycle cascade having an open N 2 /CH 4 mixed cycle at the cold end of the liquefaction process.
- the reflux condenser E 4 can be supplied with the required cooling independently of the composition and pressure of the feed fraction, in such a manner that the total amount of the nitrogen contained in the feed fraction is concentrated to the required purity and can be released as a highly concentrated nitrogen product stream. The release of an unwanted gas mixture which, in the prior art process, formed the fuel gas fraction is thereby avoided.
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Abstract
The invention relates to a process for liquefying a hydrocarbon-rich, nitrogen-containing feed fraction, preferably natural gas, wherein:
- a) the feed fraction (1) is liquefied (E1, E2),
- b) is separated by rectification (T1) into a nitrogen-enriched fraction (9), the methane content of which is a max. of 1% by volume, and a hydrocarbon-rich, nitrogen-depleted fraction (4),
- c) the hydrocarbon-rich, nitrogen-depleted fraction (4) is subcooled (E3) and expanded (b),
- d) the expanded hydrocarbon-rich, nitrogen-depleted fraction (5) is separated (D1) into a hydrocarbon-rich fraction (6), the nitrogen content of which is a max. of 1% by volume, and a nitrogen-rich fraction (7), and
- e) the nitrogen-rich fraction (7) is added to the feed fraction (1).
Description
- The invention relates to a process for liquefying a hydrocarbon-rich, nitrogen-containing feed fraction, preferably natural gas.
- Hydrocarbon-rich feed fractions or natural gases which contain nitrogen require suitable measures during their liquefaction in order to be able to limit the nitrogen concentration in the end product, liquefied natural gas (LNG), to 1% by volume. In the event of a higher nitrogen concentration, undesired and dangerous layerings occur within the LNG storage tank owing to differing densities. In order to avoid this, customarily nitrogen is removed from the process by withdrawing a nitrogen-rich fuel gas stream at the cold end of the liquefaction process. This fuel gas stream, compared with the feed fraction, has a significantly elevated nitrogen content. In this manner, the nitrogen content of the LNG product can be limited to a maximum of 1% by volume, even if the nitrogen concentration in the feed fraction to be liquefied is significantly greater than 1% by volume.
- Liquefaction processes frequently comprise gas turbines which can use the abovementioned fuel gas stream at least in part. However, in this case, it must be noted that the maximum permissible nitrogen concentration of the fuel gas stream is between 20 and 40% by volume. If the nitrogen content of the feed fraction to be liquefied is so high that the maximum permissible nitrogen content of the LNG product and also of the abovementioned fuel gas stream cannot be met, customarily a highly concentrated nitrogen fraction having a methane content of less than 1% by volume is withdrawn from the liquefaction process; this highly concentrated nitrogen fraction can be released directly to the atmosphere. This nitrogen fraction can be generated by the separation of the fuel gas stream proceeding in what is termed a nitrogen-rejection unit, or generation of the nitrogen fraction can be integrated into the liquefaction process—in this case still before withdrawal of the fuel gas stream.
-
FIG. 1 shows a process of the prior art for liquefying a hydrocarbon-rich, nitrogen-containing feed fraction, in which the production of a highly concentrated nitrogen fraction is integrated into the liquefaction process. - Via
line 101, a hydrocarbon-rich, nitrogen-containing feed fraction is fed to a liquefaction process shown by the heat exchangers or heat exchange zones E1 to E3. Thecircuit 120 drawn in dashed lines is in this case an arbitrary refrigeration process or an arbitrary refrigeration unit as can be used in the liquefaction and subcooling of the feed fraction. - In the heat exchanger or heat exchange zone E1, the feed fraction is first cooled. Then, it is fed via
line 102 to a second heat exchanger or heat exchange zone E2 where the feed fraction is completely liquefied. Vialine 103 and expansion valve a, the then liquefied feed fraction is delivered to a separation column T1. From the bottom of separation column T1, a hydrocarbon-rich, nitrogen-depleted fraction is withdrawn vialine 104 and subcooled in the heat exchanger or heat exchange zone E3. - Via
line 105, this subcooled fraction is withdrawn from the actual liquefaction process, expanded in valve b and fed to a separator D1. From the bottom of the separator D1, vialine 106, the liquid LNG product fraction is withdrawn and fed to an LNG storage tank (not shown). - From the top of the separation column T1, via
line 108, a highly concentrated nitrogen fraction is withdrawn; the nitrogen content thereof is customarily between 90 and 100% by volume. One part of this nitrogen fraction is released directly to the atmosphere vialine 109, while a further substream of this nitrogen fraction, after passage through the reflux condenser E4 arranged in the separator D1, is applied vialine 110 as reflux to the separation column T1. - However, a process as described with reference to
FIG. 1 leads to problems if no consumer is present for thefuel gas stream 107 discharged from separator D1. In contrast to the highly concentratednitrogen fraction 109,fuel gas stream 107 cannot be released directly into the atmosphere. - Thus, an aspect of the present invention is to provide a process of the type mentioned above for liquefying a hydrocarbon-rich, nitrogen-containing feed fraction, preferably natural gas, which avoids the described disadvantages and makes it possible, in particular, to release the total amount of the nitrogen contained in the feed fraction either together with the LNG product stream or together with the highly concentrated nitrogen fraction.
- Upon further study of the specification and appended claims, further aspects and advantages of this invention will become apparent to those skilled in the art.
- To achieve these aspects, according to the invention there is provided a process for liquefying a hydrocarbon-rich, nitrogen-containing feed fraction, in which
- a) the feed fraction is liquefied,
- b) is separated by rectification into a nitrogen-enriched fraction, the methane content of which is a max. of 1% by volume, and a hydrocarbon-rich, nitrogen-depleted fraction,
- c) the hydrocarbon-rich, nitrogen-depleted fraction is subcooled and expanded,
- d) the expanded hydrocarbon-rich, nitrogen-depleted fraction is separated into a liquid hydrocarbon-rich fraction, the nitrogen content of which is a max. of 1% by volume, and a nitrogen-rich fraction, and
- e) the nitrogen-rich fraction is added to the feed fraction.
- Further advantageous embodiments of the process according to the invention for liquefying a hydrocarbon-rich, nitrogen-containing feed fraction, which are subjects of dependent patent claims, are characterized in that
-
- the nitrogen-rich fraction, before it is added to the feed fraction, is compressed in a single-stage or multistage manner and/or cooled and/or the nitrogen-rich fraction, after it is added to the feed fraction, is compressed in a single-stage or multistage manner,
- provided that the feed fraction, before it is cooled, is subjected to an adsorptive drying process, characterized in that the nitrogen-rich fraction, before it is added to the feed fraction, is used as regeneration gas for the adsorptive drying process,
- a substream of the cooled feed fraction is fed as stripping gas to the subsequent separation by rectification of the liquefied feed fraction,
- the liquefaction and/or the subcooling of the hydrocarbon-rich, nitrogen-containing feed fraction proceeds using any arbitrary liquefaction process,
- provided that the liquefied hydrocarbon-rich fraction, the nitrogen content of which is a max. of 1% by volume, is stored in a tank, the boil-off gas occurring in the tank is added to the nitrogen-rich fraction and/or the feed fraction, and
- at least a substream of the nitrogen-enriched fraction is used for precooling the feed fraction.
- The invention and further details, such as features and attendant advantages, of the invention are explained in more detail below on the basis of the exemplary embodiments which are diagrammatically depicted in the drawings, and wherein:
-
FIG. 1 schematically illustrates an exemplary embodiment of the prior art; and -
FIG. 2 illustrates an exemplary embodiment of the process according to the invention. - In contrast to a prior art process, as explained with reference to the procedure shown in
FIG. 1 , in accordance with the invention the fuel gas stream which occurs at the end of the liquefaction process and after the liquefied and subcooled feed fraction has been expanded is now no longer sent to a fuel gas consumer, such as a gas turbine for example, but instead is added to the feed fraction to be liquefied before it is fed into the cooling and liquefaction process. - The process according to the invention for liquefying a hydrocarbon-rich, nitrogen-containing feed fraction, and also further configurations thereof, will be described in more detail hereinafter with reference to the exemplary embodiment shown in
FIG. 2 . - In a similar manner to the procedure described in
FIG. 1 , the hydrocarbon-rich, nitrogen-containing feed fraction is fed via thelines line 2 to a second heat exchanger E2 in which it is liquefied. Vialine 3 and expansion valve a, the liquefied feed fraction is applied to the separation column T1. - Advantageously, a substream 2′ of the cooled
feed fraction 2 is applied as stripping gas to the separation column T1 via the expansion valve c, whereby the rectification action of the separation column T1 is supported. - From the bottom of the separation column T1, via
line 4, a hydrocarbon-rich, nitrogen-depleted fraction is withdrawn and subcooled in the heat exchanger or heat exchange zone E3. - The circuit 20 which is drawn as dashed lines is an arbitrary refrigeration process or an arbitrary refrigeration unit as can be used, for example, in the liquefaction and subcooling of the feed fraction.
- Via
line 5, this subcooled fraction is withdrawn from the actual liquefaction process, expanded in valve b and fed to a separator D1. From the bottom of the separator D1, vialine 6, the liquid LNG product fraction is withdrawn and fed to an LNG storage tank (not shown). - From the top of the separation column T1, via
line 9, a highly concentrated nitrogen fraction is withdrawn; the nitrogen content thereof is customarily between 90 and 100% by volume. One part of this nitrogen fraction is released directly into the atmosphere vialine 10, while a further substream of this nitrogen fraction, after passage through the reflux condenser E4 arranged in the separator D1, is applied as reflux to the separation column T1 vialine 11. - Advantageously, the reflux condenser E4 and also the separator D1 are arranged to be high enough that the
reflux 11 can proceed to the separation column T1 by gravity without the use of a pump. In addition, the pressure in the separator D1 is at least 2 bar (absolute pressure), preferably 3 bar (absolute pressure), in order to make possible pump-free transfer of the LNG product fraction into an atmospheric LNG storage tank. - According to an advantageous configuration of the process according to the invention, at least one substream of the nitrogen-enriched
fraction 10, before it is released into the atmosphere, can be used for precooling thefeed fraction 1. If thefeed fraction 1—as described hereinafter—is subjected to a drying process, the precooling is advantageously connected upstream of this drying process. - In further development of the process according to the invention for liquefying a hydrocarbon-rich, nitrogen-containing feed fraction, it is proposed that, provided that the LNG product fraction is stored in an LNG storage tank, the boil-off gas occurring in the tank is added to the nitrogen-
rich fraction 7 and/or thefeed fraction 1. For this purpose the boil-off gas from the atmospheric LNG storage tank is preferably first compressed to the pressure of the separator D1 and then, together with the nitrogen-rich fraction 7 withdrawn from the separator D1, compressed to the pressure of thefeed fraction 1. - The nitrogen-rich fraction or fuel gas fraction withdrawn at the top of the separator D1 via
line 7 is compressed C1 according to the invention in a single stage or multiple stages, cooled in the aftercooler E5 and then added vialine 8 to the hydrocarbon-rich, nitrogen-containing feed fraction in theline 1. Provided that thefeed fraction 1 is at a comparatively low pressure, the nitrogen-rich fraction 7 can first be mixed with thefeed fraction 1 and then subjected together therewith to a compression. - Generally, the
feed fraction 1, before it is fed into the liquefaction process, is subjected to a drying A, preferably an adsorptive drying process. Provided that this is the case, the nitrogen-rich fraction can be used as a regeneration gas in the adsorptive drying process A. After regeneration has been performed, the nitrogen-rich fraction can then instead be added to the feed fraction in theline 1. - Whereas in the prior art process procedure described with reference to
FIG. 1 , three different fractions—LNG product fraction, fuel gas fraction and highly concentrated nitrogen fraction—which are withdrawn from the process occur, in the case of the process according to the invention, there are only two fractions, that is to say theLNG product fraction 6 and also the highlyconcentrated nitrogen fraction 10 withdrawn at the top of the separation column T1. - Recycling the nitrogen-
rich fraction 7 into thefeed fraction 1 has the consequence that, advantageously, an open mixed cycle is superimposed on the liquefaction process. This open mixed cycle consists essentially of the components nitrogen and methane, and also small amounts of higher hydrocarbons and possibly oxygen and traces of helium. This open mixed cycle is precooled in the heat exchanger E1, completely liquefied in the heat exchanger E2 and in the separation column T1 is fractionated into a pure nitrogen fraction, the methane content of which is less than 1% by volume, and a methane-rich bottom fraction. The methane fraction of the open mixed cycle and the remaining amount of nitrogen which is not released at the top of the separation column T1 are subcooled together with the LNG in the heat exchanger E3, vaporized in the heat exchanger E4 for the reflux condensation of the separation column T1 and fed together with the gas phase from the separator D1 again to thefeed fraction 1. - Together with the refrigeration process or the refrigeration unit 20, which can comprise all known techniques such as, for example, single-substance vaporization, mixture vaporization, work-performing fluid expansion and also any combinations thereof, there results a refrigeration cycle cascade having an open N2/CH4 mixed cycle at the cold end of the liquefaction process.
- By the formation of the open mixed cycle, the reflux condenser E4 can be supplied with the required cooling independently of the composition and pressure of the feed fraction, in such a manner that the total amount of the nitrogen contained in the feed fraction is concentrated to the required purity and can be released as a highly concentrated nitrogen product stream. The release of an unwanted gas mixture which, in the prior art process, formed the fuel gas fraction is thereby avoided.
- The entire disclosure[s] of all applications, patents and publications, cited herein and of corresponding German Application No.
DE 10 2009 038458.8, filed Aug. 21, 2009, are incorporated by reference herein. - The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
- From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.
Claims (19)
1. A process for liquefying a hydrocarbon-rich, nitrogen-containing, and methane-containing feed fraction, said process comprising:
a) liquefying (E1, E2) said feed fraction (1),
b) separating the liquefied feed fraction by rectification (T1) into a nitrogen-enriched fraction (9) having a methane content of at most 1% by volume, and a hydrocarbon-rich, nitrogen-depleted fraction (4),
c) subcooling (E3) and expanding (b) said hydrocarbon-rich, nitrogen-depleted fraction (4),
d) separating (D1) the expanded hydrocarbon-rich, nitrogen-depleted fraction (5) into a liquid hydrocarbon-rich fraction (6) having a nitrogen content of at most 1% by volume, and a nitrogen-rich fraction (7), and
e) adding said nitrogen-rich fraction (7) to said feed fraction (1).
2. The process according to claim 1 , wherein said hydrocarbon-rich, nitrogen-containing feed fraction is natural gas.
3. The process according to claim 1 , wherein
said nitrogen-rich fraction (7, 8), before being added to said feed fraction (1), is compressed (C1) in a single-stage or multistage manner and/or cooled (E5), and/or
said nitrogen-rich fraction, after being added to said feed fraction (1), is compressed in a single-stage or multistage manner.
4. The process according to claim 1 , wherein said feed fraction (1), before being cooled (E1) for liquefaction, is subjected to an adsorptive drying process (A), and said nitrogen-rich fraction (7), before being added to the feed fraction (1), is used as regeneration gas for said adsorptive drying process (A).
5. The process according to claim 1 , wherein a substream (2′) of the cooled feed fraction (2) is introduced as a stripping gas into the separation by rectification (T1) of the liquefied feed fraction (3).
6. The process according to claim 1 , wherein the liquefaction and/or the subcooling of the hydrocarbon-rich, nitrogen-containing feed fraction proceeds using any arbitrary liquefaction process.
7. The process according to claim 1 , wherein said liquid hydrocarbon-rich fraction (6) having a nitrogen content of at most 1% by volume is stored in a tank, and boil-off gas occurring in said tank is added to said nitrogen-rich fraction (7) and/or said feed fraction (1).
8. The process according to claim 1 , wherein at least a substream of said nitrogen-enriched fraction (9) is used for precooling said feed fraction (1).
9. The process according to claim 1 , wherein said feed fraction (1) is liquefied by being cooled in at least a first heat exchanger and a second heat exchanger.
10. The process according to claim 9 , wherein after said feed fraction (1) is cooled in said first heat exchanger, a substream (2′) of the cooled feed fraction (2) is introduced as a stripping gas into the separation by rectification (T1) of the liquefied feed fraction (3).
11. The process according to claim 10 , wherein said substream (2′) is expanded before being introduced as a stripping gas into the separation by rectification (T1) of the liquefied feed fraction (3).
12. The process according to claim 3 , wherein said nitrogen-rich fraction (7, 8), before being added to said feed fraction (1), is compressed (C1) in a single-stage or multistage manner and/or cooled (E5).
13. The process according to claim 3 , wherein said nitrogen-rich fraction, after being added to said feed fraction (1), is compressed in a single-stage or multistage manner.
14. The process according to claim 1 , wherein, before being added to said feed fraction (1), said nitrogen-rich fraction (7) is compressed and cooled.
15. The process according to claim 1 , wherein at least part of said nitrogen-enriched fraction (9) from said rectification (T1) is cooled in a reflux condenser (E4), arranged within a separator (D1), by heat exchange with said expanded hydrocarbon-rich, nitrogen-depleted fraction (5), and delivered to said rectification (T1) as reflux (11).
16. The process according to claim 1 , wherein at least one substream of said nitrogen-enriched fraction (10) is used to precool said feed fraction (1).
17. The process according to claim 16 , wherein said feed fraction (1), before being cooled (E1) for liquefaction, is subjected to an adsorptive drying process (A), and precooling of said feed fraction (1) by said at least one substream of said nitrogen-enriched fraction (10) is performed upstream of said adsorptive drying process.
18. The process according to claim 7 , wherein said boil-off gas occurring in said tank is added to said nitrogen-rich fraction (7), and is compressed to the pressure of said nitrogen-rich fraction (7) before being added thereto.
19. The process according to claim 7 , wherein said boil-off gas occurring in said tank is added to said feed fraction (1), and is compressed to the pressure of said feed fraction (1) before being added thereto.
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DE102009038458.8 | 2009-08-21 | ||
DE102009038458A DE102009038458A1 (en) | 2009-08-21 | 2009-08-21 | Process for separating nitrogen from natural gas |
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DE102009038458A1 (en) | 2011-02-24 |
CN101993749A (en) | 2011-03-30 |
NO20101164A1 (en) | 2012-02-22 |
MX2010009024A (en) | 2011-02-21 |
RU2537486C2 (en) | 2015-01-10 |
AU2010202992A1 (en) | 2011-03-10 |
RU2010135055A (en) | 2012-02-27 |
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