EP0641982B1 - Process and installation for the production of at least a gas from air under pressure - Google Patents
Process and installation for the production of at least a gas from air under pressure Download PDFInfo
- Publication number
- EP0641982B1 EP0641982B1 EP94401838A EP94401838A EP0641982B1 EP 0641982 B1 EP0641982 B1 EP 0641982B1 EP 94401838 A EP94401838 A EP 94401838A EP 94401838 A EP94401838 A EP 94401838A EP 0641982 B1 EP0641982 B1 EP 0641982B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pressure
- air
- column
- heat
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000009434 installation Methods 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- 239000012263 liquid product Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 238000003303 reheating Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 11
- 239000002912 waste gas Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Images
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- 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
- F25J3/04—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 for air
- F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
- F25J3/04078—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression
- F25J3/04084—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression 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
- 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
- F25J3/04—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 for air
- F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
- F25J3/04012—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of warm gaseous streams; details of intake or interstage cooling
- F25J3/04018—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of warm gaseous streams; details of intake or interstage cooling of main feed air
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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
- F25J3/04—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 for air
- F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
- F25J3/04078—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression
- F25J3/0409—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression of oxygen
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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
- F25J3/04—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 for air
- F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
- F25J3/04157—Afterstage cooling and so-called "pre-cooling" of the feed air upstream the air purification unit and main heat exchange line
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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
- F25J3/04—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 for air
- F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
- F25J3/04163—Hot end purification of the feed air
- F25J3/04169—Hot end purification of the feed air by adsorption of the impurities
- F25J3/04175—Hot end purification of the feed air by adsorption of the impurities at a pressure of substantially more than the highest pressure column
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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
- F25J3/04—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 for air
- F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
- F25J3/04284—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams
- F25J3/0429—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams of feed air, e.g. used as waste or product air or expanded into an auxiliary column
- F25J3/04296—Claude expansion, i.e. expanded into the main or high pressure column
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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
- F25J3/04—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 for air
- F25J3/04406—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 for air using a dual pressure main column system
- F25J3/04412—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 for air using a dual pressure main column system in a classical double column flowsheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
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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
- F25J3/04—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 for air
- F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
- F25J3/04563—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating
- F25J3/04575—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating for a gas expansion plant, e.g. dilution of the combustion gas in a gas turbine
- F25J3/04581—Hot gas expansion of indirect heated 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
- 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
- F25J3/04—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 for air
- F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
- F25J3/04612—Heat exchange integration with process streams, e.g. from the air gas consuming unit
- F25J3/04618—Heat exchange integration with process streams, e.g. from the air gas consuming unit for cooling an air stream fed to the air fractionation unit
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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
- F25J2200/20—Processes or apparatus using separation by rectification in an elevated pressure multiple column system wherein the lowest pressure column is at a pressure well above the minimum pressure needed to overcome pressure drop to reject the products to atmosphere
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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
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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
- F25J2215/50—Oxygen or special cases, e.g. isotope-mixtures or low purity O2
- F25J2215/52—Oxygen production with multiple purity O2
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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
- F25J2230/04—Compressor cooling arrangement, e.g. inter- or after-stage cooling or condensate removal
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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
- F25J2240/00—Processes or apparatus involving steps for expanding of process streams
- F25J2240/02—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
- F25J2240/12—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream the fluid being 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
- F25J2270/00—Refrigeration techniques used
- F25J2270/04—Internal refrigeration with work-producing gas expansion loop
Definitions
- EP-A-0 552 747 describes a process in which the waste gas from the low pressure column is withdrawn from the exchange line at a temperature intermediate and relaxed in a turbine which ensures the cold resistance of the installation.
- the invention aims to allow a reduction in the production of liquid for a given oxygen and / or nitrogen production capacity gas under pressure, economically from the point of view of energy performance.
- the invention also relates to an installation intended for setting using such a method.
- This installation of the type comprising a double distillation column comprising a low pressure column operating under a pressure known as low pressure and producing a waste gas at the top, and a medium pressure column operating under pressure so-called medium pressure; compression means for bring all of the air to be distilled to at least one high pressure significantly higher than medium pressure, these means comprising a main compressor; of means for withdrawing from the double column and pumping at least one liquid product resulting from the distillation; a heat exchange line connecting heat exchange air and said liquid product; and an expansion turbine for part of this air, the intake of this turbine being connected to an intermediate point of the heat exchange line and its exhaust being connected to the medium pressure column, is characterized in that it includes a second expansion turbine whose admission is linked to the exit of passages from heating of the waste gas from the exchange line thermal, at the hot end of it.
- the installation shown in Figure 1 is intended to produce gaseous oxygen under high pressure from about 10 to 100 bar, liquid oxygen and liquid nitrogen.
- This installation essentially includes: a main air compressor 1 itself comprising at minus a medium pressure stage 1A and a high stage pressure 1B; an adsorption purification device 2; a blower-turbine assembly comprising a blower 3 and a turbine 4 whose wheels are set on the same tree; an atmospheric or water cooler 5 for the blower; a heat exchange line 6; a first auxiliary heat exchanger 7 and a second exchanger auxiliary heat 8; a second expansion turbine 9 braked by an alternator 10; a double column of distillation 11 comprising a medium pressure column 12 and a low pressure column 13 coupled by a vaporizer-condenser 14 which puts in exchange relation thermal nitrogen at the top of column 12 and oxygen column 13 tank liquid; an oxygen pump liquid 15; a storage 16 of liquid oxygen at the atmospheric pressure; a storage 17 of liquid nitrogen at atmospheric pressure; a separator pot 18; and one subcooler 19.
- column 13 is under a pressure from about 1.7 to 5 bar, and column 11 under the corresponding pressure from 6.5 to 16 bars approximately.
- Liquid oxygen is drawn off in a tank column 13. A fraction goes directly, after sub-cooling in 19 and expansion to atmospheric pressure in an expansion valve 24, in the storage 16, while the rest is brought by pump 15 to the high desired production pressure, then vaporized and reheated at room temperature in the exchange line thermal before being recovered via a pipe 25.
- liquid nitrogen under the medium pressure withdrawn at the head of column 12, is sub-cooled in 19, expanded to atmospheric pressure in an expansion valve 26, and introduced into the pot separator 18.
- the liquid phase is sent to the storage 17, while the vapor phase is combined at the impure nitrogen at the top of column 13, then the mixture is reheated in 19 then in 6.
- the waste gas thus heated at the room temperature is overheated in 7 then relaxed to roughly at atmospheric pressure in 9 and then the gas relaxed is warmed up to 8. It can then, before being evacuated from the installation, serve to regenerate the absorbent device 2.
- the invention also applies to the production of nitrogen gas under high pressure, carried by a pump (not shown) at the desired high pressure then vaporized in the heat exchange line, and / or to the production of oxygen and / or nitrogen under several pressures, using multiple high air pressures.
- the vaporization of the liquid (s) can be carried out not concomitantly with air liquefaction, with a knee liquefying air below the oxygen vaporization temperature, or so concomitant with this liquefaction.
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Separation By Low-Temperature Treatments (AREA)
Description
La présente invention est relative à un procédé de production d'oxygène gazeux et/ou d'azote gazeux sous pression, du type dans lequel :
- on distille de l'air dans une installation comprenant un compresseur principal d'air, une double colonne de distillation comprenant une colonne basse pression fonctionnant sous une pression dite basse pression, et une colonne moyenne pression fonctionnant sous une pression dite moyenne pression, et une ligne d'échange thermique servant à refroidir l'air traité;
- on comprime la totalité de l'air à distiller jusqu'à au moins une haute pression d'air nettement supérieure à la moyenne pression;
- on refroidit l'air comprimé jusqu'à une température intermédiaire, et on en détend une partie dans une turbine jusqu'à la moyenne pression, avant de l'introduire dans la colonne moyenne pression;
- on liquéfie l'air non turbiné, puis on l'introduit, après détente, dans la double colonne;
- on amène au moins un produit liquide soutiré de la double colonne à la pression de production, et on vaporise ce produit liquide par échange de chaleur avec l'air et
- on réchauffe le gaz résiduaire de tête de la colonne basse pression jusqu'au bout chaud de la ligne d'échange thermique.
- air is distilled in an installation comprising a main air compressor, a double distillation column comprising a low pressure column operating under a pressure known as low pressure, and a medium pressure column operating under a pressure known as medium pressure, and a heat exchange line used to cool the treated air;
- all the air to be distilled is compressed to at least one high air pressure which is clearly higher than the medium pressure;
- the compressed air is cooled to an intermediate temperature, and part of it is expanded in a turbine to medium pressure, before introducing it into the medium pressure column;
- the non-turbinated air is liquefied, then introduced, after expansion, into the double column;
- at least one liquid product withdrawn from the double column is brought to production pressure, and this liquid product is vaporized by heat exchange with the air and
- the residual gas at the head of the low pressure column is heated to the hot end of the heat exchange line.
Les pressions dont il est question dans le présent mémoire sont des pressions absolues. De plus, l'expression « liquéfaction » doit être entendue au sens large, c'est-à-dire incluant la pseudo-liquéfaction dans le cas de pressions supercritiques.The pressures discussed in this brief are absolute pressures. In addition, the expression "liquefaction" should be understood in broad sense, i.e. including pseudo-liquefaction in the case of supercritical pressures.
Un procédé du type ci-dessus est décrit dans le FR-A-2 674 011. Dans ce procédé, la production gazeuse sous pression s'accompagne inévitablement d'une production de liquide, laquelle n'est pas souhaitable dans toutes les applications industrielles.A process of the above type is described in FR-A-2 674 011. In this process, gas production under pressure is inevitably accompanied production of liquid, which is not desirable in all industrial applications.
EP-A-0 552 747 décrit un procédé dans lequel le gaz résiduaire de la colonne basse pression est soutiré de la ligne d'échange à une température intermédiaire et détendu dans une turbine qui assure la tenue en froid de l'installation. EP-A-0 552 747 describes a process in which the waste gas from the low pressure column is withdrawn from the exchange line at a temperature intermediate and relaxed in a turbine which ensures the cold resistance of the installation.
L'invention a pour but de permettre une réduction de la production de liquide pour une capacité de production donnée d'oxygène et/ou d'azote gazeux sous pression, ce de manière économique du point de vue des performances énergétiques.The invention aims to allow a reduction in the production of liquid for a given oxygen and / or nitrogen production capacity gas under pressure, economically from the point of view of energy performance.
A cet effet, l'invention a pour objet un procédé du type précité, caractérisé en ce que :
- on fait fonctionner la colonne basse pression sous 1,7 à 5 bars environ, et la colonne moyenne pression sous une pression correspondante de 6,5 à 16 bars environ; et
- on détend dans une seconde turbine le gaz résiduaire de tête de la colonne basse pression, après l'avoir réchauffé jusqu'au bout chaud de la ligne d'échange thermique.
- the low pressure column is operated under 1.7 to 5 bars approximately, and the medium pressure column under a corresponding pressure of 6.5 to 16 bars approximately; and
- the residual gas at the head of the low pressure column is expanded in a second turbine, after having heated it to the hot end of the heat exchange line.
Suivant des modes particuliers de réalisation de l'invention :
- le gaz résiduaire est surchauffé, avant sa détente, par échange de chaleur avec de l'air issu d'un étage intermédiaire du compresseur principal;
- le gaz résiduaire détendu est utilisé pour refroidir l'air issu du dernier étage du compresseur principal, avant l'épuration en eau et en anhydride carbonique de cet air;
- le produit liquide est de l'oxygène impur, et on produit en outre de l'oxygène liquide plus pur, que l'on envoie à un stockage.
- the waste gas is superheated, before its expansion, by heat exchange with air from an intermediate stage of the main compressor;
- the expanded waste gas is used to cool the air coming from the last stage of the main compressor, before the purification of water and carbon dioxide from this air;
- the liquid product is impure oxygen, and purer liquid oxygen is also produced, which is sent to storage.
L'invention a également pour objet une installation destinée à la mise en oeuvre d'un tel procédé. Cette installation, du type comprenant une double colonne de distillation comprenant une colonne basse pression fonctionnant sous une pression dite basse pression et produisant en tête un gaz résiduaire, et une colonne moyenne pression fonctionnant sous une pression dite moyenne pression; des moyens de compression pour amener la totalité de l'air à distiller à au moins une haute pression nettement supérieure à la moyenne pression, ces moyens comprenant un compresseur principal; des moyens de soutirage de la double colonne et de pompage d'au moins un produit liquide résultant de la distillation; une ligne d'échange thermique mettant en relation d'échange thermique l'air et ledit produit liquide; et une turbine de détente d'une partie de cet air, l'admission de cette turbine étant reliée à un point intermédiaire de la ligne d'échange thermique et son échappement étant relié à la colonne moyenne pression, est caractérisée en ce qu'elle comprend une seconde turbine de détente dont l'admission est reliée à la sortie de passages de réchauffement du gaz résiduaire de la ligne d'échange thermique, au bout chaud de celle-ci.The invention also relates to an installation intended for setting using such a method. This installation, of the type comprising a double distillation column comprising a low pressure column operating under a pressure known as low pressure and producing a waste gas at the top, and a medium pressure column operating under pressure so-called medium pressure; compression means for bring all of the air to be distilled to at least one high pressure significantly higher than medium pressure, these means comprising a main compressor; of means for withdrawing from the double column and pumping at least one liquid product resulting from the distillation; a heat exchange line connecting heat exchange air and said liquid product; and an expansion turbine for part of this air, the intake of this turbine being connected to an intermediate point of the heat exchange line and its exhaust being connected to the medium pressure column, is characterized in that it includes a second expansion turbine whose admission is linked to the exit of passages from heating of the waste gas from the exchange line thermal, at the hot end of it.
Un exemple de mise en oeuvre de l'invention va maintenant être décrit en regard du dessin annexé, sur lequel la Figure unique représente schématiquement une installation conforme à l'invention.An example of implementation of the invention will now be described with reference to the attached drawing, on which the single figure schematically represents a installation according to the invention.
L'installation représentée à la Figure 1 est destinée à produire de l'oxygène gazeux sous une haute pression de 10 à 100 bars environ, de l'oxygène liquide et de l'azote liquide.The installation shown in Figure 1 is intended to produce gaseous oxygen under high pressure from about 10 to 100 bar, liquid oxygen and liquid nitrogen.
Cette installation comprend essentiellement:
un compresseur principal d'air 1 comprenant lui-même au
moins un étage moyenne pression 1A et un étage haute
pression 1B; un appareil 2 d'épuration par adsorption;
un ensemble soufflante-turbine comprenant une soufflante
3 et une turbine 4 dont les roues sont calées sur le même
arbre; un réfrigérant atmosphérique ou à eau 5 pour la
soufflante; une ligne d'échange thermique 6; un premier
échangeur de chaleur auxiliaire 7 et un second échangeur
de chaleur auxiliaire 8 ; une seconde turbine de détente
9 freinée par un alternateur 10; une double colonne de
distillation 11 comprenant une colonne moyenne pression
12 et une colonne basse pression 13 couplées par un
vaporiseur-condenseur 14 qui met en relation d'échange
thermique l'azote de tête de la colonne 12 et l'oxygène
liquide de cuve de la colonne 13; une pompe d'oxygène
liquide 15; un stockage 16 d'oxygène liquide à la
pression atmosphérique; un stockage 17 d'azote liquide
à la pression atmosphérique; un pot séparateur 18; et un
sous-refroidisseur 19.This installation essentially includes:
a
En fonctionnement, la colonne 13 est sous une
pression de 1,7 à 5 bars environ, et la colonne 11 sous
la pression correspondante de 6,5 à 16 bars environ.In operation,
La totalité de l'air à distiller est comprimé
en 1A, refroidi en 7, comprimé de nouveau en 1B, refroidi
en 8 vers + 5 à 15°C, épuré en eau et en C02 en 2 et
surpressé en 3 à la haute pression. Après pré-refroidissement
en 5 puis refroidissement partiel en 6 jusqu'à une
température intermédiaire T1, une partie de l'air sous
la haute pression poursuit son refroidissement dans la
ligne d'échange thermique, est liquéfié puis divisé en
deux fractions. Chaque fraction est détendue dans une
vanne de détente respective 20, 21 puis introduite dans
la colonne 12, 13 respective.All the air to be distilled is compressed
in 1A, cooled in 7, compressed again in 1B, cooled
in 8 to + 5 at 15 ° C, purified in water and in C02 in 2 and
overpressed in 3 at high pressure. After pre-cooling
in 5 then partial cooling in 6 to a
intermediate temperature T1, part of the air below
the high pressure continues to cool in the
heat exchange line, is liquefied and then divided into
two fractions. Each fraction is relaxed in a
A la température T1, le reste de l'air sous
la haute pression est sorti de la ligne d'échange
thermique, turbiné en 4 à la moyenne pression et introduit
en cuve de la colonne 12.At temperature T1, the rest of the air under
the high pressure came out of the exchange line
thermal, turbined in 4 at medium pressure and introduced
at the bottom of
De façon habituelle, du "liquide riche" (air
enrichi en oxygène) soutiré en cuve de la colonne 12 et
du "liquide pauvre" (azote à peu près pur) soutiré de la
région supérieure de cette colonne sont, après sous-refroidissement
en 19 et détente dans des vannes de
détente respectives 22 et 23, introduits à un niveau
intermédiaire et en tête, respectivement, de la colonne
13. Usually, "rich liquid" (air
enriched in oxygen) withdrawn from the tank of
De l'oxygène liquide est soutiré en cuve de
la colonne 13. Une fraction va directement, après sous-refroidissement
en 19 et détente à la pression atmosphérique
dans une vanne de détente 24, dans le stockage 16,
tandis que le reste est amené par la pompe 15 à la haute
pression de production désirée, puis vaporisé et réchauffé
à la température ambiante dans la ligne d'échange
thermique avant d'être récupéré via une conduite 25.Liquid oxygen is drawn off in a
Par ailleurs, de l'azote liquide sous la
moyenne pression, soutiré en tête de la colonne 12, est
sous-refroidi en 19, détendu à la pression atmosphérique
dans une vanne de détente 26, et introduit dans le pot
séparateur 18. La phase liquide est envoyée dans le
stockage 17, tandis que la phase vapeur est réunie à
l'azote impur de tête de la colonne 13, puis le mélange
est réchauffé en 19 puis en 6.In addition, liquid nitrogen under the
medium pressure, withdrawn at the head of
Le gaz résiduaire ainsi réchauffé à la
température ambiante est surchauffé en 7 puis détendu à
peu près à la pression atmosphérique en 9, puis le gaz
détendu est réchauffé en 8. Il peut ensuite, avant d'être
évacué de l'installation, servir à régénérer l'absorbant
de l'appareil 2.The waste gas thus heated at the
room temperature is overheated in 7 then relaxed to
roughly at atmospheric pressure in 9 and then the gas
relaxed is warmed up to 8. It can then, before being
evacuated from the installation, serve to regenerate the
On peut ainsi produire de l'oxygène gazeux haute pression, ayant une pureté donnée, avec une énergie spécifique de production réduite, un ratio production de liquide/capacité de séparation en oxygène réduit, et un rendement d'extraction élevé.We can thus produce gaseous oxygen high pressure, having a given purity, with energy specific reduced production, a production ratio of liquid / reduced oxygen separation capacity, and a high extraction yield.
Le fonctionnement sous pression de la colonne
13 a pour conséquence une baisse de pureté de l'oxygène
produit. Ainsi, l'oxygène gazeux haute pression et
l'oxygène liquide stocké en 16 ont typiquement une pureté
de l'ordre de 95%. Cependant, il est possible de prévoir
quelques plateaux de distillation entre les soutirages
d'oxygène liquide destinés d'une part au stockage 16,
d'autre part à la pompe 15, et de produire ainsi une
fraction, par exemple 20% de l'oxygène, sous forme
d'oxygène liquide à pureté élevée, typiquement à 99,5%
de pureté.Operation under pressure of the
L'invention s'applique également à la production d'azote gazeux sous haute pression, porté par une pompe (non représentée) à la haute pression désirée puis vaporisé dans la ligne d'échange thermique, et/ou à la production d'oxygène et/ou d'azote sous plusieurs pressions, en utilisant plusieurs hautes pressions d'air. De plus, la vaporisation du ou des liquides peut s'effectuer de façon non concomitante à la liquéfaction d'air, avec un genou de liquéfaction de l'air au-dessous de la température de vaporisation de l'oxygène, ou de façon concomitante à cette liquéfaction.The invention also applies to the production of nitrogen gas under high pressure, carried by a pump (not shown) at the desired high pressure then vaporized in the heat exchange line, and / or to the production of oxygen and / or nitrogen under several pressures, using multiple high air pressures. In addition, the vaporization of the liquid (s) can be carried out not concomitantly with air liquefaction, with a knee liquefying air below the oxygen vaporization temperature, or so concomitant with this liquefaction.
Claims (8)
- Process for producing gaseous oxygen and/or gaseous nitrogen under pressure, of the type in which:air is distilled in an installation comprising a main air compressor (1), a double distillation column (11) comprising a low pressure column (13) operating under a pressure described as "low pressure" and a medium pressure column (12) operating under a pressure described as "medium pressure", and a heat-exchanging line (6) serving to cool the treated air;the whole of the air to be distilled is compressed (at 1, 3) until at least a high air pressure which is distinctly higher than medium pressure is reached;the compressed air is cooled to an intermediate temperature and part of it is relieved of pressure in a turbine (4) until medium pressure is reached, before introducing it into the medium pressure column (12);the air which has not been turbined is liquefied and then introduced, after the relief of pressure (at 20, 21), into the double column;at least one liquid product drawn off from the double column is brought (at 15) to production pressure, and the said liquid product is vaporized by exchange of heat with the air, andthe residuary gas from the head of the low pressure column is reheated as far as the hot end of the heat-exchanging line,the low pressure column (13) is operated under about 1.7 to 5 bars, and the medium pressure column (11) under a corresponding pressure of about 6.5 to 16 bars; andthe residuary gas from the head of the low pressure column is relieved of pressure in a second turbine (9), after having reheated it as far as the hot end of the heat-exchanging line (6).
- Process according to claim 1, characterised in that the residuary gas is superheated, before being relieved of pressure, by exchange of heat (at 7) with air emanating from an intermediate stage (1A) of the main compressor (1).
- Process according to claim 1 or 2, characterised in that the residuary gas which has been relieved of pressure is used to cool (at 8) the air emanating from the last stage (1B) of the main compressor (1), before purification of the said air in water and in carbon dioxide.
- Process according to any one of claims 1 to 3, characterised in that the said liquid product is impure oxygen, and in that purer liquid oxygen, which is sent to a stockpiling system (16), is additionally produced.
- Installation for producing gaseous oxygen and/or gaseous nitrogen under pressure, of the type comprising a double distillation column (11) comprising a low pressure column (13) operating under a pressure described as "low pressure" and producing, at the head, a residuary gas, and a medium pressure column (12) operating under a pressure described as "medium pressure"; compression means (1, 3) for bringing the whole of the air to be distilled to at least a high pressure which is distinctly higher than medium pressure, the said means comprising a main compressor (1); means (15) for drawing off from the double column and for pumping at least one liquid product resulting from distillation; a heat-exchanging line (6) bringing the air and the said liquid product into heat-exchanging communication; and a turbine (4) for relieving the pressure of part of the said air, the inlet of the said turbine being connected to an intermediate point in the heat-exchanging line and its exit being connected to the medium pressure column (12), characterised in that it comprises a second pressure-relieving turbine (9), the inlet of which is connected to the outlet of passages for reheating the residuary gas from the heat-exchanging line (6), at the hot end of the latter.
- Installation according to claim 5, characterised in that it comprises a heat-exchanger (7) bringing the gas circulating between the said outlet and the second turbine (9) and the air emanating from an intermediate stage (1A) of the main compressor (1) into heat-exchanging communication.
- Installation according to claim 5 or 6, characterised in that it comprises a second heat-exchanger (8) bringing the gas emanating from the second turbine (9) and the air emanating from the last stage (1B) of the main compressor (1) into heat-exchanging communication.
- Installation according to any one of claims 5 to 7, characterised in that the low pressure column (13) has a distillation section between a lower offtake for liquid oxygen intended to be stockpiled and a liquid oxygen offtake connected to the intake of the pump (15).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9310418A FR2709538B1 (en) | 1993-09-01 | 1993-09-01 | Method and installation for producing at least one pressurized air gas. |
FR9310418 | 1993-09-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0641982A1 EP0641982A1 (en) | 1995-03-08 |
EP0641982B1 true EP0641982B1 (en) | 1998-05-06 |
Family
ID=9450479
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94401838A Expired - Lifetime EP0641982B1 (en) | 1993-09-01 | 1994-08-10 | Process and installation for the production of at least a gas from air under pressure |
Country Status (8)
Country | Link |
---|---|
US (1) | US5463870A (en) |
EP (1) | EP0641982B1 (en) |
JP (1) | JPH07151459A (en) |
CN (1) | CN1102700A (en) |
CA (1) | CA2131121A1 (en) |
DE (1) | DE69410040T2 (en) |
ES (1) | ES2118342T3 (en) |
FR (1) | FR2709538B1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5355682A (en) † | 1993-09-15 | 1994-10-18 | Air Products And Chemicals, Inc. | Cryogenic air separation process producing elevated pressure nitrogen by pumped liquid nitrogen |
FR2730172B1 (en) * | 1995-02-07 | 1997-03-21 | Air Liquide | METHOD AND APPARATUS FOR MONITORING THE OPERATION OF AN AIR SEPARATION INSTALLATION |
US20060000358A1 (en) * | 2004-06-29 | 2006-01-05 | Rajat Agrawal | Purification and delivery of high-pressure fluids in processing applications |
CN100443838C (en) * | 2005-04-20 | 2008-12-17 | 苏州市兴鲁空分设备科技发展有限公司 | Method and equipment for separating stream backed expansion air |
US20070095100A1 (en) * | 2005-11-03 | 2007-05-03 | Rankin Peter J | Cryogenic air separation process with excess turbine refrigeration |
PL2873938T3 (en) | 2013-11-14 | 2021-11-02 | L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Process and apparatus for the separation of air by cryogenic distillation |
CN104034123B (en) * | 2014-06-27 | 2016-05-18 | 莱芜钢铁集团有限公司 | A kind of air-separating plant hydrops is adjusted pure integration operation method |
IT202100032876A1 (en) * | 2021-12-29 | 2023-06-29 | Rita S R L | Plant and process for the production of oxygen and nitrogen gas by cryogenic separation of a gas mixture containing oxygen and nitrogen |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2461906A1 (en) * | 1979-07-20 | 1981-02-06 | Air Liquide | CRYOGENIC AIR SEPARATION METHOD AND INSTALLATION WITH OXYGEN PRODUCTION AT HIGH PRESSURE |
FR2652409A1 (en) * | 1989-09-25 | 1991-03-29 | Air Liquide | REFRIGERANT PRODUCTION PROCESS, CORRESPONDING REFRIGERANT CYCLE AND THEIR APPLICATION TO AIR DISTILLATION. |
FR2674011B1 (en) * | 1991-03-11 | 1996-12-20 | Maurice Grenier | PROCESS AND PLANT FOR PRODUCING PRESSURE GAS OXYGEN. |
US5197296A (en) * | 1992-01-21 | 1993-03-30 | Praxair Technology, Inc. | Cryogenic rectification system for producing elevated pressure product |
US5222365A (en) * | 1992-02-24 | 1993-06-29 | Praxair Technology, Inc. | Cryogenic rectification system for producing high pressure nitrogen product |
-
1993
- 1993-09-01 FR FR9310418A patent/FR2709538B1/en not_active Expired - Fee Related
-
1994
- 1994-08-10 ES ES94401838T patent/ES2118342T3/en not_active Expired - Lifetime
- 1994-08-10 DE DE69410040T patent/DE69410040T2/en not_active Expired - Fee Related
- 1994-08-10 EP EP94401838A patent/EP0641982B1/en not_active Expired - Lifetime
- 1994-08-22 JP JP6196772A patent/JPH07151459A/en active Pending
- 1994-08-29 US US08/300,196 patent/US5463870A/en not_active Expired - Lifetime
- 1994-08-30 CA CA002131121A patent/CA2131121A1/en not_active Abandoned
- 1994-08-31 CN CN94115628A patent/CN1102700A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
FR2709538B1 (en) | 1995-10-06 |
CN1102700A (en) | 1995-05-17 |
JPH07151459A (en) | 1995-06-16 |
DE69410040D1 (en) | 1998-06-10 |
ES2118342T3 (en) | 1998-09-16 |
EP0641982A1 (en) | 1995-03-08 |
US5463870A (en) | 1995-11-07 |
DE69410040T2 (en) | 1999-01-28 |
CA2131121A1 (en) | 1995-03-02 |
FR2709538A1 (en) | 1995-03-10 |
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