EP1406052A2 - Integriertes Verfahren zur Luftzerlegung und Energieerzeugung und Anlage zur Ausführung des Verfahrens - Google Patents

Integriertes Verfahren zur Luftzerlegung und Energieerzeugung und Anlage zur Ausführung des Verfahrens Download PDF

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Publication number
EP1406052A2
EP1406052A2 EP03300172A EP03300172A EP1406052A2 EP 1406052 A2 EP1406052 A2 EP 1406052A2 EP 03300172 A EP03300172 A EP 03300172A EP 03300172 A EP03300172 A EP 03300172A EP 1406052 A2 EP1406052 A2 EP 1406052A2
Authority
EP
European Patent Office
Prior art keywords
air
air separation
compressor
turbine
separator
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.)
Granted
Application number
EP03300172A
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English (en)
French (fr)
Other versions
EP1406052B1 (de
EP1406052A3 (de
Inventor
Alain l'Air Liquide SA Guillard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA a Directoire et Conseil de Surveillance pour lEtude et lExploitation des Procedes Georges Claude
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Publication date
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Application filed by Air Liquide SA, LAir Liquide SA a Directoire et Conseil de Surveillance pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP1406052A2 publication Critical patent/EP1406052A2/de
Publication of EP1406052A3 publication Critical patent/EP1406052A3/de
Application granted granted Critical
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Revoked legal-status Critical Current

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Classifications

    • 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
    • F25J3/04763—Start-up or control of the process; Details of the apparatus used
    • F25J3/04769—Operation, control and regulation of the process; Instrumentation within the process
    • F25J3/04812—Different modes, i.e. "runs" of operation
    • F25J3/04818—Start-up of the process
    • 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
    • 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
    • F25J3/04527—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general
    • F25J3/04539—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general for the H2/CO synthesis by partial oxidation or oxygen consuming reforming processes of fuels
    • F25J3/04545—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general for the H2/CO synthesis by partial oxidation or oxygen consuming reforming processes of fuels for the gasification of solid or heavy liquid fuels, e.g. integrated gasification combined cycle [IGCC]
    • 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
    • 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
    • F25J3/04593—The air gas consuming unit is also fed by an air stream
    • F25J3/04606—Partially integrated air feed compression, i.e. independent MAC for the air fractionation unit plus additional air feed from the air gas consuming unit
    • 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
    • F25J3/04763—Start-up or control of the process; Details of the apparatus used
    • F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
    • F25J3/04951—Arrangements of multiple air fractionation units or multiple equipments fulfilling the same process step, e.g. multiple trains in a network
    • 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
    • F25J3/04763—Start-up or control of the process; Details of the apparatus used
    • F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
    • F25J3/04951—Arrangements of multiple air fractionation units or multiple equipments fulfilling the same process step, e.g. multiple trains in a network
    • F25J3/04957—Arrangements of multiple air fractionation units or multiple equipments fulfilling the same process step, e.g. multiple trains in a network and inter-connecting equipments upstream of the fractionation unit (s), i.e. at the "front-end"
    • 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
    • F25J2240/10—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream the fluid being air
    • 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
    • F25J2240/80—Hot exhaust gas turbine combustion engine

Definitions

  • the present invention relates to an integrated process for the separation of air and an installation for implementing such a method.
  • EP-A-568431 describes the use of an integrated system. The difficulties of regulating this kind of system are explained in EP-A-0622595.
  • each separation device is supplied from a compressor gas turbine and sends nitrogen only to that same gas turbine.
  • An object of the invention is to overcome the shortcomings of known systems.
  • an integrated method of separation of air producing a fluid enriched in oxygen and possibly a fluid enriched in nitrogen in an installation comprising at least two air separation, each comprising at least two distillation columns, one first air compressor, a first combustion chamber, and a first expansion turbine, in which compressed air is supplied to the first air separation at least by the first air compressor which also provides compressed air to the first combustion chamber, compressed air is supplied to the second air separation unit at least by an auxiliary compressor which does not supply a combustion chamber but which also supplies the first air separation device.
  • an integrated installation comprising a first air separation device, a second air separation device air separation, a first compressor, a combustion chamber, a turbine expansion valve, an auxiliary compressor, means for sending air from the first compressor to the combustion chamber and to the first air separation device, means for sending air from the auxiliary compressor to the first apparatus for air separation and at the second air separation device, this auxiliary compressor not fueling a combustion chamber.
  • the auxiliary compressor is not connected with a unit compressed air consumer apart from the first and second separation devices air.
  • the degree of integration determines which products can be taken out of each device, generally the purest oxygen and / or argon products from the second device which will operate more stable, thanks to the low degree of integration.
  • a compressor 13 is supplied with air and sends a first air flow to a combustion chamber 17 with fuel, a second flow air to a first air separation device 1 and possibly a third flow air to a second air separation device 101, the third flow being in general lower than the second flow.
  • Means for cooling the air of the outlet temperature of the compressor 13 at a temperature close to the ambient upstream of the air separation device 1 and upstream of the air separation apparatus 101 are not illustrated.
  • Only one of the compressors 21 or 121 supplies the first and the second air separation unit (not shown).
  • the first air separation device typically of the double or triple column, produces at least one nitrogen enriched gas 3 and one high pressure gas enriched in oxygen 5 containing at most 98 mol. % oxygen, possibly at most 95 mol. % oxygen or even at most 93 mol. % oxygen which is sent to a gasifier 31.
  • the nitrogen-enriched gas is sent to the combustion chamber 17 or at another point upstream of the turbine 19.
  • the first device may eventually produce a small amount of liquid.
  • Part of the air sent to the air separation unit 1 can be there sent through an insufflation turbine (feeding the low pressure column of double or triple column).
  • the second air separation unit produces oxygen 105 containing at least 98 mol. % oxygen, argon gas and / or liquid and possibly liquids rich in nitrogen or oxygen as well as a flow of impure nitrogen 103 which can possibly sent to the combustion chamber 17.
  • part of the oxygen 105 can be sent to the gasifier 31.
  • the second device 101 is preferably of the pressurized type, therefore with a low pressure column from which the operating oxygen-enriched fluid is withdrawn at above 1.5 bara, preferably above 3 bara.
  • the second device can comprise a column for purifying a flow enriched with argon.
  • part of the air sent to the second device 101 is slackened in a Claude turbine before being sent to the distillation column of air operating at the highest pressure.
  • the ratio between the air flow rate sent from the compressor 121 to the device 101 and the air flow (if there is one) sent from the compressor 13 to this device 101 is greater than the ratio between the air flow rate sent from compressor 21 to device 1 and the air flow rate sent from compressor 13 to this device 1.
  • the two compressors 21, 121 can be replaced by a single compressor supplying the devices 1, 101.
  • a first air compressor 13 supplies air to the first air separation device 1 and a first combustion chamber 17, the combustion gases feed a first expansion turbine 19 which allows the generation of electricity.
  • a second air compressor 15 supplies air to the separation device air 1 and a second combustion chamber 23, including the combustion gases feed a second expansion turbine 25 which allows the generation of electricity.
  • a third air compressor 21 supplies air to the air separation apparatus.
  • Means for cooling the air of the outlet temperature of the compressors 13, 15 at a temperature close to the ambient upstream of the first apparatus for air separation 1 and upstream of the second air separation device 101 are not not illustrated.
  • the waste gas 3 from the separation device 1 can be sent upstream of the first and / or the second turbine, for example to the first and / or to the second combustion chamber and / or at the entrance to the first and / or second turbine.
  • the oxygen-enriched pressurized gas 5 is preferably sent to one or more several gasifiers 31, 131 where it is used to produce fuel for at least one of the combustion chambers 17, 23.
  • Compressors 13, 15, 21 can supply air at pressures different, for example different by at least 0.5 bar from each other.
  • the flow rates at higher pressures can be expanded at lower pressure so purify all air flows together.
  • debits can be sent to ASU columns operating at different pressures with suitable purification.
  • the apparatus 1 produces the same products as those described above: the apparatus 101 produces at least residual nitrogen 103 and oxygen-enriched gas possibly under several pressures or at least under high pressure.
  • Waste nitrogen 103 can be sent to the first and / or the second combustion chamber or alternatively can be released to the atmosphere, used for the regeneration of the purification of first and / or second devices 1, 101 or used otherwise.
  • the oxygen 105 can be sent to another gasifier 131, the gasifier 31 or another use, particularly if its purity is different from that of oxygen 5.
  • the apparatus 101 can mainly or only pure oxygen above 98 mol% oxygen while the first device can produce only or mainly impure oxygen at below 95 mol. % oxygen.
  • the device 101 is supplied with air from a dedicated compressor 121 and from the dedicated compressor 21 and / or a dedicated compressor which sends air to both air separation devices and possibly very partially from the first compressor 13 or the second compressor 15.

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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)
  • Power Engineering (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP03300172A 2001-01-12 2001-12-18 Integriertes Verfahren zur Luftzerlegung und Energieerzeugung und Anlage zur Ausführung des Verfahrens Revoked EP1406052B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0100403 2001-01-12
FR0100403A FR2819584B1 (fr) 2001-01-12 2001-01-12 Procede integre de separation d'air et de generation d'energie et installation pour la mise en oeuvre d'un tel procede
EP01403286.6A EP1223395B2 (de) 2001-01-12 2001-12-18 Integriertes Verfahren zur Luftzerlegung und Energieerzeugung

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP01403286.6 Division 2001-12-18
EP01403286.6A Division EP1223395B2 (de) 2001-01-12 2001-12-18 Integriertes Verfahren zur Luftzerlegung und Energieerzeugung

Publications (3)

Publication Number Publication Date
EP1406052A2 true EP1406052A2 (de) 2004-04-07
EP1406052A3 EP1406052A3 (de) 2005-01-05
EP1406052B1 EP1406052B1 (de) 2006-07-26

Family

ID=8858754

Family Applications (2)

Application Number Title Priority Date Filing Date
EP03300172A Revoked EP1406052B1 (de) 2001-01-12 2001-12-18 Integriertes Verfahren zur Luftzerlegung und Energieerzeugung und Anlage zur Ausführung des Verfahrens
EP01403286.6A Expired - Lifetime EP1223395B2 (de) 2001-01-12 2001-12-18 Integriertes Verfahren zur Luftzerlegung und Energieerzeugung

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP01403286.6A Expired - Lifetime EP1223395B2 (de) 2001-01-12 2001-12-18 Integriertes Verfahren zur Luftzerlegung und Energieerzeugung

Country Status (7)

Country Link
US (1) US6550234B2 (de)
EP (2) EP1406052B1 (de)
JP (1) JP2002243361A (de)
AT (2) ATE334365T1 (de)
DE (2) DE60121830T2 (de)
ES (2) ES2269951T3 (de)
FR (1) FR2819584B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006061368A1 (en) * 2004-12-09 2006-06-15 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Integrated process for the separation of air and an integrated installation for the separation of air

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FR2862128B1 (fr) * 2003-11-10 2006-01-06 Air Liquide Procede et installation de fourniture d'oxygene a haute purete par distillation cryogenique d'air
EP1544559A1 (de) * 2003-12-20 2005-06-22 Linde AG Verfahren und Vorrichtung zur Tieftemperaturzerlegung von Luft
US7197894B2 (en) * 2004-02-13 2007-04-03 L'air Liquide, Societe Anonyme A' Directorie Et Conseil De Survelliance Pour L'etude Et, L'exploltation Des Procedes Georges, Claude Integrated process and air separation process
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FR2898645B1 (fr) * 2006-03-14 2008-08-22 L'air Liquide Compresseur a plusieurs etages, appareil de separation d'air comprenant un tel compresseur et installation
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US20020092306A1 (en) 2002-07-18
ATE301272T1 (de) 2005-08-15
EP1223395A1 (de) 2002-07-17
DE60121830T2 (de) 2007-03-29
US6550234B2 (en) 2003-04-22
DE60112396T3 (de) 2013-10-10
FR2819584B1 (fr) 2003-03-07
EP1223395B1 (de) 2005-08-03
DE60121830D1 (de) 2006-09-07
ATE334365T1 (de) 2006-08-15
EP1406052B1 (de) 2006-07-26
EP1406052A3 (de) 2005-01-05
FR2819584A1 (fr) 2002-07-19
ES2246301T3 (es) 2006-02-16
DE60112396D1 (de) 2005-09-08
DE60112396T2 (de) 2006-06-01
ES2246301T5 (es) 2013-10-08
EP1223395B2 (de) 2013-05-15
JP2002243361A (ja) 2002-08-28
ES2269951T3 (es) 2007-04-01

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