EP2691718B1 - Method for producing a gas from pressurised air by means of cryogenic distillation - Google Patents

Method for producing a gas from pressurised air by means of cryogenic distillation Download PDF

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Publication number
EP2691718B1
EP2691718B1 EP12717421.7A EP12717421A EP2691718B1 EP 2691718 B1 EP2691718 B1 EP 2691718B1 EP 12717421 A EP12717421 A EP 12717421A EP 2691718 B1 EP2691718 B1 EP 2691718B1
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Prior art keywords
air
compressor
intermediate temperature
exchange line
sent
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EP12717421.7A
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German (de)
French (fr)
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EP2691718A2 (en
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Patrick Le Bot
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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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
    • 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
    • F25J3/04048—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of cold gaseous streams, e.g. intermediate or oxygen enriched (waste) streams
    • F25J3/04054—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of cold gaseous streams, e.g. intermediate or oxygen enriched (waste) streams of 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
    • 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
    • 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
    • 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
    • F25J3/04096—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 argon or argon enriched stream
    • 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
    • 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
    • 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
    • F25J3/04375—Details relating to the work expansion, e.g. process parameter etc.
    • F25J3/04381—Details relating to the work expansion, e.g. process parameter etc. using work extraction by mechanical coupling of compression and expansion so-called companders
    • 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
    • F25J3/04375—Details relating to the work expansion, e.g. process parameter etc.
    • F25J3/04393—Details relating to the work expansion, e.g. process parameter etc. using multiple or multistage gas work expansion
    • 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
    • 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
    • F25J2215/54—Oxygen production with multiple pressure O2
    • 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
    • F25J2240/04—Multiple expansion turbines in parallel

Definitions

  • the present invention relates to a method for producing a pressurized air gas by cryogenic distillation.
  • An object of the invention is to propose an alternative for producing process diagrams making it possible to improve the installation costs of the air separation apparatus for oxygen production between 10 and 16 bar, preferably between 14 and 16 bar. 16 bars, so the order of 15 bars.
  • the state of the art for appliances producing oxygen under pressure of the order of 15 bar is constituted by "pump" devices, using a main air compressor at a pressure of the order about 6 bars, and an air booster compressing a portion of the air flow at a pressure of about 35-40 bar.
  • this solution is not available for devices of small sizes, for which the combination of a low flow to boost and a very high discharge pressure leads to a real output flow of the booster too small to be technologically feasible .
  • the proposed solution reduces costs for such devices by using a single air compressor at a moderately high discharge pressure, which offers a competitive advantage over the two previous solutions: compressor uniqueness and avoiding an expensive oxygen compressor.
  • US Patent 20050126221 discloses an air separation process. To produce pressurized oxygen, two series boosters compress the air at intermediate temperatures of the main exchanger, the inlet temperature of the first booster being hotter than the outlet temperature of the second booster. A refrigeration unit is used to lower the inlet temperature of the second booster, thus increasing the complexity of the process.
  • US Patent 20060010912 discloses an air separation process in which medium pressure air is supercharged in two cold booster compressors in series.
  • the two boosters must not be coupled to a turbine, because the process turbines only work during a particular step to make liquid. In nominal operation, the process is kept cold by adding cryogenic liquid.
  • all the air is carried at high pressure (substantially higher than the pressure of the medium pressure column, ie at least 3 bars higher than the average pressure) and purified at this pressure, then divided into at least two parts. Only a fraction of the air, the fraction subsequently liquefying at the cold end of the main exchange line, undergoes a succession of cryogenic compressions so as to bring this flow rate to a pressure sufficient to allow the vaporization of oxygen at the pressure desired.
  • the rest of the air is expanded in at least one turbine at the pressure of the medium pressure column. At least some of the work done by the air expansion is used for cryogenic compression.
  • US Patent 5475980 discloses a method according to the preamble of claim 1.
  • An air flow 1 is compressed in a main compressor 3 to a pressure at least 3 bar above the pressure of the column 31, which is the medium pressure column of a double air separation column. cryogenic distillation.
  • the compressed air is purified in a purification unit 7 to form the purified flow 9.
  • the purified flow is sent to the exchange line 11 without having been cooled and in the exchange line it cools to a minimum first intermediate temperature. At this temperature, the air is divided into a portion 13 and a portion 14.
  • the portion 13 enters a single first booster 15 having a single stage at the first intermediate temperature where it is supercharged.
  • the supercharged air is sent to the exchange line 11 where it cools again to a second intermediate temperature, lower than the first intermediate temperature. At this second intermediate temperature, at least a portion of the air supercharged in the booster 15 or all the air 13 is supercharged in a single second booster 25 having a single stage.
  • the first intermediate temperature differs from the second temperature by at most 10 ° C and the first and second temperatures range from -145 ° C to -165 ° C.
  • the first intermediate temperature may optionally be greater than or equal to the second intermediate temperature.
  • Each of the outlet temperatures of the boosters 15, 25 is between -110 ° C and -150 ° C, preferably between -125 ° C and -145 ° C.
  • the doubly supercharged flow 13 is returned to the exchange line at the pressure required for the vaporization of a flow of oxygen under pressure.
  • the supercharged flow 13 cools to this pressure to the cold end of the exchange line 11 and condenses.
  • the flow is expanded, and is sent to the medium pressure column 31.
  • the rest of the air 14 is divided into two or three parts. According to a variant, all the air 14 is divided into two parts.
  • a part 19 is sent to a turbine 17 having an inlet temperature which is a third intermediate temperature of the exchange line, then is sent in gaseous form to the medium pressure column 31.
  • Another part 21 is sent to a turbine 27 having an inlet temperature which is a fourth intermediate temperature of the exchange line, greater than the third temperature, then is sent in gaseous form to the medium pressure column 31.
  • the parts 19, 21 are mixed to form a single flow 23.
  • a portion 26 of the air at high pressure can optionally continue cooling to the cold end of the exchange line 11 and condense.
  • the outlet of the exchanger it will be expanded in a valve and sent to the column system, for example to the medium pressure column 31.
  • the double column comprises a medium pressure column 31 and a low pressure column 33, thermally interconnected with reflux rates 39, 41 in a known manner.
  • the low pressure column 33 produces a nitrogen flow 43 which is heated in the exchange line 11. It also produces liquid oxygen in the tank which is pressurized at 37 at a pressure between 10 and 16 bars and vaporizes. in the exchange line to form gaseous oxygen under pressure.
  • part of the flow 13 may continue cooling until the cold end of the exchanger and not be overpressed by the booster 25. This fraction of flow will condense. At the outlet of the exchanger, it will be expanded in a valve and sent to the column system, for example to the medium pressure column 31.
  • the booster 15 is driven at least in part by one of the two turbines 17 or 25, and the booster 25 by the other turbine 25 or 17. In each case, there may also be a motor or a generator coupled to the compressor .
  • An energy dissipating device 22, 24, for example a brake, preferably an oil-brake system, will be integrated with at least one of the two turbine / compressor systems 15/17, 25/27.

Description

La présente invention est relative à un procédé de production d'un gaz de l'air sous pression par distillation cryogénique.The present invention relates to a method for producing a pressurized air gas by cryogenic distillation.

Un but de l'invention est de proposer une alternative pour réaliser des schémas de procédé permettant d'améliorer les coûts d'installation des appareil de séparation d'air pour une production d'oxygène entre 10 et 16 bars, de préférence entre 14 et 16 bars, donc de l'ordre de 15 bars.An object of the invention is to propose an alternative for producing process diagrams making it possible to improve the installation costs of the air separation apparatus for oxygen production between 10 and 16 bar, preferably between 14 and 16 bar. 16 bars, so the order of 15 bars.

L'état de l'art industriel, pour des appareils produisant de l'oxygène sous pression de l'ordre de 15 bars est constitué par des appareils « à pompe », utilisant un compresseur d'air principal à une pression de l'ordre de 6 bars environ, et un surpresseur d'air comprimant une partie du débit d'air à une pression de l'ordre de 35-40 bars. Mais cette solution n'est pas disponible pour des appareils de petites tailles, pour lesquels la combinaison d'un faible débit à surpresser et d'une pression de refoulement très élevée amène à un débit réel en sortie du surpresseur trop petit pour être technologiquement réalisable.The state of the art for appliances producing oxygen under pressure of the order of 15 bar is constituted by "pump" devices, using a main air compressor at a pressure of the order about 6 bars, and an air booster compressing a portion of the air flow at a pressure of about 35-40 bar. But this solution is not available for devices of small sizes, for which the combination of a low flow to boost and a very high discharge pressure leads to a real output flow of the booster too small to be technologically feasible .

Dès lors, pour les petits appareils, on doit avoir recours à l'utilisation de compresseurs d'oxygène, coûteux.Therefore, for small appliances, we must resort to the use of expensive oxygen compressors.

La solution proposée permet de réduire les coûts pour de tels appareils, par l'utilisation d'un compresseur d'air unique, à une pression de refoulement modérément élevée, ce qui propose un avantage compétitif par rapport aux deux solutions précédentes : unicité du compresseur et évitement d'un compresseur d'oxygène coûteux.The proposed solution reduces costs for such devices by using a single air compressor at a moderately high discharge pressure, which offers a competitive advantage over the two previous solutions: compressor uniqueness and avoiding an expensive oxygen compressor.

US-A-20050126221 décrit un procédé de séparation d'air. Pour produire de l'oxygène sous pression, deux surpresseurs en série compriment l'air à des températures intermédiaires de l'échangeur principal, la température d'entrée du premier surpresseur étant plus chaude que la température de sortie du deuxième surpresseur. Un groupe frigorifique est utilisé pour abaisser la température d'entrée du deuxième surpresseur, ainsi augmentant la complexité du procédé. US Patent 20050126221 discloses an air separation process. To produce pressurized oxygen, two series boosters compress the air at intermediate temperatures of the main exchanger, the inlet temperature of the first booster being hotter than the outlet temperature of the second booster. A refrigeration unit is used to lower the inlet temperature of the second booster, thus increasing the complexity of the process.

US-A-20060010912 décrit un procédé de séparation d'air dans lequel de l'air à la moyenne pression est surpressé dans deux surpresseurs froids en série. US Patent 20060010912 discloses an air separation process in which medium pressure air is supercharged in two cold booster compressors in series.

Les deux surpresseurs ne doivent pas être couplés à une turbine, car les turbines du procédé ne marchent que pendant une marche particulière permettant de fabriquer du liquide. En marche nominale, le procédé est tenu en froid par rajout de liquide cryogénique.The two boosters must not be coupled to a turbine, because the process turbines only work during a particular step to make liquid. In nominal operation, the process is kept cold by adding cryogenic liquid.

Toutes les pressions sont des pressions absolues.All pressures are absolute pressures.

Selon l'invention, tout l'air est porté à haute pression (sensiblement plus haute que la pression de la colonne moyenne pression, c'est à dire supérieure d'au moins 3 bars à la moyenne pression) et épuré à cette pression, puis divisé en au moins deux parties. Seule une fraction de l'air, la fraction se liquéfiant ultérieurement au bout froid de la ligne d'échange principale, subit une succession de compressions cryogéniques de façon à porter ce débit à une pression suffisante pour permettre la vaporisation d'oxygène à la pression souhaitée. De préférence, le reste de l'air est détendu dans au moins une turbine à la pression de la colonne moyenne pression. Au moins une partie du travail dégagé par la détente de l'air est utilisée pour la compression cryogénique.According to the invention, all the air is carried at high pressure (substantially higher than the pressure of the medium pressure column, ie at least 3 bars higher than the average pressure) and purified at this pressure, then divided into at least two parts. Only a fraction of the air, the fraction subsequently liquefying at the cold end of the main exchange line, undergoes a succession of cryogenic compressions so as to bring this flow rate to a pressure sufficient to allow the vaporization of oxygen at the pressure desired. Preferably, the rest of the air is expanded in at least one turbine at the pressure of the medium pressure column. At least some of the work done by the air expansion is used for cryogenic compression.

US-A-5475980 décrit un procédé selon le préambule de la revendication 1. US Patent 5475980 discloses a method according to the preamble of claim 1.

Selon un objet de l'invention, il est prévu un procédé selon la revendication 1.According to one object of the invention, there is provided a method according to claim 1.

Selon d'autres caractéristiques optionnelles :

  • les deux turbines ont des températures d'entrée égales ou différentes, constituées par la troisième température intermédiaire et une quatrième température intermédiaire de la ligne d'échange ;
  • la troisième température est inférieure à la première température.
  • la troisième température diffère de la quatrième température d'au plus 20°C, voire d'au plus 10°C ;
  • la première température est supérieure à la deuxième température ;
  • la première température est inférieure ou égale à la deuxième température ;
  • on dissipe une partie de l'énergie générée par au moins une des turbines ;
  • on dissipe une partie de l'énergie au moyen d'un système à frein d'huile relié à la turbine ;
  • une partie de l'air se liquéfié à la haute pression, de préférence dans la ligne d'échange ;
  • l'air d'au moins une des turbines est envoyé à la colonne opérant à la pression la plus élevée ;
  • tout l'air surpressé dans le premier surpresseur est envoyé au deuxième surpresseur ;
  • tout l'air épuré dans l'unité d'épuration est envoyé à la ligne d'échange à la pression de sortie de l'unité d'épuration ;
  • le système comprend une double colonne de séparation d'air comprenant une première colonne et une deuxième colonne opérant à plus basse pression que la première, l'air détendu dans les deux turbines étant envoyé à la première colonne ;
  • la première température est plus froide que la température de sortie du deuxième surpresseur ;
  • les températures de sortie du premier et du deuxième surpresseur sont entre -125°C et -145°C.
According to other optional features:
  • the two turbines have equal or different inlet temperatures constituted by the third intermediate temperature and a fourth intermediate temperature of the exchange line;
  • the third temperature is lower than the first temperature.
  • the third temperature differs from the fourth temperature by at most 20 ° C, or even at most 10 ° C;
  • the first temperature is higher than the second temperature;
  • the first temperature is less than or equal to the second temperature;
  • part of the energy generated by at least one of the turbines is dissipated;
  • a portion of the energy is dissipated by means of an oil brake system connected to the turbine;
  • part of the air is liquefied at high pressure, preferably in the exchange line;
  • the air of at least one of the turbines is sent to the column operating at the highest pressure;
  • all the supercharged air in the first booster is sent to the second booster;
  • all the purified air in the purification unit is sent to the exchange line at the outlet pressure of the purification unit;
  • the system comprises a double air separation column comprising a first column and a second column operating at a lower pressure than the first, the air expanded in the two turbines being sent to the first column;
  • the first temperature is colder than the outlet temperature of the second booster;
  • the outlet temperatures of the first and second boosters are between -125 ° C and -145 ° C.

L'invention sera décrite en plus de détail en se référant à la figure qui illustre un procédé de séparation d'air selon l'invention.The invention will be described in more detail with reference to the figure which illustrates an air separation method according to the invention.

Un débit d'air 1 est comprimé dans un compresseur principal 3 jusqu'à une pression au moins 3 bars au-dessus de la pression de la colonne 31, qui est la colonne moyenne pression d'une double colonne de séparation d'air par distillation cryogénique. L'air comprimé est épuré dans une unité d'épuration 7 pour former le débit épuré 9. Le débit épuré est envoyé à la ligne d'échange 11 sans avoir été refroidi et dans la ligne d'échange il se refroidit jusqu'à une première température intermédiaire. A cette température, l'air est divisé en une partie 13 et une partie 14. La partie 13 rentre dans un seul premier surpresseur 15 ayant un seul étage à la première température intermédiaire où elle est surpressée. L'air surpressé est envoyé à la ligne d'échange 11 où il se refroidit de nouveau jusqu'à une deuxième température intermédiaire, inférieure à la première température intermédiaire. A cette deuxième température intermédiaire, au moins une partie de l'air surpressé dans le surpresseur 15 voire tout l'air 13 est surpressé dans un seul deuxième surpresseur 25 ayant un seul étage.An air flow 1 is compressed in a main compressor 3 to a pressure at least 3 bar above the pressure of the column 31, which is the medium pressure column of a double air separation column. cryogenic distillation. The compressed air is purified in a purification unit 7 to form the purified flow 9. The purified flow is sent to the exchange line 11 without having been cooled and in the exchange line it cools to a minimum first intermediate temperature. At this temperature, the air is divided into a portion 13 and a portion 14. The portion 13 enters a single first booster 15 having a single stage at the first intermediate temperature where it is supercharged. The supercharged air is sent to the exchange line 11 where it cools again to a second intermediate temperature, lower than the first intermediate temperature. At this second intermediate temperature, at least a portion of the air supercharged in the booster 15 or all the air 13 is supercharged in a single second booster 25 having a single stage.

La première température intermédiaire diffère de la deuxième température d'au plus 10°C et les première et deuxième températures sont comprises entre -145°C et -165°C.The first intermediate temperature differs from the second temperature by at most 10 ° C and the first and second temperatures range from -145 ° C to -165 ° C.

La première température intermédiaire peut éventuellement être supérieure ou égale à la deuxième température intermédiaire.The first intermediate temperature may optionally be greater than or equal to the second intermediate temperature.

Chacune des températures de sortie des surpresseurs 15, 25 est entre - 110°C et -150°C, de préférence entre -125°C et -145°C.Each of the outlet temperatures of the boosters 15, 25 is between -110 ° C and -150 ° C, preferably between -125 ° C and -145 ° C.

Le débit doublement surpressé 13 est renvoyé à la ligne d'échange à la pression requise pour la vaporisation d'un débit d'oxygène sous pression. Le débit surpressé 13 se refroidit à cette pression jusqu'au bout froid de la ligne d'échange 11 et se condense. En sortie d'échangeur, le débit est détendu, et est envoyé à la colonne moyenne pression 31.The doubly supercharged flow 13 is returned to the exchange line at the pressure required for the vaporization of a flow of oxygen under pressure. The supercharged flow 13 cools to this pressure to the cold end of the exchange line 11 and condenses. At the outlet of the exchanger, the flow is expanded, and is sent to the medium pressure column 31.

Le reste de l'air 14 est divisé en deux ou trois parties. Selon une variante, tout l'air 14 est divisé en deux parties. Une partie 19 est envoyée à une turbine 17 ayant une température d'entrée qui est une troisième température intermédiaire de la ligne d'échange, puis est envoyée sous forme gazeuse à la colonne moyenne pression 31. Une autre partie 21 est envoyée à une turbine 27 ayant une température d'entrée qui est une quatrième température intermédiaire de la ligne d'échange, supérieure à la troisième température, puis est envoyée sous forme gazeuse à la colonne moyenne pression 31. De préférence les parties 19, 21 sont mélangées pour former un seul débit 23.The rest of the air 14 is divided into two or three parts. According to a variant, all the air 14 is divided into two parts. A part 19 is sent to a turbine 17 having an inlet temperature which is a third intermediate temperature of the exchange line, then is sent in gaseous form to the medium pressure column 31. Another part 21 is sent to a turbine 27 having an inlet temperature which is a fourth intermediate temperature of the exchange line, greater than the third temperature, then is sent in gaseous form to the medium pressure column 31. Preferably the parts 19, 21 are mixed to form a single flow 23.

Autrement en plus des parties 19, 21, une partie 26 de l'air à la haute pression peut éventuellement poursuivre son refroidissement jusqu'au bout froid de la ligne d'échange 11 et se condenser. En sortie d'échangeur, elle sera détendue dans une vanne et envoyée au système de colonnes, par exemple à la colonne moyenne pression 31.Otherwise in addition to the parts 19, 21, a portion 26 of the air at high pressure can optionally continue cooling to the cold end of the exchange line 11 and condense. At the outlet of the exchanger, it will be expanded in a valve and sent to the column system, for example to the medium pressure column 31.

La double colonne comprend une colonne moyenne pression 31 et une colonne basse pression 33, thermiquement reliées entre elles avec des débits de reflux 39, 41 de manière connue.The double column comprises a medium pressure column 31 and a low pressure column 33, thermally interconnected with reflux rates 39, 41 in a known manner.

La colonne basse pression 33 produit un débit d'azote 43 qui se réchauffe dans la ligne d'échange 11. Elle produit également de l'oxygène liquide 35 en cuve qui est pressurisé en 37 à une pression entre 10 et 16 bars et se vaporise dans la ligne d'échange pour former de l'oxygène gazeux sous pression.The low pressure column 33 produces a nitrogen flow 43 which is heated in the exchange line 11. It also produces liquid oxygen in the tank which is pressurized at 37 at a pressure between 10 and 16 bars and vaporizes. in the exchange line to form gaseous oxygen under pressure.

Il est envisageable de vaporiser de l'oxygène liquide à deux pressions différentes de cette manière ou de vaporiser de l'azote liquide ou de l'argon liquide, éventuellement pressurisé en même temps que l'oxygène liquide.It is conceivable to vaporize liquid oxygen at two different pressures in this way or vaporize liquid nitrogen or liquid argon, possibly pressurized together with liquid oxygen.

Dans le cas où deux produits se vaporisent dans la ligne d'échange (ou un produit à deux niveaux de pression différentes), une partie du débit 13 pourra poursuivre son refroidissement jusqu'au bout froid de l'échangeur et ne pas être surpressée par le surpresseur 25. Cette fraction de débit se condensera. En sortie d'échangeur, elle sera détendue dans une vanne et envoyée au système de colonnes, par exemple à la colonne moyenne pression 31.In the case where two products vaporize in the exchange line (or a product with two different pressure levels), part of the flow 13 may continue cooling until the cold end of the exchanger and not be overpressed by the booster 25. This fraction of flow will condense. At the outlet of the exchanger, it will be expanded in a valve and sent to the column system, for example to the medium pressure column 31.

Le surpresseur 15 est entraîné au moins en partie par l'une des deux turbines 17 ou 25, et le surpresseur 25 par l'autre turbine 25 ou 17. Dans chaque cas, il peut également y avoir un moteur ou un générateur couplé au compresseur. Un dispositif de dissipation d'énergie 22, 24, par exemple un frein, préférablement un système à frein d'huile, sera intégré à au mois un des deux systèmes turbine/ compresseur 15/17, 25/27.The booster 15 is driven at least in part by one of the two turbines 17 or 25, and the booster 25 by the other turbine 25 or 17. In each case, there may also be a motor or a generator coupled to the compressor . An energy dissipating device 22, 24, for example a brake, preferably an oil-brake system, will be integrated with at least one of the two turbine / compressor systems 15/17, 25/27.

Claims (14)

  1. Method for separating air by cryogenic distillation in an installation comprising a column system (31, 33), of which one column (31) operating the highest pressure called the average pressure, wherein:
    - all the air is brought to a high pressure, higher than at least 3 bars to the average pressure, purified at this pressure in a purification unit (7)
    - all the air is sent at the release temperature from the purification unit to an exchange line (11);
    - all the air is cooled in the exchange line (11) and a part of the purified air is compressed by means of at least one first compressor (15) at one single stage and sucking at a first intermediate temperature from the exchange line;
    - at least one part of the compressed air in the first compressor is compressed by means of at least one second compressor (25) at one single stage and sucking at a second intermediate temperature from the exchange line and is sent into the exchange line where it is cooled, then liquified, possibly at the cold end of the exchange line and is sent into the column system after release;
    - another part of the purified air under high pressure is cooled in the exchange line then at least in the released part in at least two turbines (17, 27) having one or several start temperatures which is an intermediate temperature or which are intermediate temperatures of the exchange line then sent to the column system to be separated;
    - the work released by the release of air is used at least partially for the cryogenic compression carried out by the first and the second compressor, by coupling the first compressor to one of the two turbines and the second compressor to the other of the two turbines;
    - the liquid oxygen is pressurised at a pressure less than or equal to 16 bars, preferably between 10 and 16 bars, and is vaporised in the exchange line, characterised in that the part of air compressed in the first compressor constitutes between 10% and 35% of the purified air and the part of released air in at least two turbines constitutes between 65% and 90% of the purified air, the part of air compressed in the first compressor is cooled in the exchange line above the second compressor, an energy dissipation device (22, 24) is coupled with at least one of the compressors, the first intermediate temperature differs from the second intermediaite temperature by at most 10°C, and the first and second temperatures are between -145°C and -165°C, and the release temperatures of the first and second compressor (15, 25) are between -110°C and -150°C.
  2. Method according to claim 1, wherein the two turbines (17, 27) have different start temperatures, constituted by a third intermediate temperature and a fourth intermediate temperature of the exchange line.
  3. Method according to claim 2, wherein the third intermediate temperature is less than the first intermediate temperature.
  4. Method according to claim 2 or 3, wherein the third intermediate temperature differs from the fourth intermediate temperature by at most 20°C, or even at most 10°C.
  5. Method according to one of the preceding claims, wherein the first intermediate temperature is higher than the second intermediate temperature.
  6. Method according to one of the claims 1 to 4, wherein the first intermediate temperature is less than or equal to the second intermediate temperature.
  7. Method according to one of the preceding claims, wherein a part of the energy generated is dissipated by at least one of the turbines.
  8. Method according to claim 7, wherein a part of the energy is dissipated by means of an oil brake system (22, 24) connected to the turbine.
  9. Method according to one of the preceding claims, wherein all the air compressed in the first compressor (15) is sent to the second compressor (25).
  10. Method according to one of the preceding claims, wherein all the purified air in the purification unit (7) is sent to the exchange line at the release pressure of the purification unit.
  11. Method according to one of the preceding claims, wherein the system comprises two columns for separating air, comprising a first column (31) and a second column (33) operating at a lower pressure than the first column, and wherein the air released into the two turbines (17, 27) is sent to the first column.
  12. Method according to one of the preceding claims, wherein all the air intended to be separated is sent to the hot end of the exchange line (11).
  13. Method according to one of the preceding claims, wherein the first intermediate temperature is colder than the release temperature of the second compressor (25).
  14. Method according to one of the preceding claims, wherein the release temperatures of the first and of the second compressor (15, 25) are between -125°C and -145°C.
EP12717421.7A 2011-03-31 2012-03-30 Method for producing a gas from pressurised air by means of cryogenic distillation Active EP2691718B1 (en)

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FR1152734A FR2973487B1 (en) 2011-03-31 2011-03-31 PROCESS AND APPARATUS FOR PRODUCING PRESSURIZED AIR GAS BY CRYOGENIC DISTILLATION
PCT/FR2012/050701 WO2012131277A2 (en) 2011-03-31 2012-03-30 Method for producing a gas from pressurised air by means of cryogenic distillation

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PL2963369T3 (en) * 2014-07-05 2018-10-31 Linde Aktiengesellschaft Method and device for the cryogenic decomposition of air
EP3101374A3 (en) * 2015-06-03 2017-01-18 Linde Aktiengesellschaft Method and installation for cryogenic decomposition of air
EP3290843A3 (en) * 2016-07-12 2018-06-13 Linde Aktiengesellschaft Method and device for extracting pressurised nitrogen and pressurised nitrogen by cryogenic decomposition of air
US20220185815A1 (en) 2019-03-06 2022-06-16 Daiichi Sankyo Company, Limited Pyrrolopyrazole derivative

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CN103827613A (en) 2014-05-28
FR2973487B1 (en) 2018-01-26
TR201808938T4 (en) 2018-07-23
FR2973487A1 (en) 2012-10-05
WO2012131277A2 (en) 2012-10-04
US20140007617A1 (en) 2014-01-09
ES2675668T3 (en) 2018-07-11
CN103827613B (en) 2016-03-16
EP2691718A2 (en) 2014-02-05

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