EP0504029B1 - Verfahren zur Herstellung von gasförmigem Sauerstoff unter Druck - Google Patents

Verfahren zur Herstellung von gasförmigem Sauerstoff unter Druck Download PDF

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Publication number
EP0504029B1
EP0504029B1 EP92400600A EP92400600A EP0504029B1 EP 0504029 B1 EP0504029 B1 EP 0504029B1 EP 92400600 A EP92400600 A EP 92400600A EP 92400600 A EP92400600 A EP 92400600A EP 0504029 B1 EP0504029 B1 EP 0504029B1
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EP
European Patent Office
Prior art keywords
pressure
air
oxygen
turbine
column
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.)
Revoked
Application number
EP92400600A
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English (en)
French (fr)
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EP0504029A1 (de
Inventor
Maurice Grenier
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 pour lEtude et lExploitation des Procedes Georges Claude
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Priority claimed from FR9102917A external-priority patent/FR2674011B1/fr
Priority claimed from FR9115935A external-priority patent/FR2685460B1/fr
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP0504029A1 publication Critical patent/EP0504029A1/de
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Anticipated expiration legal-status Critical
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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
    • F25J3/04187—Cooling of the purified feed air by recuperative heat-exchange; Heat-exchange with product streams
    • F25J3/04236—Integration of different exchangers in a single core, so-called integrated cores
    • 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
    • F25J3/04078—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
    • F25J3/04151—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
    • F25J3/04284—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
    • F25J3/04303—Lachmann expansion, i.e. expanded into oxygen producing or low 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.
    • 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
    • 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
    • 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
    • F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
    • 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
    • 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
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/10—Mathematical formulae, modeling, plot or curves; Design methods
    • 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
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/62—Details of storing a fluid in a tank
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S62/00—Refrigeration
    • Y10S62/939—Partial feed stream expansion, air
    • Y10S62/94—High pressure column

Definitions

  • the present invention relates to a process for the production of gaseous oxygen under a high oxygen pressure by air distillation in a double column installation, pumping of liquid oxygen withdrawn from the bottom of the low pressure column, and vaporization of liquid oxygen compressed by heat exchange, in the heat exchange line of the installation, with air brought to a high air pressure, in which all of the air is compressed at high air pressure the air to be distilled; at an intermediate cooling temperature, a fraction of this air is expanded in a turbine, at the pressure of the medium pressure column.
  • the pressures discussed below are absolute pressures.
  • the pressures in the medium pressure column and the low pressure column will be referred to as “medium pressure” and “low pressure”, respectively.
  • Pump processes make it possible to eliminate any gaseous oxygen compressor. To obtain a competitive energy expenditure, it is necessary to compress a large air flow, of the order of 1.5 times the flow of oxygen to be vaporized, to a sufficient pressure allowing it to liquefy against -current oxygen.
  • EP-A-0.024.962 describes a process for vaporizing liquid oxygen, using a Claude turbine with production of liquid nitrogen.
  • EP-A-0.042.676 describes a process for vaporizing liquid oxygen by heat exchange with nitrogen. The process frigories are supplied only by nitrogen expansion.
  • the invention aims to provide a "pump" process requiring only a reduced investment.
  • the process according to the invention is characterized in that the air fraction is in excess with respect to the refrigerating needs of the heat exchange line, the turbine is braked by an air booster and the temperature difference at the hot end of the exchange line by evacuating at least one liquid product from the installation.
  • the abovementioned small temperature differences are obtained, and therefore a low specific energy expenditure, while avoiding the appearance of liquid at the inlet of the wheel of the expansion turbine.
  • the invention also relates to a process for producing gaseous oxygen under a high oxygen pressure of at least Approximately 13 bar by air distillation in a double column installation comprising a low pressure column and a medium pressure column, pumping of liquid oxygen withdrawn from the bottom of the low pressure column, and vaporization of the compressed liquid oxygen by exchange of heat with air brought to a high pressure markedly higher than the medium pressure, in which all of the air to be distilled is compressed to a first high pressure markedly higher than the medium pressure, and a first fraction of this is cooled air under the first high pressure and, at an intermediate cooling temperature, at least part of it is relieved at medium pressure in a turbine before introducing it into the double column, characterized in that the rest of the air is boosted at a second high pressure under the first high pressure, at least part of the compressed air, the flow rate of which is lower than the flow rate of liquid oxygen to be vaporized, being cooled and liquefied then, after expansion, introduced into the double column, the second high pressure being on the one hand
  • the air distillation installation shown in FIG. 1 essentially comprises: an air compressor 1, an apparatus 2 for purifying the compressed air into water and CO 2 by adsorption, this apparatus comprising two bottles of adsorption 2A, 2B, one of which operates in adsorption while the other is being regenerated; a turbine-booster assembly 3 comprising an expansion turbine 4 and a booster 5 whose shafts are coupled; a heat exchanger 6 constituting the heat exchange line of the installation; a double distillation column 7 comprising a medium pressure column 8 surmounted by a low pressure column 9, with a vaporizer-condenser 10 putting the overhead vapor (nitrogen) from column 8 in heat exchange relation with the tank liquid (oxygen) from column 9; a liquid oxygen tank 11, the bottom of which is connected to a liquid oxygen pump 12; and a liquid nitrogen tank 13, the bottom of which is connected to a liquid nitrogen pump 14.
  • This installation is intended to supply, via a pipe 15, gaseous oxygen under a predetermined high pressure, which can be between a few bars and a few tens of bars (in the present specification, the pressures considered are absolute pressures).
  • liquid oxygen withdrawn from the tank of the column 9 via a pipe 16 and stored in the tank 11, is brought to high pressure by the pump 12 in the liquid state, then vaporized and heated --- under this high pressure in passages 17 of exchanger 6.
  • the heat necessary for this vaporization and this reheating, as well as for the reheating and possibly for the vaporization of other fluids drawn from the double column, is supplied by the air to be distilled, under the following conditions.
  • All of the air to be distilled is compressed by compressor 1 at a pressure higher than the medium pressure of column 8 but lower than the high pressure. Then the air, precooled in 18 and cooled to around ambient temperature in 19, is purified in one, 2A for example, of the adsorption bottles, and entirely pressurized at high pressure by the booster 5, which is driven by the turbine 4.
  • the air is then introduced at the hot end of the exchanger 6 and completely cooled to an intermediate temperature. At this temperature, a fraction of the air continues to cool and is liquefied in passages 20 of the exchanger, then is expanded at low pressure in an expansion valve 21 and introduced at an intermediate level into column 9. The rest of the air, or excess air, is expanded to medium pressure in the turbine 4 and then sent directly, via a pipe 22, to the base of the column 8.
  • the low-pressure nitrogen is heated in passages 28 of the exchanger 6 and then discharged via a line 29, while the residual gas, after heating in passages 30 of the exchanger, is used to regenerate an adsorption bottle, the bottle 2B in the example considered, before being evacuated via a pipe 31.
  • part of the medium pressure liquid nitrogen is, after expansion in an expansion valve 32, stored in the reservoir 13, and a production of liquid nitrogen and / or liquid oxygen is supplied via a line 33 (for nitrogen) and / or 34 (for oxygen).
  • this air pressure is the pressure of condensation of the air by heat exchange with the oxygen being vaporized under the high pressure, i.e. - say the pressure for which the knee G of air liquefaction, on the heat exchange diagram (temperatures on the abscissa, quantities of heat exchanged on the ordinate) is located slightly to the right of the vertical stage P of vaporization of oxygen under high pressure ( Figure 3).
  • the temperature difference at the hot end of the exchange line is adjusted by means of the turbine, the suction temperature of which is indicated in A. The irreversibility of the heat exchange is thus minimal.
  • Such air pressure is worn depending on the high pressure, on the left portion C1 of the curve in Figure 2.
  • a high pressure of around 13 bars corresponds in this way to an air pressure of around 30 bars (more precisely, around 28.5 bars).
  • an air pressure of the order of 30 bars is chosen, whatever this high pressure, as indicated on the straight portion C2 of the curve of FIG. 2.
  • nitrogen gas under pressure can, in addition, be produced in an analogous manner, by bringing liquid nitrogen to the desired pressure, by drawing off at the top of the column 8 or by means of a pump such as 14 sucking the liquid nitrogen there or in the reservoir 13, and passing this liquid nitrogen through suitable vaporization-heating passages for the exchanger 6.
  • part of the gaseous oxygen produced can be produced under a different high pressure, by vaporizing it under this pressure in other suitable passages of the exchanger 6.
  • the two high pressures are one less than approximately 13 bars and the other greater than approximately 13 bars
  • all of the air is preferably compressed to approximately 30 bars (or above as explained above), and in any case so that the liquefaction knee G is opposite the vaporization level P1 of the oxygen at the lowest high pressure, and the suction temperature of the turbine (point A) is higher than that of the stage P2 for vaporizing the oxygen at the highest high pressure.
  • a tight heat exchange diagram is obtained, which is very favorable from an energy point of view.
  • a second turbine (not shown) can be provided, de-energizing a fraction of the medium pressure to the low pressure. in the order of 10 to 25% of the treated air flow, the low pressure air thus obtained being blown into column 9. If the high oxygen pressure is less than approximately 13 bars, this fraction can be taken with exhaust of the turbine 4, the temperature of which is sufficiently high. In the opposite case, said fraction is taken from the bottom of the column 8, or taken from the exhaust of the turbine 4 and separated from its liquid phase, and reheated before expansion.
  • This variant makes it possible to increase the production of liquid while slightly reducing the production of liquid at medium pressure, and consequently the operating pressure of the installation, that is to say the high air pressure.
  • the turbine 4 can also be braked by a device other than a booster.
  • the booster 5 is eliminated, and the compressor 1 directly compresses all of the air at the high air pressure defined above.
  • the installation shown in Figure 6 is intended to produce gaseous oxygen at a pressure at least equal to about 13 bars and, in this example, 35 bars. It essentially comprises a double distillation column 41, a main heat exchange line 42, a sub-cooler 43, a compressor single air 44, a blower 45 for air overpressure, an expansion turbine 46 whose wheel is mounted on the same shaft as that of the booster 45, an additional blower 47 driven by an electric motor 48, and a pump liquid oxygen 49.
  • the double column consists, in a conventional manner, of a medium pressure column 50 operating at about 6 bars and surmounted by a low pressure column 51 operating slightly above atmospheric pressure, with, in tank from the latter, a vaporizer-condenser 52 which brings the liquid oxygen from the bottom of the low pressure column into heat exchange relation with the nitrogen at the head of the medium pressure column.
  • the first stream is cooled under this first high pressure in passages 53 of the exchange line 42. Part of this first stream continues to cool, and is liquefied, until the cold end of the exchange line, then is expanded at medium pressure and at low pressure in expansion valves 54 and 55 respectively and distributed between columns 50 and 51. The rest of the first stream left the exchange line at an intermediate temperature T1, expanded in the turbine 46 at medium pressure and introduced at the base of column 50.
  • the second stream of pressurized air is again pressurized, up to a second high pressure of the order of 35 to 40 bars, by the blower 47, then cooled and liquefied in passages 56 of the exchange line, up to 'at the cold end of it.
  • the liquid thus obtained is expanded in an expansion valve 57 and sent to the base of the column 50.
  • blower or "blower” is understood here to mean a single-wheel compressor whose energy expenditure, by the flow rate of treated gas and the compression ratio, is considerably lower than that of the main compressor 44 of the installation. , and for example of the order of 2 to 3% of the latter.
  • the compression ratio of such a blower is generally less than 2.
  • Each of the blowers in question here comprises at its outlet a water or atmospheric air refrigerant, not shown.
  • Liquid oxygen withdrawn from the tank of the column 51 is brought by the pump 49 to the desired production pressure, then vaporized and heated in passages 58 of the exchange line before being evacuated from the installation via a pipe. of production 59.
  • the temperature T1 of turbine inlet 46 is lower than the temperature of the stage 69 of vaporization of oxygen under the production pressure, and the refrigeration balance of the installation is balanced, in order to maintain a small temperature difference at hot end of the exchange line, by drawing off via the lines 64 and / or 65 certain quantities of liquid nitrogen and / or liquid oxygen, as explained above with reference to FIGS. 1 to 5.
  • the pressure of the air at the discharge of compressor 44 is of the order of 23 bars, this equilibrium is obtained for a withdrawal of liquid of the order of 5% of the treated air flow.
  • the aforementioned second high pressure is on the one hand lower than the condensation pressure of the air by heat exchange with the oxygen being vaporized under the production pressure, and on the other hand chosen so that the air brought to this second high pressure begins to condense at a temperature close to T1.
  • This ensures a significant supply of calories in the vicinity of this temperature T1 and allows the turbine 46 to operate in good conditions, that is to say without producing liquid at the entrance of its wheel, while maintaining gaps optimal temperatures, of the order of 2 to 3 ° C, at the two ends of the exchange line as well as at the location of the vaporization bearing 69.
  • the air compressor 44 of the installation directly compresses all of the air at the first high pressure of the order of 23 bars, and a first stream of this air is treated as previously in the passages 53, the turbine 46 and the expansion valve 54 then sent to the base of the column 50.
  • a first blower 70 which, like the blower 45 in Figure 6, is directly coupled to the turbine 46, and a second blower 71 directly coupled to a second expansion turbine 72.
  • the air boosted at 70 passes entirely through the blower 71 then through the passages 56 of the exchange line 42, and part of this air is exited from the exchange line at a temperature T2 higher than the temperature T1 in order to be expanded in the turbine 72.
  • the exhaust of the latter at medium pressure, is connected to the base of the column 50 like that of the turbine 46.
  • the air at the highest pressure which is not expanded in the turbine 72 continues to cool and is liquefied in the passages 56 to the cold end of the exchange line, then is expanded in expansion valves 57 and 57A and distributed between the two columns 50 and 51.
  • the valve 57A replaces the valve 55 in FIG. 6.
  • the temperature T2 can be chosen slightly above the stage 69 of oxygen vaporization. Taking into account the relatively low flow rate of the expanded air in the turbine 72, an air cooling curve is obtained which is roughly parallel to the warming curve for liquid oxygen and nitrogen gas at the temperature T2 knee 73 of condensation or pseudo-condensation of the air under the highest pressure.
  • an air flow taken between the two blowers 70 and 71, is cooled and liquefied in additional passages 74 of the exchange line, until the cold end thereof, then expanded to the medium pressure in an expansion valve 75 and sent to the base of the column 50.
  • the turbine 72 can be supplied with air flowing in the passages 74, which are then interrupted at the temperature T2.
  • the expansion valve 75 is then eliminated, and it is the air circulating in the passages 56 which is entirely liquefied in the passages 56 and then expanded at medium pressure in the expansion valve 57.
  • the highest air pressure can be increased by passing the air coming from the blower 71 into an additional blower 76 driven by an electric motor 77.
  • the installation represented in FIG. 11 is a variant of that of FIG. 8. It differs from it only in that the exhaust of the two turbines 46 and 72 opens into a phase separator 78 of which the liquid and a part of the vapor phase are sent to the bottom of the column 50 while the rest of the vapor phase, after partial reheating in passages 79 of the exchange line, is expanded at low pressure in an additional turbine 80 braked by an appropriate brake 81. The low pressure air leaving the turbine 80 is blown into the column 51 via a pipe 82.
  • This solution is applicable when the oxygen product gas under pressure is of low purity (less than 99.5%).

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Claims (17)

  1. Verfahren zur Herstellung gasförmigen Sauerstoffs unter hohem Sauerstoffdruck durch Destillation von Luft in einer Doppelkolonnen-Anlage (7), Pumpen (12) von am Sumpf der Niederdruckkolonne (9) entnommenem, flüssigem Sauerstoff und Verdampfen (6) des verdichteten, flüssigen Sauerstoffs durch in einer Wärmeaustauschleitung (6) der Vorrichtung erfolgenden Wärmeaustausch gegen auf einen hohen Luftdruck gebrachte Luft, bei dem die gesamte zu destillierende Luft auf den hohen Luftdruck gebracht wird; und ein Teil dieser Luft bei einer Zwischenkühltemperatur in einer Turbine (4) auf den Druck der Mitteldruckkolonne (8) entspannt wird; dadurch gekennzeichnet, daß dieser Teil der Luft, bezogen auf den Kältebedarf der Wärmeaustauschleitung, überschüssig ist, daß die Turbine (4) durch einen Nachverdichter (5) gebremst wird, und daß der Temperaturunterschied am warmen Ende der Austauschleitung durch Entnahme zumindest eines Flüssigprodukts aus der Vorrichtung verringert wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß für einen hohen Sauerstoffdruck kleiner als etwa 13 bar als hoher Luftdruck der aus dem Wärmeaustausch mit dem Sauerstoff im Verlauf der Verdampfung unter dem hohen Sauerstoffdruck resultierende Luftkondensationsdruck gewählt wird.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß für einen hohen Sauerstoffdruck größer als etwa 13 bar als hoher Luftdruck unabhängig von dem hohen Sauerstoffdruck ein Druck gewählt wird, der kleiner als der aus dem Wärmeaustausch mit dem Sauerstoff im Verlauf der Verdampfung unter dem hohen Sauerstoffdruck resultierende Luftkondensationsdruck ist und zumindest etwa 30 bar beträgt.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß der hohe Luftdruck in der Nähe von 30 bar liegt und die entnommene Flüssigproduktmenge etwa 25% der Produktion gasförmigen Sauerstoffs unter dem hohen Sauerstoffdruck beträgt.
  5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß zur Herstellung gasförmigen Sauerstoffs unter zwei unterschiedlich hohen, unterhalb bzw. oberhalb von etwa 13 bar liegenden Sauerstoffdrücken die beiden durch Wärmeaustausch gegen komprimierte Luft auf einem einzigen, hohen Luftdruck, der zum einen kleiner als der aus dem Wärmeaustausch gegen den Sauerstoff im Verlauf der Verdampfung unter dem höheren Sauerstoffdruck resultierende Luftkondensationsdruck ist, zum anderen zumindest etwa 30 bar beträgt und insbesondere gleich einem hohen Luftdruck in der Nähe von 30 bar ist, sowie in jedem Fall größer als der aus dem Wärmeaustausch gegen den Sauerstoff im Verlauf der Verdampfung unter dem niedrigeren Sauerstoffdruck resultierende Luftkondensationsdruck ist, verdichteten Flüssigsauerstoffströme verdampft werden.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Luft in zwei Stufen verdichtet wird, wobei die letzte Stufe mittels des durch die Turbine (4) angetriebenen Nachverdichters (5) verwirklicht wird.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß in der Wärmeaustauschleitung (6) durch Wärmeaustausch gegen die Luft auf dem hohen Luftdruck auch der aus der Doppelkolonne (7) entnommene und gegebenenfalls durch eine Pumpe (14) verdichtete, unter Druck stehende, flüssige Stickstoff verdampft wird.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß ein Teil der Mitteldruckluft, gegebenenfalls nach Abtrennung ihrer flüssigen Phase, in einer zweiten Turbine auf den niedrigen Druck entspannt und in die Niederdruckkolonne (9) eingeblasen wird.
  9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß die auf den niedrigen Druck entspannte Luft am Sumpf der Mitteldruckkolonne (8) entnommen wird.
  10. Verfahren zur Herstellung gasförmigen Sauerstoffs unter hohem Sauerstoffdruck von zumindest etwa 13 bar durch Destillation von Luft in einer eine Niederdruckkolonne (51) und eine Mitteldruckkolonne (50) umfassenden Doppelkolonnen-Anlage, Pumpen (49) von am Sumpf der Niederdruckkolonne (51) entnommenem, flüssigem Sauerstoff und Verdampfen (42) des verdichteten, flüssigen Sauerstoffs durch Wärmeaustausch gegen auf einen hohen Luftdruck, der deutlich größer ist als der mittlere Druck, gebrachte Luft, bei dem die gesamte zu destillierende Luft auf einen ersten hohen Luftdruck, der deutlich größer ist als der mittlere Druck, gebracht wird; ein erster Teil dieser Luft unter dem ersten hohen Druck abgekühlt (53) und auf einer Zwischenkühltemperatur zumindest ein Teil derselben in einer Turbine (46) auf den Druck der Mitteldruckkolonne (8) entspannt wird, bevor er in die Doppelkolonne (41) eingeleitet wird; dadurch gekennzeichnet, daß der Rest der Luft unter dem ersten hohen Druck auf einen zweiten hohen Druck nachverdichtet wird, zumindest ein Teil der nachverdichteten Luft, deren Menge kleiner ist als die Menge zu verdampfenden, flüssigen Sauerstoffs, abgekühlt und verflüssigt (56) wird, dann, nach Entspannung (57, 57A), in die Doppelkolonne (41) eingeleitet wird, wobei der zweite hohe Druck zum einen kleiner als der aus dem Wärmeaustausch gegen den Sauerstoff im Verlauf der Verdampfung unter dem höheren Sauerstoffdruck resultierende Kondensations- oder Pseudo-Kondensationsluftdruck ist und zumindest etwa 30 bar beträgt, und zum anderen so gewählt ist, daß die Kondensation oder Pseudo-Kondensation der Luft unter diesem zweiten hohen Druck in der Nähe der Einlaßtemperatur der Turbine (46) stattfindet, und der Temperaturunterschied am warmen Ende einer Wärmeaustauschleitung (6) durch Entnahme zumindest eines Flüssigprodukts (64, 65) aus der Vorrichtung verringert wird.
  11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß der Nachverdichtungsdruck durch einen Verdichter (47) mit einem Verdichtungsverhältnis kleiner als 2 erzeugt wird.
  12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß der Verdichter (47) durch eine externe Energiequelle (48) (Fig. 1) angetrieben wird.
  13. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß der Nachverdichtungsdruck durch zwei in Reihe angeordnete und jeweils mit einer Entspannungsturbine (46, 72) gekuppelte Verdichter (70, 71) erzeugt wird, wobei der erste Verdichter (70) mit der Turbine (46) zur Entspannung der Luft unter dem ersten hohen Druck gekuppelt und der zweite Verdichter (71) mit einer zweiten Turbine (72) zur Entspannung eines Teils der nachverdichteten Luft gekuppelt ist, und wobei die Einlaßtemperatur der zweiten Turbine (72) größer ist als die der ersten Turbine (46) (Fig. 10 und 11).
  14. Verfahren nach Anspruch 13, dadurch gekennzeichnet, daß eine Luftmenge zwischen den beiden Verdichtern (70, 71) entnommen und, zumindest teilweise, abgekühlt, verflüssigt (74) und nach Entspannung (75) dann in die Doppelkolonne (41) eingeleitet wird (Fig. 10).
  15. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß der Nachverdichtungsdruck durch einen mit der Turbine (46) zum Entspannen der Luft unter dem ersten hohen Druck gekuppelten Verdichter (70) erzeugt wird, wobei ein erster Teil der nachverdichteten Luft in einer zweiten Turbine (72) entspannt wird, die mit einem zweiten Verdichter (71) gekoppelt ist, welcher durch den Rest der nachverdichteten Luft gespeist wird, und wobei die aus dem zweiten Verdichter (71) austretende Luft gekühlt und verflüssigt und nach Entspannung (57) dann in die Doppelkolonne (41) eingeleitet wird (Fig. 10).
  16. Verfahren nach einem der Ansprüche 13 bis 15, dadurch gekennzeichnet, daß die aus dem zweiten Verdichter austretende Luft durch einen durch ein externe Energiequelle (77) (Fig. 10) angetriebenen, dritten Verdichter (76) erneut nachverdichtet wird.
  17. Verfahren nach einem der Ansprüche 10 bis 16, dadurch gekennzeichnet, daß ein Teil der gasförmigen Phase der aus der bzw. jeder der Turbinen (46, 72) austretenden Luft in einer zusätzlichen Turbine (80) auf den niedrigen Druck entspannt und dann in die Niederdruckkolonne (51) eingeblasen wird.
EP92400600A 1991-03-11 1992-03-09 Verfahren zur Herstellung von gasförmigem Sauerstoff unter Druck Revoked EP0504029B1 (de)

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FR9102917A FR2674011B1 (fr) 1991-03-11 1991-03-11 Procede et installation de production d'oxygene gazeux sous pression.
FR9102917 1991-03-11
FR9115935 1991-12-20
FR9115935A FR2685460B1 (fr) 1991-12-20 1991-12-20 Procede et installation de production d'oxygene gazeux sous pression par distillation d'air

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EP0504029B1 true EP0504029B1 (de) 1996-10-23

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EP3101374A3 (de) 2015-06-03 2017-01-18 Linde Aktiengesellschaft Verfahren und anlage zur tieftemperaturzerlegung von luft
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DE69214693D1 (de) 1996-11-28
ES2093799T3 (es) 1997-01-01
ZA921777B (en) 1992-11-25
KR920017943A (ko) 1992-10-21
JPH0579753A (ja) 1993-03-30
CA2062506A1 (fr) 1992-09-12
AU1215792A (en) 1992-09-17
JP2909678B2 (ja) 1999-06-23
DE69214693T2 (de) 1997-02-20
US5329776A (en) 1994-07-19
EP0504029A1 (de) 1992-09-16
AU655630B2 (en) 1995-01-05
CA2062506C (fr) 2004-07-20

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