EP0576314B1 - Process and installation for the production of gaseous oxygen under pressure - Google Patents

Process and installation for the production of gaseous oxygen under pressure Download PDF

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Publication number
EP0576314B1
EP0576314B1 EP93401395A EP93401395A EP0576314B1 EP 0576314 B1 EP0576314 B1 EP 0576314B1 EP 93401395 A EP93401395 A EP 93401395A EP 93401395 A EP93401395 A EP 93401395A EP 0576314 B1 EP0576314 B1 EP 0576314B1
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EP
European Patent Office
Prior art keywords
air
pressure
turbine
column
compressed
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German (de)
French (fr)
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EP0576314A1 (en
EP0576314B2 (en
Inventor
Maurice Grenier
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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
    • 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
    • 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
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • 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
    • F25J3/04193—Division of the main heat exchange line in consecutive sections having different functions
    • F25J3/042—Division of the main heat exchange line in consecutive sections having different functions having an intermediate feed connection
    • 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
    • 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.
    • 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
    • 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
    • F25J3/04642—Recovering noble gases from air
    • F25J3/04648—Recovering noble gases from air argon
    • F25J3/04654—Producing crude argon in a crude argon column
    • F25J3/04666—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system
    • F25J3/04672—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system having a top condenser
    • F25J3/04678—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system having a top condenser cooled by oxygen enriched liquid from high pressure column bottoms
    • 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
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/40—Processes or apparatus involving steps for recycling of process streams the recycled stream being air
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/10—Mathematical formulae, modeling, plot or curves; Design methods
    • 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
    • Y10S62/912—External refrigeration system
    • Y10S62/913—Liquified gas

Definitions

  • the present invention relates to a process for the production of gaseous oxygen under pressure by air distillation in an installation comprising a heat exchange line and a double distillation column which itself comprises a first column, called the medium pressure column. , operating under medium pressure, and a second column, called low pressure column, operating under low pressure, pumping liquid oxygen withdrawn from the tank of the low pressure column, and vaporization of the compressed oxygen by heat exchange with compressed air at a high air pressure, all of the air to be treated being compressed at a first pressure P1 significantly higher than the medium pressure, the air at pressure P1 is divided into two parts, the first being cooled and the second part being overpressed to a second high pressure P2 and cooled, at least most of the separated oxygen being withdrawn in the l state iquid from the low pressure column, compressed by a pump to at least a first vaporization pressure at which it vaporizes by condensation of air at one of said high pressures P1, P2, and vaporized by condensation of air at one of these pressures.
  • condensation means either a condensation or a vaporization proper, or a pseudo-condensation or a pseudo-vaporization, depending on whether the pressures in question are subcritical or supercritical.
  • the object of the invention is to provide a method using a single air compressor and having high overall thermodynamic efficiency.
  • the invention also relates to an installation for producing gaseous oxygen under pressure for the implementation of the process described above, of the type comprising a double air distillation column comprising a column, called a low pressure column, operating under low pressure, and a column, called medium pressure column operating under medium pressure, a liquid oxygen compression pump drawn from the bottom of the low pressure column, compression means for bringing the air to be distilled to a high air pressure significantly higher than the medium pressure, and a heat exchange line for bringing the high pressure air and compressed liquid oxygen into heat exchange relationship, the compression means comprising a compressor for supplying all of the air to be distilled at a first high pressure P1 significantly higher than the medium pressure, and means for overpressuring a fraction of the air under this p first high pressure to a second high pressure P2, characterized in that these overpressure means comprise at least two blowers in series each coupled to an expansion turbine, one blower being coupled to an air expansion turbine under the first high pressure P1 and another blower being coupled to a second turbine for expanding part of the compressed air, and in that
  • the installation shown in FIG. 1 is intended to produce gaseous oxygen under two different pressures, gaseous nitrogen under two different pressures, liquid oxygen and liquid nitrogen.
  • the installation essentially comprises a double distillation column 1, a heat exchange line 2, a main air compressor 3, two blowers in series 4 and 5 provided at the outlet with a refrigerant 6, a "hot” turbine 7 , a “cold” turbine 8, two liquid oxygen pumps 9, 10 and a liquid nitrogen pump 11.
  • Double column 1 includes a column medium pressure operating at 5 to 6 bar, a low pressure column 13 of the "minaret" type operating slightly above atmospheric pressure, a vaporizer-condenser 14 which puts the overhead vapor (nitrogen) from column 12 into heat exchange relationship with the tank liquid (oxygen) of column 13, and an auxiliary column 15 for the production of impure argon coupled to column 13.
  • the fan wheel 4 is rigidly coupled to that of the turbine 8, and, similarly, the fan wheel 5 is rigidly coupled to that of the turbine 7.
  • the air to be distilled is completely compressed by the compressor 3 at a pressure P1 of the order of 25 to 35 bars and purified in water and carbon dioxide in an adsorber 21, then divided into two streams.
  • the first stream at pressure P1, is cooled to an intermediate temperature T1 between 0 ° C and - 60 ° C. Part of this first stream continues to cool, is liquefied, then is expanded at medium pressure in an expansion valve and sent to column 12 via a line 22. The rest of the first stream is taken out of the exchange line at temperature T1, expanded at medium pressure in turbine 7, reintroduced into the exchange line, cooled and liquefied, then sent to column 12 via a line 23.
  • the rest of the air leaving the adsorber 21 is boosted in two stages by the blowers 4 and 5, up to a pressure P2 of the order of 35 to 50 bars, precooled in 6 and then cooled in the line of exchange up to a second intermediate temperature T2 much lower than T1 and between -80 ° C and -130 ° C. Part of this air continues to cool, is liquefied, then is expanded at medium pressure in an expansion valve and introduced into column 12 via line 22 above. The rest of the air at pressure P2 is taken out of the exchange line at temperature T2, expanded to medium pressure in the turbine 8 and introduced into the column 12 via the above-mentioned pipe 23.
  • the exchange diagram includes a curve C1 corresponding to all of the heated fluids, and a curve C2 corresponding to the air treated during cooling.
  • the installation may include a third turbine 30, for example braked by an alternator 31, adapted to relieve some of the medium pressure air coming from the turbine at low pressure. 7.
  • the exhaust of the turbine 30 is connected to an intermediate point of the column 13 or to the pipe carrying the residual impure nitrogen.
  • the inlet of the turbine 30 is at a temperature of from -100 ° C to about -150 ° C.
  • Such a low pressure turbine is advantageous in two cases: on the one hand, to exploit the low separation energy when the oxygen is produced at a purity of between 85% and 98%, by increasing the production of liquid without appreciable reduction in the oxygen extraction yield; on the other hand, to increase the production of liquid at the expense of that of oxygen. If, as shown, the installation produces argon, it is preferable to send the low pressure air into impure nitrogen to maintain a good extraction yield of argon. Otherwise, this low pressure air can be blown into column 13.
  • the diagram of Figure 4 differs from that of Figure 1 only by the assembly of the turbines 7 and 8.
  • it is the "hot” turbine 7 which is supplied with air at the highest pressure P2
  • the "cold” turbine 8 is supplied with air at pressure P1.
  • the turbine 7 escapes a pressure P3 greater than the medium pressure and, in practice, between this medium pressure and the pressure P1.
  • the air at pressure P3 is cooled and liquefied in the exchange line, by vaporization of oxygen, then expanded at medium pressure in an expansion valve 34 before being sent to column 12. This arrangement is particularly interesting for an oxygen pressure between 3 bars and 8 bars.
  • the exchange line 2 of the installation includes air cooling passages at three different pressures.
  • One or more of these pressures can be used to condense the air by counter-current vaporization, with a small temperature difference of around 2 ° C, of at least most of the separated, compressed oxygen. in the liquid state at a corresponding pressure and vaporized under this pressure, additional oxygen at another pressure and / or nitrogen which may optionally be further compressed in the liquid state and vaporized in line d exchange 2.
  • the pressures P1 and P3 can be chosen at will, and the pressure P2 can be adjusted by adjusting the turbinated air flow rates and the pressure P1, this results in a very great flexibility in the choice of the vaporization pressures of oxygen and possibly nitrogen.
  • the flow of this air can be adjusted to the flow of oxygen to be vaporized, that is to say that this air flow is adjusted between 20% 30% of the treated air flow; such a flow rate through the "hot" turbine 7 indeed makes it possible to remain in the vicinity of the thermodynamic optimum.
  • the installation produces a fraction of oxygen and nitrogen in liquid form with excellent specific energy due to the use of two expansion turbines at very different inlet temperatures.

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Description

La présente invention est relative à un procédé de production d'oxygène gazeux sous pression par distillation d'air dans une installation comprenant une ligne d'échange thermique et une double colonne de distillation qui comporte elle-même une première colonne, dite colonne moyenne pression, fonctionnant sous une moyenne pression, et une seconde colonne, dite colonne basse pression, fonctionnant sous une basse pression, pompage d'oxygène liquide soutiré en cuve de la colonne basse pression, et vaporisation de l'oxygène comprimé par échange de chaleur avec de l'air comprimé à une haute pression d'air, la totalité de l'air à traiter étant comprimée à une première pression P1 nettement supérieure à la moyenne pression, l'air à la pression P1 est divisé en deux parties, la première étant refroidie et la deuxième partie étant surpressée à une seconde haute pression P2 et refroidie, la majeure partie au moins de l'oxygène séparé étant soutirée à l'état liquide de la colonne basse pression, comprimée par une pompe à au moins une première pression de vaporisation à laquelle il se vaporise par condensation d'air à l'une desdites hautes pressions P1, P2, et vaporisé par condensation d'air à une de ces pressions.The present invention relates to a process for the production of gaseous oxygen under pressure by air distillation in an installation comprising a heat exchange line and a double distillation column which itself comprises a first column, called the medium pressure column. , operating under medium pressure, and a second column, called low pressure column, operating under low pressure, pumping liquid oxygen withdrawn from the tank of the low pressure column, and vaporization of the compressed oxygen by heat exchange with compressed air at a high air pressure, all of the air to be treated being compressed at a first pressure P1 significantly higher than the medium pressure, the air at pressure P1 is divided into two parts, the first being cooled and the second part being overpressed to a second high pressure P2 and cooled, at least most of the separated oxygen being withdrawn in the l state iquid from the low pressure column, compressed by a pump to at least a first vaporization pressure at which it vaporizes by condensation of air at one of said high pressures P1, P2, and vaporized by condensation of air at one of these pressures.

Un procédé de ce type est connu de EP-A-0.024.962.A process of this type is known from EP-A-0.024.962.

Les pressions dont il est question ci-dessous sont des pressions absolues. De plus, on entend par "condensation" et "vaporisation" soit une condensation ou une vaporisation proprement dite, soit une pseudo-condensation ou une pseudo-vaporisation, selon que les pressions en question sont subcritiques ou supercritiques.The pressures discussed below are absolute pressures. In addition, the expression "condensation" and "vaporization" means either a condensation or a vaporization proper, or a pseudo-condensation or a pseudo-vaporization, depending on whether the pressures in question are subcritical or supercritical.

Les procédés de ce type, dits "procédés à pompe", permettent de supprimer tout compresseur d'oxygène gazeux. Pour obtenir une dépense d'énergie acceptable, il est nécessaire de comprimer un débit d'air important, de l'ordre de 1,5 fois le débit d'oxygène à vaporiser, jusqu'à une pression suffisante permettant de le liquéfier à contre-courant de l'oxygène. Pour ceci, la technique habituelle, illustrée dans EP-A-0.024.962, utilise deux compresseurs en série, le second ne traitant que la fraction de l'air destinée à la vaporisation de l'oxygène liquide, ce qui accroît sensiblement l'investissement de l'installation.Processes of this type, called "pump processes", make it possible to eliminate any gaseous oxygen compressor. To obtain an acceptable 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. For this, the usual technique, illustrated in EP-A-0.024.962, uses two compressors in series, the second only treating the fraction of air intended for the vaporization of liquid oxygen, which appreciably increases the installation investment.

L'invention a pour but de fournir un procédé utilisant un compresseur d'air unique et ayant une grande efficacité thermodynamique globale.The object of the invention is to provide a method using a single air compressor and having high overall thermodynamic efficiency.

A cet effet, l'invention a pour objet un procédé du type précité, caractérisé en ce que :

  • la première partie de cet air est refroidie jusqu'à une première température intermédiaire T1, où une première fraction est détendue dans une première turbine, tandis que le reste est refroidi et liquéfié, détendu et introduit dans la colonne moyenne pression ;
  • la deuxième partie est refroidie jusqu'à une seconde température intermédiaire T2, où un premier débit est détendu dans une seconde turbine, tandis que le reste de cette deuxième partie est refroidi et liquéfié, détendu et introduit dans la colonne moyenne pression ;
    • éventuellement la pression d'échappement de l'une des turbines est réglée à une pression P3 comprise entre ladite première haute pression P1 et la moyenne pression,
    • et l'oxygène comprimé se vaporise par condensation d'air à une ou plusieurs des pressions P1, P2, P3.
To this end, the subject of the invention is a method of the aforementioned type, characterized in that:
  • the first part of this air is cooled to a first intermediate temperature T1, where a first fraction is expanded in a first turbine, while the rest is cooled and liquefied, expanded and introduced into the medium pressure column;
  • the second part is cooled to a second intermediate temperature T2, where a first flow is expanded in a second turbine, while the rest of this second part is cooled and liquefied, expanded and introduced into the medium pressure column;
    • optionally the exhaust pressure of one of the turbines is adjusted to a pressure P3 between said first high pressure P1 and the medium pressure,
    • and the compressed oxygen is vaporized by condensation of air at one or more of the pressures P1, P2, P3.

Suivant d'autres caractéristiques :

  • les températures intermédiaires T1 et T2 sont choisies l'une entre 0°C et -60°C environ et l'autre entre -80°C et -130°C environ ;
  • le débit d'air alimentant la turbine chaude est de l'ordre de 20 à 30 % du débit d'air traité ;
  • l'oxygène liquide additionnel soutiré de la colonne basse pression est comprimé par pompe à au moins une seconde pression de vaporisation et vaporisé à cette ou à ces pressions dans la ligne d'échange thermique ;
  • l'azote liquide est soutiré de la double colonne, comprimé par pompe à au moins une pression de vaporisation d'azote, et vaporisé à cette ou à ces pressions dans la ligne d'échange thermique ;
  • on détend à la basse pression dans une troisième turbine une partie au moins de l'air issu de la première ou de la seconde turbine, l'air issu de la troisième turbine étant introduit dans la colonne basse pression ou dans le gaz résiduaire évacué de la partie supérieure de cette colonne ;
  • on détend dans la troisième turbine la totalité dudit air issu de la première ou de la deuxième turbine, cet air se trouvant sensiblement à la moyenne pression, ainsi qu'un débit complémentaire d'air soutiré en cuve de la colonne moyenne pression ;
  • la surpression de l'air est réalisée au moyen d'au moins deux soufflantes en série couplées chacune à l'une des turbines.
According to other characteristics:
  • the intermediate temperatures T1 and T2 are chosen one between 0 ° C and -60 ° C approximately and the other between -80 ° C and -130 ° C approximately;
  • the air flow supplying the hot turbine is of the order of 20 to 30% of the treated air flow;
  • the additional liquid oxygen withdrawn from the low pressure column is compressed by pump to at least a second vaporization pressure and vaporized at this or these pressures in the heat exchange line;
  • the liquid nitrogen is withdrawn from the double column, compressed by pump to at least one nitrogen vaporization pressure, and vaporized at this or these pressures in the heat exchange line;
  • at least part of the air from the first or second turbine is expanded at low pressure in a third turbine, the air from the third turbine being introduced into the low pressure column or into the waste gas discharged from the top of this column;
  • all of said air from the first or second turbine is expanded in the third turbine, this air being substantially at medium pressure, as well as an additional flow of air drawn from the bottom of the medium pressure column;
  • the air pressure is achieved by means of at least two blowers in series each coupled to one of the turbines.

L'invention a également pour objet une installation de production d'oxygène gazeux sous pression pour la mise en oeuvre du procédé décrit ci-dessus, du type comprenant une double colonne de distillation d'air comprenant une colonne, dite colonne basse pression, fonctionnant sous une basse pression, et une colonne, dite colonne moyenne pression fonctionnant sous une moyenne pression, une pompe de compression d'oxygène liquide soutiré en cuve de la colonne basse pression, des moyens de compression pour amener de l'air à distiller à une haute pression d'air nettement supérieure à la moyenne pression, et une ligne d'échange thermique pour mettre en relation d'échange thermique l'air à la haute pression et l'oxygène liquide comprimé, les moyens de compression comprenant un compresseur pour amener la totalité de l'air à distiller à une première haute pression P1 nettement supérieure à la moyenne pression, et des moyens de surpression d'une fraction de l'air sous cette première haute pression jusqu'à une seconde haute pression P2,
   caractérisée en ce que ces moyens de surpression comprennent au moins deux soufflantes en série couplées chacune à une turbine de détente, une soufflante étant couplée à une turbine de détente d'air sous la première haute pression P1 et une autre soufflante étant couplée à une seconde turbine de détente d'une partie de l'air surpressé, et en ce que la ligne d'échange thermique comprend des passages de refroidissement de l'air issu de la turbine ayant la plus haute température d'admission et/ou la température T1 d'admission de l'une des deux turbines est comprise entre 0°C et 60°C environ, tandis que celle T2 de l'autre turbine est comprise entre -80°C et -130°C.The invention also relates to an installation for producing gaseous oxygen under pressure for the implementation of the process described above, of the type comprising a double air distillation column comprising a column, called a low pressure column, operating under low pressure, and a column, called medium pressure column operating under medium pressure, a liquid oxygen compression pump drawn from the bottom of the low pressure column, compression means for bringing the air to be distilled to a high air pressure significantly higher than the medium pressure, and a heat exchange line for bringing the high pressure air and compressed liquid oxygen into heat exchange relationship, the compression means comprising a compressor for supplying all of the air to be distilled at a first high pressure P1 significantly higher than the medium pressure, and means for overpressuring a fraction of the air under this p first high pressure to a second high pressure P2,
characterized in that these overpressure means comprise at least two blowers in series each coupled to an expansion turbine, one blower being coupled to an air expansion turbine under the first high pressure P1 and another blower being coupled to a second turbine for expanding part of the compressed air, and in that the heat exchange line comprises passages for cooling the air coming from the turbine having the highest inlet temperature and / or the temperature T1 intake of one of the two turbines is between 0 ° C and 60 ° C, while that T2 of the other turbine is between -80 ° C and -130 ° C.

Des exemples de mise en oeuvre de l'invention vont maintenant être décrits en regard des dessins annexés, sur lesquels :

  • la figure 1 représente schématiquement une installation de production d'oxygène gazeux conforme à l'invention ;
  • la figure 2 est un diagramme d'échange thermique, obtenu par calcul, correspondant à cette installation ; et
  • les figures 3 et 4 représentent schématiquement deux autres modes de réalisation de l'installation suivant l'invention.
Examples of implementation of the invention will now be described with reference to the accompanying drawings, in which:
  • FIG. 1 schematically represents an installation for producing gaseous oxygen in accordance with the invention;
  • Figure 2 is a heat exchange diagram, obtained by calculation, corresponding to this installation; and
  • Figures 3 and 4 schematically show two other embodiments of the installation according to the invention.

L'installation représentée sur la figure 1 est destinée à produire de l'oxygène gazeux sous deux pressions différentes, de l'azote gazeux sous deux pressions différentes, de l'oxygène liquide et de l'azote liquide.The installation shown in FIG. 1 is intended to produce gaseous oxygen under two different pressures, gaseous nitrogen under two different pressures, liquid oxygen and liquid nitrogen.

L'installation comprend essentiellement une double colonne de distillation 1, une ligne d'échange thermique 2, un compresseur d'air principal 3, deux soufflantes en série 4 et 5 munies en sortie d'un réfrigérant 6, une turbine "chaude" 7, une turbine "froide" 8, deux pompes d'oxygène liquide 9, 10 et une pompe d'azote liquide 11.The installation essentially comprises a double distillation column 1, a heat exchange line 2, a main air compressor 3, two blowers in series 4 and 5 provided at the outlet with a refrigerant 6, a "hot" turbine 7 , a "cold" turbine 8, two liquid oxygen pumps 9, 10 and a liquid nitrogen pump 11.

La double colonne 1 comprend une colonne moyenne pression fonctionnant sous 5 à 6 bars, une colonne basse pression 13 du type "à minaret" fonctionnant un peu au-dessus de la pression atmosphérique, un vaporiseur-condenseur 14 qui met la vapeur de tête (azote) de la colonne 12 en relation d'échange thermique avec le liquide de cuve (oxygène) de la colonne 13, et une colonne auxiliaire 15 de production d'argon impur couplée à la colonne 13.Double column 1 includes a column medium pressure operating at 5 to 6 bar, a low pressure column 13 of the "minaret" type operating slightly above atmospheric pressure, a vaporizer-condenser 14 which puts the overhead vapor (nitrogen) from column 12 into heat exchange relationship with the tank liquid (oxygen) of column 13, and an auxiliary column 15 for the production of impure argon coupled to column 13.

On retrouve les conduites classiques 16 de remontée de "liquide riche" (air enrichi en oxygène) de la cuve de la colonne 12 à un point intermédiaire de la colonne 15 et/ou au condenseur de tête de la colonne 15, 17 de remontée de "liquide pauvre inférieur" (azote impur) d'un point intermédiaire de la colonne 12 à un point intermédiaire de la colonne 13, 18 de remontée de "liquide pauvre supérieur" (azote pur) du sommet de la colonne 12 au sommet de la colonne 13, les conduites 16, 17 et 18 étant chacune équipées d'une vanne de détente. Les liquides véhiculés par ces trois conduites sont sous-refroidis dans la partie froide de la ligne d'échange 2. Un embranchement 19 de la conduite 18, équipé d'une vanne de détente, conduit à un stockage d'azote liquide 20.We find the conventional lines 16 for raising "rich liquid" (oxygen-enriched air) from the tank of column 12 to an intermediate point of column 15 and / or to the head condenser of column 15, 17 for raising "lower lean liquid" (impure nitrogen) from an intermediate point in column 12 to an intermediate point in column 13, 18 for raising "upper lean liquid" (pure nitrogen) from the top of column 12 to the top of the column 13, the lines 16, 17 and 18 each being equipped with an expansion valve. The liquids carried by these three pipes are sub-cooled in the cold part of the exchange line 2. A branch 19 of the pipe 18, equipped with an expansion valve, leads to a storage of liquid nitrogen 20.

La roue de la soufflante 4 est rigidement accouplée à celle de la turbine 8, et, de même, la roue de la soufflante 5 est rigidement accouplée à celle de la turbine 7.The fan wheel 4 is rigidly coupled to that of the turbine 8, and, similarly, the fan wheel 5 is rigidly coupled to that of the turbine 7.

En fonctionnement, l'air à distiller est comprimé en totalité par le compresseur 3 à une pression P1 de l'ordre de 25 à 35 bars et épuré en eau et en anhydride carbonique dans un adsorbeur 21, puis divisé en deux courants.In operation, the air to be distilled is completely compressed by the compressor 3 at a pressure P1 of the order of 25 to 35 bars and purified in water and carbon dioxide in an adsorber 21, then divided into two streams.

Le premier courant, à la pression P1, est refroidi jusqu'à une température intermédiaire T1 comprise entre 0°C et - 60°C. Une partie de ce premier courant poursuit son refroidissement, est liquéfiée, puis est détendue à la moyenne pression dans une vanne de détente et envoyée dans la colonne 12 via une conduite 22. Le reste du premier courant est sorti de la ligne d'échange à la température T1, détendu à la moyenne pression dans la turbine 7, réintroduit dans la ligne d'échange, refroidi et liquéfié, puis envoyé dans la colonne 12 via une conduite 23.The first stream, at pressure P1, is cooled to an intermediate temperature T1 between 0 ° C and - 60 ° C. Part of this first stream continues to cool, is liquefied, then is expanded at medium pressure in an expansion valve and sent to column 12 via a line 22. The rest of the first stream is taken out of the exchange line at temperature T1, expanded at medium pressure in turbine 7, reintroduced into the exchange line, cooled and liquefied, then sent to column 12 via a line 23.

Le reste de l'air sortant de l'adsorbeur 21 est surpressé en deux stades par les soufflantes 4 et 5, jusqu'à une pression P2 de l'ordre de 35 à 50 bars, prérefroidi en 6 puis refroidi dans la ligne d'échange jusqu'à une seconde température intermédiaire T2 nettement inférieure à T1 et comprise entre -80°C et -130°C. Une partie de cet air poursuit son refroidissement, est liquéfiée, puis est détendue à la moyenne pression dans une vanne de détente et introduite dans la colonne 12 via la conduite 22 précitée. Le reste de l'air à la pression P2 est sorti de la ligne d'échange à la température T2, détendu à la moyenne pression dans la turbine 8 et introduit dans la colonne 12 via la conduite 23 précitée.The rest of the air leaving the adsorber 21 is boosted in two stages by the blowers 4 and 5, up to a pressure P2 of the order of 35 to 50 bars, precooled in 6 and then cooled in the line of exchange up to a second intermediate temperature T2 much lower than T1 and between -80 ° C and -130 ° C. Part of this air continues to cool, is liquefied, then is expanded at medium pressure in an expansion valve and introduced into column 12 via line 22 above. The rest of the air at pressure P2 is taken out of the exchange line at temperature T2, expanded to medium pressure in the turbine 8 and introduced into the column 12 via the above-mentioned pipe 23.

Le refroidissement de l'air est assuré par circulation à contre-courant, dans la ligne d'échange 2, de plusieurs fluides :

  • l'azote gazeux basse pression issu du sommet de la colonne 13, et l'azote impur ou "waste" produit par cette même colonne, ces deux gaz parcourant la ligne d'échange de son bout froid à son bout chaud, puis étant évacués via des conduites respectives 24 et 25.
  • la majeure partie de l'oxygène séparé est soutirée en cuve de la colonne 13 sous forme liquide, amenée à une première pression P01, relativement basse, par la pompe 9, vaporisée en condensant de l'air soit à la pression P1, ce qui correspond à PO1 = 11 à 17 bars, soit à la pression P2, ce qui correspond à PO1 = 17 à 22 bars, réchauffée à la température ambiante puis évacuée en tant que produit via une conduite 26;
  • une autre partie de l'oxygène séparé, que l'on désire, dans cet exemple, produire sous forme gazeuse à une seconde pression PO2, relativement élevée, typiquement comprise entre 11 et 60 bars, soutirée en cuve de la colonne 13 sous forme liquide, amenée à cette seconde pression PO2, vaporisée dans la ligne d'échange par prélèvement de chaleur sur l'air, sans que cette vaporisation soit nécessairement concomitante à la condensation de cet air, puis réchauffée à la température ambiante et évacuée en tant que produit via une conduite 27; et
  • de l'azote, que l'on désire, dans cet exemple, produire sous forme gazeuse sous une pression de l'ordre de 5 à 60 bars et de préférence de 25 à 35 bars, soutiré sous forme liquide en tête de la colonne 12, amené par la pompe 11 à cette pression de production, vaporisé dans la ligne d'échange par prélèvement de chaleur sur l'air sans que cette vaporisation soit nécessairement concomitante à la condensation de cet air, réchauffé à la température ambiante, et évacué en tant que produit via une conduite 28.
The air is cooled by circulation against the current, in exchange line 2, of several fluids:
  • low pressure gaseous nitrogen from the top of column 13, and impure nitrogen or "waste" produced by this same column, these two gases passing through the exchange line from its cold end to its hot end, then being discharged via respective lines 24 and 25.
  • most of the separated oxygen is drawn off in the bottom of column 13 in liquid form, brought to a first pressure P01, relatively low, by pump 9, vaporized by condensing air either at pressure P1, which corresponds to PO1 = 11 to 17 bars, i.e. at pressure P2, which corresponds to PO1 = 17 to 22 bars, warmed to room temperature and then discharged as a product via a pipe 26;
  • another part of the separated oxygen, which it is desired, in this example, to produce in gaseous form at a second PO2 pressure, relatively high, typically between 11 and 60 bars, drawn off from the bottom of column 13 in liquid form , brought to this second pressure PO2, vaporized in the exchange line by drawing heat from the air, without this vaporization necessarily being concomitant with the condensation of this air, then warmed to ambient temperature and discharged as a product via a pipe 27; and
  • nitrogen, which it is desired, in this example, to produce in gaseous form under a pressure of the order of 5 to 60 bars and preferably from 25 to 35 bars, withdrawn in liquid form at the top of the column 12 , brought by the pump 11 to this production pressure, vaporized in the exchange line by drawing heat from the air without this vaporization necessarily being concomitant with the condensation of this air, warmed to ambient temperature, and evacuated in as a product via a pipe 28.

Simultanément à la production d'oxygène et d'azote gazeux, l'installation produit des quantités notables de liquide (oxygène et/ou azote). Pour de l'air à 25 bars à la sortie du compresseur 3, la quantité de liquide peut atteindre 40% du débit d'oxygène séparé. On a indiqué sur la Figure 1, outre la conduite 19 d'azote liquide, une conduite 29 de production d'oxygène liquide.Simultaneously with the production of oxygen and nitrogen gas, the installation produces significant quantities of liquid (oxygen and / or nitrogen). For air at 25 bars at the outlet of compressor 3, the quantity of liquid can reach 40% of the separated oxygen flow rate. It was indicated in Figure 1, in addition to the pipe 19 of liquid nitrogen, a pipe 29 for producing liquid oxygen.

Le diagramme d'échange thermique de la Figure 2 correspond au schéma de la Figure 1 décrit ci-dessus, avec les données numériques suivantes :

  • débit d'air traité : 26.000 Nm2/h
  • P1 = 27,5 bars, P2 = 39,5 bars
  • T1 = - 35°C, T2 = - 122°C
  • la production d'oxygène gazeux est répartie en deux tiers à 12 bars (conduite 26) et un tiers à 42 bars (conduite 27)
  • l'installation produit également 1.600 Nm2/h d'azote gazeux pur sous 42 bars (conduite 28), et 1.900 Nm2/h de liquide.
The heat exchange diagram in Figure 2 corresponds to the diagram in Figure 1 described above, with the following numerical data:
  • treated air flow: 26,000 Nm 2 / h
  • P1 = 27.5 bars, P2 = 39.5 bars
  • T1 = - 35 ° C, T2 = - 122 ° C
  • the production of gaseous oxygen is divided into two thirds at 12 bars (line 26) and one third at 42 bars (line 27)
  • the installation also produces 1,600 Nm 2 / h of pure nitrogen gas at 42 bars (line 28), and 1,900 Nm 2 / h of liquid.

Le diagramme d'échange comporte une courbe C1 correspondant à l'ensemble des fluides réchauffés, et une courbe C2 correspondant à l'air traité en cours de refroidissement.The exchange diagram includes a curve C1 corresponding to all of the heated fluids, and a curve C2 corresponding to the air treated during cooling.

Sur la courbe C1, on voit en A le palier de vaporisation de l'oxygène sous 12 bars, en B une inflexion correspondant au pseudo-palier de vaporisation de l'azote sous 42 bars, et en C le palier de vaporisation de l'oxygène sous 42 bars (plus court que le palier A puisque le débit est plus faible).On curve C1, we see in A the oxygen vaporization level under 12 bars, in B an inflection corresponding to the pseudo-level of nitrogen vaporization under 42 bars, and in C the level of vaporization of the oxygen under 42 bars (shorter than level A since the flow is lower).

Sur la courbe C2, le point D correspond à l'entrée d'air à la pression P2, à = 32°C, E à l'entrée d'air à la pression P1, à = 12°C, où l'écart de température entre les courbes C2 et C1 est minimal (2°C), ce qui est très favorable, F à l'admission de la turbine 7, qui réduit la pente de la courbe, G à l'admission de la turbine 8, au voisinage du palier C, qui provoque un effet analogue, H au pseudo-palier de condensation de l'air sous la pression P2, au voisinage du pseudo-palier B, et I au genou de condensation de l'air sous la pression P1, en regard du palier A, avec un écart de température minimal et à peu près de même longueur que ce palier A.On curve C2, point D corresponds to the air inlet at pressure P2, at = 32 ° C, E at the air inlet at pressure P1, at = 12 ° C, where the difference temperature between curves C2 and C1 is minimal (2 ° C), which is very favorable, F at the intake of the turbine 7, which reduces the slope of the curve, G at the intake of the turbine 8, in the vicinity of level C, which causes a similar effect, H at the pseudo level of air condensation under pressure P2, in the region of pseudo level B, and I at the knee of air condensation under pressure P1 , opposite bearing A, with a minimum temperature difference and about the same length as this bearing A.

On voit sur la Figure 2 que, sur toute la gamme des températures couverte par la ligne d'échange, les deux courbes sont remarquablement proches l'une de l'autre, ce qui correspond à une grande efficacité thermodynamique globale du procédé.It can be seen in FIG. 2 that, over the whole range of temperatures covered by the exchange line, the two curves are remarkably close to each other, which corresponds to a high overall thermodynamic efficiency of the process.

En variante, comme représenté en trait interrompu sur la Figure 1, l'installation peut comporter une troisième turbine 30, par exemple freinée par une alternateur 31, adaptée pour détendre à la basse pression une partie de l'air moyenne pression issu de la turbine 7. Comme représenté, l'échappement de la turbine 30 est relié à un point intermédiaire de la colonne 13 ou à la conduite véhiculant l'azote impur résiduaire. L'admission de la turbine 30 est à une température de -100°C à -150°C environ.As a variant, as shown in broken lines in FIG. 1, the installation may include a third turbine 30, for example braked by an alternator 31, adapted to relieve some of the medium pressure air coming from the turbine at low pressure. 7. As shown, the exhaust of the turbine 30 is connected to an intermediate point of the column 13 or to the pipe carrying the residual impure nitrogen. The inlet of the turbine 30 is at a temperature of from -100 ° C to about -150 ° C.

Une telle turbine basse pression est intéressante dans deux cas : d'une part, pour valoriser la faible énergie de séparation lorsque l'oxygène est produit à une pureté comprise entre 85% et 98%, en augmentant la production de liquide sans diminution notable du rendement d'extraction en oxygène; d'autre part, pour augmenter la production de liquide au détriment de celle d'oxygène. Si, comme représenté, l'installation produit de l'argon, il est préférable d'envoyer l'air basse pression dans l'azote impur pour maintenir un bon rendement d'extraction en argon. Dans le cas inverse, cet air basse pression peut être insufflé dans la colonne 13.Such a low pressure turbine is advantageous in two cases: on the one hand, to exploit the low separation energy when the oxygen is produced at a purity of between 85% and 98%, by increasing the production of liquid without appreciable reduction in the oxygen extraction yield; on the other hand, to increase the production of liquid at the expense of that of oxygen. If, as shown, the installation produces argon, it is preferable to send the low pressure air into impure nitrogen to maintain a good extraction yield of argon. Otherwise, this low pressure air can be blown into column 13.

L'installation de la Figure 3 diffère de la précédente par les points suivants :

  • la turbine basse pression 30 est freinée par une troisième soufflante 32, dont la roue est rigidement accouplée à celle de cette turbine et qui est montée en série avec les soufflantes 4 et 5, en amont de celles-ci;
  • le débit à détendre dans la turbine 30 est supérieur à celui détendu dans la turbine 7. Par suite, la turbine 30 est alimentée d'une part par la totalité de l'air moyenne pression issu de la turbine 7, d'autre part par un complément d'air moyenne pression provenant de la colonne 12 via une conduite 33 et réchauffé dans la ligne d'échange jusqu'à la température convenable;
  • seule la pompe 9 est affectée à l'oxygène, qui est donc produit sous une seule pression et vaporisé en totalité par condensation d'air à l'une des trois pressions disponibles (P1, P2 et la moyenne pression), tandis que les pompes 10 et 11 sont affectées à l'azote, qui est ainsi produit sous deux pressions différentes et, également, vaporisé par condensation d'air.
The installation of Figure 3 differs from the previous one in the following points:
  • the low pressure turbine 30 is braked by a third blower 32, the wheel of which is rigidly coupled to that of this turbine and which is mounted in series with the blowers 4 and 5, upstream thereof;
  • the flow to be expanded in the turbine 30 is greater than that expanded in the turbine 7. As a result, the turbine 30 is supplied on the one hand by all of the medium pressure air coming from the turbine 7, on the other hand by additional medium pressure air from from column 12 via line 33 and heated in the exchange line to the suitable temperature;
  • only the pump 9 is assigned to the oxygen, which is therefore produced under a single pressure and vaporized entirely by condensation of air at one of the three available pressures (P1, P2 and the medium pressure), while the pumps 10 and 11 are assigned to nitrogen, which is thus produced under two different pressures and, also, vaporized by air condensation.

Le schéma de la Figure 4 ne diffère de celui de la Figure 1 que par le montage des turbines 7 et 8. En effet, c'est la turbine "chaude" 7 qui est alimentée par de l'air à la plus haute pression P2, tandis que la turbine "froide" 8 est alimentée par de l'air à la pression P1. De plus, la turbine 7 échappe à une pression P3 supérieure à la moyenne pression et, en pratique, comprise entre cette moyenne pression et la pression P1. L'air à la pression P3 est refroidi et liquéfié dans la ligne d'échange, par vaporisation d'oxygène, puis détendu à la moyenne pression dans une vanne de détente 34 avant d'être envoyé dans la colonne 12. Cette disposition est particulièrement intéressante pour une pression d'oxygène comprise entre 3 bars et 8 bars.The diagram of Figure 4 differs from that of Figure 1 only by the assembly of the turbines 7 and 8. In fact, it is the "hot" turbine 7 which is supplied with air at the highest pressure P2 , while the "cold" turbine 8 is supplied with air at pressure P1. In addition, the turbine 7 escapes a pressure P3 greater than the medium pressure and, in practice, between this medium pressure and the pressure P1. The air at pressure P3 is cooled and liquefied in the exchange line, by vaporization of oxygen, then expanded at medium pressure in an expansion valve 34 before being sent to column 12. This arrangement is particularly interesting for an oxygen pressure between 3 bars and 8 bars.

Dans chacun des exemples décrits ci-dessus, la ligne d'échange 2 de l'installation comporte des passages de refroidissement d'air à trois pressions différentes. Une ou plusieurs de ces pressions peuvent être utilisées pour condenser l'air par vaporisation à contre-courant, avec un faible écart de températures de l'ordre de 2°C, d'au moins la majeure partie de l'oxygène séparé, comprimé à l'état liquide à une pression correspondante et vaporisé sous cette pression, de l'oxygène additionnel à une autre pression et/ou de l'azote pouvant éventuellement être, en outre, comprimés à l'état liquide et vaporisés dans la ligne d'échange 2.In each of the examples described above, the exchange line 2 of the installation includes air cooling passages at three different pressures. One or more of these pressures can be used to condense the air by counter-current vaporization, with a small temperature difference of around 2 ° C, of at least most of the separated, compressed oxygen. in the liquid state at a corresponding pressure and vaporized under this pressure, additional oxygen at another pressure and / or nitrogen which may optionally be further compressed in the liquid state and vaporized in line d exchange 2.

Comme on peut choisir à volonté les pressions P1 et P3, et régler la pression P2 en jouant sur les débits d'air turbiné et sur la pression P1, il en résulte une très grande souplesse de choix des pressions de vaporisation de l'oxygène et éventuellement de l'azote. Lorsque la vaporisation majoritaire d'oxygène condense l'air à la pression P3, on peut ajuster le débit de cet air au débit d'oxygène à vaporiser, c'est-à-dire que ce débit d'air est réglé entre 20% à 30% du débit d'air traité; un tel débit à travers la turbine "chaude" 7 permet en effet de rester au voisinage de l'optimum thermodynamique.As the pressures P1 and P3 can be chosen at will, and the pressure P2 can be adjusted by adjusting the turbinated air flow rates and the pressure P1, this results in a very great flexibility in the choice of the vaporization pressures of oxygen and possibly nitrogen. When the majority vaporization of oxygen condenses the air at the pressure P3, the flow of this air can be adjusted to the flow of oxygen to be vaporized, that is to say that this air flow is adjusted between 20% 30% of the treated air flow; such a flow rate through the "hot" turbine 7 indeed makes it possible to remain in the vicinity of the thermodynamic optimum.

Il est à noter que, en ce qui concerne la partie minoritaire de l'oxygène et l'azote, leurs pressions de vaporisation peuvent n'être liées en aucune façon aux pressions P1, P2 et P3.It should be noted that, with regard to the minor part of oxygen and nitrogen, their vaporization pressures may not be linked in any way to the pressures P1, P2 and P3.

Par ailleurs, l'installation produit une fraction de l'oxygène et de l'azote sous forme liquide avec une excellente énergie spécifique du fait de l'utilisation de deux turbines de détente à températures d'admission très différentes.Furthermore, the installation produces a fraction of oxygen and nitrogen in liquid form with excellent specific energy due to the use of two expansion turbines at very different inlet temperatures.

Claims (14)

  1. Process for producing gaseous oxygen under pressure by distilling air in an installation comprising a heat exchange line (2) and a double distillation column (1) which itself comprises a first column (12), a so-called medium pressure column, operating at a medium pressure, and a second column (13), a so-called low pressure column, operating at a low pressure, pumping (in 9,10) liquid oxygen withdrawn from the vessel of the low pressure column, and vaporizing compressed oxygen by heat exchange with air compressed to a high air pressure, all the air to be treated being compressed to a first pressure P1 markedly greater than the medium pressure, the air at pressure P1 is divided into two parts, the first being cooled and the second part being compressed to a second high pressure P2 and cooled, at least the major part of the oxygen separated being withdrawn in the liquid state from the low pressure column (13), compressed by a pump (9, 10) to at least a first vaporization pressure at which it vaporizes by condensation of air and vaporized by condensation of air,
       characterized in that :
    - the first part of this air is cooled to a first intermediate temperature T1, where a first fraction is expanded in a first turbine (7), while the rest of this second part is cooled and liquefied, expanded and introduced into the medium pressure column (12);
    - the second part is cooled to a second intermediate temperature T2, where a first stream is expanded in a second turbine (8), while the remainder of this second part is cooled and liquefied, expanded and introduced into the medium pressure column (12);
    as required, the exhaust pressure from one of the turbines (7, 8) is adjusted to a pressure P3 between the said first high pressure P1 and the medium pressure,
    and the compressed oxygen vaporizes by condensation of air to one or more pressures P1, P2, P3.
  2. Process according to claim 1, characterized in that the intermediate temperatures T1 and T2 are selected, one between about 0°C and -60°C and the other between about -80°C and -130°C.
  3. Process according to either of claims 1 or 2,
    characterized in that the air flow feeding the first turbine (7) is of the order of 20 to 30 % of the flow of treated air.
  4. Process according to any one of claims 1 to 3,
    characterized in that additional liquid oxygen withdrawn from the low pressure column (13) is compressed by pump to at least a second vaporization pressure and vaporized at this pressure or at these pressures in the heat exchange line (2).
  5. Process according to any one of claims 1 to 4,
    characterized in that liquid nitrogen is withdrawn from the double column (1), compressed by pump (10, 11) to at least a vaporization pressure of nitrogen, and vaporized at this pressure or at these pressures in the heat exchange line (2).
  6. Process according to any one of claims 1 to 5,
    characterized in that at least part of the air coming from the first or second turbine (7, 8) is expanded to the low pressure in a third turbine (30), the air coming from the third turbine being introduced into the low pressure column (13) or into the residual gas evacuated from the upper part of this column.
  7. Process according to claim 6, characterized in that there is expanded in the third turbine (30) all the said air coming from the first or second turbine (7, 8), this air being substantially at the medium pressure, as well as a supplementary stream of air withdrawn from the vessel of the medium pressure column (12).
  8. Process according to any one of claims 1 to 7,
    characterized in that the air is pressurized by means of at least two blowers (4, 5, 32) in series each coupled to one of the turbines (7, 8, 30).
  9. Installation for producing gaseous oxygen under pressure for the application of a process according to any one of claims 1 to 8, of the type comprising a double air distillation column (1) comprising one column, the so-called low pressure column (13), operating at a low pressure, and a column, the so-called medium pressure column (12) operating at a medium pressure, a pump (9, 10) for compressing liquid oxygen withdrawn from the vessel of the low pressure column (13), means of compression (3, 4, 5, 32) for bringing the air to be distilled to a high pressure, markedly greater than the medium pressure, and a heat exchange line (2) for putting the air at a high pressure and the compressed liquid oxygen in a heat exchange relationship, the means of compression comprising a compressor (3) for bringing all the air to be distilled to a first high pressure P1 markedly greater than the medium pressure, and means (4, 5, 32) for pressurizing a fraction of the air at this first high pressure to a second high pressure P2,
       characterized in that these means of pressurizing comprise at least two blowers in series each coupled to an expansion turbine (7, 8, 30), a blower (4, 5) being coupled to a first turbine (7) for expanding air at the first high pressure P1 and another blower (5, 4) being coupled to a second turbine (8) for expanding part of the compressed air, and in that the heat exchange line (2) comprises passages for cooling the air coming from the first turbine (7) having the higher inlet temperature and/or the inlet temperature T1 of one (7) of the two turbines is between about 0°C and -60°C, while that T2 of the second turbine (8) is between about -80°C and -130°C.
  10. Installation according to claim 9, characterized in that it comprises a second pump (10) for liquid oxygen or liquid nitrogen, and possibly a third pump (11) for liquid oxygen or liquid nitrogen, and in that the heat exchange line (2) comprises corresponding vaporisation-reheating passages.
  11. Installation according to either of claims 9 or 10,
    characterized in that it comprises a third turbine (30) for expanding to the low pressure at least part of the air coming from the turbine (7) having the higher inlet temperature, and means for introducing the air coming from the third turbine into the low pressure column (13) or into a residual gas pipe of this column.
  12. Installation according to claim 11, characterized in that it comprises means (33) for supplementing the feed to the third turbine (30) with air withdrawn from the vessel of the medium pressure column (12), the said air coming from the turbine (7) having the higher inlet temperature being substantially at the medium pressure.
  13. Installation according to either of claims 11 or 12,
    wherein the third turbine (30) is held back by an alternator (31) or by an air blower (32).
  14. Installation according to claim 13, wherein the blower (32) coupled to the third turbine (30) is mounted in series with the other blowers (4, 5).
EP93401395A 1992-06-23 1993-06-02 Process and installation for the production of gaseous oxygen under pressure Expired - Lifetime EP0576314B2 (en)

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FR9207662A FR2692664A1 (en) 1992-06-23 1992-06-23 Process and installation for producing gaseous oxygen under pressure.
FR9207662 1992-06-23

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EP0576314A1 (en) 1993-12-29
CN1080390A (en) 1994-01-05
JPH0658662A (en) 1994-03-04
ZA934204B (en) 1994-01-10
AU660260B2 (en) 1995-06-15
AU4135793A (en) 1994-01-06
DE69305246T3 (en) 2001-03-08
CA2098895A1 (en) 1993-12-24
DE69305246T2 (en) 1997-05-07
FR2692664A1 (en) 1993-12-24
DE69305246D1 (en) 1996-11-14
EP0576314B2 (en) 2000-03-29
US5400600A (en) 1995-03-28
CN1077275C (en) 2002-01-02

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