AU2012230171B2 - Device and method for separating air by cryogenic distillation - Google Patents
Device and method for separating air by cryogenic distillation Download PDFInfo
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- AU2012230171B2 AU2012230171B2 AU2012230171A AU2012230171A AU2012230171B2 AU 2012230171 B2 AU2012230171 B2 AU 2012230171B2 AU 2012230171 A AU2012230171 A AU 2012230171A AU 2012230171 A AU2012230171 A AU 2012230171A AU 2012230171 B2 AU2012230171 B2 AU 2012230171B2
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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
- F25J3/0228—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 characterised by the separated product stream
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
- F25J3/04078—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression
- F25J3/0409—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression of oxygen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04006—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
- F25J3/04103—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 using solely hydrostatic liquid head
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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
- F25J3/04193—Division of the main heat exchange line in consecutive sections having different functions
- F25J3/04206—Division of the main heat exchange line in consecutive sections having different functions including a so-called "auxiliary vaporiser" for vaporising and producing a gaseous product
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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
- F25J3/04218—Parallel arrangement of the main heat exchange line in cores having different functions, e.g. in low pressure and high pressure cores
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
- F25J3/04284—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams
- F25J3/0429—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams of feed air, e.g. used as waste or product air or expanded into an auxiliary column
- F25J3/04303—Lachmann expansion, i.e. expanded into oxygen producing or low pressure column
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04406—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system
- F25J3/04412—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system in a classical double column flowsheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04406—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
- F25J3/04418—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 with thermally overlapping high and low pressure columns
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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
- F25J3/04763—Start-up or control of the process; Details of the apparatus used
- F25J3/04769—Operation, control and regulation of the process; Instrumentation within the process
- F25J3/04812—Different modes, i.e. "runs" of operation
- F25J3/04824—Stopping of the process, e.g. defrosting or deriming; Back-up procedures
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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
- F25J3/04763—Start-up or control of the process; Details of the apparatus used
- F25J3/04769—Operation, control and regulation of the process; Instrumentation within the process
- F25J3/04812—Different modes, i.e. "runs" of operation
- F25J3/04836—Variable air feed, i.e. "load" or product demand during specified periods, e.g. during periods with high respectively low power costs
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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
- F25J3/04763—Start-up or control of the process; Details of the apparatus used
- F25J3/04769—Operation, control and regulation of the process; Instrumentation within the process
- F25J3/04854—Safety aspects of operation
- F25J3/0486—Safety aspects of operation of vaporisers for oxygen enriched liquids, e.g. purging of liquids
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/50—Processes or apparatus using separation by rectification using multiple (re-)boiler-condensers at different heights of the column
- F25J2200/54—Processes or apparatus using separation by rectification using multiple (re-)boiler-condensers at different heights of the column in the low pressure column of a double pressure main column system
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2215/00—Processes characterised by the type or other details of the product stream
- F25J2215/50—Oxygen or special cases, e.g. isotope-mixtures or low purity O2
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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
- F25J2250/00—Details related to the use of reboiler-condensers
- F25J2250/30—External or auxiliary boiler-condenser in general, e.g. without a specified fluid or one fluid is not a primary air component or an intermediate fluid
- F25J2250/40—One fluid being air
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2250/00—Details related to the use of reboiler-condensers
- F25J2250/30—External or auxiliary boiler-condenser in general, e.g. without a specified fluid or one fluid is not a primary air component or an intermediate fluid
- F25J2250/50—One fluid being oxygen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
- F25J2290/62—Details of storing a fluid in a tank
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Separation By Low-Temperature Treatments (AREA)
Abstract
Device for separating air comprises a pipe for withdrawing liquid oxygen from the low-pressure column and for sending it to a first pump (39), a pipe for sending liquid oxygen that has been pressurized to a pressure of below 9 bar abs from the first pump to a vaporizer (41), a pipe for sending gaseous oxygen from the vaporizer to a main exchanger (21) where it is heated up, a pipe for sending liquid oxygen for purging from the vaporizer to a second pump (63) to pressurize it and a pipe for sending the pressurized oxygen from the second pump to an exchanger where it vaporizes to form gaseous oxygen.
Description
1 2012230171 24 Jan 2017
DEVICE AND METHOD FOR SEPARATING AIR BY CRYOGENIC
DISTILLATION
This invention relates to a device and method for 5 separating air by air distillation.
In particular, it relates to the production of gaseous oxygen at a pressure below 9 bars abs, even below 5 bars abs. The gaseous oxygen can possibly contain less than 98% mol. oxygen. 10 It is required to produce large quantities of oxygen having these characteristics in order to supply oxy-combustion apparatuses, among others.
It is disclosed in WO-A-1 0/ 1 09 1 4 9 to vaporise a flow of liquid oxygen at low pressure in an exterior vaporiser 15 in order to produce gaseous oxygen which is then heated in a main exchanger.
It is disclosed to vaporise the bleed of a distillation column in order to recover the frigories of it, for example in US-A-5408831. 20 US-A-5765396 and US-A-5251451 describe installations according to the preamble of claim 1.
However this invention proposes to vaporise the deconcentration bleed of a vaporiser in an exchanger in order to recover the frigories, this vaporiser being the exchanger 25 making it possible to vaporise a liquid of the apparatus 2 2012230171 24 Jan 2017 under pressure in order to produce a pressurised gaseous product.
It is desirable to send the bleed to a storage of pressurised gases making it possible to maintain stable 5 production in terms of flow as well as in terms of pressure .
According to one aspect of the invention, a device for separating air is provided comprising a double column comprising a medium-pressure column and a low-pressure column, 10 a main exchanger, a vaporiser, a main compressor, means for sending all of the air to be treated in the double column to the main compressor in order to produce air substantially at the pressure PI of the medium-pressure column, means for sending a portion of the air substantially at a high pressure 15 P2 to the main exchanger and then to the vaporiser, a pipe for sending air at least partially condensed in the vaporiser to at least one of the columns, a pipe for sending air at the pressure PI to the medium-pressure column, means of pressurising, a pump, a pipe for withdrawing 20 the liquid oxygen from the low-pressure column and for sending it to the means of pressurising, a pipe for sending liquid oxygen that has been pressurised at a pressure below 9 bar abs from the means of pressurising to the vaporiser, a pipe for sending gaseous oxygen from the vaporiser to the main exchanger 25 to be heated in order to form a first flow of gaseous oxygen, a bleed pipe for sending liquid bleed oxygen from the vaporiser to the pump in order to pressurise it characterised in that the bleed pipe is not connected to a bleed liquid storage and in that it comprises a pipe for sending pressurised 30 oxygen from the pump to an exchanger in order to be vaporised, with the exchanger being connected to a pipe for compressed air connected to the main compressor and to a pipe connected to the double column, in order to form a second flow of gaseous oxygen. 3 2012230171 24 Jan 2017
Optionally: - the exchanger connected to the oxygen bleed pipe is the main exchanger. the exchanger connected to the oxygen bleed pipe is 5 an exchanger separate from the main exchanger. - the exchanger comprises passages connected to a supply air inlet pipe and passages connected to a liquid refrigerant inlet pipe, possibly coming from the double column. - the apparatus comprises a storage of pressurised gases 10 connected to the bleed oxygen vaporisation exchanger in order to collect the gaseous oxygen.
According to another aspect of the invention, a method is provided for separating air in an apparatus comprising a double column comprising a medium-pressure column and a low-pressure 15 column, a main exchanger, a vaporiser, a main compressor, means of pressurising, a pump, wherein all the air to be treated is sent in the double column to the main compressor in order to produce air substantially at the pressure PI of the medium-pressure column, a portion of the air substantially at 10 a high pressure P2 is sent to the main exchanger and then to the vaporiser, air at least partially condensed in the vaporiser is sent to at least one of the columns, air at the pressure PI is sent to the medium-pressure column, liquid oxygen is withdrawn from the low-pressure column and it is 25 pressurised, the liquid oxygen that has been pressurised is sent at a pressure below 5 bar abs to the vaporiser, a first flow of gaseous oxygen is sent from the vaporiser to the main exchanger to be heated and liquid bleed oxygen of the vaporiser is pressurised in the pump characterised in that 30 the liquid bleed oxygen is pressurised without having been stored and is then vaporised in an exchanger through exchange of heat with the air, compressed in the main compressor and intended for the double column, in order to form a second flow of gaseous oxygen. 3a 2012230171 18 Sep 2013 least one of the columns, a pipe for sending air at the pressure Pi to the medium-pressure column, means of pressurising, a pump, a pipe for withdrawing the liquid oxygen from the low-pressure column and for sending it to the means of 5 pressurising, a pipe for sending liquid oxygen that has been pressurised at a pressure below 9 bar abs from the means of pressurising to the vaporiser, a pipe for sending gaseous oxygen from the vaporiser to the main exchanger to be heated in order to form a first flow of gaseous oxygen, a purge pipe for 10 sending liquid purge oxygen from the vaporiser to the pump in order to pressurise it characterised in that the purge pipe is not connected to a purge liquid storage and in that it comprises a pipe for sending pressurised oxygen from the pump to an exchanger in order to be vaporised, with the exchanger 15 being connected to a pipe for compressed air connected to the main compressor and to a pipe connected to the double column, in order to form a second flow of gaseous oxygen.
Optionally : - the exchanger connected to the oxygen purge pipe is the 20 main exchanger. - the exchanger connected to the oxygen purge pipe is an exchanger separate from the main exchanger. - the exchanger comprises passages connected to a supply air inlet pipe and passages connected to a liquid refrigerant 25 inlet pipe, possibly coming from the double column. - the apparatus comprises a storage of pressurised gases connected to the purge oxygen vaporisation exchanger in order to collect the gaseous oxygen.
According to yet another aspect of the invention, a method 30 is provided for separating air in an apparatus comprising a double column comprising a medium-pressure column and a low-pressure column, a main exchanger, a vaporiser, a main compressor, means of pressurising, a pump, wherein all the air to be treated is sent in the double column to the main 2012230171 18 Sep 2013 3b compressor in order to produce air substantially at the pressure PI of the medium-pressure column, a portion of the air substantially at a high pressure P2 is sent to the main exchanger and then to the vaporiser, air at least partially 5 condensed in the vaporiser is sent to at least one of the columns, air at the pressure PI is sent to the medium-pressure column, liquid oxygen is withdrawn from the low-pressure column and it is pressurised, the liquid oxygen that has been pressurised is sent at a pressure below 5 bar abs to the 10 vaporiser, a first flow of gaseous oxygen is sent from the vaporiser to the main exchanger to be heated and liquid purge oxygen of the vaporiser is pressurised in the pump characterised in that the liquid purge oxygen is pressurised without having been stored and is then 4 2012230171 01 Feb 2017
According to another aspect of the invention, there is provided an apparatus for separating air comprising a double column comprising a medium-pressure column and a low-pressure column, a main exchanger, a vaporiser, a main 5 compressor, means for sending all of the air to be treated in the double column to the main compressor in order to produce air substantially at the pressure PI of the medium-pressure column, means for sending a portion of the air substantially at a high pressure P2 to the main L0 exchanger and then to the vaporiser, a pipe for sending air at least partially condensed in the vaporiser to at least one of the columns, a pipe for sending air at the pressure PI to the medium-pressure column, means of pressurising, a pump, a pipe for withdrawing liquid oxygen from the 15 low-pressure column and for sending it to the means of pressurising, a pipe for sending the liquid oxygen that has been pressurised at a pressure below 5 bars abs from the means of pressurising to the vaporiser, a pipe for sending gaseous oxygen from the vaporiser to the main exchanger to be 20 heated for forming a first flow of gaseous oxygen, a bleed pipe for sending the liquid bleed oxygen from the vaporiser to the pump in order to pressurise it, wherein the bleed pipe is not connected to a bleed liquid storage and in that it comprises a pipe for sending the pressurised oxygen from the pump to an 25 exchanger to be vaporised, the exchanger being connected to a pipe for compressed air connected to the main compressor and to a pipe connected to the double column, in order to form a second flow of gaseous oxygen, wherein the exchanger connected to the oxygen bleed pipe is an exchanger separate from the main 30 exchanger.
According to yet another aspect of the invention, there is provided a method for separating air in an apparatus comprising a double column comprising a medium-pressure column and a low-pressure column, a main exchanger, a vaporiser, a main 4a 2012230171 24 Jan 2017 compressor, means of pressurising, a pump, wherein all of the air to be treated in the double column is sent to the main compressor in order to produce air substantially at the pressure PI of the medium-pressure column, a portion of the air 5 substantially at a high pressure P2 is sent to the main exchanger and then to the vaporiser, air at least partially condensed in the vaporiser is sent to at least one of the columns, air at the pressure PI is sent to the medium-pressure column, liquid oxygen is withdrawn from the low-10 pressure column and it is pressurised, the liquid oxygen that has been pressurised at a pressure below 5 bar abs is sent to the vaporiser, a first flow of gaseous oxygen is sent from the vaporiser to the main exchanger to be heated and the liquid bleed oxygen of the vaporiser is pressurised in the pump 15 wherein the liquid bleed oxygen is pressurised without having been stored and is then vaporised in an exchanger via heat exchange with the air, compressed in the main compressor and intended for the double column, in order to form a second flow of gaseous oxygen, wherein the bleed oxygen is vaporised 20 in an exchanger other than the main exchanger.
Optionally: - the bleed oxygen is pressurised at a pressure of at least 10 bars abs, more preferably at least 15 bars abs, even at least 20 bars abs in the second pump. 25 - the bleed oxygen is vaporised in the main exchanger. - the bleed oxygen is vaporised in an exchanger other than the main exchanger. the second flow of gaseous oxygen is sent to a 30 storage of pressurised gases and is used for backup production. - a variable quantity of the second flow of gaseous oxygen is mixed with the first flow in order to produce a substantially constant mixed flow. - the liquid oxygen withdrawn from the low-pressure 2012230171 24 Jan 2017 4b column contains at least 80% mol. oxygen - the liquid oxygen withdrawn from the low-pressure column oxygen constitutes the only flow containing withdrawn from the low-pressure column at least 80% mol. column the liquid oxygen contains at most 98% withdrawn from mol. oxygen. the low-pressure 2012230171 14 Nov 2013 5
The invention shall be described in more detail by referring to the figures which show apparatuses for separating air according to the invention.
In Figure 1, the apparatus comprises an exchange 5 line 21 and a double column constituted of a medium-pressure column 27 and a low-pressure column 29.
All of the air 1 is compressed in the main compressor 2 in order to produce air at the pressure PI substantially equal to the pressure of the medium-10 pressure column 27. The air at the pressure PI is cooled in a cooler 7, purified in a purification unit 9 and divided into three fractions. The first fraction 11 is supercharged in a supercharger, able to be constituted of the last stage of the main compressor, with this last 15 stage being part of the second portion of the compressor. The pressure PI is below 5 bars abs, even 4.5 bar abs, preferably below 4 bar, and even below 3.5 bar abs.
The first fraction 11 is brought to a pressure P2 by the booster 5 or an independent compressor 5 and cooled 20 at this pressure in a cooler (not shown) before being sent to the exchange line 21. The exchange line is comprised of a brazed-plate aluminium indirect heat exchanger. The fraction 11 is then sent in gaseous form to a vaporiser 41 where it is condensed at least 25 partially before being expanded and sent to the medium-pressure column 27. The pressure P2 is below 15 bar abs, preferably below 10 bar, and even below 6 bar abs. The fraction 11 is less than half of the flow 1, and preferably less than a third of the flow 1. 30 The second fraction 13 at the pressure Pi is cooled entirely in the exchange line 21 and is divided into two flows. The first flow 23 is sent to a tank reboiler 33 2012230171 14 Nov 2013 30 6 from the low-pressure column 29 where it is condensed at least partially and is sent to the medium-pressure column, mixed with the flow 11. The second flow 25 is sent in gaseous form to the medium-pressure column 27. 5 The third fraction 15 is supercharged in a supercharger 17, partially cooled in the exchange line 21, withdrawn from the exchange line at an intermediary level of the latter and expanded in a turbine 19 coupled to the supercharger 17 before being sent to the low-pressure 10 column 29. A flow of oxygen-rich liquid 55, an intermediate flow 53 and a flow of nitrogen-rich liquid 51 are withdrawn from the medium-pressure column 27, cooled in the exchanger 31, expanded and sent to different levels 15 of the low-pressure column 29.
Medium-pressure gaseous nitrogen 49 is condensed in an intermediate vaporiser 35 of the low-pressure column 29 and sent as a reflux at the head of the medium- pressure column 27. Another flow of medium-pressure 20 gaseous nitrogen 47 is heated in the exchange line.
Liquid oxygen 37, containing at least 80% mol. oxygen and possibly at most 98% mol. oxygen, is withdrawn from the tank of the low-pressure column 29, pressurised by a pump 39 at a pressure below 9 bars abs, even below 5 25 bars abs and sent to the vaporiser 41. Other than a liquid bleed 43, the oxygen is vaporised in the vaporiser 41 by exchange of heat with the fraction of air 11 at the pressure P2. This oxygen then forms the first flow of pressurised gaseous oxygen 45 which is heated in the exchange line 21. The fraction or air 11 is partially condensed and is sent to the double column. 2012230171 14 Nov 2013 7
The bleed liquid 43 is pressurised to a pressure of at least 10 bars abs, or at least 15 bar abs, even at least 20 bars abs in a pump 63 then is vaporised in the exchange line 21. The second gaseous flow produced as 5 such 59 is sent to a storage of pressurised gases 3 and expanded in order to be mixed with the flow 45 via the pipe 61.
Here the vaporisation of bleed liquid is carried by using primarily substantial heat, in such a way that no 10 airflow exiting the exchanger 21 is fully condensed, or even is not condensed.
Alternatively as shown in Figure 2, the pressurised bleed liquid 43 can be vaporised in an auxiliary exchanger 21A, separate from the exchange line, against 15 an airflow 25A and with a liquid refrigerant, for example a flow of nitrogen 57A heated with the method of separating.
The flow 25A cooled in the exchanger 21A is mixed with the cooled flow 25 and the flow of nitrogen 57A 20 heated in the exchanger 21A is mixed with the heated flow 57.
The second flow of gaseous oxygen 59, 61 formed by the vaporisation can be used as a backup gas during an interruption of the production of gaseous oxygen 45. 25 As such the only airflow which is used to vaporise the bleed oxygen 43 remains in gaseous form in the exchanger 21A and the vaporisation is carried out by substantial heat exchange.
The pressurisation by the pump 39 and/or 63 can be 30 replaced with a hydrostatic pressurisation in all of the cases described. 8 2012230171 24 Jan 2017
For all of the figures, a variable quantity of the second flow of gaseous oxygen is mixed with the first flow in order to produce a substantially constant mixed flow.
This variable quantity of the vaporised bleed liquid 5 can be mixed with the first flow 45 in order to smooth out the variations of flow, due, for example to variations of the pressure of the oxygen network.
By detecting a reduction in pressure in the line 45, due, for example to an increased oxygen demand, oxygen can be 10 expanded and sent from storage 3 to the line 45 via the pipe 61 .
In the event of a breakdown of the device for separating air, the flow of oxygen 45 will be reduced or will be nonexistent. In this case, the flow of oxygen 63 from 15 storage 3 can supply a client, the time for a backup vaporiser to be operational in order to prevent any stoppage of production.
The flow 37 is the only flow containing more than 60% mol. oxygen withdrawn from the low-pressure column. The storage 3 20 operates at a pressure that is higher than the flow 45.
Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification (including the claims) they are to be interpreted as specifying the presence of the stated features, integers, steps or components, but not 25 precluding the presence of one or more other features, integers, steps or components, or group thereof.
The discussion of documents, acts, materials, devices, articles and the like is included in this specification solely for the purpose of providing a context for the present 30 invention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application.
Claims (13)
- The claims defining the invention are as follows:1. Apparatus for separating air comprising a double column comprising a medium-pressure column and a low-pressure column, a main exchanger, a vaporiser, a main compressor, means for sending all of the air to be treated in the double column to the main compressor in order to produce air substantially at the pressure PI of the medium-pressure column, means for sending a portion of the air substantially at a high pressure P2 to the main exchanger and then to the vaporiser, a pipe for sending air at least partially condensed in the vaporiser to at least one of the columns, a pipe for sending air at the pressure PI to the medium-pressure column, means of pressurising, a pump, a pipe for withdrawing liquid oxygen from the low-pressure column and for sending it to the means of pressurising, a pipe for sending the liquid oxygen that has been pressurised at a pressure below 5 bars abs from the means of pressurising to the vaporiser, a pipe for sending gaseous oxygen from the vaporiser to the main exchanger to be heated for forming a first flow of gaseous oxygen, a bleed pipe for sending the liquid bleed oxygen from the vaporiser to the pump in order to pressurise it, wherein the bleed pipe is not connected to a bleed liquid storage and in that it comprises a pipe for sending the pressurised oxygen from the pump to an exchanger to be vaporised, the exchanger being connected to a pipe for compressed air connected to the main compressor and to a pipe connected to the double column, in order to form a second flow of gaseous oxygen, wherein the exchanger connected to the oxygen bleed pipe is an exchanger separate from the main exchanger.
- 2. Apparatus according to claim 1, wherein the exchanger comprises passages connected to a supply air inlet pipe and passages connected to a liquid refrigerant inlet pipe, possibly coming from the double column.
- 3. Apparatus according to claim 1 or 2 comprising a storage of pressurised gases connected to the exchanger for the vaporisation of bleed oxygen in order collect the gaseous oxygen.
- 4. Method for separating air in an apparatus comprising a double column comprising a medium-pressure column and a low-pressure column, a main exchanger, a vaporiser, a main compressor, means of pressurising, a pump, wherein all of the air to be treated in the double column is sent to the main compressor in order to produce air substantially at the pressure PI of the medium-pressure column, a portion of the air substantially at a high pressure P2 is sent to the main exchanger and then to the vaporiser, air at least partially condensed in the vaporiser is sent to at least one of the columns, air at the pressure PI is sent to the medium-pressure column, liquid oxygen is withdrawn from the low-pressure column and it is pressurised, the liquid oxygen that has been pressurised at a pressure below 5 bar abs is sent to the vaporiser, a first flow of gaseous oxygen is sent from the vaporiser to the main exchanger to be heated and the liquid bleed oxygen of the vaporiser is pressurised in the pump wherein the liquid bleed oxygen is pressurised without having been stored and is then vaporised in an exchanger via heat exchange with the air, compressed in the main compressor and intended for the double column, in order to form a second flow of gaseous oxygen, wherein the bleed oxygen is vaporised in an exchanger other than the main exchanger.
- 5. Method according to claim 4 wherein the bleed oxygen is pressurised at a pressure of at least 10 bars abs in the second pump
- 6. Method according to claim 5, wherein the purge oxygen is pressurised at a pressure is of at least 15 bars abs in the second pump.
- 7. Method according to claim 5, wherein the purge oxygen is pressurised at a pressure is of at least 20 bars abs in the second pump.
- 8. Method according to any one of claims 4 to 7 wherein the second flow of gaseous oxygen is sent to a storage of pressurised gases and is used for backup production.
- 9. Method according to any one of claims 4 to 8 wherein a variable quantity of the second flow of gaseous oxygen is mixed with the first flow of gaseous oxygen in order to produce a substantially constant mixed flow.
- 10. Method according to any one of claims 4 to 9 wherein the liquid oxygen withdrawn from the low-pressure column contains at least 80% mol. oxygen.
- 11. Method according to claim 10 wherein the liquid oxygen withdrawn from the low-pressure column constitutes the only flow containing at least 80% mol. oxygen withdrawn from the low-pressure column.
- 12. Method according to any one of claims 4 to 11 wherein the liquid oxygen withdrawn from the low-pressure column contains at most 98% mol. oxygen.
- 13. Method according to any one of claims 4 to 12 wherein no airflow is fully condensed, even is not condensed in the exchanger wherein the bleed oxygen is vaporised.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FR1152272 | 2011-03-18 | ||
FR1152272A FR2972794B1 (en) | 2011-03-18 | 2011-03-18 | APPARATUS AND METHOD FOR AIR SEPARATION BY CRYOGENIC DISTILLATION |
PCT/FR2012/050500 WO2012127148A2 (en) | 2011-03-18 | 2012-03-09 | Device and method for separating air by cryogenic distillation |
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AU2012230171A1 AU2012230171A1 (en) | 2013-10-10 |
AU2012230171B2 true AU2012230171B2 (en) | 2017-03-30 |
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AU2012230171A Active AU2012230171B2 (en) | 2011-03-18 | 2012-03-09 | Device and method for separating air by cryogenic distillation |
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US (1) | US20130340476A1 (en) |
EP (1) | EP2686628B1 (en) |
AU (1) | AU2012230171B2 (en) |
CA (1) | CA2828716C (en) |
ES (1) | ES2859549T3 (en) |
FR (1) | FR2972794B1 (en) |
WO (1) | WO2012127148A2 (en) |
ZA (1) | ZA201306723B (en) |
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JP5997105B2 (en) * | 2013-06-05 | 2016-09-28 | 神鋼エア・ウォーター・クライオプラント株式会社 | Air separation method |
WO2015127648A1 (en) * | 2014-02-28 | 2015-09-03 | Praxair Technology, Inc. | Pressurized product stream delivery |
Citations (3)
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EP1199532A1 (en) * | 2000-10-20 | 2002-04-24 | Linde Aktiengesellschaft | Three-column system for the cryogenic separation of air |
EP1746374A2 (en) * | 2005-07-21 | 2007-01-24 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and apparatus for the separation of air by cryogenic distillation |
WO2010109149A2 (en) * | 2009-03-27 | 2010-09-30 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Apparatus and method for separating air by cryogenic distillation |
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GB1425450A (en) * | 1972-01-21 | 1976-02-18 | Air Prod & Chem | Air separation |
AT386279B (en) * | 1986-04-02 | 1988-07-25 | Voest Alpine Ag | DEVICE FOR THE DISASSEMBLY OF GASES BY MEANS OF COAXIAL INTERLECTED RECTIFICATION COLONES |
US4796431A (en) * | 1986-07-15 | 1989-01-10 | Erickson Donald C | Nitrogen partial expansion refrigeration for cryogenic air separation |
US5251451A (en) * | 1992-08-28 | 1993-10-12 | Air Products And Chemicals, Inc. | Multiple reboiler, double column, air boosted, elevated pressure air separation cycle and its integration with gas turbines |
FR2699992B1 (en) | 1992-12-30 | 1995-02-10 | Air Liquide | Process and installation for producing gaseous oxygen under pressure. |
FR2706195B1 (en) * | 1993-06-07 | 1995-07-28 | Air Liquide | Method and unit for supplying pressurized gas to an installation consuming an air component. |
US5765396A (en) * | 1997-03-19 | 1998-06-16 | Praxair Technology, Inc. | Cryogenic rectification system for producing high pressure nitrogen and high pressure oxygen |
JP3488695B2 (en) * | 2001-02-09 | 2004-01-19 | エア・ウォーター株式会社 | Nitrogen production equipment |
DE10217091A1 (en) * | 2002-04-17 | 2003-11-06 | Linde Ag | Three-column system for low-temperature air separation with argon extraction |
FR2842124B1 (en) * | 2002-07-09 | 2005-03-25 | Air Liquide | METHOD FOR CONDUCTING AN ELECTRIC POWER GAS-GENERATING PLANT AND THIS PRODUCTION PLANT |
GB0219415D0 (en) * | 2002-08-20 | 2002-09-25 | Air Prod & Chem | Process and apparatus for cryogenic separation process |
US6957153B2 (en) * | 2003-12-23 | 2005-10-18 | Praxair Technology, Inc. | Method of controlling production of a gaseous product |
DE102011113668A1 (en) * | 2011-09-20 | 2013-03-21 | Linde Aktiengesellschaft | Method and apparatus for the cryogenic separation of air |
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2011
- 2011-03-18 FR FR1152272A patent/FR2972794B1/en not_active Expired - Fee Related
-
2012
- 2012-03-09 AU AU2012230171A patent/AU2012230171B2/en active Active
- 2012-03-09 EP EP12714763.5A patent/EP2686628B1/en active Active
- 2012-03-09 WO PCT/FR2012/050500 patent/WO2012127148A2/en active Application Filing
- 2012-03-09 CA CA2828716A patent/CA2828716C/en active Active
- 2012-03-09 US US14/003,902 patent/US20130340476A1/en not_active Abandoned
- 2012-03-09 ES ES12714763T patent/ES2859549T3/en active Active
-
2013
- 2013-09-06 ZA ZA2013/06723A patent/ZA201306723B/en unknown
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EP1199532A1 (en) * | 2000-10-20 | 2002-04-24 | Linde Aktiengesellschaft | Three-column system for the cryogenic separation of air |
EP1746374A2 (en) * | 2005-07-21 | 2007-01-24 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and apparatus for the separation of air by cryogenic distillation |
WO2010109149A2 (en) * | 2009-03-27 | 2010-09-30 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Apparatus and method for separating air by cryogenic distillation |
Also Published As
Publication number | Publication date |
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FR2972794A1 (en) | 2012-09-21 |
US20130340476A1 (en) | 2013-12-26 |
CN104067079A (en) | 2014-09-24 |
CA2828716C (en) | 2020-02-25 |
EP2686628B1 (en) | 2021-01-13 |
AU2012230171A1 (en) | 2013-10-10 |
WO2012127148A3 (en) | 2014-12-04 |
ZA201306723B (en) | 2015-03-25 |
FR2972794B1 (en) | 2015-11-06 |
WO2012127148A2 (en) | 2012-09-27 |
CA2828716A1 (en) | 2012-09-27 |
ES2859549T3 (en) | 2021-10-04 |
EP2686628A2 (en) | 2014-01-22 |
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