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EP3913310A1 - Verfahren und gerät zur trennung von luft durch kryogene destillation - Google Patents

Verfahren und gerät zur trennung von luft durch kryogene destillation Download PDF

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Publication number
EP3913310A1
EP3913310A1 EP21170059.6A EP21170059A EP3913310A1 EP 3913310 A1 EP3913310 A1 EP 3913310A1 EP 21170059 A EP21170059 A EP 21170059A EP 3913310 A1 EP3913310 A1 EP 3913310A1
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EP
European Patent Office
Prior art keywords
column
air
flow
sent
pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21170059.6A
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English (en)
French (fr)
Inventor
Jean-Pierre Tranier
Richard Dubettier-Grenier
Maxime ROZIERES
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP3913310A1 publication Critical patent/EP3913310A1/de
Pending legal-status Critical Current

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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes 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
    • F25J3/04Processes 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
    • F25J3/04006Providing pressurised feed air or process streams within or from the air fractionation unit
    • F25J3/04048Providing pressurised feed air or process streams within or from the air fractionation unit by compression of cold gaseous streams, e.g. intermediate or oxygen enriched (waste) streams
    • F25J3/04054Providing pressurised feed air or process streams within or from the air fractionation unit by compression of cold gaseous streams, e.g. intermediate or oxygen enriched (waste) streams of air
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    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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    • F25J3/02Processes 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
    • F25J3/04Processes 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
    • F25J3/04406Processes 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
    • F25J3/04412Processes 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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    • F25J3/04006Providing pressurised feed air or process streams within or from the air fractionation unit
    • F25J3/04012Providing pressurised feed air or process streams within or from the air fractionation unit by compression of warm gaseous streams; details of intake or interstage cooling
    • F25J3/04018Providing pressurised feed air or process streams within or from the air fractionation unit by compression of warm gaseous streams; details of intake or interstage cooling of main feed air
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    • F25J3/04078Providing 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
    • F25J3/0409Providing 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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    • F25J3/04163Hot end purification of the feed air
    • F25J3/04169Hot end purification of the feed air by adsorption of the impurities
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    • F25J3/04187Cooling of the purified feed air by recuperative heat-exchange; Heat-exchange with product streams
    • F25J3/04218Parallel 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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    • F25J3/04721Producing pure argon, e.g. recovered from a crude argon column
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    • F25J3/04951Arrangements of multiple air fractionation units or multiple equipments fulfilling the same process step, e.g. multiple trains in a network
    • F25J3/04957Arrangements of multiple air fractionation units or multiple equipments fulfilling the same process step, e.g. multiple trains in a network and inter-connecting equipments upstream of the fractionation unit (s), i.e. at the "front-end"
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    • F25J2205/32Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes as direct contact cooling tower to produce a cooled gas stream, e.g. direct contact after cooler [DCAC]
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    • F25J2205/60Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
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    • F25J2215/00Processes characterised by the type or other details of the product stream
    • F25J2215/42Nitrogen or special cases, e.g. multiple or low purity N2
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    • F25J2215/50Oxygen or special cases, e.g. isotope-mixtures or low purity O2
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    • F25J2220/00Processes or apparatus involving steps for the removal of impurities
    • F25J2220/40Separating high boiling, i.e. less volatile components from air, e.g. CO2, hydrocarbons
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    • F25J2230/00Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/30Compression of the feed stream
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    • F25J2230/40Processes or apparatus involving steps for increasing the pressure of gaseous process streams the fluid being air
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    • F25J2240/00Processes or apparatus involving steps for expanding of process streams
    • F25J2240/02Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
    • F25J2240/10Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream the fluid being air
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    • F25J2245/00Processes or apparatus involving steps for recycling of process streams
    • F25J2245/58Processes or apparatus involving steps for recycling of process streams the recycled stream being argon or crude argon
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    • F25J2270/00Refrigeration techniques used
    • F25J2270/90External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J2290/00Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/12Particular process parameters like pressure, temperature, ratios

Definitions

  • the present invention relates to a process and an apparatus for separating air by cryogenic distillation.
  • the overhead gas from the first column is used to heat the bottom of the second column.
  • the second column can be in two sections and can be connected to an argon separation column.
  • the apparatus is kept cold by a turbine sending gaseous or liquid air to the first column and / or by a turbine sending air to the second column.
  • US4964901 describes a process where a single air compressor produces air at two different pressures which is purified at these different pressures and sent to the column system.
  • the process produces oxygen at relatively low purities and does not produce argon.
  • EP1357342 A1 describes a three-column process with an argon column supplied with purified air at two different pressures.
  • the pressures used are significantly greater than those used according to the invention.
  • a air separation device can when even have a strong injection of low pressure air directly into the low pressure column of a column system comprising one column operating at lower pressure than the other.
  • an apparatus for separating air by cryogenic distillation using a column system consisting of a first column operating at a first pressure and a second column operating at a second pressure lower than the first. pressure, the head of the first column being thermally connected to the bottom of the second column, a first adsorption unit, a second adsorption unit, means for sending a first air flow constituting between 75 and 98% of the air sent to the column system compressed at a third pressure above the first pressure to cooling means and then at the third pressure to the first adsorption unit to be purified of water and carbon dioxide and means for sending all of the first purified flow to the first column and possibly to the second column, means for sending a second air flow constituting between 5 and 25% of the air sent to the compressed column system at a fourth pressure between 1.2 and 2 bars abs and above the second pressure but below the third pressure, at the fourth pressure at the second adsorption unit to be purified of water and carbon dioxide and means for sending all of the second purified flow to
  • the column system only comprises the first and the second columns.
  • FIG. 1 shows that a first air flow 1 constituting between 75 and 98% of the total air sent to the column system is compressed from atmospheric pressure to a pressure slightly above the pressure of a first column 101.
  • the difference between the pressure of the first column and the pressure of the compressed air 3 in the compressor 2 corresponds to the pressure drop due to the cooling and purification which takes place after the compression and before entering the compressor. the column.
  • Other means of cooling the air 35 can be envisaged, for example refrigeration units.
  • the air 3 can therefore be at between 5 and 6 bars abs and is sent to a first cooling tower 4 fed at the head with water 94 and at an intermediate level with water 98.
  • the cooled air 5 withdrawn from the top of the tower 4 is sent to a first adsorption unit 6 to remove the water and the carbon dioxide it contains.
  • the purified air 7 is divided into three parts. Part 8 cools in the gaseous state in the first heat exchanger 80 and enters the column 101 in the gaseous form mixed with the air 32 to form the flow 10.
  • Another part 12 is supercharged in a booster 13 to form a supercharged flow 14 which is cooled in the first exchanger 80 to form a cooled flow 15 extracted at an intermediate temperature level of the exchanger.
  • This flow 15 is expanded in a turbine 16 to form a gas 17 at the pressure of the second column 102 and is sent to the column 102.
  • Another part 19 is boosted in a booster 20 to form the flow 21 and then is divided into two fractions.
  • a fraction 22 is cooled in the first exchanger 80, extracted at an intermediate temperature level (typically around -120 ° C, not shown), is boosted in a cold booster 24, is reintroduced into the exchanger 80, cools in the exchanger 80 and is expanded in the turbine 27 to form a liquid 28 (or possibly a two-phase) which is sent to the first column 101.
  • an intermediate temperature level typically around -120 ° C, not shown
  • the other fraction 29 cools in the exchanger 80 and is extracted at an intermediate temperature level (not shown) to form a flow 30 which is expanded in a turbine 31 coupled to the cold booster 24.
  • the expanded air 32 is released. at the pressure of the first column 101.
  • a second air flow 33 constituting between 5 and 25%, preferably more than 10%, of the total air sent to the column system is compressed from atmospheric pressure to a pressure slightly above the pressure d 'a second column 102.
  • the difference between the pressure of the second column and the pressure of the compressed air in the compressor 34 corresponds to the pressure drop due to the cooling and purification which takes place after the compression and before the entry in column 102.
  • the air 35 is at between 1.2 and 2 bars abs and is sent to a second cooling tower 36 fed at the head with water 97 and at an intermediate level with water 90.
  • the cooled air 37 withdrawn at the top of the tower 36 is sent to a second adsorption unit 38 to remove the water and the carbon dioxide it contains.
  • Other means of cooling the air 35 can be envisaged, for example refrigeration units.
  • the use of a tower is nevertheless preferred for the air at lower pressure in order to reduce the associated pressure drops.
  • the purified air 39 cools in the gaseous state in the second heat exchanger 81 to form the flow 40 and enters the column 102 in gaseous form mixed with the air 17 to form the flow 120.
  • the flow 120 represents between 3 and 5% of the total air flow.
  • the air flow 120 is sent to the second column 102 to be separated at the same level of the column as the expanded bottom liquid 48 and above the arrival of the vaporized rich liquid 72.
  • the flow 40 sent to the second column 102 represents between 5 and 25% of the total air, preferably more than 10% of the total air sent to the column system.
  • the flow rate 120 represents between 10 and 25% of the total air sent to the column system, being a mixture of the flow rate 40 and the blown air 17.
  • argon from a third column preferably with a yield of around 65% that it was possible to simultaneously obtain a production of oxygen at a purity of more than 99% and of preferably greater than 99.5% with a good oxygen yield typically around 99% (at least greater than 95%).
  • the Figure 2 illustrates with constant oxygen purity 99.5% and constant oxygen yield 99%, the quantity of air, in terms of percentage of the total air flow sent to the distillation, which can be injected directly into the second column 102 as a function of the argon yield of the unit on the abscissa.
  • the oxygen yield is defined by the quantity of oxygen contained in the oxygen productions which may be gaseous and / or liquid divided by the quantity of oxygen contained in all of the air flows introduced into the device.
  • the maximum percentage of air to be sent to the second column is located around the point of the yield of 65% for argon.
  • the argon from the third column is either mixed with the residual nitrogen, or produced in liquid or gaseous form after passing through a denitrogenation column.
  • a column system consisting of a first column 101 operating at a first pressure and a second column 102 operating at a second pressure lower than the first pressure.
  • the overhead gas from the first column is used to heat the bottom of the second column.
  • the second column can be in two sections and can be connected to an argon separation column.
  • the air is separated by distillation in the first column 101 to produce an oxygen enriched bottom liquid 41, an overhead liquid 53 enriched in nitrogen and an intermediate liquid 49 enriched in nitrogen.
  • the liquids 53,49 are cooled in a sub-cooler 80 to form the liquids 54,50 and are expanded by the valves 55,51 respectively before being sent to the second column 102.
  • the oxygen enriched liquid is divided into two parts 42,46. Part 46 is expanded in valve 47 and sent as flow 48 to second column 102. Part 42 is expanded in valve 43 and sent as liquid 44 to an overhead condenser 45 of an argon separation column 103. .
  • Nitrogen gas from the top of column 101 condenses in bottom reboiler 83 of second column 102 to heat the bottom of second column.
  • the condensed nitrogen is returned to the top of the first column 102 and to the top of the second column 101.
  • the argon separation column 103 is supplied with gas by a flow 58 taken at an intermediate level of the low pressure column 102.
  • the bottom liquid 57 of the column 103 is returned to the column 102.
  • a fluid rich in argon is obtained.
  • the fluid may contain about 2% oxygen and may subsequently be mixed with nitrogen gas from the column system or purified by catalysis. Otherwise the fluid may contain less than 2 ppm of oxygen and serve as a product after passing through a denitrogenation column (not shown in the diagram)
  • Liquid oxygen 59 containing at least 99% oxygen, preferably at least 99.5% oxygen, is withdrawn from the bottom of the second column 102, pressurized by a pump 60 and sent as a pressurized flow 61 to the bottom. heat exchanger 80 where it vaporizes completely to form the main product of the apparatus, gaseous oxygen 62 at a pressure of at least 10 bar a. Lower pressures can be considered.
  • Overhead gas 63 from column 102 heats up in sub-cooler 82 and then is split in two. A portion 67 heats up in the second heat exchanger 81 and the remainder 65 heats up in the first heat exchanger 80.
  • the reheated flow 65 is the flow 66 and serves to regenerate the second adsorption unit 38 as the flow 68. It It is also possible to divide the overhead gas 63 of the column 102 into two parts before it is introduced into the sub-cooler 82. In this case, the part 67 which heats up in the second heat exchanger 81 is introduced into said heat exchanger.
  • the flow 67,69 is used in part 70 to regenerate the first adsorption unit 6 and in part 71 to cool the water in the water cooling tower 91.
  • the water 90 is sent to the top of the column and leaves. cooled 92 in the tank to be sent by a pump 93 to the two air cooling towers 4.36.
  • the two air cooling towers 4.36 are supplied with cooling water coming from a single water cooling tower 91 cooled by nitrogen coming from the column system.
  • the water 95 intended for the second air cooling tower 36 is cooled between the water cooling tower 91 and the second tower 36 by a cooler 96, for example a refrigeration unit for cooling the water to a temperature between 5 and 30 ° C below the temperature of the water 94 arriving at the head of the first tower 4, preferably between 8 and 15 ° C below this temperature.
  • a cooler 96 for example a refrigeration unit for cooling the water to a temperature between 5 and 30 ° C below the temperature of the water 94 arriving at the head of the first tower 4, preferably between 8 and 15 ° C below this temperature.
  • the cooling tower producing the chilled water intended to cool the second air cooling tower would have to be supplied with the nitrogen 67 coming from the second heat exchanger 81 because it is cooler than the nitrogen 62 coming from. of the first heat exchanger 80.
  • the second heat exchanger 91 performs a heat exchange between just two fluids, air 39,40 and nitrogen 67.
  • the second compressor and the second adsorption unit could be added to an existing apparatus having the first compressor and the first adsorption unit in order to exceed the production limits of the existing apparatus.
  • the second purified flow 120 is sent to the second column 102 to be separated at the same level of the column as a flow of liquid enriched in oxygen coming from the first column (not shown) or as a flow of liquid enriched in oxygen. from the first column and vaporized in an overhead condenser of the third column, flow rate 72.
  • the argon-rich fluid produced at the top of column 103 contains between 20 and 80% of the argon contained in the first and second air flow rates 1.33, preferably between 45 and 75%.
  • the oxygen efficiency of the device is greater than 95%.
  • the air 20 sent to the second column constitutes between 10 and 25%, or even between 14 and 25%, of the total air sent to the column system.
  • the remaining at least 5% of the air destined for the second column will be part of the first flow 1 and at least 5% of the total air will be expanded in the insufflation turbine 16 so that the air flow sent to the second column is at least 10% of the total air.
  • a first step during periods when energy is cheap, the air is compressed exclusively in the compressor 2 and the flow 33 does not exist.
  • the second column is supplied with air by the turbine 16 exclusively.
  • at least one liquid product for example liquid nitrogen, is produced and can be stored and possibly partly used as a product.
  • the air is compressed in the compressors 2 and 34 and preferably the air flow sent to the compressor 2 will be reduced compared to the flow during the first run.
  • energy costs more and therefore operating costs are reduced by lowering the amount of compressed air to the highest pressure.
  • the device will be kept cold in part by sending liquid nitrogen produced during the first run.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Separation By Low-Temperature Treatments (AREA)
EP21170059.6A 2020-05-20 2021-04-23 Verfahren und gerät zur trennung von luft durch kryogene destillation Pending EP3913310A1 (de)

Applications Claiming Priority (1)

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FR2005220A FR3110685B1 (fr) 2020-05-20 2020-05-20 Procédé et appareil de séparation d’air par distillation cryogénique

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JPS5538423A (en) * 1978-09-11 1980-03-17 Hitachi Ltd Method of extracting low purity oxygen
JPH01174878A (ja) * 1987-12-28 1989-07-11 Nippon Sanso Kk 低純度酸素製造方法
US4964901A (en) 1988-05-20 1990-10-23 Linde Aktiengesellschaft Low-temperature separation of air using high and low pressure air feedstreams
US5469710A (en) * 1994-10-26 1995-11-28 Praxair Technology, Inc. Cryogenic rectification system with enhanced argon recovery
DE19537910A1 (de) * 1995-10-11 1997-04-17 Linde Ag Doppelsäulenverfahren und -vorrichtung zur Tieftemperaturzerlegung von Luft
US5765396A (en) * 1997-03-19 1998-06-16 Praxair Technology, Inc. Cryogenic rectification system for producing high pressure nitrogen and high pressure oxygen
EP1357342A1 (de) 2002-04-17 2003-10-29 Linde Aktiengesellschaft Drei-Säulen-System zur Tieftemperaturzerlegung mit Argongewinnung
WO2013014252A2 (en) * 2011-07-27 2013-01-31 Norwegian University Of Science And Technology (Ntnu) Air separation
CN102809261B (zh) * 2012-04-19 2014-07-23 四川空分设备(集团)有限责任公司 从空气中制取低纯度氧气的深冷法分离方法及其装置

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JPS5528301A (en) 1977-12-19 1980-02-28 Toyota Central Res & Dev Lab Inc Surface treating method for iron, nickel, or cobalt base metal
GB9412182D0 (en) * 1994-06-17 1994-08-10 Boc Group Plc Air separation
GB9505645D0 (en) * 1995-03-21 1995-05-10 Boc Group Plc Air separation
US6269659B1 (en) 1998-04-21 2001-08-07 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method and installation for air distillation with production of argon
US20080223077A1 (en) * 2007-03-13 2008-09-18 Neil Mark Prosser Air separation method
US20120036891A1 (en) * 2010-08-12 2012-02-16 Neil Mark Prosser Air separation method and apparatus
US11635254B2 (en) * 2017-12-28 2023-04-25 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Utilization of nitrogen-enriched streams produced in air separation units comprising split-core main heat exchangers
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Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5538423A (en) * 1978-09-11 1980-03-17 Hitachi Ltd Method of extracting low purity oxygen
JPH01174878A (ja) * 1987-12-28 1989-07-11 Nippon Sanso Kk 低純度酸素製造方法
US4964901A (en) 1988-05-20 1990-10-23 Linde Aktiengesellschaft Low-temperature separation of air using high and low pressure air feedstreams
US5469710A (en) * 1994-10-26 1995-11-28 Praxair Technology, Inc. Cryogenic rectification system with enhanced argon recovery
DE19537910A1 (de) * 1995-10-11 1997-04-17 Linde Ag Doppelsäulenverfahren und -vorrichtung zur Tieftemperaturzerlegung von Luft
US5765396A (en) * 1997-03-19 1998-06-16 Praxair Technology, Inc. Cryogenic rectification system for producing high pressure nitrogen and high pressure oxygen
EP1357342A1 (de) 2002-04-17 2003-10-29 Linde Aktiengesellschaft Drei-Säulen-System zur Tieftemperaturzerlegung mit Argongewinnung
WO2013014252A2 (en) * 2011-07-27 2013-01-31 Norwegian University Of Science And Technology (Ntnu) Air separation
CN102809261B (zh) * 2012-04-19 2014-07-23 四川空分设备(集团)有限责任公司 从空气中制取低纯度氧气的深冷法分离方法及其装置

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FR3110685B1 (fr) 2022-12-23
FR3110685A1 (fr) 2021-11-26
CN113701451A (zh) 2021-11-26
US11852408B2 (en) 2023-12-26

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