US20170003073A1 - Method and apparatus for separation at subambient temperature - Google Patents

Method and apparatus for separation at subambient temperature Download PDF

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Publication number
US20170003073A1
US20170003073A1 US15/105,269 US201415105269A US2017003073A1 US 20170003073 A1 US20170003073 A1 US 20170003073A1 US 201415105269 A US201415105269 A US 201415105269A US 2017003073 A1 US2017003073 A1 US 2017003073A1
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fluid
column
heated
gas mixture
magnetocaloric
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Benoit Davidian
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Publication of US20170003073A1 publication Critical patent/US20170003073A1/en
Assigned to L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude reassignment L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DAVIDIAN, BENOIT
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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
    • F25J3/0204—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 feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04278—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using external refrigeration units, e.g. closed mechanical or regenerative refrigeration units
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    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B21/00—Machines, plants or systems, using electric or magnetic effects
    • 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
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    • 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
    • F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
    • F25J3/04612—Heat exchange integration with process streams, e.g. from the air gas consuming unit
    • 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
    • F25J5/00—Arrangements of cold exchangers or cold accumulators in separation or liquefaction plants
    • 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
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2321/00—Details of machines, plants or systems, using electric or magnetic effects
    • F25B2321/002—Details of machines, plants or systems, using electric or magnetic effects by using magneto-caloric effects
    • 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
    • F25J2200/02—Processes or apparatus using separation by rectification in a single pressure main column system
    • 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
    • F25J2200/04—Processes or apparatus using separation by rectification in a dual pressure main column system
    • F25J2200/06—Processes or apparatus using separation by rectification in a dual pressure main column system in a classical double column flow-sheet, 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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/40—Features relating to the provision of boil-up in the bottom of a 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
    • 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
    • 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
    • F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/70—Flue or combustion exhaust gas
    • 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
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/40—Separating high boiling, i.e. less volatile components from air, e.g. CO2, hydrocarbons
    • 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
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/80—Separating impurities from carbon dioxide, e.g. H2O or water-soluble contaminants
    • F25J2220/82—Separating low boiling, i.e. more volatile components, e.g. He, H2, CO, Air gases, CH4
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2240/00—Processes or apparatus involving steps for expanding of process streams
    • F25J2240/02—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
    • F25J2240/10—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream the fluid 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
    • 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
    • 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
    • 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
    • F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
    • F25J2260/02—Integration in an installation for exchanging heat, e.g. for waste heat recovery
    • 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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/908—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by regenerative chillers, i.e. oscillating or dynamic systems, e.g. Stirling refrigerator, thermoelectric ("Peltier") or magnetic refrigeration
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to a process and to an apparatus for separation at subambient temperature, or even cryogenic temperature.
  • the separation may be separation by distillation and/or by dephlegmation and/or by absorption.
  • the separation is carried out using at least one column which, reduced in its simplest form, may be a phase separator.
  • Magnetic refrigeration is based on the use of magnetic materials which have a magnetocaloric effect. This effect, which is reversible, results in a variation in their temperature when they are subjected to the application of an external magnetic field.
  • the optimum ranges within which these materials are used lie in the vicinity of their Curie temperature (Tc). This is because the greater the variations in magnetization and consequently in changes in magnetic entropy, the greater the changes in their temperature.
  • the magnetocaloric effect is said to be direct when the temperature of the material increases when it is placed in a magnetic field, and indirect when it cools when it is placed in a magnetic field. The remainder of the description will be given for the direct case, but it is obvious to those skilled in the art how to reapply this to the indirect case.
  • a conventional magnetic refrigeration cycle consists i) in magnetizing the material in order to increase the temperature thereof, ii) in cooling the material in a constant magnetic field in order to dissipate heat, iii) in demagnetizing the material in order to cool it, and iv) in heating the material in a constant (generally zero) magnetic field in order to absorb heat.
  • a magnetic refrigeration device uses elements made of magnetocaloric material, which generate heat when they are magnetized and absorb heat when they are demagnetized. It may use a magnetocaloric material regenerator in order to amplify the temperature difference between the “hot source” and the “cold source”: the magnetic refrigeration is then said to be magnetic refrigeration using active regeneration.
  • the magnetocaloric materials are subjected to a temperature which varies, their magnetic conductivity varies.
  • the optimum ranges within which these materials are used lie in the vicinity of their Curie temperature (Tc).
  • a heat pump is a thermodynamic device which makes it possible to transfer an amount of heat from a medium considered to be the “emitter” (supply medium), referred to as the “cold” source, to a heat “receiver” medium, referred to as the “hot” source.
  • the cold source is the medium from which heat is extracted and the hot source is the medium into which the heat is reinjected, the cold source being at a temperature colder than the hot source.
  • thermodynamic cycle of compressing—cooling (condensing)—expanding—reheating (vaporizing) a refrigerating fluid.
  • An ambient temperature is the temperature of the ambient air in which the process is situated or, alternatively, a temperature of a cooling water circuit connected with the air temperature.
  • a subambient temperature is at least 10° C. below the ambient temperature.
  • a cryogenic temperature is below ⁇ 20° C., or even below ⁇ 55° C., or even below ⁇ 100° C.
  • EP-A-2604824 describes a process according to the preamble of claim 1 .
  • An objective of the present invention is to overcome all or some of the prior art drawbacks raised above.
  • An object of the present invention is to exploit the cold generated by the vaporization of a cryogenic liquid in a process for separation at subambient temperature.
  • a process for separating a gas mixture at subambient temperature, or even cryogenic temperature, wherein a gas mixture is sent to a thermally insulated chamber, is cooled and is separated in a column, placed inside the chamber, so as to produce at least two fluids, each of which is enriched with a component of the gas mixture, at least one fluid from the process being heated inside the chamber, or even vaporized, by heat exchange with at least one heating member, characterized in that the at least one heating member comprises at least one element having magnetocaloric properties, and integrated into a circuit capable of conducting a magnetic flux, said at least one element being alternatingly in thermal contact with a cold source, made up of the fluid to be heated, or even the liquid to be vaporized, and a hot source made up of the surrounding environment or another source that is hotter than the fluid to be heated, and the variation in the magnetic flux via the magnetocaloric effect generates electrical and/or mechanical energy, the fluid to be heated being the gas mixture to be separated.
  • an apparatus for separating a gas mixture at subambient temperature, or even cryogenic temperature, comprising a thermally insulated chamber, a heat exchanger and at least one separating column which are placed inside the chamber, a pipe for sending the gas mixture to the heat exchanger for it to cool, a pipe for sending the cooled mixture to the column, means for withdrawing at least two fluids, each of which is enriched with a component of the gas mixture from the column, a member for heating at least one fluid from the process, located inside the chamber, characterized in that the at least one heating member comprises at least one element having magnetocaloric properties and integrated into a circuit capable of conducting a magnetic flux, said at least one element being alternatingly in thermal contact with a cold source made up of the fluid to be heated, or even the liquid to be vaporized, and a hot source made up of the surrounding environment or another source that is hotter than the fluid to be heated and means for generating electrical and/or mechanical energy from the variation in the magnetic flux via the magneto
  • the invention can also relate to any alternative device or process comprising any combination of the characteristics above or below.
  • FIG. 1 represents a diagrammatic and partial view illustrating the structure and operation of a first example of a facility for producing gas according to the invention
  • FIGS. 2 and 3 represent diagrammatic and partial views illustrating the structure and the operation of, respectively, a second and a third example of a facility for producing gas according to the invention.
  • FIG. 1 shows a process for separating air by cryogenic distillation.
  • air 1 is compressed in a compressor 3 , cooled in a cooler 5 to form a cooled flow 7 and purified in a purification unit 9 .
  • the purified air enters a thermally insulated chamber E and cools in a heat exchanger 17 .
  • the air cooled at a cryogenic temperature is sent to an intermediate level of a distillation column 23 .
  • the distillation column 23 is a simple column equipped with a top condenser 8 and with a bottom reboiler 10 .
  • the bottom reboiler 10 is heated by means of a heating member G comprising at least one element having magnetocaloric properties and integrated into a circuit capable of conducting a magnetic flux.
  • the element is alternatingly in thermal contact with a cold source, made up of the liquid to be vaporized in the bottom of the column 23 , through the reboiler 10 , and a hot source made up of a fluid 4 hotter than the liquid to be vaporized.
  • a cold source made up of the liquid to be vaporized in the bottom of the column 23
  • a hot source made up of a fluid 4 hotter than the liquid to be vaporized.
  • the cooling of the head of the column 23 may also be provided by a cooling member M comprising at least one element having magnetocaloric properties which serves to cool a top condenser 8 of the column.
  • a cooling member M comprising at least one element having magnetocaloric properties which serves to cool a top condenser 8 of the column.
  • FIG. 2 shows an apparatus for separating air by cryogenic distillation.
  • the apparatus comprises a heat exchange line 17 and a double air separation column comprising a medium-pressure column 23 and a low-pressure column 25 thermally connected by means of a reboiler 27 .
  • Air 1 is compressed in a compressor 3 to a pressure of 5.5 bara.
  • the compressed air is cooled in the cooler 5 so as to form a cooled flow 7 which is purified in order to remove the water and the carbon dioxide in an adsorption unit 9 .
  • the purified air enters a thermally insulated chamber E and is divided up into four.
  • a part 8 A cools to an intermediate temperature of the heat exchanger 17 , then is sent to a heating organ G comprising at least one element having magnetocaloric properties and integrated into a circuit capable of conducting a magnetic flux.
  • the element is alternatingly in thermal contact with a cold source, made up of the air 8 A at the intermediate temperature of the exchanger, and a cold source 4 made up of the surrounding environment or another source hotter than the air 8 A.
  • the variation in the magnetic flux via the magnetocaloric effect generates electrical and/or mechanical energy.
  • the air 8 A heated by the member G is sent back to the heat exchanger at a temperature higher than the temperature at which it is withdrawn therefrom.
  • a part 8 B cools, while entirely passing through the exchange line 17 , to a temperature of approximately ⁇ 170° C. and is mixed with the flow 8 A and then sent to the medium-pressure column in gas form.
  • a part 8 C cools while entirely passing through the exchange line 17 and then serves as a cold source for the heat pump 31 having a magnetocaloric effect.
  • the remainder 21 is sent to separate a gas form in the column 23 .
  • the part 8 C cools and liquefies by heat exchange in the heat pump 31 .
  • the part 8 C is divided up into a part 8 D which is sent to the medium-pressure column 23 and a part 8 E which is sent to the low-pressure column 25 .
  • the invention could also apply to processes for separating other mixtures.
  • the air could be replaced with a mixture containing, as main components, methane and nitrogen and/or carbon dioxide.
  • a liquid enriched with oxygen 33 is withdrawn from the bottom of the medium-pressure column 23 , cooled in the sub-cooler 43 and sent to the low-pressure column 25 .
  • a liquid enriched with nitrogen 35 is withdrawn from the top of the medium-pressure column 23 , cooled in the sub-cooler 43 and sent to the top of the low-pressure column 25 .
  • Air 11 is boosted in a booster 13 , cooled in the exchange line 17 , expanded in the turbine 15 and sent to the low-pressure column 25 .
  • a nitrogen-rich gas 45 is withdrawn from the top of the low-pressure column 25 , heated in the sub-cooler 43 and in the exchange line 17 and sent at least partly to the regeneration of the purification 9 .
  • Nitrogen-rich gas 49 is withdrawn from the top of the medium-pressure column 23 , and heated in the exchange line 17 and serves as product.
  • Liquid oxygen 47 is withdrawn from the low-pressure column 25 , pressurized by a pump 29 and partially heated in the exchange line 17 . The heated liquid is then removed from the exchange line 17 , at least partially vaporized in the heat pump 31 and sent back to the exchange line 17 , either for finishing the vaporization and heating, or solely for heating.
  • FIG. 3 illustrates a process for separating by distillation a carbon dioxide-rich gas mixture in order to produce a gas product enriched with carbon dioxide.
  • the gas mixture comes from a source 1 A which may be an oxycombustion unit followed by purification units in order to remove the water and other contaminants, such as dust, SO x or NO x .
  • the source 1 A may be a compressor.
  • the gas mixture 3 A is compressed as required for example at a pressure above 6 bar ABS.
  • the pressurized gas mixture 3 A is sent into a thermally insulated chamber E and is cooled in a brazed aluminum plate heat exchanger 5 A.
  • the cooled gas mixture is, as required, treated in a separating means 7 A.
  • This separating means 7 A may be made up of a phase separator or several phase separators in series in order to increase the carbon dioxide content of the gas mixture upstream of the column 10 A, for example in order to reach at least 80% of carbon dioxide for the liquid from a phase separator.
  • the separating means 7 A may alternatively or additionally comprise a distillation column, for example a column for removing NO x , or else an exchanger for at least partially cooling the gas mixture or a fluid derived from a part of the gas mixture.
  • the carbon dioxide-enriched liquid 9 A is sent to the top of the low-temperature separating column 10 A.
  • the top gas 13 A is withdrawn at the top of the column and is enriched with light components with respect to the liquid 9 A. It heats in the exchanger 5 A.
  • the bottom liquid contains more than 90% of carbon dioxide and is separated into three parts.
  • a part 12 A is sent to a heating member G comprising at least one element having magnetocaloric properties and integrated into a circuit capable of conducting a magnetic flux.
  • the element is alternatingly in thermal contact with a cold source, made up of the liquid to be vaporized 12 A, and a hot source 4 A made up of the surrounding environment or another source that is hotter than the liquid 12 A.
  • the variation in the magnetic flux via the magnetocaloric effect generates electrical and/or mechanical energy.
  • the heat produced by the member G makes it possible to vaporize the liquid 12 A and the vaporized liquid is sent back to the bottom of the column 10 A.
  • the remainder of the bottom liquid 11 A is divided in two so as to form a part 15 A and a part 19 A.
  • the part 15 A is expanded in a valve 17 A and vaporizes, then heats in the heat exchanger so as to form a carbon dioxide-rich gas product.
  • the remainder 19 A is sent to an intermediate level of the heat exchanger 5 A, vaporizes therein and then heats so as to form a carbon dioxide-rich gas product, optionally combined with the first CO 2 -rich gas product, after compression, thereby forming the part 23 A.
  • the variation in the magnetic flux via the magnetocaloric effect in the element can generate electrical energy to be exported or to be used in the process. Otherwise or additionally, the variation can generate mechanical energy for driving, for example, a rotating machine of the process or a generator.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
US15/105,269 2013-12-20 2014-12-19 Method and apparatus for separation at subambient temperature Abandoned US20170003073A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1363159 2013-12-20
FR1363159A FR3015306A1 (fr) 2013-12-20 2013-12-20 Procede et appareil de separation a temperature subambiante
PCT/FR2014/053468 WO2015092330A2 (fr) 2013-12-20 2014-12-19 Procédé et appareil de séparation à température subambiante

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US20170003073A1 true US20170003073A1 (en) 2017-01-05

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FR3120431B1 (fr) * 2021-03-05 2023-03-31 Air Liquide Purification de monoxyde de carbone par distillation cryogénique

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EP3084328A2 (fr) 2016-10-26
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FR3015306A1 (fr) 2015-06-26
WO2015092330A2 (fr) 2015-06-25

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