EP0628777A1 - Process and apparatus for obtaining argon - Google Patents

Process and apparatus for obtaining argon Download PDF

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Publication number
EP0628777A1
EP0628777A1 EP94107374A EP94107374A EP0628777A1 EP 0628777 A1 EP0628777 A1 EP 0628777A1 EP 94107374 A EP94107374 A EP 94107374A EP 94107374 A EP94107374 A EP 94107374A EP 0628777 A1 EP0628777 A1 EP 0628777A1
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Prior art keywords
column
argon
fraction
semi
crude argon
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EP94107374A
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German (de)
French (fr)
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EP0628777B1 (en
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Horst Dipl.-Ing. Corduan
Hartwin Dipl.-Ing. Lindner
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Linde GmbH
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Linde GmbH
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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
    • F25J3/0423—Subcooling of liquid process streams
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04406—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system
    • F25J3/04412—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system in a classical double column flowsheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04642—Recovering noble gases from air
    • F25J3/04648—Recovering noble gases from air argon
    • F25J3/04654—Producing crude argon in a crude argon column
    • F25J3/04666—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system
    • F25J3/04672—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system having a top condenser
    • F25J3/04678—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system having a top condenser cooled by oxygen enriched liquid from high pressure column bottoms
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04642—Recovering noble gases from air
    • F25J3/04648—Recovering noble gases from air argon
    • F25J3/04654—Producing crude argon in a crude argon column
    • F25J3/04666—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system
    • F25J3/04672—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system having a top condenser
    • F25J3/04703—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system having a top condenser being arranged in more than one vessel
    • 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
    • F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/58—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being argon or crude argon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/50—Processes or apparatus involving steps for recycling of process streams the recycled stream being oxygen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S62/00—Refrigeration
    • Y10S62/923—Inert gas
    • Y10S62/924—Argon

Definitions

  • the invention relates to a method and a device for the production of argon, in which method air is broken down in a rectification system with at least one air separation column and one crude argon column, an argon-containing oxygen fraction being removed from the air separation column and introduced into a raw argon column, in the upper region of the A crude argon fraction is taken from the crude argon column and a first reflux liquid is added, and a first residual fraction is taken off in the lower region of the crude argon column.
  • EP-B-377 117 discloses a special method of this type which provides for a particularly high number of theoretical plates in the crude argon column and the use of packing or packing in the crude argon column. In this way it is possible to achieve very low oxygen concentrations in the crude argon product.
  • the overall height of a crude argon column, including the top condenser is very great when packs which correspond to a large number of theoretical plates are used, so that they may reach or even exceed the height of the air separation column (s) for oxygen and nitrogen extraction.
  • a complex design of the insulating sheathing of the rectification columns may be necessary.
  • the invention is therefore based on the object of developing a method and a device of the type mentioned at the outset which are distinguished by particularly high economic efficiency, in particular by relatively little outlay in terms of apparatus for the production of crude argon.
  • This object is achieved in that the crude argon fraction is introduced into the lower region of a semi-pure column, an argon fraction depleted in oxygen being removed in the upper region of the semi-pure column and a second reflux liquid being added and a second residual fraction being removed in the lower region of the semi-pure column forms the first return liquid for the crude argon column.
  • the reflux liquid is thus formed by the liquid of a further rectification column, into which the crude argon product is conversely introduced.
  • a head capacitor for the crude argon column can thus be dispensed with.
  • the product fraction from the crude argon column is further depleted of oxygen in the semi-pure column.
  • a semi-pure column By using a semi-pure column, an essentially oxygen-free argon product can be obtained, the overall height of the crude argon column not only being reduced by dispensing with a top condenser, but also overall being able to be adapted very flexibly to the conditions of the entire air separation plant. It is deliberately avoided to achieve the lowest possible oxygen concentration in the crude argon column.
  • the method according to the invention offers economic advantages by reducing the size of the crude argon column, which in many cases outweigh the costs of the additional column.
  • the oxygen-depleted argon fraction is withdrawn as a product or intermediate product in gaseous or liquid form. It can be further cleaned, for example in a pure argon column, in particular freed of nitrogen.
  • the pressure in the lower region of the semi-pure column is preferably substantially equal to the pressure in the upper region of the crude argon column.
  • the return liquid for the semi-pure column can in principle be generated by condensation of the corresponding top fraction or can be supplied from another source.
  • At least part of the argon fraction from the upper region of the semi-pure column is preferably condensed by indirect heat exchange, at least part of the condensate forming the second reflux liquid.
  • a top condenser is generally arranged above the rectification area of the semi-pure column.
  • the liquid fraction evaporating against the condensing argon fraction is preferably formed from the pressure column by oxygen-enriched liquid.
  • the evaporated liquid fraction is then fed into the low pressure column.
  • Packings and / or ordered packings are preferably used as mass transfer elements in crude argon and / or semi-pure columns. Ordered packings are preferred because of their particularly low pressure drop. Packings or packings, in particular ordered packings, can also be used in the other rectification columns used in the process, for example in the low-pressure column of a two-stage air separator.
  • any ordered pack can be used in the method according to the invention.
  • the use of internals such as are described in the not previously published documents WO 93/19335 or WO 93/19336 is favorable.
  • the invention also relates to an apparatus for the production of argon according to claims 8 to 13.
  • an air separation process for generating oxygen and nitrogen with a double column 1, which consists of a pressure column 2 and a low pressure column 3, is indicated.
  • the invention does not depend on the special design of this process section, but can also be applied to other forms of this part of the process or the device, for example to a system with a single column or to different types of product removal of nitrogen and oxygen. Details such as turbines for the cooling relief of process streams or direct feeding of air into the low pressure column are not shown in the simplified diagram.
  • an argon-containing oxygen stream 4 which also contains impurities in the form of nitrogen and other air constituents, is taken from a location of relatively high argon concentration in the low-pressure column 3, and is separated into crude argon 6 and a first residual fraction 8 in a crude argon column 5. The latter is returned to the low-pressure column 3, possibly by means of a pump (not shown), and is fed back somewhat below the removal point for the argon-containing oxygen stream.
  • crude argon 6 obtained at the top of the crude argon column 5 is subjected to a further rectification step in a semi-pure column 9 to remove less volatile components, in particular oxygen.
  • the raw argon is preferably fed in gaseous form into the lower region of this column 9.
  • Argon depleted in oxygen is withdrawn from the upper region of the semi-pure column 9 in gaseous form (10) and / or liquid (15).
  • Return liquid 11 for the semi-pure column is generated by condensation of the top fraction by means of indirect heat exchange 13 against expanded sump liquid from the pressure column 2 of the air separator 1.
  • the resulting steam is discharged via line 16 and introduced into the low-pressure column 3 at a suitable point.
  • the crude argon column 5 does not require a top condenser. Your need for return liquid 7 is covered by sump liquid 12, which is obtained in the semi-pure column 9. As a rule, a pump 17 must be used to overcome the height difference in line 7.
  • the rectification areas shown throughout in the drawing consist in reality of several sections. Ordered packings are preferably used as mass transfer elements, especially in crude argon and semi-pure columns. However, parts of the columns can also be equipped with conventional rectification trays.
  • the crude argon column has one rectification section, the semi-pure column three.
  • the number of these sections can, however vary, in the crude argon column from one to about three, in the semi-pure column from about two to six.
  • the crude argon column 5 contains, for example, 30 to 120, preferably about 60 to 90 theoretical plates.
  • the number of theoretical plates in the semi-pure column 9 is, for example, 60 to 150, preferably approximately 90 to 120.
  • the ratio of the theoretical plate numbers (crude argon column 5 to semi-pure column 9) is, for example, 0.5.
  • the oxygen concentrations in the different streams have, for example, the following values: Transitional fraction 4 82 to 92, preferably about 86 to 90% Raw argon fraction 6 0.1 to 2.0, preferably about 0.5 to 1.0% Argon fraction 10 0.01 to 10, preferably about 0.01 to 0.1 ppm

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

Zur Gewinnung von Argon wird Luft in einem Rektifiziersystem mit mindestens einer Luftzerlegersäule (3) und einer Rohargonsäule zerlegt. Eine argonhaltige Sauerstofffraktion (4) wird aus der Luftzerlegersäule (3) entnommen und in eine Rohargonsäule (5) eingeleitet. Im oberen Bereich der Rohargonsäule (5) werden eine Rohargonfraktion (6) entnommen und eine erste Rücklaufflüssigkeit (7) aufgegeben. Aus dem unteren Bereich der Rohargonsäule (5) wird eine erste Restfraktion (8) entnommen. Die Rohargonfraktion (6) wird in den unteren Bereich einer Halbreinsäule (9) eingeleitet. Im oberen Bereich der Halbreinsäule (9) werden eine an Sauerstoff abgereicherte Argonfraktion entnommen (10, 15) und eine zweite Rücklaufflüssigkeit (11) aufgegeben. Aus dem unteren Bereich der Halbreinsäule (9) wird eine zweite Restfraktion (12) entnommen, welche die erste Rücklaufflüssigkeit (7) für die Rohargonsäule (5) bildet. <IMAGE>To obtain argon, air is broken down in a rectification system with at least one air separation column (3) and one crude argon column. An argon-containing oxygen fraction (4) is removed from the air separation column (3) and introduced into a crude argon column (5). A crude argon fraction (6) is removed from the upper area of the crude argon column (5) and a first reflux liquid (7) is added. A first residual fraction (8) is removed from the lower region of the crude argon column (5). The crude argon fraction (6) is introduced into the lower region of a semi-pure column (9). In the upper area of the semi-pure column (9), an argon fraction depleted in oxygen (10, 15) is removed and a second reflux liquid (11) is added. A second residual fraction (12) is removed from the lower area of the semi-pure column (9) and forms the first reflux liquid (7) for the crude argon column (5). <IMAGE>

Description

Die Erfindung betrifft ein Verfahren und eine Vorrichtung Zur Gewinnung von Argon, wobei in dem Verfahren Luft in einem Rektifiziersystem mit mindestens einer Luftzerlegersäule und einer Rohargonsäule zerlegt wird, wobei eine argonhaltige Sauerstofffraktion aus der Luftzerlegersäule entnommen und in eine Rohargonsäule eingeleitet wird, im oberen Bereich der Rohargonsäule eine Rohargonfraktion entnommen und eine erste Rücklaufflüssigkeit aufgegeben werden und im unteren Bereich der Rohargonsäule eine erste Restfraktion entnommen wird.The invention relates to a method and a device for the production of argon, in which method air is broken down in a rectification system with at least one air separation column and one crude argon column, an argon-containing oxygen fraction being removed from the air separation column and introduced into a raw argon column, in the upper region of the A crude argon fraction is taken from the crude argon column and a first reflux liquid is added, and a first residual fraction is taken off in the lower region of the crude argon column.

Derartige Verfahren und Anlagen zur Gewinnung von Rohargon sind allgemein aus der Fachliteratur bekannt (beispielsweise aus Hausen/Linde, Tieftemperaturtechnik, 2. Auflage, Kapitel 4.5.4.1; Winnacker/Küchler, Chemische Technologie, Band 2, 3. Auflage, Kapitel 5.231.; Latimer, Distillation of Air, Chem. Eng. Progr., 63, Seiten 35 bis 59). Bei solchen Prozessen wird im Anschluß an eine zweistufige Luftzerlegung Rohargon in einer Rohargonsäule gewonnen, die mit der Niederdrucksäule des Luftzerlegers verbunden ist. Seltener wird die Rohargongewinnung mit einer Einzelsäule zur Stickstoff- und/oder Sauerstoffgewinnung gekoppelt. Die Rücklaufflüssigkeit für die Rohargonsäule wird in einem Kopfkondensator erzeugt, der am oberen Ende dieser Säule angeordnet ist.Such methods and plants for the production of raw argon are generally known from the specialist literature (for example from Hausen / Linde, low temperature technology, 2nd edition, chapter 4.5.4.1; Winnacker / Küchler, Chemische Technologie, volume 2, 3rd edition, chapter 5.231 .; Latimer, Distillation of Air, Chem. Eng. Progr., 63 , pages 35 to 59). In such processes, after a two-stage air separation, raw argon is obtained in a raw argon column, which is connected to the low pressure column of the air separator. Rarely, crude argon production is coupled with a single column for nitrogen and / or oxygen production. The return liquid for the crude argon column is generated in a top condenser, which is arranged at the upper end of this column.

Aus der EP-B-377 117 ist ein spezielles Verfahren dieser Art bekannt, das eine besonders hohe Anzahl von theoretischen Böden in der Rohargonsäule sowie den Einsatz von Füllkörpern oder Packungen in der Rohargonsäule vorsieht. Auf diese Weise ist es möglich, sehr niedrige Sauerstoffkonzentrationen im Rohargonprodukt zu erlangen. Allerdings wird die Bauhöhe einer Rohargonsäule einschließlich Kopfkondensator beim Einsatz von Packungen, die einer hohen Anzahl von theoretischen Böden entsprechen, sehr groß, so daß sie unter Umständen die Höhe der Luftzerlegersäule(n) zur Sauerstoff- und Stickstoffgewinnung erreicht oder sogar überschreitet. Abgesehen davon, daß solch hohe Säulen zusätzlichen Aufwand für Stabilisierung und exakte vertikale Ausrichtung erfordern, kann dadurch eine aufwendige Gestaltung der isolierenden Ummantelung der Rektifiziersäulen (Cold box) notwendig werden.EP-B-377 117 discloses a special method of this type which provides for a particularly high number of theoretical plates in the crude argon column and the use of packing or packing in the crude argon column. In this way it is possible to achieve very low oxygen concentrations in the crude argon product. However, the overall height of a crude argon column, including the top condenser, is very great when packs which correspond to a large number of theoretical plates are used, so that they may reach or even exceed the height of the air separation column (s) for oxygen and nitrogen extraction. In addition to the fact that such high columns require additional effort for stabilization and exact vertical alignment, a complex design of the insulating sheathing of the rectification columns (cold box) may be necessary.

Die bekannten Verfahren und Vorrichtungen sind daher nicht in allen Fällen zufriedenstellend, insbesondere bei großer Anzahl von theoretischen Böden und/oder dem Einsatz von Füllkörpern oder Packungen in der Rohargonsäule.The known methods and devices are therefore not satisfactory in all cases, especially with a large number of theoretical plates and / or the use of packing elements or packings in the crude argon column.

Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren und eine Vorrichtung der eingangs genannten Art zu entwickeln, die sich durch besonders hohe Wirtschaftlichkeit auszeichnen, insbesondere durch relativ geringen apparativen Aufwand für die Rohargongewinnung.The invention is therefore based on the object of developing a method and a device of the type mentioned at the outset which are distinguished by particularly high economic efficiency, in particular by relatively little outlay in terms of apparatus for the production of crude argon.

Diese Aufgabe wird dadurch gelöst, daß die Rohargonfraktion in den unteren Bereich einer Halbreinsäule eingeleitet wird, wobei im oberen Bereich der Halbreinsäule eine an Sauerstoff abgereicherte Argonfraktion entnommen und eine zweite Rücklaufflüssigkeit aufgegeben werden und im unteren Bereich der Halbreinsäule eine zweite Restfraktion entnommen wird, welche die erste Rücklaufflüssigkeit für die Rohargonsäule bildet.This object is achieved in that the crude argon fraction is introduced into the lower region of a semi-pure column, an argon fraction depleted in oxygen being removed in the upper region of the semi-pure column and a second reflux liquid being added and a second residual fraction being removed in the lower region of the semi-pure column forms the first return liquid for the crude argon column.

Die Rücklaufflüssigkeit wird also durch die Flüssigkeit einer weiteren Rektifiziersäule gebildet, in die umgekehrt das Rohargonprodukt eingeleitet wird. Dadurch kann auf einen Kopfkondensator für die Rohargonsäule verzichtet werden.The reflux liquid is thus formed by the liquid of a further rectification column, into which the crude argon product is conversely introduced. A head capacitor for the crude argon column can thus be dispensed with.

Die Produktfraktion aus der Rohargonsäule wird in der Halbreinsäule weiter an Sauerstoff abgereichert. Durch die Verwendung einer Halbreinsäule kann ein im wesentlichen sauerstofffreies Argonprodukt gewonnen werden, wobei die Bauhöhe der Rohargonsäule nicht nur durch den Verzicht auf einen Kopfkondensator verringert werden, sondern auch insgesamt sehr flexibel an die Gegebenheiten der gesamten Luftzerlegungsanlage angepaßt werden kann. Es wird bewußt darauf verzichtet, schon in der Rohargonsäule die kleinstmögliche Sauerstoffkonzentration zu erreichen. Im Rahmen der Erfindung hat es sich herausgestellt, daß das erfindungsgemäße Verfahren wirtschaftliche Vorteile durch die Verringerung der Größe der Rohargonsäule bietet, die in vielen Fällen gegenüber den Kosten der zusätzlichen Säule überwiegen.The product fraction from the crude argon column is further depleted of oxygen in the semi-pure column. By using a semi-pure column, an essentially oxygen-free argon product can be obtained, the overall height of the crude argon column not only being reduced by dispensing with a top condenser, but also overall being able to be adapted very flexibly to the conditions of the entire air separation plant. It is deliberately avoided to achieve the lowest possible oxygen concentration in the crude argon column. Within the scope of the invention it has been found that the method according to the invention offers economic advantages by reducing the size of the crude argon column, which in many cases outweigh the costs of the additional column.

Die sauerstoffabgereicherte Argonfraktion wird als Produkt oder Zwischenprodukt gasförmig oder flüssig abgezogen. Sie kann, beispielsweise in einer Reinargonsäule, weiter gereinigt, insbesondere von Stickstoff befreit werden.The oxygen-depleted argon fraction is withdrawn as a product or intermediate product in gaseous or liquid form. It can be further cleaned, for example in a pure argon column, in particular freed of nitrogen.

Vorzugsweise ist der Druck im unteren Bereich der Halbreinsäule im wesentlichen gleich dem Druck im oberen Bereich der Rohargonsäule.The pressure in the lower region of the semi-pure column is preferably substantially equal to the pressure in the upper region of the crude argon column.

In beiden Säulen herrscht also praktisch derselbe Druck. Die Forderung nach im wesentlichen gleichem Druck am Kopf der Rohargonsäule und am Boden der Halbreinsäule schließt gewisse Differenzen (beispielsweise durch den Druckabfall längs der Rohargonleitung) nicht aus. Insgesamt sollen sie jedoch nicht so groß sein, daß in der Rohargonleitung vom Kopf der Rohargonsäule zum Boden der Halbreinsäule spezielle Vorrichtungen zur Druckerhöhung oder -Verminderung (beispielsweise Verdichter oder Drosselventile) eingesetzt werden müssen. Gegebenenfalls muß eine Pumpe zur Förderung der ersten Rücklaufflüssigkeit verwendet werden.So there is practically the same pressure in both pillars. The requirement for essentially the same pressure at the top of the crude argon column and at the bottom of the semi-pure column does not exclude certain differences (for example due to the pressure drop along the crude argon line). Overall, however, they should not be so large that special devices for increasing or reducing pressure (for example compressors or throttle valves) have to be used in the crude argon line from the top of the crude argon column to the bottom of the semi-pure column. If necessary, a pump must be used to deliver the first return liquid.

Die Rücklaufflüssigkeit für die Halbreinsäule kann grundsätzlich durch Kondensation der entsprechenden Kopffraktion erzeugt oder aus einer anderen Quelle zugeführt werden.The return liquid for the semi-pure column can in principle be generated by condensation of the corresponding top fraction or can be supplied from another source.

Vorzugsweise wird mindestens ein Teil der Argonfraktion aus dem oberen Bereich der Halbreinsäule durch indirekten Wärmeaustausch kondensiert, wobei mindestens ein Teil des Kondensats die zweite Rücklaufflüssigkeit bildet. Dazu wird in der Regel oberhalb des Rektifizierbereichs der Halbreinsäule ein Kopfkondensator angeordnet.At least part of the argon fraction from the upper region of the semi-pure column is preferably condensed by indirect heat exchange, at least part of the condensate forming the second reflux liquid. For this purpose, a top condenser is generally arranged above the rectification area of the semi-pure column.

Dabei ist es insbesondere günstig, wenn bei dem indirekten Wärmeaustausch ein Prozeßstrom des Verfahrens, vorzugsweise eine flüssige Fraktion aus einer der Luftzerlegersäulen, verdampft wird. Externe Kälte für die Kühlung der Halbreinsäule wird damit nicht benötigt.It is particularly advantageous if a process stream of the process, preferably a liquid fraction from one of the air separation columns, is evaporated in the indirect heat exchange. External cooling for cooling the semi-pure column is therefore not required.

Im Falle eines Doppelsäulen-Luftzerlegungsverfahrens, falls also die Luftzerlegersäule zweistufig ausgebildet ist und eine Drucksäule und eine Niederdrucksäule aufweist (hierbei wird die argonhaltige Sauerstofffraktion der Niederdrucksäule entnommen), wird die gegen kondensierende Argonfraktion verdampfende flüssige Fraktion vorzugsweise durch sauerstoffangereicherte Flüssigkeit aus der Drucksäule gebildet. Die verdampfte flüssige Fraktion wird anschließend in die Niederdrucksäule eingespeist.In the case of a double-column air separation process, i.e. if the air separation column is of two-stage design and has a pressure column and a low-pressure column (in this case the argon-containing oxygen fraction is removed from the low-pressure column), the liquid fraction evaporating against the condensing argon fraction is preferably formed from the pressure column by oxygen-enriched liquid. The evaporated liquid fraction is then fed into the low pressure column.

Diese Variante des erfindungsgemäßen Verfahrens, bei der beispielsweise Sumpfflüssigkeit aus der Drucksäule zur Kondensation der abgereicherten Argonfraktion verwendet wird, ist energetisch besonders günstig. Die Verdampfung der flüssigen Fraktion findet in diesem Fall vorzugsweise unter im wesentlichen Niederdrucksäulendruck oder unter einem geringfügig höheren Druck statt.This variant of the method according to the invention, in which, for example, bottom liquid from the pressure column is used to condense the depleted argon fraction, is particularly advantageous in terms of energy. The evaporation of the liquid In this case, fraction preferably takes place under essentially low-pressure column pressure or under a slightly higher pressure.

Vorzugsweise werden in Rohargon- und/oder Halbreinsäule Füllkörper und/oder geordnete Packungen als Stoffaustauschelemente eingesetzt. Wegen ihres besonders geringen Druckverlustes werden dabei geordnete Packungen bevorzugt. Auch in den übrigen in dem Verfahren eingesetzten Rektifiziersäulen, beispielsweise in der Niederdrucksäule eines zweistufigen Luftzerlegers können Füllkörper oder Packungen, insbesondere geordnete Packungen, eingesetzt werden.Packings and / or ordered packings are preferably used as mass transfer elements in crude argon and / or semi-pure columns. Ordered packings are preferred because of their particularly low pressure drop. Packings or packings, in particular ordered packings, can also be used in the other rectification columns used in the process, for example in the low-pressure column of a two-stage air separator.

Beim erfindungsgemäßen Verfahren kann grundsätzlich jede geordnete Packung verwendet werden. Günstig ist beispielsweise der Einsatz von Einbauten, wie sie in den nicht vorveröffentlichten Dokumenten WO 93/19335 oder WO 93/19336 beschrieben sind.In principle, any ordered pack can be used in the method according to the invention. For example, the use of internals such as are described in the not previously published documents WO 93/19335 or WO 93/19336 is favorable.

Auch der kombinierte Einsatz verschiedener Arten von Stoffaustauschelementen (konventionelle Rektifizierböden, ungeordnete Füllkörper, geordnete Packungen) ist in jeder der in dem Verfahren eingesetzten Säulen möglich. Dadurch kann beispielsweise der Druckverlust längs einer Säule genau den spezifischen Bedürfnissen des jeweiligen Prozesses angepaßt werden.The combined use of different types of mass transfer elements (conventional rectification trays, unordered packing, ordered packings) is also possible in each of the columns used in the process. In this way, for example, the pressure loss along a column can be precisely adapted to the specific needs of the respective process.

Die Erfindung betrifft außerdem eine Vorrichtung zur Gewinnung von Argon nach den Patentansprüchen 8 bis 13.The invention also relates to an apparatus for the production of argon according to claims 8 to 13.

Im folgenden werden die Erfindung sowie weitere Einzelheiten der Erfindung anhand eines in der Zeichnung schematisch dargestellten Ausführungsbeispiels näher erläutert.The invention and further details of the invention are explained in more detail below with reference to an exemplary embodiment shown schematically in the drawing.

Im linken Teil der Zeichnung ist ein Luftzerlegungsverfahren zur Erzeugung von Sauerstoff und Stickstoff mit einer Doppelsäule 1, die aus einer Drucksäule 2 und einer Niederdrucksäule 3 besteht, angedeutet. Die Erfindung hängt jedoch nicht von der speziellen Gestaltung dieses Verfahrensabschnittes ab, sondern ist auch auf andere Ausprägungen dieses Teils des Verfahrens beziehungsweise der Vorrichtung anwendbar, beispielsweise auf eine Anlage mit einer Einzelsäule oder auf abweichende Arten der Produktentnahme von Stickstoff und Sauerstoff. Details wie Turbinen zur kälteleistenden Entspannung von Prozeßströmen oder die DirekteinSpeisung von Luft in die Niederdrucksäule sind in dem stark vereinfachten Schema nicht dargestellt.In the left part of the drawing, an air separation process for generating oxygen and nitrogen with a double column 1, which consists of a pressure column 2 and a low pressure column 3, is indicated. However, the invention does not depend on the special design of this process section, but can also be applied to other forms of this part of the process or the device, for example to a system with a single column or to different types of product removal of nitrogen and oxygen. Details such as turbines for the cooling relief of process streams or direct feeding of air into the low pressure column are not shown in the simplified diagram.

Im vorliegenden Ausführungsbeispiel wird an einer Stelle relativ hoher Argonkonzentration in der Niederdrucksäule 3 ein argonhaltiger Sauerstoffstrom 4 entnommen, der außerdem Verunreinigungen in Form von Stickstoff und anderen Luftbestandteilen enthält, und in einer Rohargonsäule 5 in Rohargon 6 und eine erste Restfraktion 8 getrennt. Letztere wird - gegebenenfalls mittels einer nicht gezeigten Pumpe - zur Niederdrucksäule 3 zurückgeführt und etwas unterhalb der Entnahmestelle für den argonhaltigen Sauerstoffstrom zurückgespeist.In the present exemplary embodiment, an argon-containing oxygen stream 4, which also contains impurities in the form of nitrogen and other air constituents, is taken from a location of relatively high argon concentration in the low-pressure column 3, and is separated into crude argon 6 and a first residual fraction 8 in a crude argon column 5. The latter is returned to the low-pressure column 3, possibly by means of a pump (not shown), and is fed back somewhat below the removal point for the argon-containing oxygen stream.

Erfindungsgemäß wird am Kopf der Rohargonsäule 5 gewonnenes Rohargon 6 in einer Halbreinsäule 9 einem weiteren Rektifizierschritt zur Entfernung schwererflüchtiger Anteile, insbesondere von Sauerstoff, unterzogen. Das Rohargon wird dazu vorzugsweise gasförmig in den unteren Bereich dieser Säule 9 eingespeist. An Sauerstoff abgereichertes Argon wird aus dem oberen Bereich der Halbreinsäule 9 gasförmig (10) und/oder flüssig (15) abgezogen.According to the invention, crude argon 6 obtained at the top of the crude argon column 5 is subjected to a further rectification step in a semi-pure column 9 to remove less volatile components, in particular oxygen. For this purpose, the raw argon is preferably fed in gaseous form into the lower region of this column 9. Argon depleted in oxygen is withdrawn from the upper region of the semi-pure column 9 in gaseous form (10) and / or liquid (15).

Rücklaufflüssigkeit 11 für die Halbreinsäule wird durch Kondensation der Kopffraktion mittels indirektem Wärmeaustausch 13 gegen entspannte Sumpfflüssigkeit aus der Drucksäule 2 des Luftzerlegers 1 erzeugt. Der dabei entstehende Dampf wird über Leitung 16 abgeführt und an geeigneter Stelle in die Niederdrucksäule 3 eingeleitet.Return liquid 11 for the semi-pure column is generated by condensation of the top fraction by means of indirect heat exchange 13 against expanded sump liquid from the pressure column 2 of the air separator 1. The resulting steam is discharged via line 16 and introduced into the low-pressure column 3 at a suitable point.

Die Rohargonsäule 5 bedarf dagegen keines Kopfkondensators. Ihr Bedarf an Rücklaufflüssigkeit 7 wird durch Sumpfflüssigkeit 12 gedeckt, die in der Halbreinsäule 9 anfällt. In der Regel muß eine Pumpe 17 eingesetzt werden, um den Höhenunterschied in der Leitung 7 zu überwinden.In contrast, the crude argon column 5 does not require a top condenser. Your need for return liquid 7 is covered by sump liquid 12, which is obtained in the semi-pure column 9. As a rule, a pump 17 must be used to overcome the height difference in line 7.

Die in der Zeichnung durchgehend dargestellten Rektifizierbereiche bestehen in der Realität aus mehreren Abschnitten. Als Stoffaustauschelemente werden - vor allem in Rohargon- und Halbreinsäule vorzugsweise geordnete Packungen eingesetzt. Es können jedoch auch Teile der Säulen mit konventionellen Rektifizierböden ausgestattet sein.The rectification areas shown throughout in the drawing consist in reality of several sections. Ordered packings are preferably used as mass transfer elements, especially in crude argon and semi-pure columns. However, parts of the columns can also be equipped with conventional rectification trays.

In dem konkreten Beispiel der Zeichnung weist die Rohargonsäule einen Rektifizierabschnitt auf, die Halbreinsäule drei. Die Zahl dieser Abschnitte kann jedoch variieren, in der Rohargonsäule von eins bis etwa drei, in der Halbreinsäule etwa von zwei bis sechs.In the concrete example of the drawing, the crude argon column has one rectification section, the semi-pure column three. The number of these sections can, however vary, in the crude argon column from one to about three, in the semi-pure column from about two to six.

Die Rohargonsäule 5 enthält beispielsweise 30 bis 120, vorzugsweise etwa 60 bis 90 theoretische Böden. Die Anzahl an theoretischen Böden in der Halbreinsäule 9 beträgt beispielsweise 60 bis 150, vorzugsweise etwa 90 bis 120. Das Verhältnis der theoretischen Bodenzahlen (Rohargonsäule 5 zu Halbreinsäule 9) beträgt beispielsweise 0,5.The crude argon column 5 contains, for example, 30 to 120, preferably about 60 to 90 theoretical plates. The number of theoretical plates in the semi-pure column 9 is, for example, 60 to 150, preferably approximately 90 to 120. The ratio of the theoretical plate numbers (crude argon column 5 to semi-pure column 9) is, for example, 0.5.

Die Sauerstoffkonzentrationen haben in den verschiedenen Strömen beispielsweise folgende Werte: Übergangsfraktion 4 82 bis 92, vorzugsweise etwa 86 bis 90 % Rohargonfraktion 6 0,1 bis 2,0 , vorzugsweise etwa 0,5 bis 1,0 % Argonfraktion 10 0,01 bis 10, vorzugsweise etwa 0,01 bis 0,1 ppm The oxygen concentrations in the different streams have, for example, the following values: Transitional fraction 4 82 to 92, preferably about 86 to 90% Raw argon fraction 6 0.1 to 2.0, preferably about 0.5 to 1.0% Argon fraction 10 0.01 to 10, preferably about 0.01 to 0.1 ppm

Claims (13)

Verfahren zur Gewinnung von Argon, bei dem Luft in einem Rektifiziersystem mit mindestens einer Luftzerlegersäule (1) und einer Rohargonsäule zerlegt wird, wobei eine argonhaltige Sauerstofffraktion (4) aus der Luftzerlegersäule (1) entnommen und in eine Rohargonsäule (5) eingeleitet wird, im oberen Bereich der Rohargonsäule (5) eine Rohargonfraktion (6) entnommen und eine erste Rücklaufflüssigkeit (7) aufgegeben werden und im unteren Bereich der Rohargonsäule (5) eine erste Restfraktion (8) entnommen wird, dadurch gekennzeichnet, daß die Rohargonfraktion (6) in den unteren Bereich einer Halbreinsäule (9) eingeleitet wird, wobei im oberen Bereich der Halbreinsäule (9) eine an Sauerstoff abgereicherte Argonfraktion entnommen (10, 15) und eine zweite Rücklaufflüssigkeit (11) aufgegeben werden und im unteren Bereich der Halbreinsäule (9) eine zweite Restfraktion (12) entnommen wird, welche die erste Rücklaufflüssigkeit (7) für die Rohargonsäule (5) bildet.Process for the production of argon, in which air is broken down in a rectification system with at least one air separation column (1) and one crude argon column, an argon-containing oxygen fraction (4) being removed from the air separation column (1) and introduced into a crude argon column (5), im a crude argon fraction (6) is removed from the upper region of the crude argon column (5) and a first reflux liquid (7) is added, and a first residual fraction (8) is withdrawn from the lower region of the crude argon column (5), characterized in that the crude argon fraction (6) in the lower region of a semi-pure column (9) is introduced, an argon fraction depleted in oxygen being removed (10, 15) and a second reflux liquid (11) being taken off in the upper region of the semi-pure column (9) and one in the lower region of the semi-pure column (9) second residual fraction (12) is removed, which forms the first return liquid (7) for the crude argon column (5). Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Druck im unteren Bereich der Halbreinsäule (9) im wesentlichen gleich dem Druck im oberen Bereich der Rohargonsäule (5) ist.Method according to Claim 1, characterized in that the pressure in the lower region of the semi-pure column (9) is substantially equal to the pressure in the upper region of the crude argon column (5). Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß mindestens ein Teil der Argonfraktion aus dem oberen Bereich der Halbreinsäule (9) durch indirekten Wärmeaustausch (13) kondensiert wird und mindestens ein Teil des Kondensats die zweite Rücklaufflüssigkeit (11) bildet.Method according to claim 1 or 2, characterized in that at least part of the argon fraction from the upper region of the semi-pure column (9) is condensed by indirect heat exchange (13) and at least part of the condensate forms the second return liquid (11). Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß bei dem indirekten Wärmeaustausch (13) eine flüssige Fraktion (14) aus einer der Luftzerlegersäulen (1; 2) verdampft wird.Method according to claim 3, characterized in that in the indirect heat exchange (13) a liquid fraction (14) is evaporated from one of the air separation columns (1; 2). Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Luftzerlegersäule (1) zweistufig ausgebildet ist und eine Drucksäule (2) und eine Niederdrucksäule (3) aufweist, wobei die argonhaltige Sauerstofffraktion (4) der Niederdrucksäule (3) entnommen wird, die gegen kondensierende Argonfraktion verdampfende flüssige Fraktion durch sauerstoffangereicherte Flüssigkeit (14) aus der Drucksäule (2) gebildet wird und die verdampfte flüssige Fraktion (16) in die Niederdrucksäule (3) eingespeist wird.Method according to claim 4, characterized in that the air separation column (1) is constructed in two stages and has a pressure column (2) and a low pressure column (3), the argon-containing oxygen fraction (4) being taken from the low pressure column (3), which counteracts the condensing argon fraction evaporating liquid fraction is formed by oxygen-enriched liquid (14) from the pressure column (2) and the evaporated liquid fraction (16) is fed into the low pressure column (3). Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Rohargonsäule (5) Füllkörper und/oder geordnete Packungen enthält.Method according to one of claims 1 to 5, characterized in that the crude argon column (5) contains packing elements and / or ordered packings. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Halbreinsäule (9) Füllkörper und/oder geordnete Packungen enthält.Method according to one of claims 1 to 6, characterized in that the semi-pure column (9) contains packing elements and / or ordered packings. Vorrichtung zur Gewinnung von Argon mit einem Rektifiziersystem, das mindestens eine Luftzerlegersäule (1) und eine Rohargonsäule (5) aufweist, wobei Luftzerlegersäule (1) und Rohargonsäule (5) über eine Leitung (4) für eine argonhaltige Sauerstofffraktion verbunden sind, gekennzeichnet durch eine Halbreinsäule (9), eine Rohargonleitung (6), die vom oberen Bereich der Rohargonsäule (5) in den unteren Bereich der Halbreinsäule (9) führt, und Mittel (7; 11) zur Zuführung von Rücklaufflüssigkeit in die oberen Bereiche von Rohargonsäule (5) und Halbreinsäule (9) und mit Restfraktionsleitungen (8; 12), die jeweils aus den unteren Bereichen von Rohargonsäule (5) und Halbreinsäule (9) herausführen, wobei die Restfraktionsleitung (12) der Halbreinsäule (9) mit den Mitteln (7) zur Zuführung von Rücklaufflüssigkeit in die Rohargonsäule (5) verbunden ist.Apparatus for the production of argon with a rectification system, which has at least one air separation column (1) and one crude argon column (5), the air separation column (1) and raw argon column (5) being connected via a line (4) for an argon-containing oxygen fraction, characterized by a Semi-pure column (9), a crude argon line (6) which leads from the upper region of the crude argon column (5) into the lower region of the semi-pure column (9), and means (7; 11) for supplying reflux liquid into the upper regions of crude argon column (5 ) and semi-pure column (9) and with residual fraction lines (8; 12), each leading out of the lower areas of crude argon column (5) and semi-pure column (9), the residual fraction line (12) of the semi-pure column (9) with the means (7) for supplying return liquid into the crude argon column (5). Vorrichtung nach Anspruch 8, dadurch gekennzeichnet, daß die Rohargonleitung (6) keine Mittel zur Verminderung oder Erhöhung des Drucks aufweist.Device according to claim 8, characterized in that the crude argon line (6) has no means for reducing or increasing the pressure. Vorrichtung nach Anspruch 8 oder 9, gekennzeichnet durch einen Kopfkondensator (13), dessen Kondensationsseite mit dem oberen Bereich der Halbreinsäule (9) verbunden ist.Apparatus according to claim 8 or 9, characterized by a top condenser (13), the condensation side of which is connected to the upper region of the semi-pure column (9). Vorrichtung nach Anspruch 10, gekennzeichnet durch eine Flüssigleitung, die von der Luftzerlegersäule (1) zur Verdampfungsseite des Kopfkondensators (13) führt.Apparatus according to claim 10, characterized by a liquid line leading from the air separation column (1) to the evaporation side of the top condenser (13). Vorrichtung nach einem der Ansprüche 8 bis 12, dadurch gekennzeichnet, daß die Rohargonsäule (5) Füllkörper und/oder geordnete Packungen enthält.Device according to one of claims 8 to 12, characterized in that the crude argon column (5) contains packing elements and / or ordered packings. Vorrichtung nach einem der Ansprüche 8 bis 13, dadurch gekennzeichnet, daß die Halbreinsäule (9) Füllkörper und/oder geordnete Packungen enthält.Device according to one of claims 8 to 13, characterized in that the semi-pure column (9) contains packing elements and / or ordered packings.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19543953C1 (en) * 1995-11-25 1996-12-19 Linde Ag Recovery of oxygen@ and nitrogen@ under super-atmospheric pressure
EP0752565A2 (en) * 1995-07-06 1997-01-08 The BOC Group plc Production of Argon
EP0870524A1 (en) * 1997-04-11 1998-10-14 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Plant for separating a gas mixture by distillation
DE19651280C1 (en) * 1996-10-02 1999-05-12 Linde Ag Production of pure argon in an air separation plant
US6205815B1 (en) 1997-04-11 2001-03-27 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Plant for separation of a gas mixture by distillation
US6612129B2 (en) 2001-10-31 2003-09-02 Linde Aktiengesellschaft Process and apparatus for producing krypton and/or xenon by low-temperature fractionation of air

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2142317A1 (en) * 1994-02-24 1995-08-25 Anton Moll Process and apparatus for the recovery of pure argon
DE4443190A1 (en) * 1994-12-05 1996-06-13 Linde Ag Method and apparatus for the cryogenic separation of air
US5557951A (en) * 1995-03-24 1996-09-24 Praxair Technology, Inc. Process and apparatus for recovery and purification of argon from a cryogenic air separation unit
FR2739438B1 (en) * 1995-09-29 1997-10-24 Air Liquide PROCESS AND PLANT FOR THE PRODUCTION OF ARGON BY CRYOGENIC DISTILLATION
GB9605171D0 (en) * 1996-03-12 1996-05-15 Boc Group Plc Air separation
US5682767A (en) * 1996-11-18 1997-11-04 Air Liquide Process And Construction Argon production
US5682765A (en) * 1996-12-12 1997-11-04 Praxair Technology, Inc. Cryogenic rectification system for producing argon and lower purity oxygen
WO1999054673A1 (en) * 1998-04-21 1999-10-28 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
DE19921949A1 (en) * 1999-05-12 2000-11-16 Linde Ag Method and device for the low-temperature separation of air
US6321567B1 (en) 2000-10-06 2001-11-27 Praxair Technology, Inc. Structured packing system for reduced distillation column height
DE102007035619A1 (en) 2007-07-30 2009-02-05 Linde Ag Process and apparatus for recovering argon by cryogenic separation of air
EP2026024A1 (en) 2007-07-30 2009-02-18 Linde Aktiengesellschaft Process and device for producing argon by cryogenic separation of air
DE102009016043A1 (en) 2009-04-02 2010-10-07 Linde Ag Method for operating a pure argon column, comprises initiating a nitrogen-containing argon stream into an upper- or middle area of the pure argon column from which lower area of the argon column is drawn-off to a pure argon product
EP2447653A1 (en) 2010-11-02 2012-05-02 Linde Aktiengesellschaft Process for cryogenic air separation using a side condenser
DE102012006479A1 (en) 2012-03-29 2013-10-02 Linde Ag Transportable package with a coldbox and method of manufacturing a cryogenic air separation plant
EP2645031A1 (en) 2012-03-29 2013-10-02 Linde Aktiengesellschaft Separating column for a low temperature air separator facility, low temperature air separator facility and method for low temperature separation of air
DE102012006484A1 (en) 2012-03-29 2013-10-02 Linde Aktiengesellschaft Transportable package with a coldbox and method of manufacturing a cryogenic air separation plant
DE102012008415A1 (en) 2012-04-27 2013-10-31 Linde Aktiengesellschaft Transportable package comprising a cold box, cryogenic air separation plant and method of manufacturing a cryogenic air separation plant
CA2900122C (en) 2013-03-06 2023-10-31 Linde Aktiengesellschaft Air separation plant, method for obtaining a product containing argon, and method for creating an air separation plant
DE102013018664A1 (en) 2013-10-25 2015-04-30 Linde Aktiengesellschaft Process for the cryogenic separation of air and cryogenic air separation plant
EP3040665A1 (en) 2014-12-30 2016-07-06 Linde Aktiengesellschaft Distillation system and plant for the production of oxygen by crygenic separation of air
EP3048401A1 (en) 2015-01-20 2016-07-27 Linde Aktiengesellschaft Method and device for variable extraction of argon by cryogenic separation of air
CN209524679U (en) * 2018-10-29 2019-10-22 乔治洛德方法研究和开发液化空气有限公司 By low temperature distillation come the equipment of air distillation

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0377117A1 (en) * 1988-12-01 1990-07-11 Linde Aktiengesellschaft Air separation process and apparatus

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1034545B (en) * 1975-03-26 1979-10-10 Siad PROCESS AND PLANT FOR OBTAINING THE ARGON STARTING FROM AN AIR FRACTION PROCESS
GB2107597B (en) * 1981-10-01 1985-02-27 Lummus Co Process and apparatus for fractionating close-boiling components of a multi-component system
US4836836A (en) * 1987-12-14 1989-06-06 Air Products And Chemicals, Inc. Separating argon/oxygen mixtures using a structured packing
DE3806523A1 (en) * 1988-03-01 1989-09-14 Linde Ag METHOD FOR CLEANING ROHARGON
US4983194A (en) * 1990-02-02 1991-01-08 Air Products And Chemicals, Inc. Production of high purity argon
US5076823A (en) * 1990-03-20 1991-12-31 Air Products And Chemicals, Inc. Process for cryogenic air separation
US5159816A (en) * 1991-05-14 1992-11-03 Air Products And Chemicals, Inc. Method of purifying argon through cryogenic adsorption
US5161380A (en) * 1991-08-12 1992-11-10 Union Carbide Industrial Gases Technology Corporation Cryogenic rectification system for enhanced argon production
US5207066A (en) * 1991-10-22 1993-05-04 Bova Vitaly I Method of air separation
US5237823A (en) * 1992-03-31 1993-08-24 Praxair Technology, Inc. Cryogenic air separation using random packing
US5282365A (en) * 1992-11-17 1994-02-01 Praxair Technology, Inc. Packed column distillation system

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0377117A1 (en) * 1988-12-01 1990-07-11 Linde Aktiengesellschaft Air separation process and apparatus

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0752565A2 (en) * 1995-07-06 1997-01-08 The BOC Group plc Production of Argon
EP0752565A3 (en) * 1995-07-06 1998-01-28 The BOC Group plc Production of Argon
DE19543953C1 (en) * 1995-11-25 1996-12-19 Linde Ag Recovery of oxygen@ and nitrogen@ under super-atmospheric pressure
EP0775881A2 (en) 1995-11-25 1997-05-28 Linde Aktiengesellschaft Process and apparatus for recovering oxygen and nitrogen at superatmospheric pressure
DE19651280C1 (en) * 1996-10-02 1999-05-12 Linde Ag Production of pure argon in an air separation plant
EP0870524A1 (en) * 1997-04-11 1998-10-14 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Plant for separating a gas mixture by distillation
FR2761897A1 (en) * 1997-04-11 1998-10-16 Air Liquide INSTALLATION FOR SEPARATING A GAS MIXTURE BY DISTILLATION
US6205815B1 (en) 1997-04-11 2001-03-27 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Plant for separation of a gas mixture by distillation
US6272883B2 (en) 1997-04-11 2001-08-14 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Plant for separation of a gas mixture by distillation
US6612129B2 (en) 2001-10-31 2003-09-02 Linde Aktiengesellschaft Process and apparatus for producing krypton and/or xenon by low-temperature fractionation of air

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US5426946A (en) 1995-06-27
EP0628777B1 (en) 1998-11-04
DE4317916A1 (en) 1994-12-01
ES2125370T3 (en) 1999-03-01
DE59407206D1 (en) 1998-12-10

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