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EP0019905B1 - Apparatus for the separation of a gas mixture by rectification - Google Patents

Apparatus for the separation of a gas mixture by rectification Download PDF

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Publication number
EP0019905B1
EP0019905B1 EP80102953A EP80102953A EP0019905B1 EP 0019905 B1 EP0019905 B1 EP 0019905B1 EP 80102953 A EP80102953 A EP 80102953A EP 80102953 A EP80102953 A EP 80102953A EP 0019905 B1 EP0019905 B1 EP 0019905B1
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EP
European Patent Office
Prior art keywords
liquid
sump
evaporator
condenser
adsorber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP80102953A
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German (de)
French (fr)
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EP0019905A1 (en
Inventor
Wilhelm Rohde
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linde GmbH
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Linde GmbH
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Publication date
Application filed by Linde GmbH filed Critical Linde GmbH
Priority to AT80102953T priority Critical patent/ATE2178T1/en
Publication of EP0019905A1 publication Critical patent/EP0019905A1/en
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Publication of EP0019905B1 publication Critical patent/EP0019905B1/en
Expired legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04763—Start-up or control of the process; Details of the apparatus used
    • F25J3/04769—Operation, control and regulation of the process; Instrumentation within the process
    • F25J3/04854—Safety aspects of operation
    • F25J3/0486—Safety aspects of operation of vaporisers for oxygen enriched liquids, e.g. purging of liquids
    • 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
    • F25J3/04763—Start-up or control of the process; Details of the apparatus used
    • F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
    • F25J3/04872—Vertical layout of cold equipments within in the cold box, e.g. columns, heat exchangers etc.
    • F25J3/04884—Arrangement of reboiler-condensers
    • 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
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • 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
    • 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
    • F25J2250/02—Bath type boiler-condenser using thermo-siphon effect, e.g. with natural or forced circulation or pool boiling, i.e. core-in-kettle heat exchanger
    • 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
    • F25J2250/20—Boiler-condenser with multiple exchanger cores in parallel or with multiple re-boiling or condensing streams
    • 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
    • Y10S62/902—Apparatus
    • Y10S62/903—Heat exchange structure
    • 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
    • Y10S62/902—Apparatus
    • Y10S62/908—Filter or absorber

Definitions

  • the invention relates to a device for the separation of a gas mixture by rectification with a rectification column, an adsorber which is connected on the one hand to the bottom liquid in the rectification column and on the other hand to a condenser-evaporator which is connected to the vapor space above the bottom liquid.
  • Such a device is known from DE-B-1 143 526.
  • a gas separation plant with a rectification column is described, in the sump of which a condenser-evaporator is arranged.
  • the column sump is connected to an adsorber in which undesirable constituents from the rectifying liquid are removed from the column sump.
  • Higher-boiling components such as hydrocarbons, which freeze out on the evaporator walls and can block flow cross sections, are regarded as undesirable constituents.
  • Egungsanlagen at Gutze d is also at a high acetylene concentration in the oxygen-rich rectifier liquid explosion.
  • the downstream end of the adsorber is connected to an outer condenser-evaporator, in which the cleaned rectification liquid is partially evaporated.
  • the upper end of the outer condenser-evaporator is connected to the rectification column by a connecting line. The rising steam creates a flow with which the rectifying liquid is circulated through the adsorber.
  • the present invention is therefore based on the object of developing a device of the type mentioned at the outset in which freezing out of higher-boiling constituents of the rectifying liquid in the condenser-evaporator is largely prevented.
  • the upper end of the condenser-evaporator is open, so that the non-evaporated portions of the rectifying liquid, which are carried upwards with the rising steam, can pass freely over the edge of the condenser-evaporator and can flow into the surrounding bottom liquid.
  • the lower end of the condenser-evaporator is sealed off from the rectifying liquid so that only rectifying liquid that has been freed of impurities in the adsorber can get into the evaporator cross-sections.
  • the subject of the invention prevents the formation of freezes on the evaporator walls of the condenser-evaporator and the formation of undesirably high concentrations of higher-boiling components in the rectifying liquid in a simple, yet effective manner.
  • a header is provided on the underside of the condenser-evaporator.
  • the header serves on the one hand to seal the condenser-evaporator against the bottom liquid and on the other hand to distribute the rectifying liquid supplied by the adsorber over the flow cross-sections of the evaporator.
  • the adsorber is bridged by a lockable bypass. In this way, the amount of liquid passed through the adsorber can be set independently of the amount of liquid circulated.
  • a liquid indicator be arranged parallel to the condenser-evaporator. This allows the liquid level in the condenser-evaporator to be checked from the outside and, if necessary, changed by throttling or increasing the circulated amount of liquid.
  • a further embodiment of the invention is particularly advantageous, in which the connecting line between the condenser-evaporator and the adsorber is connected to a gas separator.
  • the pipeline runs in front of the connection point of the liquid level indicator vertical direction upwards and has a horizontal or downward sloping section between the connection point and the condenser-evaporator at least for a short time, while the gas separator is arranged essentially perpendicularly above the connection point. Gas bubbles contained in the liquid can therefore rise freely into the gas separator.
  • Analog components have the same reference numbers in both figures.
  • 1 denotes a two-stage rectification column, as is used for the low-temperature separation of air.
  • the device according to the invention is also suitable for use in the rectification of another gas mixture.
  • a single-stage rectification column could be used instead of the two-stage rectification column with a high-pressure stage 2 and a low-pressure stage 3 arranged above the high-pressure stage.
  • an oxygen-enriched liquid 4 collects during airing.
  • a nitrogen-rich gaseous gas is removed from the top of the column 2 Fraction removed (line 6) and fed to the condenser-evaporator 5, in which the gas is partially liquefied in the heat exchange with the oxygen-rich bottom liquid 4, a portion of the bottom liquid 4 evaporating.
  • the condensed liquid is returned via line 7 to the high pressure stage 2.
  • the bottom liquid 4 still contains undesirable constituents, especially hydrocarbons such as acetylene
  • part of the liquid is circulated through an adsorber 8, in which these constituents are removed.
  • nitrogen is used, for example, which is supplied via line 9 and discharged via line 10.
  • the adsorber 8 is arranged at a lower level than the liquid bath 4.
  • a condenser-evaporator 11 which is arranged in the sump 4 of the rectification column and which partially immerses in the liquid bath during operation of the column is used for liquid circulation.
  • the condenser-evaporator 11, e.g. a plate heat exchanger, is open at its upper end projecting over the liquid 4 to the inside of the low-pressure stage 3, its lower end immersed in the liquid is closed against the bottom liquid, for example with a header 12.
  • the condenser-evaporator 11 is parallel to the condenser Evaporator 5 connected to nitrogen lines 6, 7.
  • the condenser-evaporator can, as shown in the figure, be an additional evaporator, but it is also possible to form part of the heat exchange channels of the condenser-evaporator 5 such that a direct connection between the heat exchange channels and the bottom liquid is prevented.
  • a liquid extraction line 13 is provided, which is connected to the adsorber 8.
  • a flow meter 14 is arranged in line 13. The other end of the adsorber 8 is connected to a line 15 which opens into the header 12 of the condenser-evaporator 11.
  • liquid is removed from the column sump 4 via line 13, reaches the adsorber 8, where it is freed of hydrocarbons, and from there via line 15 into the header 12, from which it reaches the heat exchange channels of the condenser-evaporator 11 is distributed.
  • the liquid rises in the condenser-evaporator 11 to a height which is the same as the liquid level of the bottom liquid 4 minus an amount which corresponds to the flow resistance in the liquid extraction line 13, 15 and in the adsorber 8.
  • a portion of the liquid in the condenser-evaporator 11 evaporates due to the warm nitrogen, which is supplied via line 6.
  • Liquid is taken away by the withdrawing steam and thrown over the upper edge of the condenser-evaporator 11 into the liquid bath.
  • the evaporated amount of liquid is replaced by liquid flowing out of the rectification trays.
  • the liquid level of the bath which had dropped as a result of the liquid withdrawal, thus rises again and the static liquid pressure in the pipeline 13 increases. The process therefore works continuously.
  • liquid is also thrown over in the evaporator condenser 5.
  • the liquid is supplemented via the connection that the evaporator condenser 5 has on its underside with the liquid bath 4.
  • a direct backflow of liquid through the header 12 is prevented in the heat exchanger 11.
  • the liquid flows here via the pipes 13, 15 back into the heat exchanger until, according to the principle of the communicating tubes, a liquid level corresponding to the liquid level of the sump liquid 4 is reached. Since at the same time further liquid is evaporated from the heat exchanger and thrown over, the liquid level lags behind the state of equilibrium and a continuous liquid circuit is guaranteed.
  • it is conceivable to turn on the condenser-evaporator 11 instead of the one shown, several condenser evaporators can also be provided - instead of heating with air using nitrogen.
  • the amount of liquid circulated through the adsorber 8 should correspond approximately to the amount of oxygen obtained in the rectification.
  • a bypass line 16 is provided parallel to the adsorber 8 and is provided with a control valve 17. With this bypass line 16, the level of the liquid level in the heat exchanger can be influenced at the same time. A total evaporation of the liquid in the condenser-evaporator 11 must namely be avoided in order to prevent the heat exchanger surfaces from encrusting. There is also a risk of explosion if acetylene crystallizes out.
  • the heat exchanger should be filled to about 80% with liquid.
  • Figure 2 shows essentially the same arrangement as Figure 1.
  • a gas separator 18 is also provided here, which is connected in parallel to the condenser-evaporator 11.
  • liquid level indicators 21, 22 the height of the liquid level in the column sump and in the condenser-evaporator 11 can be easily checked from the outside and thus the optimal liquid level can always be adjusted.
  • the bypass line 16 and the line 15 coming from the adsorber run vertically upward after their union below the connection point 19 of the gas separator 18, while the connecting piece 20 between the connection point 19 and the condenser-evaporator 11 runs horizontally at least over a short section.
  • the gas separator 18 is arranged vertically above the connection point 19. If gas bubbles are now contained in the liquid rising via the lines 15, 16, these rise from the connection point 19 into the gas separator 18 and are separated from the liquid which flows via line 20 into the condenser-evaporator 11.
  • the extraction line therefore does not have to be led exactly vertically upward to the connection point 19 and the line 20 can, for example, have a section running downwards from the connection point 19.

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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)
  • Separation Of Gases By Adsorption (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

In the fractionation of a gaseous mixture, e.g., air, by rectification, wherein liquid in the sump of a rectifying column is heated and thereby partially vaporized; and simultaneously sump liquid is withdrawn from a lower zone of the sump liquid bath, and is recycled into the bath above the point of withdrawal, the improvement, prior to the recycle step, of passing the withdrawn sump liquid from the lower zone into a heat exchanger disposed in the sump, said heat exchanger having a substantially sealed bottom end at a level below the liquid level of the sump, and an open top end at a level higher than the liquid level of the sump; said withdrawn sump liquid being passed into the bottom end of said heat exchanger and partially vaporized therein, and removing resultant liquid-vapor mixture from the heat exchanger at the top end above the level of the liquid bath. This system provides pump-free circulation of the sump liquid and the use incorporates an on-line adsorber to remove deleterious impurities from the sump liquid, e.g., hydrocarbons from oxygen.

Description

Die Erfindung betrifft eine Vorrichtung zur Zerlegung eines Gasgemisches durch Rektifikation mit einer Rektifiziersäule, einem Adsorber, der einerseits mit der Sumpfflüssigkeit in der Rektifiziersäule und andererseits mit einem Kondensator-Verdampfer verbunden ist, welcher mit dem Dampfraum über der Sumpfflüssigkeit in Verbindung steht.The invention relates to a device for the separation of a gas mixture by rectification with a rectification column, an adsorber which is connected on the one hand to the bottom liquid in the rectification column and on the other hand to a condenser-evaporator which is connected to the vapor space above the bottom liquid.

Eine derartige Vorrichtung ist aus der DE-B-1 143 526 bekannt. Dort ist eine Gaszerlegungsanlage mit einer Rektifiziersäule beschrieben, in deren Sumpf ein Kondensator-Verdampfer angeordnet ist. Der Säulensumpf ist an einen Adsorber angeschlossen, in dem unerwünschte Bestandteile aus der Rektifizierflüssigkeit aus dem Säulensumpf entfernt werden. Als unerwünschte Bestandteile werden insbesondere höhersiedende Komponenten, wie Kohlenwasserstoffe, angesehen, die an den Verdampferwänden ausfrieren und Strömungsquerschnitte blockieren können. Bei Luftzedegungsanlagen besteht überdies bei einer zu hohen Acetylen-Konzentration in der sauerstoffreichen Rektifizierflüssigkeit Explosionsgefahr. Das stromab gelegene Ende des Adsorbers ist mit einem äußeren Kondensator-Verdampfer verbunden, in dem die gereinigte Rektifizierflüssigkeit teilweise verdampft wird. Das obere Ende des äußeren Kondensator-Verdampfers ist durch eine Verbindungsleitung mit der Rektifiziersäule verbunden. Durch den aufsteigenden Dampf entsteht eine Strömung, mit deren Hilfe die Rektifizierflüssigkeit über den Adsorber umgewälzt wird.Such a device is known from DE-B-1 143 526. There, a gas separation plant with a rectification column is described, in the sump of which a condenser-evaporator is arranged. The column sump is connected to an adsorber in which undesirable constituents from the rectifying liquid are removed from the column sump. Higher-boiling components such as hydrocarbons, which freeze out on the evaporator walls and can block flow cross sections, are regarded as undesirable constituents. Egungsanlagen at Luftze d is also at a high acetylene concentration in the oxygen-rich rectifier liquid explosion. The downstream end of the adsorber is connected to an outer condenser-evaporator, in which the cleaned rectification liquid is partially evaporated. The upper end of the outer condenser-evaporator is connected to the rectification column by a connecting line. The rising steam creates a flow with which the rectifying liquid is circulated through the adsorber.

Diese anordnung hat jedoch den Nachteil, daß ein Teil der im äußeren Kondensator-Verdampfer nicht verdampften Rektifizierflüssigkeit zwar mit dem aufsteigenden verdampften Anteil der Rektifizierflüssigkeit ein Stück mitgerissen wird,, jedoch beispielsweise in der Verbindungsleitung zur Rektifiziersäule hängenbleibt und in die Verdampferquerschnitte des äußeren Kondensator-Verdampfers zurückfließt. Da in dem vorangeschalteten Adsorber aber nicht alle höhersiedenden Verunreinigungen aus der Rektifizierflüssigkeit restlos entfernt werden können, kommt es mit der Zeit zu einer Anreicherung dieser Komponenten in der im äußeren Kondensator-Verdampfer befindlichen Rektifizierflüssigkeit. Folglich werden zwar mit dieser Anordnung die unerwünschten Bestandteile aus der im Säulensumpf befindlichen Rektifizierflüssigkeit und damit auch aus den verdampferseitigen Strömungsquerschnitten des in der Rektifiziersäule befindlichen Kondensator-Verdampfers entfernt, dagegen findet nunmehr eine Anreicherung an diesen Bestandteilen in den verdampferseitigen Strömungsquerschnitten des äußeren Kondensator-Verdampfers statt.However, this arrangement has the disadvantage that a part of the rectifying liquid which has not evaporated in the outer condenser-evaporator is entrained to a certain extent with the ascending evaporated part of the rectifying liquid, but remains stuck, for example, in the connecting line to the rectifying column and in the evaporator cross sections of the outer condenser-evaporator flows back. However, since not all of the higher-boiling impurities can be removed completely from the rectifying liquid in the preceding adsorber, these components accumulate over time in the rectifying liquid located in the outer condenser-evaporator. Consequently, although this arrangement removes the undesirable constituents from the rectification liquid located in the column sump and thus also from the evaporator-side flow cross sections of the condenser evaporator located in the rectification column, an enrichment of these constituents now takes place in the evaporator-side flow cross sections of the outer condenser evaporator .

Der vorliegenden Erfindung liegt daher die Aufgabe zugrunde, eine Vorrichtung der eingangs genannten Art zu entwickeln, bei der ein Ausfrieren von höhersiedenden Bestandteilen der Rektifizierflüssigkeit im Kondensator-Verdampfer weitgehend verhindert wird.The present invention is therefore based on the object of developing a device of the type mentioned at the outset in which freezing out of higher-boiling constituents of the rectifying liquid in the condenser-evaporator is largely prevented.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß der Kondensator-Verdampfer zum Teil in die Sumpflüssigkeit eintaucht, wobei sein mit dem Adsorber verbundenes unteres Ende gegenüber der Sumpfflüssigkeit abgedichtet und sein oberes Ende zum Dampfraum über der Sumpfflüssigkeit hin offen ist.This object is achieved in that the condenser-evaporator is partially immersed in the sump liquid, its lower end connected to the adsorber being sealed off from the sump liquid and its upper end being open to the vapor space above the sump liquid.

Erfindungsgemäß ist das obere Ende des Kondensator-Verdampfers offen, so daß die nicht verdampften Anteile der Rektifizierflüssigkeit, die mit dem aufsteigenden Dampf nach oben mitgerissen werden, ungehindert über den Rand des Kondensator-Verdampfers gelangen und in die umgebende Sumpfflüssigkeit abgließen können. Das untere Ende des Kondensator-Verdampfers ist gegenüber der Rektifizierflüssigkeit abgedichtet, damit nur Rektifizierflüssigkeit, die im Adsorber von Verunreinigungen befreit worden ist, in die Verdampferquerschnitte gelangen kann.According to the invention, the upper end of the condenser-evaporator is open, so that the non-evaporated portions of the rectifying liquid, which are carried upwards with the rising steam, can pass freely over the edge of the condenser-evaporator and can flow into the surrounding bottom liquid. The lower end of the condenser-evaporator is sealed off from the rectifying liquid so that only rectifying liquid that has been freed of impurities in the adsorber can get into the evaporator cross-sections.

Auf einfache und dennoch wirkungsvolle Weise ist durch den Erfindungsgegenstand die Bildung von Ausfrierungen an den Verdampferwänden des Kondensator-Verdampfers sowie die Entstehung unerwünscht hoher Konzentrationen an höhersiedenden Bestandteilen in der Rektifizierflüssigkeit verhindert.The subject of the invention prevents the formation of freezes on the evaporator walls of the condenser-evaporator and the formation of undesirably high concentrations of higher-boiling components in the rectifying liquid in a simple, yet effective manner.

Gemäß einer bevorzugten Weiterbildung des Erfindungsgegenstandes ist an der Unterseite des Kondensator-Verdampfers ein Header vorgesehen. Der Header dient einerseits zur Abdichtung des Kondensator-Verdampfers gegenüber der Sumpfflüssigkeit und andererseits zur Verteilung der vom Adsorber zugeführten Rektifizierflüssigkeit auf die Strömungsquerschnitte des Verdampfers.According to a preferred development of the subject matter of the invention, a header is provided on the underside of the condenser-evaporator. The header serves on the one hand to seal the condenser-evaporator against the bottom liquid and on the other hand to distribute the rectifying liquid supplied by the adsorber over the flow cross-sections of the evaporator.

Es ist zweckmäßig, wenn gemäß einer Ausgestaltung des Erfindungsgegenstandes der Adsorber durch einen absperrbaren Bypass überbrückt ist. Auf diese Weise kann die über den Adsorber geführte Flüssigkeitsmenge unabhängig von der umgewälzten Flüssigkeitsmenge eingestellt werden.It is expedient if, according to an embodiment of the subject matter of the invention, the adsorber is bridged by a lockable bypass. In this way, the amount of liquid passed through the adsorber can be set independently of the amount of liquid circulated.

In weiterer Ausgestaltung des Erfindungsgegenstandes wird vorgeschlagen, daß parallel zu dem Kondensator-Verdampfer ein Flüssigkeitsanzeiger angeordnet ist. Damit läßt sich der Flüssigkeitsstand im Kondensator-Verdampfer von außen kontrollieren und gegebenenfalls durch Drosselung oder Steigerung der umgewälzten Flüssigkeitsmenge verändern.In a further embodiment of the subject matter of the invention it is proposed that a liquid indicator be arranged parallel to the condenser-evaporator. This allows the liquid level in the condenser-evaporator to be checked from the outside and, if necessary, changed by throttling or increasing the circulated amount of liquid.

Besonders vorteilhaft ist eine weitere Ausgestaltung des Erfindungsgengenstandes, bei der die Verbindungsleitung zwischen dem Kondensator-Verdampfer und dem Adsorber mit einem Gasabscheider verbunden ist. Zu diesem Zweck verläuft die Rohrleitung vor der Anschlußstelle des Flüssigkeitsstandsanzeigers in vertikaler Richtung nach oben und weist zwischen Anschlußstelle und dem Kondensator-Verdampfer mindestens kurzzeitig einen waagrechten oder abwärts geneigten Abschnitt auf, während der Gasabscheider im wesentlichen lotrecht über der Anschlußstelle angeordnet ist. In der Flüssigkeit enthaltene Gasblasen Gasblasen können somit unbehindert in den Gasabscheider aufsteigen.A further embodiment of the invention is particularly advantageous, in which the connecting line between the condenser-evaporator and the adsorber is connected to a gas separator. For this purpose the pipeline runs in front of the connection point of the liquid level indicator vertical direction upwards and has a horizontal or downward sloping section between the connection point and the condenser-evaporator at least for a short time, while the gas separator is arranged essentially perpendicularly above the connection point. Gas bubbles contained in the liquid can therefore rise freely into the gas separator.

Die Erfindung sowie weitere Einzelheiten der Erfindung werden anhand eines schematisch dargestellten Ausführungsbeispiels beschrieben.The invention and further details of the invention are described with reference to a schematically illustrated embodiment.

Hierbei zeigen:

  • Figur 1 eine erfindungsgemäße Vorrichtung zur Rektifikation eines Gasgemisches.
  • Figur 2 eine modifizierte Rektifiziervorrichtung gemäß Vorrichtung 1.
Here show:
  • Figure 1 shows an inventive device for the rectification of a gas mixture.
  • FIG. 2 shows a modified rectification device according to device 1.

Analoge Bauteile tragen in beiden Figuren dieselben Bezugszeichen. Mit 1 ist eine zweistufige Rektifiziersäule bezeichnet, wie sie zur Tieftemperaturzerlegung von Luft verwendet wird. Die erfindungsgemäße Vorrichtung eignet sich jedoch ebenso zur Anwendung bei der Rektifikation eines anderen Gasgemisches. Genausgut könnte statt der dargestellten zweistufigen Rektifiziersäule mit einer Hochdruckstufe 2 und einer oberhalb der Hochdruckstufe angeordneten Niederdruckstufe 3 eine einstufige Rektifiziersäule verwendet werden.Analog components have the same reference numbers in both figures. 1 denotes a two-stage rectification column, as is used for the low-temperature separation of air. However, the device according to the invention is also suitable for use in the rectification of another gas mixture. Exactly, a single-stage rectification column could be used instead of the two-stage rectification column with a high-pressure stage 2 and a low-pressure stage 3 arranged above the high-pressure stage.

Im Sumpf der Niederdrucksäule 3 sammelt sich während der Luftierlegung eine mit Sauerstoff angereicherte Flüssigkeit 4. Ein Kondensator-Verdampfer 5, der in der Sumpflüssigkeit angeordnet ist, erzeugt Rücklaufflüssigkeit für die Hochdrucksäule 2. Zu diesem Zweck wird vom Kopf der'Säule 2 eine stickstoffreiche gasförmige Fraktion entnommen (Leitung 6) und dem Kondensator-Verdampfer 5 zugeführt, in dem das Gas teilweise im Wärmetausch mit der sauerstoffreichen Sumpfflüssigkeit 4 verflüssigt wird, wobei ein Teil der Sumpfflüssigkeit 4 verdampft. Die kondensierte Flüssigkeit wird über Leitung 7 in die Hochdruckstufe 2 zurückgeleitet.In the sump of the low-pressure column 3, an oxygen-enriched liquid 4 collects during airing. A condenser-evaporator 5, which is arranged in the sump liquid, produces return liquid for the high-pressure column 2. For this purpose, a nitrogen-rich gaseous gas is removed from the top of the column 2 Fraction removed (line 6) and fed to the condenser-evaporator 5, in which the gas is partially liquefied in the heat exchange with the oxygen-rich bottom liquid 4, a portion of the bottom liquid 4 evaporating. The condensed liquid is returned via line 7 to the high pressure stage 2.

Da in der Sumpfflüssigkeit 4 noch unerwünschte Bestandteile, vor allem Kohlenwasserstoffe wie Acetylen, enthalten sind, wird ein Teil der Flüssigkeit über einen Adsorber 8 umgewälzt, in dem diese Bestandteile entfernt werden. Zum Regenerieren der Adsorber wird beispielsweise Stickstoff verwendet, der über Leitung 9 zu- und über Leitung 10 abgeführt wird. Der Adsorber 8 ist auf tieferem Niveau angeordnet als das Flüssigkeitsbad 4.Since the bottom liquid 4 still contains undesirable constituents, especially hydrocarbons such as acetylene, part of the liquid is circulated through an adsorber 8, in which these constituents are removed. To regenerate the adsorber, nitrogen is used, for example, which is supplied via line 9 and discharged via line 10. The adsorber 8 is arranged at a lower level than the liquid bath 4.

Erfindungsgemäß dient zur Flüssigkeitsumwälzung ein im Sumpf 4 der Rektifiziersäule angeordneter Kondensator-Verdampfer 11, der beim Betrieb der Säule teilweise in das Flüssigkeitsbad eintaucht. Der Kondensator-Verdampfer 11, z.B. ein Plattenwärmetauscher, ist an seinem über die Flüssigkeit 4 ragenden oberen Ende zur Innenseite der Niederdruckstufe 3 hin offen, sein in die Flüssigkeit eintauchendes unteres Ende ist gegen die Sumpfflüssigkeit verschlossen, beispielsweise mit einem Header 12. Der Kondensator-Verdampfer 11 ist parallel zum Kondensator-Verdampfer 5 an die Stickstoffleitungen 6, 7 angeschlossen. Der Kondensator-Verdampfer kann, wie in der Figur dargestellt, ein zusätzlicher Verdampfer sein, es ist aber auch möglich, einen Teil der Wärmetauschkanäle des Kondensator-Verdampfers 5 derart auszubilden, daß eine direkte Verbindung zwischen den Wärmetauschkanälen und der Sumpfflüssigkeit verhindert ist. Am unteren Ende der Niederdruckstufe 3 ist eine Flüssigkeitsentnahmeleitung 13 vorgesehen, die mit dem Adsorber 8 verbunden ist. In der Leitung 13 ist ein Strömungsmesser 14 angeordnet. Das andere Ende des Adsorbers 8 ist an eine Leitung 15 angeschlossen, die in den Header 12 des Kondensator-Verdampfers 11 mündet.According to the invention, a condenser-evaporator 11 which is arranged in the sump 4 of the rectification column and which partially immerses in the liquid bath during operation of the column is used for liquid circulation. The condenser-evaporator 11, e.g. a plate heat exchanger, is open at its upper end projecting over the liquid 4 to the inside of the low-pressure stage 3, its lower end immersed in the liquid is closed against the bottom liquid, for example with a header 12. The condenser-evaporator 11 is parallel to the condenser Evaporator 5 connected to nitrogen lines 6, 7. The condenser-evaporator can, as shown in the figure, be an additional evaporator, but it is also possible to form part of the heat exchange channels of the condenser-evaporator 5 such that a direct connection between the heat exchange channels and the bottom liquid is prevented. At the lower end of the low-pressure stage 3, a liquid extraction line 13 is provided, which is connected to the adsorber 8. A flow meter 14 is arranged in line 13. The other end of the adsorber 8 is connected to a line 15 which opens into the header 12 of the condenser-evaporator 11.

Bei der Durchführung des Rektifikationsverfahrens wird über Leitung 13 Flüssigkeit aus dem Säulensumpf 4 entnommen, gelangt in den Adsorber 8, wo sie von Kohlenwasserstoffen befreit wird, und von dort über Leitung 15 in den Header 12, von dem sie auf die Wärmetauschkanäle des Kondensator - Verdampfers 11 verteilt wird. Die Flüssigkeit steigt im Kondensator-Verdampfer 11 bis in eine Höhe, die gleich ist dem Flüssigkeitspiegel der Sumpfflüssigkeit 4 abzüglich eines Betrags, der dem Strömungswiderstand in der Flüssigkeitsentnahmeleitung 13, 15 und im Adsorber 8 entspricht. Durch den warmen Stickstoff, der über Leitung 6 zugeführt wird, verdampft ein Teil der Flüssigkeit im Kondensator-Verdampfer 11. Vom abziehenden Dampf wird Flüssigkeit mitgenommen und über den oberen Rand des Kondensator-Verdampfers 11 in das Flüssigkeitsbad übergeworfen. Die verdampfte Flüssigkeitsmenge wird durch von den Rektifizierböden abfließende Flüssigkeit ersetzt. Damit steigt der Flüssigkeitsspiegel des Bades, der durch die Flüssigkeitsentnahme abgesunken war, wieder an und der statische Flüssigkeitsdruck in der Rohrleitung 13 erhöht sich. Das Verfahren arbeitet somit kontinuierlich.When the rectification process is carried out, liquid is removed from the column sump 4 via line 13, reaches the adsorber 8, where it is freed of hydrocarbons, and from there via line 15 into the header 12, from which it reaches the heat exchange channels of the condenser-evaporator 11 is distributed. The liquid rises in the condenser-evaporator 11 to a height which is the same as the liquid level of the bottom liquid 4 minus an amount which corresponds to the flow resistance in the liquid extraction line 13, 15 and in the adsorber 8. A portion of the liquid in the condenser-evaporator 11 evaporates due to the warm nitrogen, which is supplied via line 6. Liquid is taken away by the withdrawing steam and thrown over the upper edge of the condenser-evaporator 11 into the liquid bath. The evaporated amount of liquid is replaced by liquid flowing out of the rectification trays. The liquid level of the bath, which had dropped as a result of the liquid withdrawal, thus rises again and the static liquid pressure in the pipeline 13 increases. The process therefore works continuously.

Es sei noch darauf hingewiesen, daß ein Überwerfen von Flüssigkeit auch im Verdampfer-Kondensator 5 erfolgt. Die Flüssigkeit wird über die Verbindung, die der Verdampfer-Kondensator 5 an seiner Unterseite mit dem Flüssigkeitsbad 4 besitzt, ergänzt. Dagegen ist beim Wärmetauscher 11 ein direktes Rückströmen von Flüssigkeit durch den Header 12 verhindert. Die Flüssigkeit strömt hier über die Rohrleitungen 13, 15 in den Wärmetauscher zurück, bis nach dem Prinzip der kommunizierenden Röhren ein dem Flüssigkeitsspiegel der Sumpfflüssigkeit 4 entsprechender Flüssigkeitsstand erreicht wird. Da gleichzeitig weitere Flüssigkeit aus dem Wärmetauscher verdampft und übergeworfen wird, hinkt der Flüssigkeitsspiegel dem Gleichgewichtszustand nach und es ist ein kontinuierlicher Flüssigkeitskreislauf gewährleistet. Es ist denkbar, den Kondensator-Verdampfer 11 - anstelle des einen gezeichneten können ebensogut auch mehrere Kondensator-Verdampfer vorgesehen sein - statt mit Stickstoff mit Luft zu beheizen.It should also be pointed out that liquid is also thrown over in the evaporator condenser 5. The liquid is supplemented via the connection that the evaporator condenser 5 has on its underside with the liquid bath 4. In contrast, a direct backflow of liquid through the header 12 is prevented in the heat exchanger 11. The liquid flows here via the pipes 13, 15 back into the heat exchanger until, according to the principle of the communicating tubes, a liquid level corresponding to the liquid level of the sump liquid 4 is reached. Since at the same time further liquid is evaporated from the heat exchanger and thrown over, the liquid level lags behind the state of equilibrium and a continuous liquid circuit is guaranteed. It is conceivable to turn on the condenser-evaporator 11 Instead of the one shown, several condenser evaporators can also be provided - instead of heating with air using nitrogen.

Die über den Adsorber 8 umgewälzte Flüssigkeitsmenge sollte etwa der Menge des bei der Rektifikation gewonnen Sauerstoffs entsprechen. Um die Flüssigkeitsmenge unabhängig von der umgewälzten Menge regeln zu können, ist parallel zum Adsorber 8 eine Bypassleitung 16 vorgesehen, die mit einem Regelventil 17 versehen ist. Mit dieser Bypassleitung 16 kann zugleich die Höhe des Flüssigkeitsstandes im Wärmetauscher beeinflußt werden. Eine Totalverdampfung der Flüssigkeit im Kondensator-Verdampfer 11 muß nämlich vermieden werden, um eine Verkrustung der Wärmetauscherflächen zu verhindern. Außerdem besteht bei Auskristallisieren von Acetylen Explosionsgefahr. Der Wärmetauscher soll etwa zu 80% mit Flüssigkeit gefüllt sein.The amount of liquid circulated through the adsorber 8 should correspond approximately to the amount of oxygen obtained in the rectification. In order to be able to regulate the amount of liquid independently of the amount circulated, a bypass line 16 is provided parallel to the adsorber 8 and is provided with a control valve 17. With this bypass line 16, the level of the liquid level in the heat exchanger can be influenced at the same time. A total evaporation of the liquid in the condenser-evaporator 11 must namely be avoided in order to prevent the heat exchanger surfaces from encrusting. There is also a risk of explosion if acetylene crystallizes out. The heat exchanger should be filled to about 80% with liquid.

Figur 2 zeigt im wesentlichen dieselbe Anordnung wie Figur 1. Zusätzlich ist hier noch ein Gasabscheider 18 vorgesehen, der parallel zum Kondensator-Verdampfer 11 geschaltet ist. Mit Hilfe von Flüssigkeitsstandsanzeigern 21, 22 läßt sich die Höhe des Flüssigkeitsstandes im Säulensumpf und im Kondensator-Verdampfer 11 von außen leicht kontrollieren und somit stets die optimale Flüssigkeitshöhe einregulieren.Figure 2 shows essentially the same arrangement as Figure 1. In addition, a gas separator 18 is also provided here, which is connected in parallel to the condenser-evaporator 11. With the help of liquid level indicators 21, 22, the height of the liquid level in the column sump and in the condenser-evaporator 11 can be easily checked from the outside and thus the optimal liquid level can always be adjusted.

Die Bypassleitung 16 und die vom Adsorber kommende Leitung 15 verlaufen nach ihrer Vereinigung unterhalb der Anschlußstelle 19 des Gasabscheiders 18 vertikal nach oben, während das Verbindungstück 20 zwischen der Anschlußstelle 19 und dem Kondensator-Verdampfer 11 zumindest auf einem kurzen Abschnitt waagrecht verläuft. Der Gasabscheider 18 ist lotrecht über der Anschlußstelle 19 angeordnet. Falls nun in der über die Leitungen 15, 16 aufsteigenden Flüssigkeit Gasblasen enthalten sind, so steigen diese von der Anschlußstelle 19 in den Gasabscheider 18 nach oben und werden von der Flüssigkeit abgetrennt, die über Leitung 20 in den Kondensator-Verdampfer 11 strömt. Selbstverständlich läßt sich die beschriebene und gezeigte Anordnung abändern, ohne das Prinzip der Gasabscheidung abzuändern. Die Entnahmeleitung muß demnach nicht genau vertikal zur Anschlußstelle 19 nach oben geführt sein und die Leitung 20 kann zum Beispiel einen von der Anschlußstelle 19 nach abwärts verlaufenden Abschnitt aufweisen.The bypass line 16 and the line 15 coming from the adsorber run vertically upward after their union below the connection point 19 of the gas separator 18, while the connecting piece 20 between the connection point 19 and the condenser-evaporator 11 runs horizontally at least over a short section. The gas separator 18 is arranged vertically above the connection point 19. If gas bubbles are now contained in the liquid rising via the lines 15, 16, these rise from the connection point 19 into the gas separator 18 and are separated from the liquid which flows via line 20 into the condenser-evaporator 11. Of course, the arrangement described and shown can be changed without changing the principle of gas separation. The extraction line therefore does not have to be led exactly vertically upward to the connection point 19 and the line 20 can, for example, have a section running downwards from the connection point 19.

Claims (5)

1. Apparatus for the rectification of a gas mixture comprising a rectifying column (1) and an adsorber (8) which is connected, on the one hand, to the sump liquid (4) in the rectifying column and on the other hand to a condenser-evaporator which is connected to the vapour space above the sump liquid, characterised in that the condenser-evaporator (11) is partially immersed in the sump liquid, the lower end of the condenser-evaporator, which is connected to the adsorber (8), being sealed from the sump liquid and its upper end being open to the vapour space above the sump liquid.
2. Apparatus according to Claim 1, characterised in that a header (12) is arranged on the underside of the condenser-evaporator (11).
3. Apparatus according to Claim 1 or Claim 2, characterised in that the adsorber (8) is bridged by a by-pass (16) which can be closed.
4. Apparatus according to one of Claims 1 to 3, characterised in that a liquid level-indicator (22) is arranged parallel to the condenser-evaporator (11).
5. Apparatus according to one of Claims 1 to 4, characterised in that the connecting line (20) between the condenser (11) and the adsorber (8) is connected to a gas separator (18).
EP80102953A 1979-05-30 1980-05-27 Apparatus for the separation of a gas mixture by rectification Expired EP0019905B1 (en)

Priority Applications (1)

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AT80102953T ATE2178T1 (en) 1979-05-30 1980-05-27 DEVICE FOR DECOMPOSING A GAS MIXTURE BY RECTIFICATION.

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DE2922028 1979-05-30
DE19792922028 DE2922028A1 (en) 1979-05-30 1979-05-30 METHOD AND DEVICE FOR DISASSEMBLING A GAS MIXTURE BY RECTIFICATION

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EP0019905B1 true EP0019905B1 (en) 1983-01-05

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EP (1) EP0019905B1 (en)
AT (1) ATE2178T1 (en)
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DE (2) DE2922028A1 (en)
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US4883519A (en) * 1988-10-06 1989-11-28 Air Products And Chemicals, Inc. Process for the production of high pressure nitrogen with split reboil-condensing duty
US4957524A (en) * 1989-05-15 1990-09-18 Union Carbide Corporation Air separation process with improved reboiler liquid cleaning circuit
US5669236A (en) * 1996-08-05 1997-09-23 Praxair Technology, Inc. Cryogenic rectification system for producing low purity oxygen and high purity oxygen
US5836174A (en) * 1997-05-30 1998-11-17 Praxair Technology, Inc. Cryogenic rectification system for producing multi-purity oxygen
US5956972A (en) * 1997-12-23 1999-09-28 The Boc Group, Inc. Method of operating a lower pressure column of a double column distillation unit
US6330812B2 (en) * 2000-03-02 2001-12-18 Robert Anthony Mostello Method and apparatus for producing nitrogen from air by cryogenic distillation
FR2853723B1 (en) * 2003-04-10 2007-03-30 Air Liquide PROCESS AND PLANT FOR TREATING AN OXYGEN-RICH LIQUID BATH COLLECTED ON THE FOOT OF A CRYOGENIC DISTILLATION COLUMN
CN110388241B (en) * 2019-07-31 2021-07-20 东北师范大学 A thermal cycle system for automobile engine waste heat recovery

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DE624966C (en) * 1934-09-28 1936-01-31 Linde Eismasch Ag Process for reducing the condensation pressure during the decomposition of air by liquefaction and rectification
US2650482A (en) * 1948-04-29 1953-09-01 Kellogg M W Co Method of separating gas mixtures
US2590909A (en) * 1948-10-08 1952-04-01 Hanson Vegetable cutter
US2903859A (en) * 1955-09-22 1959-09-15 Union Carbide Corp Process and apparatus for separating gas mixtures
DE1033689B (en) * 1957-03-20 1958-07-10 Linde Eismasch Ag Process for evaporation of hydrocarbon-containing liquid oxygen and device for carrying out the process
US3174293A (en) * 1960-11-14 1965-03-23 Linde Eismasch Ag System for providing gas separation products at varying rates
DE1143526B (en) * 1962-01-12 1963-02-14 Linde Eismasch Ag Method and device for cryogenic gas separation, in particular air separation
GB1325166A (en) * 1969-10-20 1973-08-01 Kobe Steel Ltd Air rectification process for the production of gaseous or liquid nitrogen

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EP0019905A1 (en) 1980-12-10
US4337070A (en) 1982-06-29
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ZA803204B (en) 1981-05-27
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ATE2178T1 (en) 1983-01-15
BR8003260A (en) 1980-12-30

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