US1963809A - Process of obtaining constituents of air having a higher boiling point than oxygen - Google Patents

Process of obtaining constituents of air having a higher boiling point than oxygen Download PDF

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US1963809A
US1963809A US634779A US63477932A US1963809A US 1963809 A US1963809 A US 1963809A US 634779 A US634779 A US 634779A US 63477932 A US63477932 A US 63477932A US 1963809 A US1963809 A US 1963809A
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krypton
oxygen
air
liquid
column
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Schuftan Paul
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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
    • F25J3/04763—Start-up or control of the process; Details of the apparatus used
    • F25J3/04769—Operation, control and regulation of the process; Instrumentation within the process
    • F25J3/04812—Different modes, i.e. "runs" of operation
    • F25J3/04842—Intermittent process, so-called batch process
    • 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
    • F25J3/04624—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 integrated mass and heat exchange, so-called non-adiabatic rectification, e.g. dephlegmator, reflux 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
    • 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
    • F25J3/04745—Krypton and/or Xenon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/04—Processes or apparatus using separation by rectification in a dual pressure main column system
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/34—Processes or apparatus using separation by rectification using a side column fed by a stream from the low pressure column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/50—Processes or apparatus using separation by rectification using multiple (re-)boiler-condensers at different heights of the column
    • F25J2200/52—Processes or apparatus using separation by rectification using multiple (re-)boiler-condensers at different heights of the column in the high pressure column of a double pressure main column system
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/82—Processes or apparatus using other separation and/or other processing means using a reactor with combustion or catalytic reaction
    • 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
    • F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2250/00—Details related to the use of reboiler-condensers
    • F25J2250/30—External or auxiliary boiler-condenser in general, e.g. without a specified fluid or one fluid is not a primary air component or an intermediate fluid
    • F25J2250/50—One fluid being oxygen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/12—Particular process parameters like pressure, temperature, ratios
    • 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
    • Y10S62/925—Xenon or krypton

Definitions

  • the present invention relates to a process for obtaining constituents of air having a higher boiling point than oxygen; for example, krypton and xenon.
  • krypton will 5 be used in the following specification and claims as representative of such higher boiling constituents.
  • krypton-free or practically krypton-free washing liquid is essential for the successful operation of the process.
  • the liquid nitrogen obtained in the separation of air could be used for this'purpose, because it has the greatest difference in boiling point from krypton of any of the constituents of air.
  • krypton-free oxygen is used as the washing liquid, which is obtained by liquefying a portion of the separated oxygen by deep cooling in the upper part of the washer.
  • the counter-current washing of the krypton out of the gaseous oxygen is effected most simply in a vertical tube sheaf, into the lower part of which the gaseous oxygen from the evaporator of the separation apparatus flows at about its boiling temperature.
  • the tube sheaf is suitably cooled externally, advantageously by the cold nitrogen coming from the apparatus, which in temperature and amount suffices for the formation of the necessary amount of washing liquid.
  • the formation of the washing liquid can also be effected in a condenser located at the head of the washing column and supplied with liquid air or liquid nitrogen.
  • the further enrichment of the washing liquid in krypton can be effected most simply by returning the washing liquid from the washer into the oxygen evaporator of the air separation apparatus. In this way the krypton becomes more and more concentrated in the liquid oxygen in the evaporator, which at the end of a period of operation may be drawn 01f and worked up into pure krypton.
  • Another method of enrichment which affords the possibility of continuously producing krypton of any desired concentration consists in passing the liquid oxygen coming from the washing column into a rectification column, advantageously situated under the washing column, and heated at its lower end. The vapors coming from this auxiliary column are returned to the lower part of the washingcolumn.
  • this method of operation in order to obtain a quantitative yield of krypton, it is advantageous at' the end of a period of operation of the separation system to vaporize the liquid oxygen remaining in the evaporator into the washing column, or a small amount of liquid oxygen in the evaporator may be allowed to continuously flow into the auxiliary column, in order to avoid the concentrating of krypton in the condenser.
  • l is a diagrammatic representation of apparatus for carrying out one embodiment of the invention
  • Fig. 2 is a diagrammatic representation of apparatus for carrying out another em"- bodiment of the invention.
  • the washing out and concentration of the krypton is efiected in rectification columns.
  • the kryptoncontaining gaseous oxygen from the evaporator 3 of the air separation apparatus is led into the washing column 4, which is provided with rectifying plates.
  • the condensation of the kryptonfree washing liquid takes place in condenser 5 which is cooled with liquid nitrogen supplied through valve 8.
  • the operation of column 4 corresponds in principle with the previously described operation of tube sheaf 5 of Figure 1.
  • the krypton-containing liquid oxygen at the bottom of the column passes into the enriching column 6 and is there further concentrated.
  • the heating of this column isefiected by means of compressed air the amount of which is regulated by valve 9.
  • the highly concentrated krypton can be drawn oil in gaseous form at 10 or can be drawn off from the evaporator 7 in liquid form. By this method of operation it is possible to obtain a continuous production of krypton of any desired concentration.
  • the concentration of krypton in the oxygen depends on the length of time the air separation apparatus is operated.
  • substantially all of the krypton present in the air'treated in a given period of operation will be found in the evaporator liquid. Since the amount of liquid in the evaporator is relatively large and the amount of krypton in the air is only 1:1,000,000, at the end of a normal period of operation only a small percentage of krypton will be found in the evaporator liquid.
  • a further advantage of the new method is that by utilizing gaseous oxygen no obstruction of the rectifier plates by impurities is encountered, since it contains no noticeable trace of harmful impurities.
  • the method of the invention provides a continuous and quantitative separation of krypton from the air in heretofore unattained concentration. It can be operated with the simplest means and at very low cost. Together with the krypton, other substanceshaving higher boiling points than oxygen are obtained, particularly xenon.
  • An improvement in the method for obtaining krypton and xenon and other constituents of air having a higher boiling point than oxygen which comprises separating air by low temperature cooling and rectification into a low'boiling portion consisting of constituents of air of lower boilng point than oxygen and a high boiling portion containing substantially all of the oxygen, vaporizing oxygen from said high boiling portion, and subjecting all of the oxygen vaporized from said high boiling portion to countercurrent washing with liquid oxygen which has been freed of its krypton content by rectification.
  • krypton and xenon and other constituents of air having a higher boiling point than oxygen which comprises separating air by low temperature cooling and rectification into a low boiling portion consisting of constituents of air of lower boiling point than oxygen and a high boiling portion containing substantially all of the oxygen, vaporizing oxygen from said high'boiling portion, passing all of the oxygen vaporized from said high boiling portion into the lower part of a rectification column cooled at its head with liquid nitrogen and subjecting the krypton-containing liquid from said column to rectification in a subjacent column from which the vapors pass into the upper column.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Description

June 19, 1934. P, SCHUFTAN 1,963,309
PROCESS OF OBTAINING CONSTITUENTS OF AIR HAVING A HIGHER BOILING POINT THAN OXYGEN Filed Sept. 24, 1932 0: IV: fl: +1; 1 5 4 man I):
Patented June 19, 1934 PROCESS OF OBTAINING CONSTITUENTS OF AIR HAVING A HIGHER BOILING POINT THAN OXYGEN Paul Schuftan, Hollriegelskreuth, near Munich, Germany, assignor to Gesellschaft fiir Lindes Eismaschinen A. G.,
Munich, Germany Hollriegelskreuth, near Application September 24, 1932, Serial No. 634,779 In Germany November 14, 1931 3 Claims.
The present invention relates to a process for obtaining constituents of air having a higher boiling point than oxygen; for example, krypton and xenon. For the sake of brevity, krypton will 5 be used in the following specification and claims as representative of such higher boiling constituents.
It is known that in the separation of the constituents of air by cooling to low temperatures 0 only a small portion of the krypton is found in the liquid oxygen remaining in the evaporator. The greater portion of the krypton is contained in the gaseous oxygen withdrawn, and in fact in about five times the concentration in which it is found in atmospheric air. It has previously been proposed to obtain the krypton from the gaseous oxygen by selective absorption in carbon or silica gel, but this method has serious disadvantages, of which only the discontinuity of the process, the
relatively small adsorptive capacity of the adsorbents for krypton at its low partial pressure, and the diificult removal and working up of the absorbates will be mentioned. It has also been proposed to obtain the krypton from the liquid portion of the oxygen which remains in the evaporator of the separation apparatus. For the reasons mentioned above, a quantitative recovery of krypton cannot be obtained in this manner. Moreover, difiiculties are met in the rectification of the liquid because of the rapid obstruction of the plates of the column with the solid impurities, such as ice and'solid carbon dioxide contained in the liquid oxygen.
All of these disadvantages are avoided by the present invention. It has been found that the krypton can be obtained in very high concentration and yield by washing it out of the gaseous oxygen by means of krypton-free oxygen in countercurrent. This result was all the more sur- 40 prising in that it appeared quite improbable that a constituent contained in a gas in the extremely low concentration of 5 parts per million could be obtained in good yields by a technical washing process.
Nevertheless, the washing out of krypton can be effected very satisfactorily when carried out in accordance with the invention, particularly if an efficient rectification column is used. A more satisfactory and uniform method of operation is obtained by using the gaseous oxygen, because this no longer contains any impurities which can seperate on the rectifier plates in solid form.
The use of a krypton-free or practically krypton-free washing liquid is essential for the successful operation of the process. The liquid nitrogen obtained in the separation of air could be used for this'purpose, because it has the greatest difference in boiling point from krypton of any of the constituents of air. However, since it mingles with the separated oxygen in the washing process and therefore seriously contaminates it, krypton-free oxygen is used as the washing liquid, which is obtained by liquefying a portion of the separated oxygen by deep cooling in the upper part of the washer.
The counter-current washing of the krypton out of the gaseous oxygen is effected most simply in a vertical tube sheaf, into the lower part of which the gaseous oxygen from the evaporator of the separation apparatus flows at about its boiling temperature. The tube sheaf is suitably cooled externally, advantageously by the cold nitrogen coming from the apparatus, which in temperature and amount suffices for the formation of the necessary amount of washing liquid. The formation of the washing liquid can also be effected in a condenser located at the head of the washing column and supplied with liquid air or liquid nitrogen.
It is particularly advantageous to use an efficient rectifying column for the washing apparatus, into the lower part of which the oxygen vapor from the evaporator is supplied, while a condenser is provided at the top of the column.
The further enrichment of the washing liquid in krypton can be effected most simply by returning the washing liquid from the washer into the oxygen evaporator of the air separation apparatus. In this way the krypton becomes more and more concentrated in the liquid oxygen in the evaporator, which at the end of a period of operation may be drawn 01f and worked up into pure krypton.
Another method of enrichment which affords the possibility of continuously producing krypton of any desired concentration consists in passing the liquid oxygen coming from the washing column into a rectification column, advantageously situated under the washing column, and heated at its lower end. The vapors coming from this auxiliary column are returned to the lower part of the washingcolumn. In this method of operation, in order to obtain a quantitative yield of krypton, it is advantageous at' the end of a period of operation of the separation system to vaporize the liquid oxygen remaining in the evaporator into the washing column, or a small amount of liquid oxygen in the evaporator may be allowed to continuously flow into the auxiliary column, in order to avoid the concentrating of krypton in the condenser.
The invention will be moreparticularly described for. the purpose of illustration'with reference to the accompanying drawing in which Fig.
l is a diagrammatic representation of apparatus for carrying out one embodiment of the invention, and Fig. 2 is a diagrammatic representation of apparatus for carrying out another em"- bodiment of the invention.
In Figure 1, 1 is the high pressure column, 2-
the upper column, and 3 the evaporator and condenser of an air separating apparatus. The krypton-containing gaseous oxygen coming from the evaporator at 4 passes into-the vertical tube sheaf 5. Gaseous nitrogen from the separator flows through the jacket 6 and passes out at 8.
Since the nitrogen is-about 13 colder than the oxygen, and in amount is about 4 times the amount of the oxygen, a copious condensation of oxygen takes place in the upper part of 5. The downwardly'fiowing liquid'washes the krypton out of the upwardly flowing gaseous oxygen and is thereby largely revaporized and thus enriched takes place. At the end'of the period of operation of the separation system the liquid in the evaporator, containing substantially all of the krypton of the treated air, is drawn 01f at 9 and worked up into pure krypton in known manner.
In the method illustrated in Figure 2 the washing out and concentration of the krypton is efiected in rectification columns. The kryptoncontaining gaseous oxygen from the evaporator 3 of the air separation apparatus is led into the washing column 4, which is provided with rectifying plates. The condensation of the kryptonfree washing liquid takes place in condenser 5 which is cooled with liquid nitrogen supplied through valve 8. The operation of column 4 corresponds in principle with the previously described operation of tube sheaf 5 of Figure 1. The krypton-containing liquid oxygen at the bottom of the column passes into the enriching column 6 and is there further concentrated. The heating of this column isefiected by means of compressed air the amount of which is regulated by valve 9. The highly concentrated krypton can be drawn oil in gaseous form at 10 or can be drawn off from the evaporator 7 in liquid form. By this method of operation it is possible to obtain a continuous production of krypton of any desired concentration.
The operation of column 4 and condenser 5 will be explained in more detail by an example:
It will be assumed that 100 cubic meters of krypton-containing gaseous oxygen pass from 3 into column 4 and that this gas is in equilibrium with a liquid containing 10 times its concentration of krypton. If the liquid passingv from column 4 into column 6 is to contain all of the krypton, its amount must be 10 cubic meters; that is, on the assumption of the same heat of vaporization for krypton and oxygen, 10 cubic meters of oxygen must be condensed in condenser 5.
When the system is put into operation a krypton-containing liquid will at first condense in 5,
and in fact the first drops condensing will have a krypton content ten times that of the gas, a
corresponding to the equilibrium; in the course of further condensation, however, because of the progressive impoverishment of the gas phase in krypton, the condensate-becomes poorer and poorer in krypton. On the whole, therefore, immediately after putting the system in operation the condensate will contain, it is true, some krypton, but in much lower concentration than and likewise the condensate therefrom. The
impoverishment of the rising vapors in krypton continues until a permanent condition is finally reached wherein only krypton-free oxygen reaches the condenser, in which 10 cubic meters of krypton-free oxygen are condensed, while 10 cubic meters of a mixture of liquid oxygen with all of thekrypton in the entering vapors leave the bottom'of the column.
The operation of the apparatus of Figure 1 differs only from a structural point of view, the principle of operation being the same.
In a prior method krypton-containing oxygen was fed into the top of a column in liquid form.
The gasesdrawn off had to be in equilibrium with this liquid and therefore must contain krypton, so that an'appreciable part of the krypton must be lost with the vapors. On the contrary, by the process of the invention,'it is possible for the first time to obtain all of the krypton contained in the air.
The concentration of krypton in the oxygen depends on the length of time the air separation apparatus is operated. In the method of operation illustrated in Fig. 1 substantially all of the krypton present in the air'treated in a given period of operation will be found in the evaporator liquid. Since the amount of liquid in the evaporator is relatively large and the amount of krypton in the air is only 1:1,000,000, at the end of a normal period of operation only a small percentage of krypton will be found in the evaporator liquid. In the method of operation illustrated in Fig. 2, it is possible to further concentrate the krypton-containing oxygen by rectification in column 6, so that it is possible, after a sufliciently long period of operation,'to draw ofl pure krypton at 10.
A further advantage of the new method is that by utilizing gaseous oxygen no obstruction of the rectifier plates by impurities is encountered, since it contains no noticeable trace of harmful impurities.
The method of the invention provides a continuous and quantitative separation of krypton from the air in heretofore unattained concentration. It can be operated with the simplest means and at very low cost. Together with the krypton, other substanceshaving higher boiling points than oxygen are obtained, particularly xenon.
I claim:
1. An improvement in the method for obtaining krypton and xenon and other constituents of air having a higher boiling point than oxygen which comprises separating air by low temperature cooling and rectification into a low'boiling portion consisting of constituents of air of lower boilng point than oxygen and a high boiling portion containing substantially all of the oxygen, vaporizing oxygen from said high boiling portion, and subjecting all of the oxygen vaporized from said high boiling portion to countercurrent washing with liquid oxygen which has been freed of its krypton content by rectification.
2. An improvement in the method for obtaining krypton and xenon and other constituents of air having a higher boiling point than oxygen which krypton-containing condensate to said high boiling portion. 1
ing krypton and xenon and other constituents of air having a higher boiling point than oxygen which comprises separating air by low temperature cooling and rectification into a low boiling portion consisting of constituents of air of lower boiling point than oxygen and a high boiling portion containing substantially all of the oxygen, vaporizing oxygen from said high'boiling portion, passing all of the oxygen vaporized from said high boiling portion into the lower part of a rectification column cooled at its head with liquid nitrogen and subjecting the krypton-containing liquid from said column to rectification in a subjacent column from which the vapors pass into the upper column.
' PAUL SCHUFTAN.
US634779A 1931-11-14 1932-09-24 Process of obtaining constituents of air having a higher boiling point than oxygen Expired - Lifetime US1963809A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DEG81157D DE566151C (en) 1931-11-14 1931-11-14 Extraction of air components with a higher boiling point than oxygen
DEG83534D DE629297C (en) 1931-11-14 1932-09-09 Process for eliminating the hydrocarbon-related difficulties in the recovery of krypton and xenon from air by rectification
DE438196X 1933-05-13

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US724821A Expired - Lifetime US2060940A (en) 1931-11-14 1934-05-09 Process for obtaining krypton and xenon

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BE (2) BE391302A (en)
DE (4) DE566151C (en)
ES (1) ES127972A1 (en)
FR (2) FR44782E (en)
GB (3) GB390069A (en)
NL (2) NL39016C (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2423274A (en) * 1945-07-06 1947-07-01 Air Reduction Recovery of the components of air
US2464891A (en) * 1943-08-28 1949-03-22 Linder Air Products Company Process of and apparatus for producing compressed oxygen
US2480093A (en) * 1943-05-27 1949-08-23 Air Prod Inc Method of and apparatus for pumping liquid oxygen
US2497589A (en) * 1947-04-18 1950-02-14 Air Reduction Separation and recovery of the constituents of air
US2509044A (en) * 1947-07-03 1950-05-23 Standard Oil Dev Co Separation of low molecular weight hydrocarbons from petroleum mixtures
US2587820A (en) * 1947-05-16 1952-03-04 Independent Engineering Compan Vapor oxygen recondenser
US3191393A (en) * 1959-12-30 1965-06-29 Air Reduction Krypton-xenon separation from a gas mixture
US3222879A (en) * 1962-02-27 1965-12-14 Stoklosinski Roman Recovery of krypton and xenon from air separation plants
US3751934A (en) * 1970-11-10 1973-08-14 K Frischbier Concentrating krypton and xenon in air separation by liquid oxygen wash
US3779028A (en) * 1970-10-12 1973-12-18 British Oxygen Co Ltd Improved krypton xenon recovery method
JP2004205203A (en) * 2002-12-12 2004-07-22 Air Products & Chemicals Inc Process and apparatus for recovering krypton and/or xenon

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2514921A (en) * 1944-11-16 1950-07-11 Linde Air Prod Co Process and apparatus for separating gas mixtures
US2615312A (en) * 1949-05-07 1952-10-28 Union Carbide & Carbon Corp Process and apparatus for eliminating impurities during the separation of gas mixtures
US2698523A (en) * 1950-04-28 1955-01-04 Carthage Hydrocol Inc Manufacture of krypton and xenon
US2962868A (en) * 1956-02-17 1960-12-06 Air Reduction Method of concentrating kryptonxenon
US2990690A (en) * 1958-10-27 1961-07-04 Spencer Chem Co Argon purification process
DE1099564B (en) * 1959-09-09 1961-02-16 Linde S Eismaschinen Ag Zweign Process and device for the enrichment of high-boiling substances during the decomposition of gas mixtures by low-temperature rectification
DE1158534B (en) * 1961-07-05 1963-12-05 Inst Chemie Und Kaelteausruest Process for obtaining a highly concentrated krypton-xenon mixture
JPS5743186A (en) * 1980-08-29 1982-03-11 Nippon Oxygen Co Ltd Production of krypton and xenon
GB8610766D0 (en) * 1986-05-02 1986-06-11 Colley C R Yield of krypton xenon in air separation
GB2453141A (en) * 2007-09-27 2009-04-01 Hd Inspiration B V Method of forming a visor
US20160197669A1 (en) * 2014-12-11 2016-07-07 Tesla Wireless Company LLC Communication method and system that uses low latency/low data bandwidth and high latency/high data bandwidth pathways

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2480093A (en) * 1943-05-27 1949-08-23 Air Prod Inc Method of and apparatus for pumping liquid oxygen
US2464891A (en) * 1943-08-28 1949-03-22 Linder Air Products Company Process of and apparatus for producing compressed oxygen
US2423274A (en) * 1945-07-06 1947-07-01 Air Reduction Recovery of the components of air
US2497589A (en) * 1947-04-18 1950-02-14 Air Reduction Separation and recovery of the constituents of air
US2587820A (en) * 1947-05-16 1952-03-04 Independent Engineering Compan Vapor oxygen recondenser
US2509044A (en) * 1947-07-03 1950-05-23 Standard Oil Dev Co Separation of low molecular weight hydrocarbons from petroleum mixtures
US3191393A (en) * 1959-12-30 1965-06-29 Air Reduction Krypton-xenon separation from a gas mixture
US3222879A (en) * 1962-02-27 1965-12-14 Stoklosinski Roman Recovery of krypton and xenon from air separation plants
US3779028A (en) * 1970-10-12 1973-12-18 British Oxygen Co Ltd Improved krypton xenon recovery method
US3751934A (en) * 1970-11-10 1973-08-14 K Frischbier Concentrating krypton and xenon in air separation by liquid oxygen wash
JP2004205203A (en) * 2002-12-12 2004-07-22 Air Products & Chemicals Inc Process and apparatus for recovering krypton and/or xenon

Also Published As

Publication number Publication date
FR44782E (en) 1935-04-06
FR743380A (en) 1933-03-29
BE403024A (en)
NL42092C (en)
DE629297C (en) 1936-04-27
GB390069A (en) 1933-03-30
DE566151C (en) 1932-12-16
DE631639C (en) 1936-06-24
GB413518A (en) 1934-07-19
DE641715C (en) 1937-02-11
US2060940A (en) 1936-11-17
NL39016C (en)
ES127972A1 (en) 1932-11-01
GB438196A (en) 1935-11-07
BE391302A (en)

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