DE1023061B - Process for the decomposition of gas mixtures containing hydrogen, in particular coke oven gas, and device for carrying out the process - Google Patents

Process for the decomposition of gas mixtures containing hydrogen, in particular coke oven gas, and device for carrying out the process

Info

Publication number
DE1023061B
DE1023061B DEG20593A DEG0020593A DE1023061B DE 1023061 B DE1023061 B DE 1023061B DE G20593 A DEG20593 A DE G20593A DE G0020593 A DEG0020593 A DE G0020593A DE 1023061 B DE1023061 B DE 1023061B
Authority
DE
Germany
Prior art keywords
nitrogen
air
gas
cold
heat exchange
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
DEG20593A
Other languages
German (de)
Inventor
Max Seidel
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
Original Assignee
Gesellschaft fuer Lindes Eismaschinen AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to BE560978D priority Critical patent/BE560978A/xx
Application filed by Gesellschaft fuer Lindes Eismaschinen AG filed Critical Gesellschaft fuer Lindes Eismaschinen AG
Priority to DEG20593A priority patent/DE1023061B/en
Priority to US676112A priority patent/US2962867A/en
Priority to FR1182607D priority patent/FR1182607A/en
Publication of DE1023061B publication Critical patent/DE1023061B/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/02—Preparation of nitrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
    • C10K1/165—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids at temperatures below zero degrees Celsius
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0219—Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
    • 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
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0276—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of H2/N2 mixtures, i.e. of ammonia synthesis gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • 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
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04284—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams
    • F25J3/0429—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams of feed air, e.g. used as waste or product air or expanded into an auxiliary column
    • F25J3/04296—Claude expansion, i.e. expanded into the main or 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
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04284—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams
    • F25J3/0429—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams of feed air, e.g. used as waste or product air or expanded into an auxiliary column
    • F25J3/04303—Lachmann expansion, i.e. expanded into oxygen producing or 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
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04406—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system
    • F25J3/04412—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system in a classical double column flowsheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
    • F25J3/04563—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating
    • F25J3/04587—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating for the NH3 synthesis, e.g. for adjusting the H2/N2 ratio
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
    • F25J3/04612—Heat exchange integration with process streams, e.g. from the air gas consuming unit
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • 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
    • F25J3/0489—Modularity and arrangement of parts of the air fractionation unit, in particular of the cold box, e.g. pre-fabrication, assembling and erection, dimensions, horizontal layout "plot"
    • 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
    • F25J2205/24—Processes or apparatus using other separation and/or other processing means using regenerators, cold accumulators or reversible heat exchangers
    • 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
    • F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/14—Coke-ovens gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/42—Nitrogen
    • 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
    • F25J2250/42—One fluid being nitrogen
    • 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
    • F25J2250/52—One fluid being oxygen enriched compared to air, e.g. "crude oxygen"
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
    • F25J2260/02—Integration in an installation for exchanging heat, e.g. for waste heat recovery
    • 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
    • Y10S62/931—Recovery of hydrogen
    • Y10S62/934—From nitrogen

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Description

DEUTSCHESGERMAN

Es ist bekannt, Wasserstoff und Wasserstoff-Stickstoff-Gemische aus Wasserstoff enthaltenden Gasgemischen, insbesondere Koksofengas, herzustellen, indem zunächst die schwerer flüchtigen Bestandteile, z. B. niedere aliphatische Kohlenwasserstoffe, und dann die Hauptmengen der leichter flüchtigen Bestandteile Methan, Kohlenmonoxyd und Stickstoff bei tiefer Temperatur auskondensiert werden. Die nur schwer auskondensierbaren Reste von Kohlenmonoxyd und Methan werden anschließend mit flüssigem Stickstoff aus dem Gasgemisch ausgewaschen. Der Stickstoffgehalt des bei der Wäsche anfallenden Stickstoff-Wasserstoff-Gemisches hängt vom Waschdruck und der Waschtemperatur ab, bei deren Wahl indessen zu beachten ist, wie weit insbesondere das Kohlenmonoxyd entfernt werden muß. Um die für den Waschvorgang erforderliche Kälte aufzubringen, wird mehr Stickstoff verflüssigt, als für die Wäsche eigentlich erforderlich wäre. Bei Raumtemperatur auf Hochdruck, z. B. 180 at, verdichteter Stickstoff, wird im Gegenstrom mit kalten Zerlegungsprodukten und mit sich selbst abgekühlt, entspannt und verflüssigt. Ein Teil wird nur auf den Waschdruck, der andere, als Kältemittel verwendete Teil auf einen niedrigeren Druck entspannt. Es wurde auch bereits ein in sich geschlossener Stickstoff-Kälte-Kreislauf verwendet. Nachteilig ist, daß große Stickstoffmengen auf Hochdruck verdichtet werden müssen.It is known to produce hydrogen and hydrogen-nitrogen mixtures from gas mixtures containing hydrogen, in particular coke oven gas, by first removing the less volatile constituents, z. B. lower aliphatic hydrocarbons, and then the main amounts of the more volatile components Methane, carbon monoxide and nitrogen are condensed out at low temperatures. That only Hardly condensable residues of carbon monoxide and methane are then mixed with liquid nitrogen washed out of the gas mixture. The nitrogen content of the nitrogen-hydrogen mixture produced during washing depends on the washing pressure and the washing temperature, while their choice depends on it is important to note how far, in particular, the carbon monoxide must be removed. To the for the To apply the cold required for the washing process, more nitrogen is liquefied than is actually used for the laundry would be required. At room temperature to high pressure, e.g. B. 180 at, compressed nitrogen, is im Countercurrent with cold decomposition products and with itself cooled, relaxed and liquefied. A Part is only due to the washing pressure, the other part, used as a refrigerant, to a lower one Pressure relaxed. A closed nitrogen-refrigeration cycle has also already been used. The disadvantage is that large amounts of nitrogen have to be compressed to high pressure.

Um den Hochdruck-Stickstoff-Kreislauf zu vermeiden, wurde bereits vorgeschlagen, flüssigen Stickstoff einer Luftzerlegungsanlage zu entnehmen und damit die Wasserstoff enthaltenden Gasgemische zu waschen, die für die Wäsche erforderliche Kälte also der Luftzerlegungsanlage zu entnehmen. Der bei der Wäsche anzuwendende Druck liegt aber über dem zur Luftzerlegung hinreichenden Druck. Die ganze zu zerlegende Luft muß also auf einen höheren Druck verdichtet werden; das ist unwirtschaftlich. Überdies ist die Gasgemisch- mit der Luftzerlegungsanlage durch Rohrleitungen frei und offen verbunden, so daß bei unachtsamer Bedienung Knallgasgemische entstehen können. Ferner ist der Kältehaushalt der Kälteaustauscher in der Luftzerlegungsanlage gestört, da ein Produkt, nämlich der Stickstoff, flüssig entnommen wird; dessen Kälteinhalt ist für die Abkühlung der zu zerlegenden Luft nicht verfügbar. Es strömt mehr warme Luft in die Kälteaustauscher hinein, als kalte Zerlegungsprodukte durch sie herausströmen.In order to avoid the high pressure nitrogen cycle, it has already been proposed to use liquid nitrogen to be taken from an air separation plant and thus to the gas mixtures containing hydrogen wash, so to take the cold required for the laundry from the air separation plant. The one at the However, the pressure to be applied to laundry is above the pressure sufficient for air separation. The whole to be dismantled Air must therefore be compressed to a higher pressure; that is uneconomical. Moreover is the gas mixture with the air separation plant through pipes freely and openly connected, so that at Careless operation can produce oxyhydrogen mixtures. Furthermore, the cold balance is the cold exchanger Disturbed in the air separation plant because a product, namely nitrogen, was removed in liquid form will; its cold content is not available for cooling the air to be separated. There is more flowing warm air into the cold exchangers as cold decomposition products flow out through them.

Das Verfahren nach der Erfindung besitzt die geschilderten Nachteile nicht. Dieses Verfahren zur Zerlegung von Wasserstoff enthaltenden Gasgemischen, insbesondere Koksofengas, wobei die schwer kondensierbaren Bestandteile des Gasgemisches mit flüssigem, durch Luftzerlegung gewonnenem Stickstoff ge-Verfahren zur Zerlegung von WasserstoffThe method according to the invention has those described Disadvantages are not. This process for the decomposition of gas mixtures containing hydrogen, in particular coke oven gas, whereby the difficult to condense constituents of the gas mixture with liquid, Nitrogen obtained through air separation ge process for the separation of hydrogen

enthaltenden Gasgemischen,containing gas mixtures,

insbesondere Koksofengas,in particular coke oven gas,

und Vorrichtung zur Durchführungand device for implementation

des Verfahrensof the procedure

Anmelder:
Gesellschaft für Linde's EismaschinenApplicant:
Society for Linde's ice machines

Aktiengesellschaft,
Höllriegelskreuth bei MünchenCorporation,
Höllriegelskreuth near Munich

Max Seidel, München-Solln,
ist als Erfinder genannt wordenMax Seidel, Munich-Solln,
has been named as the inventor

waschen werden, der aus gasförmig bei Umgebungstemperatur auf Hochdruck verdichtetem, im Gegen-be washed out of gaseous form at ambient temperature compressed at high pressure, on the contrary

a5 strom mit sich selbst und mit Bestandteilen des Gasgemisches abgekühltem Stickstoff erzeugt wird, ist dadurch gekennzeichnet, daß der abgekühlte Stickstoff in indirektem Wärmeaustausch mit kalter, zu zerlegender Luft zumindest teilweise verflüssigt wird. In der Luftzerlegungsanlage können beliebige Luftmengen zerlegt werden, obwohl die Luft- und die Gasgemischzerlegungsanlage funktionell verbunden sind. Die Luftzerlegungsanlage kann also für große Luftmengen bemessen werden; sie kann mit Expansionsturbinen ausgerüstet werden, die erst bei großem Durchsatz wirtschaftlich günstig einsatzfähig sind. In die Luftzerlegungsanlage strömen gewichtsmäßig gleiche Luftmengen hinein, wie Zerlegungsprodukte herausströmen. Der Druck, unter dem die Luft rektifiziert wird, ist vom Waschdruck unabhängig; es muß also nicht die gesamte zu zerlegende Luft auf den Waschdruck verdichtet werden. Zwischen der Luft- und der Gasgemischzerlegungsanlage besteht keine freie offene Verbindung. Trotzdem dient die Luftzerlegungsanlage als Kältequelle, wobei die Kälte kalter zu zerlegender Luft, also weder kaltem Sauerstoff noch kaltem Stickstoff, entzogen wird. Der Kältehaushalt der Kälteaustauscher in der Luftzerlegungsanlage ist daher immer ausgeglichen. a 5 stream is generated with itself and with components of the gas mixture cooled nitrogen, is characterized in that the cooled nitrogen is at least partially liquefied in indirect heat exchange with cold air to be decomposed. Any amount of air can be broken down in the air separation plant, although the air and gas mixture separation plants are functionally linked. The air separation plant can therefore be dimensioned for large amounts of air; it can be equipped with expansion turbines, which can only be used economically with a high throughput. The same amounts of air flow into the air separation unit in terms of weight as the decomposition products flow out. The pressure under which the air is rectified is independent of the washing pressure; It is therefore not necessary for all of the air to be broken down to be compressed to the washing pressure. There is no free open connection between the air and gas mixture separation plants. Nevertheless, the air separation plant serves as a cold source, whereby the cold is extracted from cold air to be separated, i.e. neither cold oxygen nor cold nitrogen. The cold balance of the cold exchangers in the air separation plant is therefore always balanced.

In Luftzerlegungsanlagen, die mit einer Doppel-Rektifikationssäule ausgerüstet sind, kann ein Teil der zu zerlegenden kalten Luft unmittelbar in die obere, unter etwa Atmosphärendruck stehende Säule eingeblasen werden. Bei dem Verfahren nach der Er-In air separation plants with a double rectification column are equipped, part of the cold air to be decomposed can flow directly into the the upper column, which is under approximately atmospheric pressure, is blown in. In the procedure after the

709 850/148709 850/148

findung wird von dieser Arbeitsweise auf zwei verschiedene Weisen Gebrauch gemacht. Auf die eine Weise wird der abgekühlte, für die Wäsche bestimmte Stickstoff in indirektem Wärmeaustausch mit an Sauerstoff angereicherter flüssiger Luft zumindest teilweise verflüssigt; dabei wird ein Teil dieser angereicherten flüssigen Luft \rerdampft. Das Flüssigkeits-Gas-Gemisch, kann dann in der oberen Säule in reinen Stickstoff und reinen Sauerstoff zerlegt werden. Auf die andere Weise wird der abgekühlte Stickstoff in indirektem Wärmeaustausch mit auf Kondensationstemperatur abgekühlter und anschließend arbeitsleistend zu entspannender gasförmiger Luft zumindest teilweise verflüssigt. Bei dieser Arbeitsweise wird also die Verflüssigungswärme des Stickstoffs auf kalte zu zerlegende Luft übertragen. Die Luft wird dabei angewärmt und anschließend z. B. in einer Turbine auf etwa Kondensationstemperatur entspannt, worauf sie unmittelbar in die obere Säule geleitet wird.This method of operation is used in two different ways. In one way, the cooled nitrogen intended for laundry is at least partially liquefied in indirect heat exchange with oxygen-enriched liquid air; some of this enriched liquid air is \ r vaporized. The liquid-gas mixture can then be broken down into pure nitrogen and pure oxygen in the upper column. In the other way, the cooled nitrogen is at least partially liquefied in indirect heat exchange with gaseous air that has been cooled to the condensation temperature and then to be relaxed for work. In this way of working, the liquefaction heat of the nitrogen is transferred to the cold air to be broken down. The air is warmed up and then z. B. relaxed in a turbine to about the condensation temperature, whereupon it is passed directly into the upper column.

Das bei der Wäsche entstehende Wasserstoff-Stickstoff-Gemisch hat zumeist noch nicht die gewünschte Zusammensetzung. Es ist bereits bekannt, flüssigen Stickstoff zuzusetzen. Kältetechnisch vorteilhafter ist es jedoch, die Waschstickstoffmenge nur so gering zu bemessen, daß die Gemische ausreichend gereinigt werden, und für das gewünschte Wasserstoff-Stickstoff-Verhältnis gegebenenfalls noch erforderlichen Stickstoff erst dem wieder angewärmten, beim Waschen entstandenen Gemisch zuzusetzen.The hydrogen-nitrogen mixture produced during washing is mostly not yet the desired one Composition. It is already known to add liquid nitrogen. Is more advantageous in terms of refrigeration It is, however, only necessary to measure the amount of scrubbing nitrogen so small that the mixtures are adequately cleaned and possibly also required for the desired hydrogen-nitrogen ratio Only add nitrogen to the mixture that has been warmed up and created during washing.

Soll Wasserstoff erzeugt werden, so muß flüssiger Stickstoff in indirektem Wärmeaustausch mit dem gewaschenen Gasgemisch unter einem Druck, der unterhalb des Waschdruckes liegt, verdampft werden. Nur so kann eine zum Auskondensieren des im Wasserstoff verbliebenen Stickstoffs ausreichend tiefe Temperatur erzielt werden. Der erforderliche flüssige Stickstoff wird vom Waschstickstoff abgezweigt und in indirektem Wärmeaustausch mit dem zu reinigenden Gasgemisch unter Unterdruck verdampft.If hydrogen is to be produced, liquid nitrogen must be in indirect heat exchange with the washed gas mixture under a pressure which is below the scrubbing pressure, evaporated. This is the only way to ensure that the nitrogen remaining in the hydrogen condenses out sufficiently deep Temperature can be achieved. The required liquid nitrogen is branched off from the scrubbing nitrogen and evaporated in indirect heat exchange with the gas mixture to be cleaned under negative pressure.

Eine Vorrichtung für das Verfahren nach der Erfindung besteht in ihren Hauptteilen aus einer Koksofengas- und einer Luftzerlegungsanlage, wobei beide Anlagen eigene Isolationsmäntel besitzen und durch zwei isolierte Leitungen, eine für kalten gasförmigen und die andere für zumindest teilweise verflüssigten Waschstickstoff, miteinander verbunden sind. Gewiß wiese eine Vorrichtung, bei der beide Zerlegungsanlagen gemeinsam isoliert wären, etwas niedrigere Kälteverluste auf. Jedoch besitzen getrennte Isolierungen den Vorzug, daß sich explosionsfähige Gasmischungen in den Isolationsmänteln auch dann nicht bilden können, wenn z. B. Flansche oder Stoffbüchsen undicht werden. Aus demselben Grunde ist es auch zweckmäßiger, Waschstickstoff in die Luftzerlegungsanlage als flüssige oder kalte gasförmige Luft in die Koksofengasanlage zu schicken.An apparatus for the method according to the invention consists in its main parts of a coke oven gas and an air separation plant, both of which Systems have their own insulation jackets and two insulated lines, one for cold gaseous ones and the other for at least partially liquefied scrubbing nitrogen, are connected to one another. Certainly had a device in which both dismantling plants would be isolated together, somewhat lower Cold losses. However, separate insulation has the advantage that explosive gas mixtures can form can not form in the insulation jackets even if, for. B. flanges or cans leak. For the same reason, it is also more expedient to put scrubbing nitrogen in the air separation plant to be sent as liquid or cold gaseous air into the coke oven gas system.

In der Luftzerlegungsanlage befindet sich, falls der Waschstickstoff im Wärmeaustausch mit flüssiger Luft verflüssigt wird, ein Verdampferkondensator, der auf der Verdampferseite von an Sauerstoff angereicherter flüssiger Luft durchflossen wird, die vom Fuß der unteren Säule zur oberen Säule einer Doppel-Rektifikationssäule strömt. Wird der Waschstickstoff in indirektem Wärmeaustausch mit kalter gasförmiger Luft verflüssigt, so befindet sich in der Luftzerlegungsanlage ein Wärmeaustauscher für Waschstickstoff und gasförmige kalte, in einer Expansionsturbine zu entspannende und dann in die obere Säule einer Doppel-Rektifikationssäule - einzublasende Luft.If the scrubbing nitrogen is in heat exchange with liquid in the air separation plant Air is liquefied, an evaporator condenser, which is traversed on the evaporator side by oxygen-enriched liquid air, which from the Flows from the foot of the lower column to the upper column of a double rectification column. Will the washing nitrogen liquefied in indirect heat exchange with cold gaseous air, it is located in the air separation plant a heat exchanger for scrubbing nitrogen and gaseous cold, in an expansion turbine air to be relaxed and then into the upper column of a double rectification column - air to be blown.

Zwei Ausführungsbeispiele des erfindungsgemäßen Verfahrens sind in den Fig. 1 und 2 schematisch dargestellt. Alle dasselbe nicht kennzeichnenden Hilfseinrichtungen, wie Ammoniakvorkühler, Geltrockner, Filter, Unterkühlungseinrichtungen, CO.,-Ausscheidungseinrichtungen, Ausscheidungseinrichtungen für höhersiedende Beimengungen usw., sind dabei nicht gezeichnet. Gleiche oder ähnliche Teile beider Figuren sind mit der gleichen Ziffer bezeichnet, wobei Leitungen, Ventile usw. mit einstelligen Ziffern, die Apparate der Luftzerlegungsanlage mit Ziffern ab 11 und die der Gaszerlegungsanlage mit Ziffern ab 21 bezeichnet sind.Two exemplary embodiments of the method according to the invention are shown schematically in FIGS. All auxiliary equipment not identifying the same, such as ammonia precooler, gel dryer, Filters, subcooling devices, CO., - elimination devices, Elimination facilities for higher-boiling additions, etc., are not included drawn. Identical or similar parts of both figures are denoted by the same number, with lines, Valves etc. with single-digit numbers, the apparatus of the air separation plant with numbers from 11 and those of the gas separation plant are marked with numbers from 21 onwards.

Fig. 1 zeigt eine geeignete Verbindung einer Gas-Zerlegungsanlage für die Herstellung eines Wasserstoff-Stickstoff-Gemisches mit einer Luftzerlegungsanlage mit Rohrgegenströmern als Wärmeaustauscher und mit der Rektifikationssäule vorgeschalteter Entspannungsmaschine. Fig. 1 shows a suitable connection of a gas separation plant for the production of a hydrogen-nitrogen mixture with an air separation plant with tube countercurrent as a heat exchanger and with the rectification column upstream expansion machine.

Die Luftzerlegungsanlage besteht aus dem Kompressor 11, dem Wärmeaustauscher 12, der Entspannungsmaschine 13, dem Verflüssiger 14, der Drucksäule 15, der oberen Säule 16, der Lufteintrittsleitung 1, der Austrittsleitung für reinen Stickstoff 2 und der Austrittsleitung für Sauerstoff 3.The air separation plant consists of the compressor 11, the heat exchanger 12, the expansion machine 13, the condenser 14 and the pressure column 15, the upper column 16, the air inlet line 1, the outlet line for pure nitrogen 2 and the outlet line for oxygen 3.

Die Gaszerlegungsanlage besteht aus dem Hochdruck-Stickstoff-Kompressor 21, den Wärmeaustauschern 22 und 23, der Waschsäule 24, dem Wärmeaustauscher 25, dem Restgasverdampfer 27, der Rohgaseintrittsleitung 5, der Stickstoffaustrittsleitung 6. der Restgasaustrittsleitung 7 und den Entspannungsventilen 8. The gas separation plant consists of the high pressure nitrogen compressor 21, the heat exchangers 22 and 23, the washing column 24, the heat exchanger 25, the residual gas evaporator 27, the raw gas inlet line 5, the nitrogen outlet line 6, the residual gas outlet line 7 and the expansion valves 8.

Beide Anlagen sind durch den Wärmeaustauscher 31 verbunden, der in diesem Fall ein Verdampferkondensator ist.Both systems are connected by the heat exchanger 31, which in this case is an evaporator condenser is.

Die Luft für die Luftzerlegungsanlage wird vom Kompressor 11 auf beispielsweise 26 ata verdichtet. im Wärmeaustauscher 12 abgekühlt und dann in zwei Ströme geteilt. Der eine Teilstrom wird im Verflüssiger 14 verflüssigt und dann in die Drucksäule 15 entspannt. Der andere Teilstrom wird in der Entspannungsmaschine 13 arbeitsleistend entspannt und dann ebenfalls in die Drucksäule 15 eingeleitet. Die sich im Fuß der Drucksäule 15 sammelnde, an Sauerstoff angereicherte Flüssigkeit wird nach Entspannung durch den Wärmeaustauscher 31 geführt, wo sie teilweise verdampfend den verdichteten, abgekühlten Waschstickstoff aus der Gaszerlegungsanlage im indirekten Wärmeaustausch verflüssigt, bevor sie in die obere Säule 16 an geeigneter Stelle eingeführt und dort mit dem entspannten im Kopf der Säule aufgegebenen flüssigen Stickstoff aus der Drueksäule 15 in reinen Stickstoff und unreinen Sauerstoff zerlegt wird. Der reine Stickstoff wird durch die Leitung 2 und der unreine Sauerstoff wird durch die Leitung 3 aus der oberen Säule 16 durch den \rerflüssiger 14 und den Wärmeaustauscher 12 geführt, wo sie Kälte abgeben. Die Leitung 2 führt zum Hochdruck-Stickstoff-Kompressor 21 der Gaszerlegungsanlage. Der hier auf beispielsweise 200 ata verdichtete, anschließend in den Wärmeaustauschern 22 und 23 gekühlte und in den Entspannungsventilen 8 auf 16 bis 17 ata entspannte Waschstickstoff wird dem Erfindungsgedanken entsprechend im Wärmeaustauscher 31 verflüssigt und dann oben in die Waschsäule 24 geleitet.The air for the air separation plant is compressed by the compressor 11 to, for example, 26 ata. cooled in the heat exchanger 12 and then divided into two streams. One partial flow is liquefied in the liquefier 14 and then expanded into the pressure column 15. The other partial flow is expanded to perform work in the expansion machine 13 and then likewise introduced into the pressure column 15. The oxygen-enriched liquid that collects in the foot of the pressure column 15 is passed through the heat exchanger 31 after expansion, where it partially evaporates and liquefies the compressed, cooled scrubbing nitrogen from the gas separation plant in indirect heat exchange before it is introduced into the upper column 16 at a suitable point and there it is broken down into pure nitrogen and impure oxygen with the relaxed liquid nitrogen from the pressure column 15 which has been released in the head of the column. The pure nitrogen is supplied through line 2 and the impure oxygen is passed through the conduit 3 from the upper column 16 through the \ r erflüssiger 14 and the heat exchanger 12, where they give cold. The line 2 leads to the high pressure nitrogen compressor 21 of the gas separation plant. The scrubbing nitrogen, compressed here to 200 ata, for example, then cooled in the heat exchangers 22 and 23 and relaxed in the expansion valves 8 to 16 to 17 ata, is liquefied in the heat exchanger 31 according to the inventive concept and then passed into the scrubbing column 24 at the top.

Das bei 5 unter einem geeigneten Druck von beispielsweise 15 ata eintretende Rohgas gelangt durch den Wärmeaustauscher 25 und den Restgasverdampfer 27 unten in die Waschsäule 24, in der der flüssige Stickstoff niederläuft und die Verunreinigungen aus-That at 5 under a suitable pressure of, for example 15 ata incoming raw gas passes through the heat exchanger 25 and the residual gas evaporator 27 down into the washing column 24, in which the liquid nitrogen runs down and the impurities

wäscht. Das am Kopf der Waschsäule 24 austretende Reingas gibt seine Kälte in dem Wärmeaustauscher 25 an das Rohgas und im Wärmeaustauscher 23 an einen Teil des Hochdruckstickstoffes ab und verläßt bei 6 die Anlage, wobei für die Gemischzusammen-Setzung etwa noch fehlender Stickstoff durch eine Leitung direkt vom Hochdruckstickstoffverdichter 21 zur Leitung 6 zugesetzt werden kann. Das Restgas erwärmt sich im Wärmeaustauscher 22 im Gegenstrom zum anderen Teil des Hochdruckstickstoffes und tritt bei 7 aus.washes. The clean gas exiting at the top of the washing column 24 releases its cold in the heat exchanger 25 to the raw gas and in the heat exchanger 23 to a part of the high-pressure nitrogen and leaves at 6 the system, where for the mixture composition about still missing nitrogen through a pipe can be added directly from the high pressure nitrogen compressor 21 to line 6. The residual gas is heated in the heat exchanger 22 in countercurrent to the other part of the high-pressure nitrogen and occurs at 7 off.

Fig. 2 stellt die Erzeugung von hochprozentigem Wasserstoff in einer Gaszerlegungsanlage dar, wobei die zusätzlich aufzubringende Kälte einer Linde-Fränkl-Luftzerlegungsanlage mit Wärmeaustausch durch Regeneratoren entnommen wird.Fig. 2 shows the production of high percentage hydrogen in a gas separation plant, wherein the additional cold of a Linde-Fränkl air separation plant with heat exchange is withdrawn by regenerators.

Die Luftzerlegungsanlage besteht aus dem Kompressor 11, den Regeneratoren 17 und 18, der Drucksäule 15, der oberen Säule 16, der Entspannungsturbine 13, den Rohrschlangen 19, der Lufteintrittsleitung 1, der Austrittsleitung für reinen Stickstoff 2, der Austrittsleitung für Sauerstoff 3 und der Austrittsleitung für unreinen Stickstoff 4.The air separation plant consists of the compressor 11, the regenerators 17 and 18, the pressure column 15, the upper column 16, the expansion turbine 13, the coils 19, the air inlet line 1, the outlet line for pure nitrogen 2, the outlet line for oxygen 3 and the outlet line for impure nitrogen 4.

Die Gaszerlegungsanlage besteht aus dem Hochdruck-Stickstoff-Kompressor 21, den Wärmeaustauschern 22 und 23, der Waschsäule 24, den Wärmeaustauschern 25 und 26, dem Restgasverdampfer 27, dem Stickstoff-Vakuumverdampfer 28, der Vakuumpumpe 29, der Rohgaseintrittsleitung 5, der Wasserstoffaustrittsleitung 9 und der Restgasaustrittsleitung 7.The gas separation plant consists of the high pressure nitrogen compressor 21, the heat exchangers 22 and 23, the washing column 24, the heat exchangers 25 and 26, the residual gas evaporator 27, the nitrogen vacuum evaporator 28, the vacuum pump 29, the raw gas inlet line 5, the hydrogen outlet line 9 and the residual gas outlet line 7th

Die beiden Anlagen sind im Wärmeaustauscher 32 miteinander verbunden.The two systems are connected to one another in the heat exchanger 32.

Die Luft für die Luftzerlegungsanlage wird durch den hier als Turboverdichter ausgebildeten Kornpressor 11 auf beispielsweise 5,6 ata verdichtet, in den Regeneratoren 17 und 18 abgekühlt und zum wesentlichen Teil der Drucksäule 15 zugeführt. Ein kleiner Teil der Druckluft wird aus der Mitte der Regeneratoren 17 entnommen und zur Entspannungsturbine 13 geführt. Ein Teil der in den Regeneratoren 17 und 18 vollständig abgekühlten Druckluft wird im Wärmeaustauscher 32 durch sich verflüssigenden verdichteten Waschstickstoff aus der Gaszerlegungsanlage wieder etwas erwärmt und zusammen mit dem aus der Mitte *5 der Regeneratoren 17 entnommenen Teil der Druckluft der Entspannungsturbine 13 zugeleitet, arbeitsleistend entspannt und in die obere Säule 16 eingeleitet. Der reine Stickstoff wird vom Kopf der oberen Säule 16 entnommen und durch die Rohrschlangen 19 5<> in den Regeneratoren 17 und die Leitung 2 ganz oder teilweise vom Hochdruck-Stickstoff-Kompressor 21 angesaugt. Der unreine Stickstoff wird durch einen sogenannten Lachmann-Anstich zwischen dem Kopf der oberen Säule 16 und der Einleitungsstelle des flüssigen Rohsauerstoffs aus dem Fuß der Drucksäule 15 abgezogen, durch die Regeneratoren 17 erwärmt und verläßt bei 4 die Anlage. Der Sauerstoff aus der oberen Säule 16 verläßt durch die Regeneratoren 18 bei 3 die Anlage.The air for the air separation plant is produced by the granulator, which is designed here as a turbo compressor 11 compressed to, for example, 5.6 ata, cooled in the regenerators 17 and 18 and to the essentials Part of the pressure column 15 is supplied. A small part of the compressed air comes from the middle of the regenerators 17 removed and led to the expansion turbine 13. Some of the in regenerators 17 and 18 Completely cooled compressed air is compressed in the heat exchanger 32 by liquefying Scrubbing nitrogen from the gas separation plant is reheated a little and together with that from the middle * 5 The part of the compressed air taken from the regenerators 17 is fed to the expansion turbine 13, performing work relaxed and introduced into the upper column 16. The pure nitrogen is from the top of the top Column 16 removed and through the coils 19 5 <> in the regenerators 17 and the line 2 in whole or in part from the high-pressure nitrogen compressor 21 sucked in. The impure nitrogen is put through a so-called Lachmann prick between the head the upper column 16 and the point of introduction of the liquid raw oxygen from the foot of the pressure column 15 withdrawn, heated by the regenerators 17 and leaves the system at 4. The oxygen from the upper column 16 leaves the plant through the regenerators 18 at 3.

Das bei 5 mit einem geeigneten Druck von beispielsweise 30 ata eintretende Rohgas gelangt durch die Wärmeaustauscher 25 und 26, durch den Restgasverdampfer 27 nach unten in die Waschsäule 24, inder die Verunreinigungen durch herunterlaufenden flüssigen Stickstoff ausgewaschen werden. Im Hochdruck-Stickstoff-Kompressor 21 wird der Stickstoff auf beispielsweise 180 ata verdichtet, dann in den Wärmeaustauschern 22 und 23 abgekühlt und danach im Wärmeaustauscher 32 entsprechend dem Erfindungsgedanken im indirekten Wärmeaustausch mit Druckluft verflüssigt. Der eine Teil wird nach entsprechender Entspannung oben in die Waschsäule 24 geleitet. Der andere Teil wird gegebenenfalls unter Zwischenschaltung einer Unterkühlung, z. B. durch den abziehenden Wasserstoff, in den in der Zeichnung über der Waschsäule 24 angeordneten Stickstoff-Vakuumverdampfer entspannt. Der unter Vakuum verdampfte Stickstoff wird durch den Wärmeaustauscher 23 von der Vakuumpumpe 29 angesaugt. Durch die Verdampfung des Stickstoffs unter Vakuum wird die für die weitgehende Kondensation des Stickstoffs bis auf einen geringen Rest von beispielsweise 2% aus dem aus der Waschsäule 24 kommenden Wasserstoff-Stickstoff-Gemisch nötige Kälte bei genügend tiefer Temperatur erzeugt, so daß reiner oder fast reiner Wasserstoff die Gaszerlegungsanlage bei 9 verläßt, nachdem er seine Kälte im Wärmeaustauscher 25 an einen Teil des Rohgases abgegeben hat. Das verflüssigte Restgas wird unten aus der Waschsäule 24 entnommen, im Restgasverdampfer 27 durch sich abkühlendes Rohgas verdampft und verläßt bei 7 die Anlage, nachdem seine Kälte teilweise im Wärmeaustauscher 26 an das Rohgas und teilweise im Wärmeaustauscher an den Hochdruckstickstoff ausgetauscht ist.That at 5 with a suitable pressure of, for example 30 ata incoming raw gas passes through the heat exchangers 25 and 26, through the residual gas evaporator 27 down into the washing column 24, in which the impurities from running down liquid Nitrogen to be washed out. In the high-pressure nitrogen compressor 21, the nitrogen is increased to, for example 180 ata compressed, then cooled in the heat exchangers 22 and 23 and then in Heat exchanger 32 according to the concept of the invention in indirect heat exchange with compressed air liquefied. One part is passed into the washing column 24 at the top after corresponding relaxation. Of the other part is optionally with the interposition of a subcooling, z. B. by the withdrawing Hydrogen, in the nitrogen vacuum evaporator arranged above the washing column 24 in the drawing relaxed. The nitrogen evaporated under vacuum is passed through the heat exchanger 23 of the Vacuum pump 29 sucked in. By the evaporation of the nitrogen under vacuum the for the extensive Condensation of the nitrogen except for a small residue of, for example, 2% from that from the Washing column 24 coming hydrogen-nitrogen mixture required cold at a sufficiently low temperature generated so that pure or almost pure hydrogen leaves the gas separation plant at 9 after it has given off its cold in the heat exchanger 25 to part of the raw gas. The liquefied residual gas is taken from the bottom of the washing column 24, in the residual gas evaporator 27 by cooling Raw gas evaporates and leaves the system at 7 after it has been partially cooled in the heat exchanger 26 to the raw gas and partly to the high pressure nitrogen in the heat exchanger.

Claims (8)

Patentansprüche:Patent claims: 1. Verfahren zur Zerlegung von Wasserstoff enthaltenden Gasgemischen, insbesondere Koksofengas, wobei die schwer kondensierbaren Bestandteile des Gasgemisches mit flüssigem, durch Luftzerlegung gewonnenem Stickstoff gewaschen werden, der aus gasförmig bei Umgebungstemperatur auf Hochdruck verdichtetem, im Gegenstrom mit sich selbst und mit Bestandteilen des Gasgemisches abgekühltem Stickstoff erzeugt wird, dadurch gekennzeichnet, daß der abgekühlte Stickstoff in indirektem Wärmeaustausch mit kalter, zu zerlegender Luft zumindest teilweise verflüssigt wird.1. Process for the decomposition of gas mixtures containing hydrogen, in particular coke oven gas, whereby the difficult to condense constituents of the gas mixture with liquid, through Nitrogen obtained by air separation can be washed out of gaseous form at ambient temperature compressed at high pressure, in countercurrent with itself and with components of the gas mixture cooled nitrogen is generated, characterized in that the cooled nitrogen at least partially liquefied in indirect heat exchange with cold air to be decomposed will. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der abgekühlte Stickstoff in indirektem Wärmeaustausch mit an Sauerstoff angereicherter flüssiger Luft zumindest teilweise verflüssigt wird.2. The method according to claim 1, characterized in that the cooled nitrogen in indirect Heat exchange with oxygen-enriched liquid air at least partially liquefied will. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der abgekühlte Stickstoff in indirektem Wärmeaustausch mit auf Kondensationstemperatur abgekühlter und anschließend arbeitsleistend zu entspannender gasförmiger Luft zumindest teilweise verflüssigt wird.3. The method according to claim 1, characterized in that the cooled nitrogen in indirect Heat exchange with cooled to condensation temperature and then work-performing to relax gaseous air is at least partially liquefied. 4. Verfahren nach Anspruch 1 bis 3 zur Erzeugung von Wasserstoff-Stickstoff-Gemischen, dadurch gekennzeichnet, daß die Waschstickstoffmenge nur so gering bemessen wird, daß diese Gemische ausreichend gereinigt werden, und daß für das gewünschte Wasserstoff-Stickstoff-Verhältnis gegebenenfalls noch erforderlicher Stickstoff erst dem wiederangewärmten, beim Waschen entstandenen Gemisch zugesetzt wird.4. The method according to claim 1 to 3 for the production of hydrogen-nitrogen mixtures, characterized in that the amount of scrubbing nitrogen is only so small that this Mixtures are sufficiently purified, and that for the desired hydrogen-nitrogen ratio If necessary, nitrogen is not required until it is rewarmed during washing resulting mixture is added. 5. Verfahren nach Anspruch 1 bis 3 zur Erzeugung von Wasserstoff, dadurch gekennzeichnet, daß flüssiger Stickstoff vom Waschstickstoff abgezweigt und in indirektem Wärmeaustausch mit dem zu reinigenden Gasgemisch unter Unterdruck verdampft wird.5. The method according to claim 1 to 3 for the production of hydrogen, characterized in that that liquid nitrogen is branched off from the scrubbing nitrogen and in indirect heat exchange with the gas mixture to be cleaned is evaporated under negative pressure. 6. Vorrichtung für das Verfahren nach Anspruch 1 bis 5, bestehend aus einer Koksofengas- und einer Luftzerlegungsanlage, dadurch gekennzeichnet, daß die beiden Anlagen eigene Isola-6. Device for the method according to claim 1 to 5, consisting of a coke oven gas and an air separation plant, characterized in that the two plants have their own isolation tionsmäntel besitzen und durch zwei isolierte Leitungen, eine für kalten gasförmigen und die andere für zumindest teilweise verflüssigten Wasehstickstoff miteinander verbunden sind.tion jackets and have two insulated lines, one for cold gaseous and the others are connected to one another for at least partially liquefied wasehnitrogen. 7. Vorrichtung nach Anspruch 6 und für das Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß sich in der Luftzerlegungsanlage ein Verdampferkondensator für den Wärmeaustausch zwischen Wasehstickstoff und an Sauerstoff angereicherter flüssiger Luft befindet, die vom Fuß7. Apparatus according to claim 6 and for the method according to claim 2, characterized in that that there is an evaporator condenser for the heat exchange in the air separation plant between whirlpool and oxygenated liquid air coming from the foot der unteren Säule zur oberen Säule einer Doppel-Rektifikationssäule strömt.the lower column to the upper column of a double rectification column flows. 8. Vorrichtung nach Anspruch 6 und für das Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß sich in der Luftzerlegungsanlage ein Wärmeaustauscher für Wasehstickstoff und gasförmige kalte, in einer Expansionsturbine zu entspannende, und dann in die obere Säule einer Doppel-Rektifikationssäule einzublasende Luft befindet. 8. Apparatus according to claim 6 and for the method according to claim 3, characterized in that that there is a heat exchanger for wasehnitrogen and gaseous in the air separation plant cold, to be relaxed in an expansion turbine, and then in the upper column of a Double rectification column air to be injected is located. Hierzu 1 Blatt Zeichnungen1 sheet of drawings © 709 850/148 1.58© 709 850/148 1.58
DEG20593A 1956-09-20 1956-09-20 Process for the decomposition of gas mixtures containing hydrogen, in particular coke oven gas, and device for carrying out the process Pending DE1023061B (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE560978D BE560978A (en) 1956-09-20
DEG20593A DE1023061B (en) 1956-09-20 1956-09-20 Process for the decomposition of gas mixtures containing hydrogen, in particular coke oven gas, and device for carrying out the process
US676112A US2962867A (en) 1956-09-20 1957-08-05 Process for decomposing hydrogencontaining gas mixtures
FR1182607D FR1182607A (en) 1956-09-20 1957-09-11 Process for the decomposition of gas mixtures containing hydrogen, and in particular coke oven gases

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEG20593A DE1023061B (en) 1956-09-20 1956-09-20 Process for the decomposition of gas mixtures containing hydrogen, in particular coke oven gas, and device for carrying out the process

Publications (1)

Publication Number Publication Date
DE1023061B true DE1023061B (en) 1958-01-23

Family

ID=7121549

Family Applications (1)

Application Number Title Priority Date Filing Date
DEG20593A Pending DE1023061B (en) 1956-09-20 1956-09-20 Process for the decomposition of gas mixtures containing hydrogen, in particular coke oven gas, and device for carrying out the process

Country Status (4)

Country Link
US (1) US2962867A (en)
BE (1) BE560978A (en)
DE (1) DE1023061B (en)
FR (1) FR1182607A (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3089311A (en) * 1959-12-21 1963-05-14 Linde Eismasch Ag Regenerative heat-transfer process
DE1135020B (en) * 1960-04-14 1962-08-23 Linde Eismasch Ag Process and device for the low-temperature decomposition of a hydrogen-rich gas mixture
US3092283A (en) * 1960-07-29 1963-06-04 Sulzer Ag Means for insulating elements of a low temperature unit
DE1467202A1 (en) * 1963-03-21 1969-03-13 Linde Eismasch Ag Method and device for regulating the cold balance when producing NH3 synthesis gas
DE1258882B (en) * 1963-06-19 1968-01-18 Linde Ag Process and system for air separation by rectification using a high pressure gas refrigeration cycle for the pressure evaporation of liquid oxygen
US3421333A (en) * 1964-08-28 1969-01-14 Linde Ag Thawing technique for a single air separation plant
GB1096256A (en) * 1965-05-18 1967-12-20 Linde Ag Process and apparatus for the low-temperature fractionation of a hydrogen-rich gas mixture
DE1263037B (en) * 1965-05-19 1968-03-14 Linde Ag Method for the separation of air in a rectification column and the separation of a gas mixture containing hydrogen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1354380A (en) * 1914-01-07 1920-09-28 Godfrey L Cabot Apparatus for producing liquid oxygen
US1843043A (en) * 1924-02-13 1932-01-26 Patart Georges Leon Emile Process for the separation of the several components of gaseous mixtures
FR601628A (en) * 1924-11-06 1926-03-05 Ammonia Method and system of apparatus for the extraction of hydrogen contained in industrial gases and in particular in coke oven gas
US2417279A (en) * 1944-07-22 1947-03-11 Air Reduction Separation of the constituents of gaseous mixtures
US2785548A (en) * 1954-05-26 1957-03-19 Linde Eismasch Ag Process for the production of liquid oxygen by separation from air

Also Published As

Publication number Publication date
BE560978A (en)
US2962867A (en) 1960-12-06
FR1182607A (en) 1959-06-26

Similar Documents

Publication Publication Date Title
EP0505812B1 (en) Low temperature air separation process
EP0100923B1 (en) Process and apparatus for separating a gas mixture
DE1007345B (en) Process for the separation of compressed air by deep freezing, liquefaction and rectification and device for the process
DE1226616B (en) Process and device for the production of gaseous pressurized oxygen with simultaneous production of liquid decomposition products by low-temperature air separation
DE1095866B (en) Process and device for the separation of carbon dioxide from compressed gases
DE1103363B (en) Method and device for generating a balanced cold budget when extracting gas mixtures and / or gas mixture components under higher pressure by rectification
DE555818C (en) Process for separating low-boiling gas mixtures using cold storage tanks
DE2544340A1 (en) PROCEDURE FOR AIR SEPARATION
DE69305317T2 (en) Air separation process and plant for producing at least one compressed gas product and at least one liquid
WO2010017968A2 (en) Process and device for cryogenic air fractionation
DE1263037B (en) Method for the separation of air in a rectification column and the separation of a gas mixture containing hydrogen
DE3817244A1 (en) METHOD FOR DEEP TEMPERATURE DISPOSAL OF AIR
DE3528374A1 (en) METHOD AND DEVICE FOR PRODUCING NITROGEN WITH OVER-ATMOSPHERIC PRESSURE
DE1023061B (en) Process for the decomposition of gas mixtures containing hydrogen, in particular coke oven gas, and device for carrying out the process
DE3834793A1 (en) METHOD FOR OBTAINING ROHARGON
DE1205567B (en) Process for liquefying a gas
DE1159971B (en) Process for the production of gaseous and pressurized oxygen by decomposing air
DE1274092C2 (en) METHOD FOR PRODUCING AMMONIA SYNTHESIS GAS
DE1135935B (en) Method and device for the production of low-purity oxygen by low-temperature air separation
DE955867C (en) Process for separating a compressed, hydrogen-rich gas mixture
DE1046640B (en) Process and device for generating cold through work-performing relaxation
DE935195C (en) Process for the production of liquid oxygen from air and device for its implementation
DE3315930A1 (en) Process and apparatus for separating a gas mixture
DE1112095B (en) Process and device for the production of liquid gas separation products
DE1041989B (en) Process and device for gas separation, preferably air separation, by means of cryogenic rectification