DE10148166A1 - Method and device for producing liquid oxygen and liquid nitrogen - Google Patents
Method and device for producing liquid oxygen and liquid nitrogenInfo
- Publication number
- DE10148166A1 DE10148166A1 DE10148166A DE10148166A DE10148166A1 DE 10148166 A1 DE10148166 A1 DE 10148166A1 DE 10148166 A DE10148166 A DE 10148166A DE 10148166 A DE10148166 A DE 10148166A DE 10148166 A1 DE10148166 A1 DE 10148166A1
- Authority
- DE
- Germany
- Prior art keywords
- liquefied
- heat exchanger
- operating state
- gas
- oxygen
- 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.)
- Withdrawn
Links
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000007788 liquid Substances 0.000 title claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 23
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 23
- 239000012530 fluid Substances 0.000 claims abstract description 11
- 238000005057 refrigeration Methods 0.000 claims abstract description 7
- 230000006835 compression Effects 0.000 claims abstract description 3
- 238000007906 compression Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 238000003860 storage Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 12
- 238000009835 boiling Methods 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- GWVKDXOHXJEUCP-UHFFFAOYSA-N [N].[O].[Ar] Chemical compound [N].[O].[Ar] GWVKDXOHXJEUCP-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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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
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
- F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
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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
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
- F25J1/0012—Primary atmospheric gases, e.g. air
- F25J1/0015—Nitrogen
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
- F25J1/0012—Primary atmospheric gases, e.g. air
- F25J1/0017—Oxygen
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- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
- F25J1/0035—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work
- F25J1/0037—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work of a return stream
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
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- F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
- F25J1/004—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by flash gas recovery
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- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
- F25J1/0045—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by vaporising a liquid return stream
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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- F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
- F25J1/005—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by expansion of a gaseous refrigerant stream with extraction of work
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
- F25J1/007—Primary atmospheric gases, mixtures thereof
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
- F25J1/007—Primary atmospheric gases, mixtures thereof
- F25J1/0072—Nitrogen
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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- F25J1/0075—Oxygen
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- F25J1/0202—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using only internal refrigeration means, i.e. without external refrigeration in a quasi-closed internal refrigeration loop
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- F25J1/0204—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a single-component refrigerant [SCR] fluid in a closed vapor compression cycle as a single flow SCR cycle
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- F25J3/04763—Start-up or control of the process; Details of the apparatus used
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- F25J2270/00—Refrigeration techniques used
- F25J2270/58—Quasi-closed internal or closed external argon refrigeration cycle
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Abstract
Das Verfahren und die Vorrichtung dienen zur Erzeugung von flüssigem Sauerstoff und/oder flüssigem Stickstoff. Zu verflüssigendes Gas (1, 2, 5, 8, 11, 16, 21, 22, 23) wird in einem Kreislauf-Wärmetauscher (13) durch indirekten Wärmeaustausch mit einem Kreislaufmedium (15, 27, 34) abgekühlt und verflüssigt. Das Kreislaufmedium wird in einem Kältekreislauf verdichtet (9), abgekühlt (13), arbeitsleistend entspannt (14, 24) und/oder verflüssigt, in dem Kreislauf-Wärmetauscher (13) angewärmt und/oder verdampft und wieder der Verdichtung (3, 9) zugeführt. In einem ersten Betriebszustand wird das Kreislaufmedium durch ein erstes Fluid gebildet. In einem zweiten Betriebszustand wird das Kreislauf-Fluid durch ein zweites Fluid gebildet, das sich in seinen thermodynamischen Eigenschaften von dem ersten Kreislauf-Fluid unterscheidet.The method and the device are used to generate liquid oxygen and / or liquid nitrogen. Gas (1, 2, 5, 8, 11, 16, 21, 22, 23) to be liquefied is cooled and liquefied in a circuit heat exchanger (13) by indirect heat exchange with a circulation medium (15, 27, 34). The circulating medium is compressed (9), cooled (13), relieved of work (14, 24) and / or liquefied in a refrigeration circuit, warmed and / or evaporated in the circuit heat exchanger (13) and again the compression (3, 9) fed. In a first operating state, the circulating medium is formed by a first fluid. In a second operating state, the circuit fluid is formed by a second fluid which differs from the first circuit fluid in its thermodynamic properties.
Description
Die Erfindung betrifft ein Verfahren zur Erzeugung von flüssigem Sauerstoff und/oder flüssigem Stickstoff, bei dem zu verflüssigendes Gas in einem Kreislauf- Wärmetauscher durch indirekten Wärmeaustausch mit einem Kreislaufmedium verflüssigt wird, wobei das Kreislaufmedium in einem Kältekreislauf verdichtet, abgekühlt, arbeitsleistend entspannt und/oder verflüssigt, in dem Kreislauf- Wärmetauscher angewärmt und/oder verdampft und wieder der Verdichtung zugeführt wird und das Kreislaufmedium in einem ersten Betriebszustand durch ein erstes Fluid gebildet wird. The invention relates to a method for producing liquid oxygen and / or liquid nitrogen, in which the gas to be liquefied is circulated Heat exchanger through indirect heat exchange with a circulating medium is liquefied, the circulating medium compressing in a refrigeration cycle, cooled, relieved of work and / or liquefied, in the circulatory Heat exchanger warmed and / or evaporated and returned to compression and the circulating medium in a first operating state by a first fluid is formed.
Stickstoff-Verflüssigungsverfahren dieser Art sind allgemein bekannt, zum Beispiel aus DE 25 48 222 B, DE 37 32 364 A, EP 316768 A, DE 40 30 750 A, DE 43 03 771 A, DE 44 18 435 A, EP 795727 A oder EP 949471 A. Aus US 5678425 ist außerdem bekannt, ein derartiges Verfahren in zwei unterschiedlichen Betriebszuständen zu betreiben. Im einen Betriebszustand wird ausschließlich Flüssigstickstoff produziert, im anderen Flüssigstickstoff und Flüssigsauerstoff. In beiden Fällen wird Luft als Kreislaufmedium eingesetzt. Nitrogen liquefaction processes of this type are generally known, for example from DE 25 48 222 B, DE 37 32 364 A, EP 316768 A, DE 40 30 750 A, DE 43 03 771 A, DE 44 18 435 A, EP 795727 A or EP 949471 A. From US 5678425 is also known to such a method in two different operating states operate. In one operating state, only liquid nitrogen is produced other liquid nitrogen and liquid oxygen. In both cases air is considered Circulation medium used.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren der eingangs genannten Art und eine entsprechende Vorrichtung anzugeben, die sowohl für die Produktion von flüssigem Sauerstoff und flüssigem Stickstoff geeignet sind und einen besonders niedrigen Energieverbrauch aufweisen. The invention has for its object a method of the type mentioned and to provide a corresponding device that is suitable both for the production of liquid oxygen and liquid nitrogen are suitable and especially have low energy consumption.
Diese Aufgabe wird dadurch gelöst, dass das Kreislaufmedium in einem zweiten Betriebszustand durch ein zweites Fluid gebildet wird, das sich in seinen thermodynamischen Eigenschaften von dem ersten Fluid unterscheidet, das in dem ersten Betriebszustand eingesetzt wird. Dies bedeutet, dass mindestens ein thermodynamischer Parameter der beiden Fluide unterschiedlich ist, beispielweise Siedetemperatur, spezifische Verdampfungswärme und/oder spezifische Wärme. This object is achieved in that the circulating medium in a second Operating state is formed by a second fluid, which is in its distinguishes thermodynamic properties from the first fluid, which in the first operating state is used. This means at least one thermodynamic parameter of the two fluids is different, for example Boiling temperature, specific heat of vaporization and / or specific heat.
Auf diese Weise kann der Kälteerzeugungs- und Verflüssigungsprozess optimal an das zu verflüssigende Gas angepasst werden, um einen möglichst geringen Energieverbrauch bei der Verflüssigung zu erzielen. Zu verschiedenen Zeitpunkten (erster und zweiter Betriebszustand) können dabei in derselben Anlage unterschiedliche Flüssigprodukte gewonnen werden, ohne dass bei der Wirtschaftlichkeit des Prozesses Abstriche gemacht werden müssen. Beispielsweise wird bei der Erzeugung von flüssigem Sauerstoff 5% weniger Energie verbraucht, wenn als Kreislaufmedium Sauerstoff, Argon oder ein Argon und Sauerstoff enthaltendes Gemisch anstelle von Stickstoff verwendet wird. In this way, the refrigeration and liquefaction process can optimally match that gas to be liquefied can be adjusted to the lowest possible To achieve energy consumption in liquefaction. At different times (first and second operating status) can be in the same system different liquid products can be obtained without the Economics of the process have to be compromised. For example 5% less energy is used to generate liquid oxygen, if oxygen, argon or an argon and oxygen as the circulating medium containing mixture is used instead of nitrogen.
Vorzugsweise weisen zu verflüssigendes Gas und Kreislaufmedium ähnliche Siedepunkte auf. Darunter ist zu verstehen, dass sich die Siedepunkte bei den in dem Verflüssigungsverfahren vorkommenden Druck um maximal 5 K, vorzugsweise um maximal 3 K unterscheiden. Die beiden Medien können beispielsweise dieselbe chemische Zusammensetzung aufweisen. Zum Beispiel werden in dem ersten Betriebszustand das zu verflüssigende Gas und das Kreislaufmedium durch Stickstoff gebildet, wogegen in dem zweiten Betriebszustand Sauerstoff sowohl als zu verflüssigendes Gas, als auch als Kreislaufmedium eingesetzt wird. Alternativ kann im zweiten Betriebszustand Argon oder ein mindestens 80 mol%, vorzugsweise mindestens 95 mol% Argon enthaltendes Gemisch als Kreislaufmedium verwendet werden; in der Praxis ist es günstig, zu diesem Zweck ein hauptsächlich Argon und Sauerstoff enthaltendes Gemisch wie Rohargon einzusetzen, das üblicherweise in der Rohargonsäule einer Tieftemperatur-Luftzerlegungsanlage hergestellt wird. The gas to be liquefied and the circulating medium preferably have similar ones Boiling points. This means that the boiling points in the in the Liquefaction process occurring pressure by a maximum of 5 K, preferably around differ by a maximum of 3 K. For example, the two media can be the same have chemical composition. For example, in the first Operating state the gas to be liquefied and the circulating medium by nitrogen formed, whereas in the second operating state oxygen both as and liquefying gas, as well as being used as a circulating medium. Alternatively, in second operating state argon or at least 80 mol%, preferably mixture containing at least 95 mol% of argon is used as the circulating medium become; in practice it is convenient to use a mainly argon and Use oxygen-containing mixture such as raw argon, which is usually in the Raw argon column of a low-temperature air separation plant is manufactured.
Das zu verflüssigende Gas wird vorzugsweise in beiden Betriebszuständen aus einer Luftzerlegungsanlage, insbesondere einer Tieftemperatur-Luftzerlegungsanlage, entnommen. The gas to be liquefied is preferably made from one in both operating states Air separation plant, in particular a low-temperature air separation plant, taken.
Beim Umschalten vom ersten in den zweiten Betriebszustand beziehungsweise umgekehrt wird eine Spülfraktion durch den Kreislauf-Wärmetauscher geleitet und vorzugsweise in einen Speicherbehälter eingeleitet. Die Spülfraktion kann zu einem späteren Zeitpunkt der Luftzerlegungsanlage zugeführt werden. Somit lässt sich der Kälteinhalt der Spülfraktion zurückgewinnen und die Spülung stellt keinen bedeutenden Energieverlust dar. When switching from the first to the second operating state respectively conversely, a rinsing fraction is passed through the circuit heat exchanger and preferably introduced into a storage container. The rinse fraction can become one later be supplied to the air separation plant. So the Recover the cold content of the rinse fraction and the rinse does not represent a significant one Energy loss.
Die Erfindung betrifft außerdem eine Vorrichtung zur Erzeugung von flüssigem Sauerstoff und/oder flüssigem Stickstoff gemäß den Patentansprüchen 8 bis 11. The invention also relates to a device for producing liquid Oxygen and / or liquid nitrogen according to claims 8 to 11.
Die Erfindung sowie weitere Einzelheiten der Erfindung werden im Folgenden anhand zweier Ausführungsbeispiele, die in den Zeichnungen dargestellt sind, näher erläutert. Die einander entsprechenden Vorrichtungsteile und Verfahrensschritte tragen in beiden Zeichnungen dieselben Bezugszeichen. The invention and further details of the invention are described below two exemplary embodiments, which are shown in the drawings, explained in more detail. The corresponding parts of the device and method steps carry in both Drawings the same reference numerals.
Zu verflüssigendes Gas 1 wird bei dem Verfahren und der Vorrichtung von Fig. 1 unter etwa atmosphärischem Druck über Leitung 2 einem Feedgas-Verdichter 3 mit Nachkühler 4 zugeführt und dort auf einen Zwischendruck von beispielsweise 4 bis 8 bar, vorzugsweise 5 bis 6 bar komprimiert. Das Kreislaufmedium 6, 7 weist bei dem Ausführungsbeispiel von Fig. 1 in beiden Betriebszuständen jeweils die gleiche chemische Zusammensetzung wie das zu verflüssigende Gas 1 auf. Die beiden Gase werden unter dem Zwischendruck vermischt und gemeinsam über Leitung 8 einem Kreislauf-Verdichter 9 mit Nachkühler 10 zugeführt. Dort wird das Gas auf einen hohen Druck von beispielsweise 26 bis 32 bar, vorzugsweise 28 bis 30 bar verdichtet. Gas 1 to be liquefied is fed in the method and the device of FIG. 1 to a feed gas compressor 3 with aftercooler 4 under approximately atmospheric pressure via line 2 and compressed there to an intermediate pressure of, for example, 4 to 8 bar, preferably 5 to 6 bar. In the embodiment of FIG. 1, the circulating medium 6 , 7 has the same chemical composition as the gas 1 to be liquefied in both operating states. The two gases are mixed under the intermediate pressure and fed together via line 8 to a circuit compressor 9 with aftercooler 10 . There the gas is compressed to a high pressure of, for example, 26 to 32 bar, preferably 28 to 30 bar.
Ein erster Teilstrom 12 des Hochdruckgases 11 wird in einem Kreislauf- Wärmetauscher 13 auf eine erste Zwischentemperatur abgekühlt und anschließend in einer warmen Turbine 14 arbeitsleistend auf etwa den Zwischendruck entspannt. Der entspannte erste Teilstrom des Kreislaufmediums strömt über die Leitungen 15, 7 und 8 durch den Kreislauf-Wärmetauscher 13 zum Eintritt des Kreislauf-Verdichters 9 zurück. A first partial flow 12 of the high-pressure gas 11 is cooled in a circuit heat exchanger 13 to a first intermediate temperature and then expanded in a warm turbine 14 to approximately the intermediate pressure while working. The relaxed first partial flow of the circulating medium flows back via lines 15 , 7 and 8 through the circulating heat exchanger 13 to the inlet of the circulating compressor 9 .
Ein zweiter (22) und dritter (23) Teilstrom des Hochdruckgases 11 werden zunächst gemeinsam (16) in den seriell geschalteten Nachverdichtern 17, 19 mit Nachkühlern 18, 20 auf einen noch höheren Druck von beispielsweise 45 bis 60 bar, vorzugsweise 48 bis 52 bar gebracht, der in Leitung 21 herrscht. Anschließend wird der zweite Teilstrom 22 im Kreislauf-Wärmetauscher 13 auf eine zweite, niedrigere Zwischentemperatur abgekühlt und anschließend in einer kalten Turbine 24 arbeitsleistend auf etwa den Zwischendruck entspannt. Das dabei entstandene Zwei- Phasen-Gemisch 25 wird in einen Zwischendruck-Abscheider (Phasentrenner) 26 eingeführt. Dampf aus dem Zwischendruck-Abscheider 26 strömt über die Leitungen 27, 6 und 8 durch den Kreislauf-Wärmetauscher 13 zum Eintritt des Kreislauf- Verdichters 9 zurück. A second ( 22 ) and third ( 23 ) partial flow of the high pressure gas 11 are first jointly ( 16 ) in the series-connected post-compressors 17 , 19 with after-coolers 18 , 20 to an even higher pressure of, for example, 45 to 60 bar, preferably 48 to 52 bar brought that prevails in line 21 . Subsequently, the second partial flow 22 is cooled in the circuit heat exchanger 13 to a second, lower intermediate temperature and then expanded in a cold turbine 24 to approximately the intermediate pressure while working. The resulting two-phase mixture 25 is introduced into an intermediate pressure separator (phase separator) 26 . Steam from the intermediate pressure separator 26 flows back via the lines 27 , 6 and 8 through the circuit heat exchanger 13 to the inlet of the circuit compressor 9 .
Der dritte Teilstrom 23 wird bis zum kalten Ende des Kreislauf-Wärmetauschers 13 geführt, anschließend auf etwa den Zwischendruck drosselentspannt (28) und über Leitung 29 in den Zwischendruck-Abscheider (Phasentrenner) 26 eingeleitet. Die Flüssigkeit 30 wird weiter auf etwa Atmosphärendruck entspannt (31) und in einem Niederdruck-Abscheider 32 einer weiteren Phasentrennung unterworfen. Die verbleibende Flüssigkeit 33 bildet das Flüssigprodukt, während das Flashgas über die Leitungen 34, 35 und 2 durch den Kreislauf-Wärmetauscher 13 zum Eintritt des Feedgas-Verdichters 3 zurückfließt. The third partial flow 23 is led to the cold end of the circuit heat exchanger 13 , then throttle-relaxed to approximately the intermediate pressure ( 28 ) and introduced into the intermediate pressure separator (phase separator) 26 via line 29 . The liquid 30 is further expanded to approximately atmospheric pressure ( 31 ) and subjected to a further phase separation in a low-pressure separator 32 . The remaining liquid 33 forms the liquid product, while the flash gas flows back via lines 34 , 35 and 2 through the circuit heat exchanger 13 to the inlet of the feed gas compressor 3 .
In einem ersten Betriebszustand wird über Leitung 1 Stickstoff-Gas in das Kreislauf- und Verflüssigungssystem eingeleitet. In Leitung 33 wird flüssiger Stickstoff (LIN) als Produkt entnommen. In einem zweiten Betriebszustand wird über Leitung 1 Sauerstoff- Gas in das Kreislauf- und Verflüssigungssystem eingeführt. Entsprechend wird in Leitung 33 flüssiger Sauerstoff (LOX) gewonnen. In a first operating state, nitrogen gas is introduced into the circulation and liquefaction system via line 1 . Liquid nitrogen (LIN) is taken off as product in line 33 . In a second operating state, oxygen-gas is introduced into the circulation and liquefaction system via line 1 . Accordingly, liquid oxygen (LOX) is obtained in line 33 .
Beim Umschalten vom ersten in den zweiten Betriebszustand muss der Kältekreislauf gespült werden. Dazu wird zunächst die Zufuhr von Stickstoff-Gas in die Leitung 1 beendet und stattdessen Sauerstoff in den Kreislauf eingeblasen - zunächst als Spülfraktion. Gleichzeitig wird die Verbindung zwischen der Produktleitung 33 und dem Verbraucher oder Speicher für Flüssigstickstoff unterbrochen und die Flüssigkeit stattdessen in einen (nicht dargestellten) Speicherbehälter für Spülflüssigkeit geleitet. Dies wird so lange fortgesetzt, bis in der Produktleitung 33 die gewünschte Reinheit für das Flüssigsauerstoff-Produkt erreicht ist. Anschließend wird die Produktleitung 33 mit dem Verbraucher oder Speicher für Flüssigsauerstoff verbunden und der zweite Betriebszustand ist damit erreicht. (Anschließend kann die aufgefangene Spülflüssigkeit in einer Luftzerlegungsanlage, wie sie unten beschrieben wird, wieder aufgearbeitet werden.) Das Umschalten vom zweiten in den ersten Betriebszustand funktioniert analog. When switching from the first to the second operating state, the refrigeration cycle must be rinsed. For this purpose, the supply of nitrogen gas into line 1 is first stopped and instead oxygen is blown into the circuit - initially as a flushing fraction. At the same time, the connection between the product line 33 and the consumer or storage for liquid nitrogen is interrupted and the liquid is instead passed into a storage container (not shown) for flushing liquid. This continues until the desired purity for the liquid oxygen product is reached in the product line 33 . The product line 33 is then connected to the consumer or storage for liquid oxygen and the second operating state is thus achieved. (The rinsing liquid collected can then be reprocessed in an air separation unit as described below.) Switching from the second to the first operating mode works in the same way.
Sowohl Sauerstoff als auch Stickstoff werden bei dem Ausführungsbeispiel in einer Tieftemperatur-Luftzerlegungsanlage hergestellt. Diese umfasst einen Hauptwärmetauscher 36 sowie ein Zwei-Säulen-Rektifiziersystem mit Hochdrucksäule 37 und Niederdrucksäule 38, die über einen Kondensator-Verdampfer (Hauptkondensator) 39 in wärmetauschender Verbindung stehen (Linde-Doppelsäule). Über Leitung 40 wird verdichtete und gereinigte Luft dem warmen Ende des Hauptwärmetauschers 36 zugeführt, dort auf etwa Taupunktstemperatur abgekühlt und über Leitung 41 in die Hochdrucksäule 37 eingeleitet. Flüssiger Rohsauerstoff 42 und flüssiger Stickstoff 43 aus der Hochdrucksäule 37 beziehungsweise dem Hauptkondensator 39 werden in die Niederdrucksäule 38 eingedrosselt (44, 45). Über die Produktleitungen werden Sauerstoff 46, stickstoffreiches Restgas 47 und Stickstoff 48 zum Hauptwärmetauscher 36 geleitet und schließlich unter etwa Umgebungstemperatur und Atmosphärendruck aus der Luftzerlegungsanlage abgezogen (53, 49, 50). Wollte man kein Flüssigprodukt erzeugen, würden alle drei Ströme als gasförmige Produkte GOX, UN2 und GAN abgezogen. In the exemplary embodiment, both oxygen and nitrogen are produced in a low-temperature air separation plant. This comprises a main heat exchanger 36 and a two-column rectification system with high-pressure column 37 and low-pressure column 38 , which are in heat-exchanging connection via a condenser-evaporator (main condenser) 39 (Linde double column). Compressed and cleaned air is fed via line 40 to the warm end of the main heat exchanger 36 , cooled there to approximately dew point temperature and introduced into the high-pressure column 37 via line 41 . Liquid raw oxygen 42 and liquid nitrogen 43 from the high pressure column 37 and the main condenser 39 are throttled into the low pressure column 38 ( 44 , 45 ). Oxygen 46 , nitrogen-rich residual gas 47 and nitrogen 48 are conducted to the main heat exchanger 36 via the product lines and finally withdrawn from the air separation plant at approximately ambient temperature and atmospheric pressure ( 53 , 49 , 50 ). If one did not want to produce a liquid product, all three streams would be subtracted as gaseous products GOX, UN2 and GAN.
Im ersten Betriebsfall der Flüssigproduktion wird mindestens ein Teil des in der Luftzerlegungsanlage abgetrennten gasförmigen Stickstoffs 50 über Ventil 51 zur Leitung 1 geführt und strömt damit in den Verflüssigungskreislauf. Das Ventil 52 ist geschlossen. In Leitung 33 wird flüssiger Stickstoff als Endprodukt erzeugt. In the first operating case of liquid production, at least some of the gaseous nitrogen 50 separated in the air separation plant is fed to line 1 via valve 51 and thus flows into the liquefaction circuit. The valve 52 is closed. In line 33 , liquid nitrogen is produced as the end product.
Beim Umschalten in den zweiten Betriebszustand wird das Ventil 51 geschlossen, sodass das gesamte Stickstoff-Produkt der Luftzerlegungsanlage gasförmig abgezogen wird (GAN). Gleichzeitig wird das Ventil 52 geöffnet und mindestens ein Teil des gasförmigen Sauerstoffs aus Leitung 53 über Leitung 1 in den Verflüssigungskreislauf geführt. Dieser Sauerstoff dient zunächst als Spülfraktion. Die während der Spülung in Leitung 33 anfallende unreine Flüssigkeit (Sauerstoff- Stickstoff-Gemisch) wird wie oben beschrieben in einem (nicht dargestellten) Speicherbehälter aufgefangen. Sobald in der Produktleitung 33 die gewünschte Sauerstoff-Reinheit erreicht ist, wird von der Spülung auf den zweiten Betriebszustand umgeschaltet, indem die Produktflüssigkeit 33 nicht mehr in den Speicherbehälter für Spülflüssigkeit, sondern zu einem Flüssigsauerstoff-Verbraucher oder -Speicher geleitet wird. When switching to the second operating state, the valve 51 is closed, so that the entire nitrogen product of the air separation plant is drawn off in gaseous form (GAN). At the same time, the valve 52 is opened and at least some of the gaseous oxygen from line 53 is led via line 1 into the liquefaction circuit. This oxygen initially serves as a flushing fraction. The impure liquid (oxygen-nitrogen mixture) accumulating in line 33 during the rinsing is collected as described above in a storage tank (not shown). As soon as the desired oxygen purity has been reached in the product line 33 , the rinsing is switched to the second operating state in that the product liquid 33 is no longer passed into the storage container for rinsing liquid, but rather to a liquid oxygen consumer or store.
Die Spülflüssigkeit kann nach und nach an geeigneter Stelle in die Hochdrucksäule 37 und/oder die Niederdrucksäule 38 eingespeist werden. The rinsing liquid can gradually be fed into the high-pressure column 37 and / or the low-pressure column 38 at a suitable point.
Fig. 2 stimmt in weiten Teilen mit Fig. 1 überein. Im Folgenden werden nur die unterschiedlichen Merkmale näher erläutert. Fig. 2 largely corresponds to Fig. 1. Only the different features are explained in more detail below.
Bei dem Verfahren von Fig. 2 wird im zweiten Betriebszustand ein Argon-Sauerstoff- Gemisch (beispielsweise etwa 98 mol% Argon und etwa 2 mol% Sauerstoff enthaltendes Rohargon) als Kreislaufmedium zur Verflüssigung von Sauerstoff eingesetzt. Der Kreislauf-Wärmetauscher weist hier zwei Blöcke 13, 213 auf, wobei der Block 213 als Kondensator-Verdampfer ausgebildet ist. In the method of FIG. 2, an argon-oxygen mixture (for example about 98 mol% argon and raw argon containing about 2 mol% oxygen) is used as the circulating medium for the liquefaction of oxygen in the second operating state. The circuit heat exchanger here has two blocks 13 , 213 , block 213 being designed as a condenser-evaporator.
Beim Umschalten vom ersten in den zweiten Betriebszustand wird das Ventil 51 geschlossen, sodass das gesamte Stickstoff-Produkt der Luftzerlegungsanlage gasförmig abgezogen wird (GAN). Gleichzeitig wird das Ventil 258 geöffnet und Rohargon strömt über Leitung 259 in den Kältekreislauf. Das Rohargon 259 dient zunächst als Spülfraktion. Die während der Spülung in Leitung 33 anfallende unreine Flüssigkeit (Argon-Sauerstoff-Stickstoff-Gemisch) wird wie in Fig. 1 in einem (nicht dargestellten) Speicherbehälter aufgefangen. Sobald in der Spülleitung 33 der gewünschte Argon-Sauerstoff-Gehalt erreicht ist, wird von der Spülung auf den alternativen zweiten Betriebszustand umgeschaltet, indem Ventil 254 geschlossen und die Ventile 255 und 252 geöffnet werden. Danach strömt gasförmiger kalter Sauerstoff 201 in den Kondensator-Verdampfer 213, wird dort verflüssigt, über Leitung 233 als flüssiges Sauerstoffprodukt abgezogen und zu einem Flüssigsauerstoff-Verbraucher oder -Speicher geleitet (nicht dargestellt). Gegen den kondensierenden Sauerstoff wird flüssiges Kreislaufmedium 256 in den Kondensator-Verdampfer 213 geführt, verdampft dort und strömt schließlich über die Leitungen 257, 34, 35 und 2 zurück zum Feedgas- Verdichter 3. When switching from the first to the second operating state, the valve 51 is closed, so that the entire nitrogen product of the air separation plant is drawn off in gaseous form (GAN). At the same time the valve 258 is opened and raw argon flows into the refrigeration circuit via line 259 . Raw argon 259 initially serves as a rinse fraction. The impure liquid (argon-oxygen-nitrogen mixture) accumulating in line 33 during the purge is collected in a storage tank (not shown) as in FIG. 1. As soon as the desired argon-oxygen content is reached in the purge line 33 , the purge is switched to the alternative second operating state by closing valve 254 and opening valves 255 and 252 . Thereafter, gaseous cold oxygen 201 flows into the condenser-evaporator 213 , is liquefied there, taken off via line 233 as a liquid oxygen product and passed to a liquid oxygen consumer or storage device (not shown). Against the condensing oxygen, liquid circulating medium 256 is led into the condenser-evaporator 213 , evaporates there and finally flows back via lines 257 , 34 , 35 and 2 to the feed gas compressor 3 .
Die Anlage von Fig. 2 kann zusätzlich das Ventil 52 und die entsprechende Leitung aus Fig. 1 aufweisen, über die Sauerstoff in den Kreislauf eingeführt werden kann. In diesem Fall ist es möglich, die Anlage im zweiten Betriebszustand alternativ mit Sauerstoff (wie zu Fig. 1 beschrieben) oder einem anderen Medium (zum Beispiel Rohargon wie oben bei Fig. 2 beschrieben) als Kreislaufmedium zu fahren. The system of FIG. 2 can additionally have the valve 52 and the corresponding line from FIG. 1, via which oxygen can be introduced into the circuit. In this case, it is possible to run the system in the second operating state alternatively with oxygen (as described for FIG. 1) or another medium (for example crude argon as described above for FIG. 2) as the circulating medium.
Claims (11)
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DE10148166A DE10148166A1 (en) | 2001-09-28 | 2001-09-28 | Method and device for producing liquid oxygen and liquid nitrogen |
EP02019784A EP1298399A1 (en) | 2001-09-28 | 2002-09-04 | Process and apparatus producing liquid oxygen and liquid nitrogen |
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CA3063409A1 (en) * | 2017-05-16 | 2018-11-22 | Terrence J. Ebert | Apparatus and process for liquefying gases |
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US3285028A (en) * | 1964-01-06 | 1966-11-15 | Air Prod & Chem | Refrigeration method |
FR2681415B1 (en) * | 1991-09-18 | 1999-01-29 | Air Liquide | PROCESS AND PLANT FOR THE PRODUCTION OF GAS OXYGEN UNDER HIGH PRESSURE BY AIR DISTILLATION. |
US5275003A (en) * | 1992-07-20 | 1994-01-04 | Air Products And Chemicals, Inc. | Hybrid air and nitrogen recycle liquefier |
US5678425A (en) * | 1996-06-07 | 1997-10-21 | Air Products And Chemicals, Inc. | Method and apparatus for producing liquid products from air in various proportions |
US6220053B1 (en) * | 2000-01-10 | 2001-04-24 | Praxair Technology, Inc. | Cryogenic industrial gas liquefaction system |
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