EP0527501A1 - Air rectification process and apparatus - Google Patents
Air rectification process and apparatus Download PDFInfo
- Publication number
- EP0527501A1 EP0527501A1 EP92113843A EP92113843A EP0527501A1 EP 0527501 A1 EP0527501 A1 EP 0527501A1 EP 92113843 A EP92113843 A EP 92113843A EP 92113843 A EP92113843 A EP 92113843A EP 0527501 A1 EP0527501 A1 EP 0527501A1
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- EP
- European Patent Office
- Prior art keywords
- column
- argon
- crude argon
- pressure column
- 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.)
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- 238000000034 method Methods 0.000 title claims abstract description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 206
- 229910052786 argon Inorganic materials 0.000 claims abstract description 99
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000001301 oxygen Substances 0.000 claims abstract description 47
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 47
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000004781 supercooling Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 17
- 238000001816 cooling Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
- F25J3/04078—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression
- F25J3/04103—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression using solely hydrostatic liquid head
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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
- 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
- F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
- F25J3/04078—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression
- F25J3/0409—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression of oxygen
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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
- 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
- F25J3/04193—Division of the main heat exchange line in consecutive sections having different functions
- F25J3/04206—Division of the main heat exchange line in consecutive sections having different functions including a so-called "auxiliary vaporiser" for vaporising and producing a gaseous product
- F25J3/04212—Division of the main heat exchange line in consecutive sections having different functions including a so-called "auxiliary vaporiser" for vaporising and producing a gaseous product and simultaneously condensing vapor from a column serving as reflux within the or another column
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- 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
- F25J3/04327—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 argon or argon enriched stream
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- F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
- F25J3/04333—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using quasi-closed loop internal vapor compression refrigeration cycles, e.g. of intermediate or oxygen enriched (waste-)streams
- F25J3/04351—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using quasi-closed loop internal vapor compression refrigeration cycles, e.g. of intermediate or oxygen enriched (waste-)streams of 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
- 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
- F25J3/04333—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using quasi-closed loop internal vapor compression refrigeration cycles, e.g. of intermediate or oxygen enriched (waste-)streams
- F25J3/04369—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using quasi-closed loop internal vapor compression refrigeration cycles, e.g. of intermediate or oxygen enriched (waste-)streams of argon or argon enriched 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
- 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
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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
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
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- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04642—Recovering noble gases from air
- F25J3/04648—Recovering noble gases from air argon
- F25J3/04654—Producing crude argon in a crude argon column
- F25J3/04666—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system
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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
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04642—Recovering noble gases from air
- F25J3/04648—Recovering noble gases from air argon
- F25J3/04654—Producing crude argon in a crude argon column
- F25J3/04709—Producing crude argon in a crude argon column as an auxiliary column system in at least a dual pressure main column system
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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
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/20—Processes or apparatus using separation by rectification in an elevated pressure multiple column system wherein the lowest pressure column is at a pressure well above the minimum pressure needed to overcome pressure drop to reject the products to atmosphere
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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
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/50—Processes or apparatus using separation by rectification using multiple (re-)boiler-condensers at different heights of the column
- F25J2200/52—Processes or apparatus using separation by rectification using multiple (re-)boiler-condensers at different heights of the column in the high pressure column of a double pressure main column system
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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
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- F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
- F25J2235/58—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being argon or crude argon
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25J2250/00—Details related to the use of reboiler-condensers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25J2250/00—Details related to the use of reboiler-condensers
- F25J2250/30—External or auxiliary boiler-condenser in general, e.g. without a specified fluid or one fluid is not a primary air component or an intermediate fluid
- F25J2250/50—One fluid being oxygen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- 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
- F25J2250/58—One fluid being argon or crude argon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S62/00—Refrigeration
- Y10S62/923—Inert gas
- Y10S62/924—Argon
Definitions
- the invention relates to a method for air separation by rectification, in which air is compressed, cleaned, cooled and pre-separated in the high pressure column of a two-stage rectification column into an oxygen-rich liquid and into a nitrogen-rich fraction, in which the oxygen-rich liquid and / or the nitrogen-rich fraction is at least partially are fed to the rectifier column at the medium pressure column and are broken down into oxygen and nitrogen and from which an argon-containing oxygen stream and an oxygen product stream are taken from the medium pressure column, the argon-containing oxygen stream being fed to a crude argon column which is operated at a pressure which is lower than the pressure of the Is medium pressure column, and raw argon is taken from the upper area, and a device for performing this method.
- the crude argon rectification is carried out at a pressure which is lower than the pressure at which the medium pressure column of the two-stage rectification column is operated.
- the argon-containing oxygen flow from the medium pressure column is expanded to perform work before being introduced into the crude argon column.
- an oxygen-rich liquid is drawn off, which is largely used for this purpose.
- gaseous crude argon is liquefied in indirect heat exchange with relaxed, oxygen-rich liquid from the high-pressure column.
- the evaporated oxygen-rich fraction is compressed and fed into the medium pressure column.
- the known method enables the crude argon to be obtained in connection with an air separator for pressurized oxygen or pressurized nitrogen without too great a loss in argon yield due to the lower pressure in the crude argon column compared to the medium pressure column.
- it also has disadvantages.
- the expansion and recompression of the oxygen-rich fraction for head cooling of the crude argon column is very complex.
- the vaporized fraction of the oxygen-rich fraction is fed into the medium pressure column in gaseous form and is no longer available there as reflux liquid; as a result, the rectification conditions in the medium pressure column and in particular the argon yield are not completely satisfactory.
- the object on which the invention is based is to improve a method of the type mentioned at the outset in which argon production can be carried out particularly economically.
- This object is achieved in that the oxygen product stream is led out in the liquid state from the medium pressure column, that at least part of the crude argon removed from the crude argon column is condensed in indirect heat exchange with the liquid oxygen product stream, the oxygen product stream evaporating at least partially , and condensed raw argon is fed back into the raw argon column.
- the process according to the invention offers further advantages if the pressure of the liquid oxygen product stream is increased before the indirect heat exchange with the condensing crude argon. It is known to be oxygen pressurize liquid and then evaporate to produce oxygen under increased pressure economically. However, the oxygen is usually compressed against condensing feed air, which is then fed into the high-pressure column. However, this fluid task has a negative impact on rectification in the high pressure column.
- the pressure increase in liquid oxygen can be accomplished, for example, by a pump or by utilizing a hydrostatic potential between the medium pressure column and the oxygen evaporator.
- the raw argon can be compacted in one or more stages.
- the desired pressure of the raw argon and thus ultimately the pressure level of the vaporized oxygen product stream can be set by means of the compressor or compressors.
- the oxygen release pressure can thus be set in a wide range without any significant effects on the rest of the process.
- the condensed crude argon is preferably subcooled and the pressure is released before it is introduced into the crude argon column. It is advantageous if the supercooling of the condensed crude argon is brought about by indirect heat exchange with crude argon taken from the crude argon column.
- the argon-containing oxygen stream from the medium pressure column before it is introduced into the Crude argon column relaxed while working and the work gained during relaxation while working is used at least partially to compress crude argon.
- the amount of external energy required for the compression of the crude argon upstream of the condensation against evaporating oxygen can be significantly reduced.
- a part of the vaporized oxygen product stream can be introduced into the lower part of the medium pressure stage.
- the crude argon condensation also generates rising gas in the medium pressure column and thereby increases the effect of the main condenser.
- a part of the raw argon taken from the raw argon column is preferably obtained as a product.
- Compressed and pre-cleaned air is introduced via line 1, cooled in a heat exchanger 36 in indirect heat exchange with product streams, and fed into the high-pressure column 3 of a two-stage rectification column 2.
- the high pressure column 3 (operating pressure: 6 to 20 bar, preferably 8 to 17 bar) is connected to the medium pressure column 4 (operating pressure: 1.5 to 10 bar, preferably 2.0 to 8 bar) via a common condenser / evaporator 13 .
- the air introduced is pre-divided in the high pressure column into nitrogen and into an oxygen-enriched fraction.
- the oxygen-enriched fraction is discharged at the bottom of the high-pressure column via line 6 in the liquid state, subcooled in heat exchanger 32 and throttled back into the medium-pressure column 4 via valve 10.
- Nitrogen from the top of the high-pressure column 3 is also drawn off in liquid form via line 5, subcooled in heat exchanger 32 and, on the one hand, discharged as a liquid product via line 8.
- the other part of the nitrogen from the pressure column 3 is given via line 9 as a return to the medium pressure column 4.
- Liquid oxygen (line 40), gaseous pure nitrogen (line 15) and impure nitrogen (line 16) are removed as products of the medium pressure stage and the two nitrogen fractions in the heat exchangers 32 and 36 are heated.
- an argon-containing oxygen stream is also withdrawn from line 17 via line 17, heated in heat exchanger 36 and fed into crude argon column 20, which operates under a pressure of 1.1 to 2 bar, preferably 1.3 to 1.5 operated bar.
- the residual fraction obtained in the bottom of the crude argon column 20 is discharged via line 22 and brought to the pressure required for feeding back into the medium pressure column 4 by pump 23.
- the argon-rich oxygen stream 17 is expanded before it is introduced into the crude argon column 20 in an expansion turbine 18 in order to bring the argon-rich oxygen stream to the low pressure prevailing in the crude argon column 20 on the one hand and to generate the required process cold on the other hand.
- the gaseous crude argon obtained at the top of the crude argon column 20 is removed via line 21, heated in the heat exchanger 37 against cooling, condensed crude argon, further heated in the heat exchanger 36 and then divided into two partial streams 24 and 25.
- the crude argon stream in line 24 is removed as an intermediate product from the system to the consumer.
- the crude argon flow in line 25, which is not removed from the system, is compressed in two compressor stages 26 and 29 and then each cooled (water coolers 28 and 30).
- the crude argon stream is then passed through line 31 through the heat exchanger 36, further cooled there and then led into the condenser 34 attached in the condenser evaporator 33.
- the crude argon condenses against liquid oxygen brought in via line 40 and by means of pump 41.
- the condensed crude argon is then fed via line 35 into the heat exchanger 37 guided, cooled in it against crude argon taken from the crude argon column 20 and relaxed into the crude argon column 20 via valve 38.
- the liquid, pressurized oxygen product stream fed into the condenser evaporator 33 via line 40 and with the aid of the pump 41 is partially evaporated in indirect heat exchange with the partial stream of the crude argon supplied via line 31.
- the vaporous fraction of the oxygen product stream is discharged via line 42 after heating in the heat exchanger 36.
- Via line 43 and valve 44 a part of the gaseous oxygen product stream not required for delivery can be expanded again into the sump of the medium pressure column.
- a liquid oxygen product stream can be obtained from the condenser evaporator 33 by means of line 45.
- a portion of the nitrogen fraction is withdrawn from line 15 via line 50, compressed in the compressor 51, then cooled in the water cooler 52 and, after supercooling, is led via line 53 into heat exchanger 36 into the heating coil 54 attached in the sump of the high-pressure column 3.
- the nitrogen condensate formed in this way is introduced via line 55 and valve 56 into the upper region of the high-pressure column, above or below the removal point of the liquid nitrogen (line 5) (in the drawing the introduction below the removal point is drawn for the sake of clarity).
- the nitrogen condensate throttled in the upper area of the high-pressure column has a positive effect on argon production in the medium-pressure column, since the reflux conditions in the medium-pressure column are improved by the additional nitrogen task.
- the sump heater 54 can reduce the amount of air required to such an extent that any low oxygen purity can be achieved in the impure nitrogen.
- the method according to the invention can be used particularly advantageously in air separation plants which are connected to power plants (for example GUD power plants) or other plants with a gas turbine (eg for steel production) are integrated ("combined cycle").
- power plants for example GUD power plants
- gas turbine eg for steel production
- Partial areas of a column can also be filled with packing, while other areas have, for example, trays.
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Luftzerlegung durch Rektifikation, bei dem Luft verdichtet, gereinigt, abgekühlt und in der Hochdrucksäule einer zweistufigen Rektifiziersäule in eine sauerstoffreiche Flüssigkeit und in eine stickstoffreiche Fraktion vorzerlegt wird, bei dem die sauerstoffreiche Flüssigkeit und/oder die stickstoffreiche Fraktion mindestens teilweise der Mitteldrucksäule der Rektifiziersäule zugeführt und in Sauerstoff und Stickstoff zerlegt werden und bei dem der Mitteldrucksäule ein argonhaltiger Sauerstoffstrom und ein Sauerstoff-Produktstrom entnommen werden, wobei der argonhaltige Sauerstoffstrom einer Rohargonsäule zugeleitet wird, die bei einem Druck betrieben wird, der niedriger als der Druck der Mitteldrucksäule ist, und aus deren oberem Bereich Rohargon entnommen wird, sowie eine Vorrichtung zur Durchführung dieses Verfahrens.The invention relates to a method for air separation by rectification, in which air is compressed, cleaned, cooled and pre-separated in the high pressure column of a two-stage rectification column into an oxygen-rich liquid and into a nitrogen-rich fraction, in which the oxygen-rich liquid and / or the nitrogen-rich fraction is at least partially are fed to the rectifier column at the medium pressure column and are broken down into oxygen and nitrogen and from which an argon-containing oxygen stream and an oxygen product stream are taken from the medium pressure column, the argon-containing oxygen stream being fed to a crude argon column which is operated at a pressure which is lower than the pressure of the Is medium pressure column, and raw argon is taken from the upper area, and a device for performing this method.
Ein derartiges Verfahren, bei dem im Anschluß an eine Luftzerlegung Rohargon gewonnen wird, ist aus der DE-A-39 05 521 bekannt.Such a method, in which crude argon is obtained after air separation, is known from DE-A-39 05 521.
Bei diesem Verfahren wird die Rohargonrektifikation bei einem Druck durchgeführt, der niedriger ist als der Druck, bei dem die Mitteldrucksäule der zweistufigen Rektifiziersäule betrieben wird. Der argonhaltige Sauerstoffstrom aus der Mitteldrucksäule wird vor dem Einleiten in die Rohargonsäule arbeitsleistend entspannt. Am Sumpf der Hochdrucksäule wird eine sauerstoffreiche Flüssigkeit abgezogen, die zum größten Teil dazu verwendet wird, Im Kopfkondensator der Rohargonsäule wird gasförmiges Rohargon in indirektem Wärmeaustausch mit entspannter sauerstoffreicher Flüssigkeit aus der Hochdrucksäule verflüssigt. Die dabei verdampfte sauerstoffreiche Fraktion wird verdichtet und in die Mitteldrucksäule eingespeist. Das bekannte Verfahren ermöglicht durch den gegenüber der Mitteldrucksäule abgesenkten Druck in der Rohargonsäule die Rohargongewinnung im Anschluß an einen Luftzerleger für Drucksauerstoff bzw. Druckstickstoff ohne allzu große Verluste an Argonausbeute durchzuführen. Es weist jedoch auch Nachteile auf. Insbesondere ist die Entspannung und Rückverdichtung der sauerstoffreichen Fraktion zur Kopfkühlung der Rohargonsäule sehr aufwendig. Außerdem wird der verdampfte Anteil der sauerstoffreichen Fraktion gasförmig in die Mitteldrucksäule eingespeist und steht dort nicht mehr als Rücklaufflüssigkeit zur Verfügung; dadurch sind die Rektifizierbedingungen in der Mittledrucksäule und insbesondere die Argonausbeute nicht vollständig zufriedenstellend.In this method, the crude argon rectification is carried out at a pressure which is lower than the pressure at which the medium pressure column of the two-stage rectification column is operated. The argon-containing oxygen flow from the medium pressure column is expanded to perform work before being introduced into the crude argon column. At the bottom of the high-pressure column, an oxygen-rich liquid is drawn off, which is largely used for this purpose. In the top condenser of the crude argon column, gaseous crude argon is liquefied in indirect heat exchange with relaxed, oxygen-rich liquid from the high-pressure column. The evaporated oxygen-rich fraction is compressed and fed into the medium pressure column. The known method enables the crude argon to be obtained in connection with an air separator for pressurized oxygen or pressurized nitrogen without too great a loss in argon yield due to the lower pressure in the crude argon column compared to the medium pressure column. However, it also has disadvantages. In particular, the expansion and recompression of the oxygen-rich fraction for head cooling of the crude argon column is very complex. In addition, the vaporized fraction of the oxygen-rich fraction is fed into the medium pressure column in gaseous form and is no longer available there as reflux liquid; as a result, the rectification conditions in the medium pressure column and in particular the argon yield are not completely satisfactory.
Die Aufgabe, welche der Erfindung zugrunde liegt, besteht darin, ein Verfahren der eingangs genannten Art dahingehend zu verbessern, bei die Argongewinnung wirtschaftlich besonders günstig durchgeführt werden kann.The object on which the invention is based is to improve a method of the type mentioned at the outset in which argon production can be carried out particularly economically.
Diese Aufgabe wird dadurch gelöst, daß der Sauerstoff-Produktstrom in flüssigem Zustand aus der Mitteldrucksäule herausgeführt wird, daß mindestens ein Teil des aus der Rohargonsäule entnommenen Rohargons in indirektem Wärmeaustausch mit dem flüssigen Sauerstoff-Produktstrom kondensiert wird, wobei der Sauerstoff-Produktstrom mindestens teilweise verdampft, und dabei kondensiertes Rohargon wieder in die Rohargonsäule zurückgeleitet wird.This object is achieved in that the oxygen product stream is led out in the liquid state from the medium pressure column, that at least part of the crude argon removed from the crude argon column is condensed in indirect heat exchange with the liquid oxygen product stream, the oxygen product stream evaporating at least partially , and condensed raw argon is fed back into the raw argon column.
Dadurch lassen sich gegenüber dem bekannten Verfahren mehrere Verbesserungen erzielen. So kann nun die gesamte sauerstoffreiche Fraktion aus der Hochdrucksäule flüssig und relativ weit oben in die Mitteldrucksäule eingespeist werden. Das das Rücklaufverhältnis F/D verschiebt sich in Richtung 1. Auf eine störende Einspeisung einer gasförmigen Fraktion kann verzichtet werden.As a result, several improvements can be achieved compared to the known method. The entire oxygen-rich fraction from the high-pressure column can now be fed in liquid and relatively high up into the medium-pressure column. The reflux ratio F / D shifts in direction 1. A gaseous fraction can be dispensed with.
Die Rektifikation in der Mitteldrucksäule verbessert sich dadurch spürbar. Dies äußert sich - bei gleichbleibender Anzahl an theoretischen Böden - in einer verbesserten Ausbeute, insbesondere an Argon. Trotzdem kann die Rohargonsäule auf wirtschaftliche Weise mit einer der vorhandenen Fraktionen, nämlich dem Sauerstoffprodukt aus der Mitteldrucksäule, gekühlt werden.This noticeably improves rectification in the medium pressure column. This manifests itself - with the same number of theoretical plates - in an improved yield, especially in argon. Nevertheless, the crude argon column can be cooled economically with one of the existing fractions, namely the oxygen product from the medium pressure column.
Weitere Vorteile bietet das erfindungsgemäße Verfahren, wenn der Druck des flüssigen Sauerstoff-Produktstromes vor dem indirekten Wärmeaustausch mit dem kondensierenden Rohargon erhöht wird. Zwar ist es bekannt, Sauerstoff flüssig auf Druck zu bringen und anschließend zu verdampfen, um auf wirtschaftliche Weise Sauerstoff unter erhöhtem Druck zu gewinnen. Allerdings wird der Sauerstoff in der Regel gegen kondensierende Einsatzluft verdichtet, die anschließend in die Hochdrucksäule eingespeist wird. Diese flüssige Aufgabe hatjedoch negative Auswirkungen auf die Rektifikation in der Hochdrucksäule.The process according to the invention offers further advantages if the pressure of the liquid oxygen product stream is increased before the indirect heat exchange with the condensing crude argon. It is known to be oxygen pressurize liquid and then evaporate to produce oxygen under increased pressure economically. However, the oxygen is usually compressed against condensing feed air, which is then fed into the high-pressure column. However, this fluid task has a negative impact on rectification in the high pressure column.
Beim erfindungsgemäßen Verfahren tritt jedoch bei der Drucksauerstoffgewinnung kein Nachteil für die Rektifikation auf. Im Gegenteil, der flüssig auf Druck gebrachte Sauerstoff wird gegen eine Fraktion verdampft, deren Verflüssigung erwünscht ist, damit sie als Rücklauf in der Rohargonsäule dienen kann.In the process according to the invention, however, there is no disadvantage for rectification in the production of pressurized oxygen. On the contrary, the liquid, pressurized liquid, is vaporized against a fraction, the liquefaction of which is desired so that it can serve as a return in the crude argon column.
Die Druckerhöhung beim flüssigen Sauerstoff kann beispielsweise durch eine Pumpe oder durch Ausnützung eines hydrostatischen Potentials zwischen Mitteldrucksäule und Sauerstoff-Verdampfer bewerkstelligt werden.The pressure increase in liquid oxygen can be accomplished, for example, by a pump or by utilizing a hydrostatic potential between the medium pressure column and the oxygen evaporator.
Es erweist sich als vorteilhaft, wenn bei dem erfindungsgemäßen Verfahren das Rohargon vor dem indirekten Wärmeaustausch mit dem flüssigen Sauerstoff-Produktstrom erwärmt, verdichtet und abgekühlt wird.It proves to be advantageous if, in the process according to the invention, the crude argon is heated, compressed and cooled before the indirect heat exchange with the liquid oxygen product stream.
Das Verdichten des Rohargons kann in einer oder mehreren Stufen erfolgen. Mittels des bzw. der Verdichter läßt sich der gewünschte Druck des Rohargons und damit letztendlich das Druckniveau des verdampften Sauerstoff-Produktstromes einstellen. Der Sauerstoffabgagedruck kann damit in einem weiten Bereich ohne wesentliche Rückwirkungen auf das übrige Verfahren eingestellt werden.The raw argon can be compacted in one or more stages. The desired pressure of the raw argon and thus ultimately the pressure level of the vaporized oxygen product stream can be set by means of the compressor or compressors. The oxygen release pressure can thus be set in a wide range without any significant effects on the rest of the process.
Vorzugsweise wird das kondensierte Rohargon nach dem indirekten Wärmeaustausch mit dem flüssigen Sauerstoff-Produktstrom unterkühlt und vor der Einleitung in die Rohargonsäule entspannt wird. Günstig ist es dabei, wenn die Unterkühlung des kondensierten Rohargons durch indirekten Wärmeaustausch mit aus der Rohargonsäule entnommenem Rohargon bewirkt wird.After the indirect heat exchange with the liquid oxygen product stream, the condensed crude argon is preferably subcooled and the pressure is released before it is introduced into the crude argon column. It is advantageous if the supercooling of the condensed crude argon is brought about by indirect heat exchange with crude argon taken from the crude argon column.
In einer weiteren Ausgestaltung des Erfindungsgedankens wird der argonhaltige Sauerstoffstrom aus der Mitteldrucksäule vor der Einleitung in die Rohargonsäule arbeitsleistend entspannt und die bei der arbeitsleistenden Entspannung gewonnene Arbeit wird mindestens teilweise zun Verdichten von Rohargon verwendet. Hierdurch kann der für die Verdichtung des Rohargons stromaufwärts der Kondensation gegen verdampfenden Sauerstoff benötigte Aufwand an externer Energie wesentlich verringert werden.In a further embodiment of the concept of the invention, the argon-containing oxygen stream from the medium pressure column before it is introduced into the Crude argon column relaxed while working and the work gained during relaxation while working is used at least partially to compress crude argon. As a result, the amount of external energy required for the compression of the crude argon upstream of the condensation against evaporating oxygen can be significantly reduced.
In einer Variante des erfindungsgemäßen Verfahrens kann ein Teil des verdampften Sauerstoff-Produktstromes in den unteren Teil der Mitteldruckstufe eingeleitet wird. Die Rohargonkondensation erzeugt damit zusätzlich aufsteigendes Gas in der Mitteldrucksäule und verstärkt dadurch die Wirkung des Hauptkondensators.In a variant of the method according to the invention, a part of the vaporized oxygen product stream can be introduced into the lower part of the medium pressure stage. The crude argon condensation also generates rising gas in the medium pressure column and thereby increases the effect of the main condenser.
Vorzugsweise wird ein Teil des aus der Rohargonsäule entnommenen Rohargons als Produkt gewonnen.A part of the raw argon taken from the raw argon column is preferably obtained as a product.
Anhand der Zeichnung, in welcher eine Ausführungsform des erfindungsgemäßen Verfahrens schematisch dargestellt ist, werden die Erfindung und weitere Einzelheiten der Erfindung näher erläutert.The invention and further details of the invention are explained in more detail with reference to the drawing, in which an embodiment of the method according to the invention is shown schematically.
Über Leitung 1 wird verdichtete und vorgereinigte Luft herangeführt, in einem Wärmetauscher 36 im indirekten Wärmeaustausch mit Produktströmen abgekühlt und in die Hochdrucksäule 3 einer zweistufigen Rektifiziersäule 2 eingespeist. Die Hochdrucksäule 3 (Betriebsdruck: 6 bis 20 bar, vorzugsweise 8 bis 17 bar) steht mit der Mitteldrucksäule 4 (Betriebsdruck: 1,5 bis 10 bar, vorzugsweise 2,0 bis 8 bar) über einen gemeinsamen Kondensator/Verdampfer 13 in wärmetauschender Verbindung. Die eingeführte Luft wird in der Hochdrucksäule in Stickstoff und in eine sauerstoffangereicherte Fraktion vorzerlegt. Die sauerstoffangereicherte Fraktion wird am Sumpf der Hochdrucksäule über Leitung 6 in flüssigem Zustand abgeführt, in Wärmetauscher 32 unterkühlt und über Ventil 10 wieder in die Mitteldrucksäule 4 eingedrosselt. Stickstoff vom Kopf der Hochdrucksäule 3 wird über Leitung 5 ebenfalls flüssig abgezogen, in Wärmetauscher 32 unterkühlt und zum einen über Leitung 8 als flüssiges Produkt abgeführt. Der andere Teil des Stickstoffs aus der Drucksäule 3 wird über Leitung 9 als Rücklauf auf die Mitteldrucksäule 4 gegeben.Compressed and pre-cleaned air is introduced via line 1, cooled in a
Als Produkte der Mitteldruckstufe werden flüssiger Sauerstoff (Leitung 40), gasförmiger Reinstickstoff (Leitung 15) und unreiner Stickstoff (Leitung 16) entnommen und die beiden Stickstoff-Fraktionen in den Wärmetauschern 32 und 36 angewärmt.Liquid oxygen (line 40), gaseous pure nitrogen (line 15) and impure nitrogen (line 16) are removed as products of the medium pressure stage and the two nitrogen fractions in the
Sollte die Kälteleistung der Turbine 18 nicht für den Prozeß ausreichen, so ist es zweckmäßig, wegen des relativ hohen Druckes in der Mitteldrucksäule 4 den unreinen Stickstoff in Leitung 16 zur Erzeugung von fehlender Verfahrenskälte zu verwenden. Die dazu nötigen Verfahrensschritte sind in der Zeichnung jedoch nicht dargestellt.If the cooling capacity of the
Über die bisher genannten Ströme hinaus wird der Mitteldrucksäule 4 außerdem ein argonhaltiger Sauerstoffstrom über Leitung 17 entnommen, im Wärmetauscher 36 angewärmt und in die Rohargonsäule 20 eingespeist, die unter einem Druck von 1,1 bis 2 bar, vorzugsweise 1,3 bis 1,5 bar betrieben wird. Die im Sumpf der Rohargonsäule 20 anfallende Restfraktion wird über Leitung 22 abgeführt und durch Pumpe 23 auf den für die Zurückspeisung in die Mitteldrucksäule 4 erforderlichen Druck gebracht. Ferner wird der argonreiche Sauerstoffstrom 17 vor dem Einleiten in die Rohargonsäule 20 in einer Entspannungsturbine 18 arbeitsleistend entspannt, um den argonreichen Sauerstoffstrom einerseits auf den in der Rohargonsäule 20 herrschenden niedrigen Druck zu bringen und andererseits benötigte Verfahrenskälte zu erzeugen.In addition to the currents mentioned above, an argon-containing oxygen stream is also withdrawn from
Das am Kopf der Rohargonsäule 20 anfallende gasförmige Rohargon wird über Leitung 21 entnommen, im Wärmetauscher 37 gegen abkühlendes, kondensiertes Rohargon erwärmt, desweiteren im Wärmetauscher 36 erwärmt und daran anschließend in zwei Teilströme 24 und 25 aufgeteilt. Der Rohargonstrom in Leitung 24 wird als Zwischenprodukt aus der Anlage zum Verbraucher abgeführt. Der nicht aus der Anlage abgeführte Rohargonstrom in Leitung 25 wird in zwei Verdichterstufen 26 und 29 komprimiert und jeweils anschließend abgekühlt (Wasserkühler 28 und 30). Anschließend wird der Rohargonstrom über Leitung 31 durch den Wärmetauscher 36 geführt, dort weiter abgekühlt und daran anschließend in den, im Kondensatorverdampfer 33 angebrachten Kondensator 34 geführt. Im Kondensator 34 kondensiert das Rohargon gegen über Leitung 40 und mit Hilfe von Pumpe 41 herangeführten, flüssigen Sauerstoff. Das kondensierte Rohargon wird anschließend über Leitung 35 in den Wärmetauscher 37 geführt, in ihm gegen aus der Rohargonsäule 20 entnommenes Rohargon abgekühlt und über Ventil 38 in die Rohargonsäule 20 entspannt.The gaseous crude argon obtained at the top of the
Der über Leitung 40 und mit Hilfe der Pumpe 41 in den Kondensatorverdampfer 33 geführte, flüssige, unter Druck stehende Sauerstoff-Produktstrom wird im indirekten Wärmetausch mit dem Teilstrom des über Leitung 31 herangeführten Rohargons teilweise verdampft. Die dampfförmige Fraktion des Sauerstoff-Produktstromes wird über Leitung 42 nach Erwärmen im Wärmetauscher 36 abgegeben. Über Leitung 43 und Ventil 44 kann ein nicht zur Abgabe benötigter Teil des gasförmigen Sauerstoff-Produktstromes wieder in den Sumpf der Mitteldrucksäule entspannt werden. Mittels Leitung 45 läßt sich ein flüssiger Sauerstoff-Produktstrom aus dem Kondensatorverdampfer 33 gewinnen.The liquid, pressurized oxygen product stream fed into the
Die in der Zeichnung gestrichelt gezeichneten Verfahrensschritte stellen einen zusätzlichen Stickstoff-Verstärkungskreislauf dar.The process steps shown in dashed lines in the drawing represent an additional nitrogen boosting circuit.
Über Leitung 50 wird ein Teil der Stickstofffraktion aus Leitung 15 entnommen, im Verdichter 51 komprimiert, anschließend im Wasserkühler 52 abgekühlt und über Leitung 53 nach Unterkühlen in Wärmetauscher 36 in die, im Sumpf der Hochdrucksäule 3 angebrachten Heizschlange 54 geführt. Das so gebildete Stickstoffkondensat wird über Leitung 55 und Ventil 56 in den oberen Bereich der Hochdrucksäule, ober- oder unterhalb der Entnahmestelle des flüssigen Stickstoffs (Leitung 5) eingeführt (in der Zeichnung ist der Übersichtlichkeit halber die Einführung unterhalb der Entnahmestelle gezeichnet). Das im oberen Bereich der Hochdrucksäule eingedrosselte Stickstoffkondensat wirkt sich in der Mitteldrucksäule positiv für die Argongewinnung aus, da die Rücklaufverhältnisse in der Mitteldrucksäule durch die zusätzliche Stickstoff-Aufgabe verbessert werden.A portion of the nitrogen fraction is withdrawn from
Ferner läßt sich durch die Sumpfheizung 54 die benötigte Luftmenge so weit reduzieren, daß jede beliebig niedrige 5auerstoffreinheit im unreinen Stickstoff realisierbar ist.Furthermore, the
Das erfindungsgemäße Verfahren kann besonders vorteilhaft bei Luftzerlegungsanlagen eingesetzt werden, die mit Kraftwerksanlagen (beispielsweise GUD-Kraftwerke) oder anderen Anlagen mit Gasturbine (z.B. zur Stahlherstellung) integriert sind ("combined cycle").The method according to the invention can be used particularly advantageously in air separation plants which are connected to power plants (for example GUD power plants) or other plants with a gas turbine (eg for steel production) are integrated ("combined cycle").
Vorteilhaft ist außerdem der Einsatz von ungeordneten oder geordneten Packungen in einer, mehreren oder jeder der Kolonnen (Hochdrucksäule, Niederdrucksäule, Rohargonsäule). Dabei können auch Teilbereiche einer Kolonne mit Packungen gefüllt sein, während andere Bereiche beispielsweise Böden aufweisen.It is also advantageous to use disordered or ordered packings in one, more or each of the columns (high-pressure column, low-pressure column, crude argon column). Partial areas of a column can also be filled with packing, while other areas have, for example, trays.
Claims (16)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE4126945A DE4126945A1 (en) | 1991-08-14 | 1991-08-14 | METHOD FOR AIR DISASSEMBLY BY RECTIFICATION |
DE4126945 | 1991-08-14 |
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EP92113843A Withdrawn EP0527501A1 (en) | 1991-08-14 | 1992-08-13 | Air rectification process and apparatus |
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US (1) | US5251449A (en) |
EP (1) | EP0527501A1 (en) |
JP (1) | JPH05203348A (en) |
CN (1) | CN1069329A (en) |
AU (1) | AU2099392A (en) |
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JP3527609B2 (en) * | 1997-03-13 | 2004-05-17 | 株式会社神戸製鋼所 | Air separation method and apparatus |
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- 1992-08-11 CA CA002075737A patent/CA2075737A1/en not_active Abandoned
- 1992-08-13 AU AU20993/92A patent/AU2099392A/en not_active Withdrawn
- 1992-08-13 ZA ZA926089A patent/ZA926089B/en unknown
- 1992-08-13 CN CN92109305A patent/CN1069329A/en active Pending
- 1992-08-13 US US07/929,180 patent/US5251449A/en not_active Expired - Fee Related
- 1992-08-13 EP EP92113843A patent/EP0527501A1/en not_active Withdrawn
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EP0558082A1 (en) * | 1992-02-27 | 1993-09-01 | Praxair Technology, Inc. | Cryogenic rectification system with argon heat pump |
EP0580345A1 (en) * | 1992-07-20 | 1994-01-26 | Air Products And Chemicals, Inc. | Elevated pressure liquefier |
EP0775881A3 (en) * | 1995-11-25 | 1997-08-20 | Linde Ag | Process and apparatus for recovering oxygen and nitrogen at superatmospheric pressure |
US8791789B2 (en) | 2000-02-16 | 2014-07-29 | Verance Corporation | Remote control signaling using audio watermarks |
EP1357342A1 (en) * | 2002-04-17 | 2003-10-29 | Linde Aktiengesellschaft | Cryogenic triple column air separation system with argon recovery |
Also Published As
Publication number | Publication date |
---|---|
ZA926089B (en) | 1993-06-23 |
CN1069329A (en) | 1993-02-24 |
CA2075737A1 (en) | 1993-02-15 |
DE4126945A1 (en) | 1993-02-18 |
US5251449A (en) | 1993-10-12 |
AU2099392A (en) | 1993-02-18 |
JPH05203348A (en) | 1993-08-10 |
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