EP4214456B1 - Procédé et appareil de séparation cryogénique de l'air à l'aide d'une turbine à gaz mixte - Google Patents
Procédé et appareil de séparation cryogénique de l'air à l'aide d'une turbine à gaz mixte Download PDFInfo
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- EP4214456B1 EP4214456B1 EP21777405.8A EP21777405A EP4214456B1 EP 4214456 B1 EP4214456 B1 EP 4214456B1 EP 21777405 A EP21777405 A EP 21777405A EP 4214456 B1 EP4214456 B1 EP 4214456B1
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- column
- argon
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- 238000000034 method Methods 0.000 title claims description 22
- 238000000926 separation method Methods 0.000 title claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 150
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 88
- 239000007789 gas Substances 0.000 claims description 83
- 229910052786 argon Inorganic materials 0.000 claims description 75
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 46
- 229910052757 nitrogen Inorganic materials 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 40
- 238000001704 evaporation Methods 0.000 claims description 18
- 230000008020 evaporation Effects 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 5
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 7
- 238000001816 cooling Methods 0.000 claims 4
- 239000000047 product Substances 0.000 description 23
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002912 waste gas Substances 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
- F25J3/04642—Recovering noble gases from air
- F25J3/04648—Recovering noble gases from air argon
- F25J3/04721—Producing pure argon, e.g. recovered from a crude argon column
- F25J3/04727—Producing pure argon, e.g. recovered from a crude argon column using an auxiliary pure argon column for nitrogen rejection
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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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- 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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- 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
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- F25J3/04096—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 argon or argon enriched stream
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- 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
- F25J2220/00—Processes or apparatus involving steps for the removal of impurities
- F25J2220/52—Separating high boiling, i.e. less volatile components from oxygen, e.g. Kr, Xe, Hydrocarbons, Nitrous oxides, O3
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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
- 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
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2245/00—Processes or apparatus involving steps for recycling of process streams
- F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
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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
- F25J2245/00—Processes or apparatus involving steps for recycling of process streams
- F25J2245/42—Processes or apparatus involving steps for recycling of process streams the recycled stream being nitrogen
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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
- F25J2245/00—Processes or apparatus involving steps for recycling of process streams
- F25J2245/50—Processes or apparatus involving steps for recycling of process streams the recycled stream being oxygen
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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
- F25J2245/00—Processes or apparatus involving steps for recycling of process streams
- F25J2245/58—Processes or apparatus involving steps for recycling of process streams the recycled stream being argon or crude argon
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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
- F25J2270/00—Refrigeration techniques used
- F25J2270/02—Internal refrigeration with liquid vaporising loop
Definitions
- the invention concerns a process for cryogenic separation of air and a respective apparatus according to the first parts of the independent patent claims.
- Cryogenic air separation units classically comprise separation column systems in form of two-column systems, in particular Linde double columns. The may also have the form of three- or more-column systems. In addition to those columns for oxygen-nitrogen separation for generation nitrogen and/or oxygen in liquid and/or gaseous form, the separation column system may comprise additional columns for recovering further air components, in particular noble gases, or for producing particular high-purity oxygen and/or nitrogen products.
- a high-pressure column and a low-pressure column which may be at least partially located above the high-pressure column and a main condenser, are used.
- the process of the invention is of the enhanced-pressure type, so that the high-pressure column is not operated at the classical pressure of about 5.3 bar (4 to 7 bar), but at a higher pressure of e.g. 8 to 14 bar, preferably 9 to 13 bar.
- the low-pressure column is not operated at the classical pressure of about 1.3 bar (1.2 to 1.5 bar), but at a higher pressure of e.g. 2 to 5 bar, preferably 2.5 to 4.5 bar. Those pressures are absolute and to be measured at the top of the respective column and also used in the invention.
- an air separator produces pressurized gaseous products, they may be compressed in a gas compressor ("external compression”).
- an "internal compression” process may be used by withdrawing cryogenic liquid from the column, pressurizing (e.g. pumping) is to the desired pressure and transferring it to the gaseous state by warming, e.g. in the main heat exchanger.
- the invention has the object to find a further improved air separation process, in particular for co-production of pressurized nitrogen and argon and a relatively high liquid production, e.g. a liquid production (LIN equivalent [Nm3/h]: LIN [Nm3/h] + 1.07 x LOX [Nm3/h] + 0.9 x LAR [Nm3/h]) divided by pressurized GAN product amount is in a range from 0.00 to 0.06. (All those amounts are molar in this application, as long as nothing to the contrary is said.)
- the fraction withdrawn from the high-pressure column and introduced into the low-pressure column is frequently the bottom fraction of the high-pressure column. At least a part of it can be directly introduced into the low-pressure column, eventually through a subcooler, or that can be done indirectly by leading the high-pressure column fraction into the argon top condenser evaporation space and separately introducing gas and remaining liquid from the argon top condenser evaporation space to the low-pressure column.
- the gaseous oxygen stream is normally withdrawn from a lower portion of the low-pressure column, e.g. from the very bottom of the low-pressure column.
- the expansion machine may be of any type, e.g. a turbine; then it may be called a "mixed gas turbine".
- a nitrogen recycle coming from the low-pressure column and directly or indirectly leading into the separation column system, in particular into the high-pressure column and/or into the low-pressure column may be used as described in claim 2.
- the "recycle gas" stream is the one coming from the low-pressure column, being compressed in the nitrogen compressor and afterwards being cooled, but not liquefied in the main heat exchanger.
- a product gas from the low-pressure column may or may not be lead jointly with the recycle gas through the warming in the main heat exchanger and the compression in the nitrogen compressor.
- the cooled recycle gas may at least partially be directly in gaseous form led into the high-pressure column, e.g. at the top or at 3 to 11 theoretical trays below.
- An alternative is an indirect introduction into the high-pressure column and/or the low-pressure column, e.g. by liquefying the recycle gas in a condenser, e.g. the main condenser and/or another column reboiler, and then introducing at least a portion of the liquefied recycle gas into a column, in particular the high-pressure column and/or the low-pressure column.
- a condenser e.g. the main condenser and/or another column reboiler
- at least a portion of the cooled recycle gas is introduced into the high-pressure column via the liquefaction space of the main condenser.
- At least a portion of the cooled recycle gas is introduced into the low-pressure column via the liquefaction space of the bottom condenser of a pure oxygen column (preferably including subcooling this liquid in a separate channel in a subcooler and expansing the subcooled liquid in an expansion valve).
- a first portion of the recycle gas is led via a first path (e.g. directly or via the main condenser) into the high-pressure column and a second portion of the recycle gas is led via a second path (e.g. through the bottom condenser of a pure oxygen column) into the low-pressure column.
- cooled recycle gas may be directly introduced into the high-pressure column, e.g. at its top.
- Claim 3 describes a second variant, where recycle gas is introduced into the main condenser, liquefied therein and then introduced as liquid onto the top of the high-pressure column. Both variants can be combined by introducing one portion of the cold recycle gas into the main condenser, another portion directly into the column. Another portion of the recycle gas may be used at a different place in the plant.
- a pressurized pure argon product may be generated by internal compression as lined out in claim 4.
- a part of the total argon product can be produced in a liquid form and stored in the tank.
- the crude argon column may have the form of a split column as described in claim 5. There are at least two parts. In principle, there can be three or more parts.
- the separation may further comprise a pure oxygen column as described in claim 6.
- the feed liquid for the pure oxygen column comes from the bottom of the crude argon column or from an intermediate point of the crude argon column, e.g. a few theoretical trays above the bottom.
- Such pure oxygen column is preferably pure oxygen column is arranged below the first part of the crude argon column and within a common vessel with the first part of the crude argon column.
- the pure oxygen column preferably has a bottom reboiler as described in claim 8, which may be heated high-pressure column gaseous nitrogen and/or by a portion of the cooled recycle gas, which is not directly going into the high-pressure column - see claim 9.
- the recycle gas is preferably at least partially liquefied in the bottom reboiler of the pure oxygen column and then sent to the high-pressure column or to the low-pressure column as reflux liquid.
- an argon-oxygen mixture may be withdrawn from the crude argon column via an intermediate gas outlet according to claim 10. That feature reduces the load of the crude argon column.
- the argon-oxygen mixture is warmed in the main heat exchanger in order to recover its energy.
- This particular embodiment is applicable to a one-part crude argon column as well as to a split crude argon column.
- the intermediate gas outlet may be in either part of the crude argon column. Preferably it is arranged at an intermediate height of the second part.
- top gas of the high-pressure column (12) is withdrawn (302) as a pressurized gaseous nitrogen product as lined out in claim 13.
- top gas (64, 65) from the low-pressure column (13, 113/213) is compressed in a nitrogen compressor and withdrawn as a pressurized gaseous nitrogen product, in particular by admixing it the warmed top gas from the high-pressure column (12).
- the nitrogen compressor preferably does not compress further streams, in particular no recycle gas.
- atmospheric air (AIR) 1 flows through a filter 2 to a main air compressor 3 and is compressed therein to a pressure of about 11 to 12 bar.
- the compressed air stream is cooled in coolers 4 and 5 and the sent to separator 6, from where liquid water (H2O) is discharged.
- the air from separator 6 is sent to purification unit 7 removing water vapour, carbon dioxide and further impurities by adsorption.
- the purified air 8 is introduced into a main heat exchanger 9.
- the total feed air is fully cooled until the cold end of the main heat exchanger 9 and then introduced into the high-pressure column 12 of a double column further comprising a low-pressure column 13 and a main condenser 14.
- the separation column system of the embodiment of Figure 1 consists of the double column 12/13, a pure oxygen column 16, a methane rejection column 17, a single-part crude argon column 18 and a pure argon column 19.
- the pure oxygen column has a bottom reboiler 20, the crude argon column a top condenser 21 and the pure argon column a top condenser 22 and a bottom reboiler 23. All these condensers and reboilers as well as the main condenser 14 are condenser-evaporators, each having a liquefaction space and an evaporation space. An exception is the bottom reboiler 23 of the pure argon column 19, which is warmed by sensible heat.
- the crude liquid oxygen 24 from the bottom of the high-pressure column 12 is cooled in a subcooler 25.
- a first portion 27 of the cooled crude liquid oxygen 26 is partially fed through the bottom reboiler 23 of the pure argon column and then introduced into the evaporation space of the top condenser 21 of the crude argon column 18.
- the remaining liquid 28 is sent to the low-pressure column 13.
- a first part 30 of the evaporated portion 29 is sent to the low-pressure column as well.
- a second part 31 is taken as "the stream having a higher nitrogen content" 31 according to the invention and is described in detail later.
- a second portion 32 of the cooled crude liquid oxygen 26 is introduced into the evaporation space of the top condenser of the pure argon column 19. Remaining liquid 33 is sent to the low-pressure column 13.
- the evaporated portion 34 is mixed to the evaporated portion 29 from the evaporation space of the top condenser 21 of the crude argon column 18. Thereby is goes to the low-pressure column 13 or into the "the stream having a higher nitrogen content" 31.
- Most 36 of the gaseous nitrogen 35 from the top of the high-pressure column 12 is at least partially liquefied in the main condenser 14.
- the remainder 37 in at least partially liquefied in the bottom reboiler of the pure oxygen column.
- the liquid nitrogen from the pure oxygen column bottom reboiler is cooled in the subcooler 25.
- the cooled liquid nitrogen 39 is sent to the top of the low-pressure column 13.
- the liquid nitrogen 40 from the main condenser 14 is partially fed back to the top of the high-pressure column 12. Another portion 42 is cooled in the subcooler 25. A first part of the cooled liquid nitrogen 43 is sent to the top of the low-pressure column 13, whilst a second part 45 is withdrawn as pure liquid nitrogen product (PLIN).
- a gaseous argon-containing fraction, the argon transition fraction 46, from the low-pressure column 13 is introduced into the bottom of the methane rejection column 17.
- the bottom liquid 47 of the methane rejection column 17 is reintroduced into the low-pressure column 13.
- Such bottom liquid contain practically all methane from fraction 46, so that the top of the methane rejection column 17 is methane-free.
- the top gas 48 of such column is sent to the bottom of the crude argon column 18, together with the top gas 80 from the pure oxygen column 16.
- the bottom liquid 78 of the crude argon column 18 is lifted via pump 79.
- a first portion 49 enters the pure oxygen column 16 as methane-free reflux.
- ultra-high purity liquid oxygen 50 is withdrawn and led into a storage tank 51.
- the tank liquid may be pressurized in the tank or downstream the tank by a pump (not shown).
- the high-pressure liquid oxygen can be warmed in the main heat exchanger 9 and be recovered as an internally compressed ultra-high purity gaseous oxygen product (GOXIC).
- a second portion 52 of bottom liquid 78 of the crude argon column 18 is fed into the top of the methane rejection column 17.
- the liquefaction space of the top condenser 21 of the crude argon column 18 is a bath type condenser.
- a crude argon stream 58 is withdrawn from the crude argon column 18 and introduced into the pure argon column 19.
- a waste gas 60 is withdrawn and released to the atmosphere (ATM).
- ATM atmosphere
- a pure argon product 59 is recovered and the sent to an internal compression with pump 61 and (line 62) warming in main heat exchanger 9.
- an internally compressed gaseous argon product is (GARIC) withdrawn in pressurized form.
- the gaseous nitrogen fraction 64 from the top of the low-pressure column 13 is partially used as a recycle gas and first pre-warmed in subcooler 25.
- the pre-warmed gaseous nitrogen fraction 65 is sent to the cold end of the main heat exchanger 9 and fully warmed therein.
- the warmed gaseous nitrogen fraction 66 is compressed in a nitrogen compressor 67 to a product pressure of preferably 8 to 15 bar, more preferably 9,5 to 12,5 bar.
- the compressor 67 has an aftercooler.
- the compressed nitrogen fraction 68 is split into a product fraction 69, which is withdrawn as pressurized gaseous nitrogen product (PGAN) and the recycle gas 70.
- the pressurized recycle gas is fully cooled again in the main heat exchanger 9.
- the cooled recycle gas (89) is mixed with the gaseous nitrogen 35 from the top of the high-pressure column 12, i.e. liquefied either in the main condenser 14 or in the pure oxygen column bottom reboiler 20. Thereby, a portion of the recycle gas (now as liquid) enters the high-pressure column via line 41.
- Liquid oxygen 84 from the bottom of the low-pressure column 13 (or from the evaporation space of the main condenser 14) is pumped in pump 85 to the desired product pressure, fully warmed in the main heat exchanger 9 and finally recovered via line 86 as internally compressed product (GOXIC).
- the warmed stream 71 is mixed with a gaseous oxygen stream 72 from the bottom of the low-pressure column 13.
- the mixed gas 73 is partially warmed in the main heat exchanger 9 to an intermediate temperature of 150 to 230 K and work-expanded in a mixed-gas turbine 75, which is operated as a generator turbine.
- the expanded mixed gas 76 is reintroduced into the main heat exchanger 9 and fully warmed.
- the warmed low-pressure mixed gas 77/78 can be released to the atmosphere (ATM) or sent to the purification unit 7 as regeneration gas.
- some of the gas rising in the crude argon column 18 may be withdrawn via an intermediate gas outlet 81, in order to reduce the amount of argon product 59/62/63 and thereby reducing energy consumption.
- the gas withdrawn gas 82 is fully warmed in a separate passage of the main heat exchanger 9.
- the warmed gas 83 may be admixed to the expanded mixed gas 77 and either released to the atmosphere or used as regeneration gas in the purification unit 7.
- Figure 2 mainly differs from Figure 1 by a split argon column and a split low-pressure column.
- the explanations on Figure 1 above are also valid for the respective steps and units of Figure 2 .
- Reference numbers in Figure 2 are partially taken from Figure 1 in order to identify the same or similar features and functions.
- the crude argon column is split into a first part 118 and a second part 218, the argon top condenser 21 being arranged on the top of the second part 218.
- a gas fraction 190 from the top of the first part 118 is introduced into the bottom of the second part 218.
- At least a first portion 193 of the bottom liquid 191 of the second part 218 is introduced into the top of the first part 118.
- the low-pressure column is split into a bottom part 113 and a top part 213. Different from a one-part low-pressure column, those two parts are arranged side by side.
- a gaseous connection stream 195 is taken from the top gas 194 of the bottom section and introduced into the bottom of the top section 213.
- a liquid connection stream 196 is withdrawn from the bottom of the top section 213 and sent to the top of the bottom section 213 via the bottom of the first part 118 of the crude argon column, line 197, pump 198 and line 199.
- Another portion of the top gas 194 of the bottom section 113 of the low-pressure column is taken as argon transition fraction 46 and introduced into the bottom of the first part 118 of the crude argon column.
- the bottom liquid of the first part 118 (mixed with the bottom liquid 196 from the top part 213 of the low-pressure column) is sent via line 197, pump 198 and line 199 to the top of the bottom part 113 of the low-pressure column.
- the lowermost section 117 of the first part 118 of the crude argon column simultaneously acts as methane rejection column.
- the first part 118 is connected to the top of a pure oxygen column 16 by a liquid line 149 and a gas line 180.
- Ultra-high purity liquid oxygen 50 from the bottom of the pure oxygen column 16 is pressurized in this particular embodiment in a multiple tank system 200 according to US 10209004 B2 and then (via line 201) fully warmed in the main heat exchanger 9.
- the warm ultra-high purity oxygen gas 202 is recovered as a final product (UHPGOX).
- the liquid oxygen 84 from the bottom of the low-pressure column 113 (or from the evaporation space of the main condenser 14) is subcooled in subcooler 25 (not shown) and then withdrawn as a liquid oxygen product (LOX).
- the cooled recycle gas 89 is fed to the liquefaction space of the main condenser 14 (together with some of the top nitrogen 35 from the high-pressure column 12). There it is liquefied. A first portion 41 of the liquefied recycle gas is fed into the top of the high-pressure column 12; a second portion 42, 44 of the liquefied recycle gas is fed into the top of the low-pressure column 213.
- the cooled recycle gas 89 could be split into a first portion to the main condenser and a second portion, which is introduced into the liquefaction space of the bottom reboiler of the pure oxygen column 16.
- the recycle gas is completely fed to the liquefaction space of the bottom reboiler of the pure oxygen column 16, if necessary supplemented by some gaseous nitrogen 35 from the top of the high-pressure column 12.
- Figure 3 is in many parts similar or identical to Figure 2 , but deviates in two main aspects:
- the invention in general can be applied as well to systems without a methane rejection column and/or without a pure oxygen column.
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Claims (15)
- Procédé de séparation cryogénique d'air dans un système de colonne de séparation comprenant une colonne haute pression (12), une colonne basse pression (13), un condenseur principal (14), qui est un condenseur-évaporateur ayant un espace de liquéfaction et un espace d'évaporation et amène la partie supérieure d'une colonne haute pression et la partie inférieure d'une colonne basse pression en relation d'échange de chaleur, et une colonne d'argon brut (18) ayant un condenseur supérieur d'argon (21), qui est un évaporateur-condenseur ayant un espace de liquéfaction et un espace d'évaporation, comprenant- la compression (3) d'un flux d'air d'alimentation total (1),- le refroidissement de l'air d'alimentation comprimé (8) dans un échangeur de chaleur principal (9),- l'introduction (10) d'au moins une part de l'air d'alimentation dans la colonne haute pression (12),- l'introduction d'au moins une fraction (24, 26) de la colonne haute pression (12) directement ou indirectement à la colonne basse pression (13),- l'introduction d'une fraction de transition d'argon (46, 48) de la colonne basse pression (13) à la colonne d'argon brut (18),- l'introduction d'une fraction de refroidissement liquide (27) de la colonne haute pression (12) dans l'espace d'évaporation du condenseur supérieur d'argon (21),- le retrait d'un flux d'oxygène gazeux (72) à partir de la colonne basse pression (13),- le mélange du flux d'oxygène gazeux (72) avec un autre flux gazeux ayant une teneur en azote plus élevée que le flux d'oxygène gazeux pour former un flux gazeux mélangé (73),- le chauffage du flux gazeux mélangé dans l'échangeur de chaleur principal (9),- la détente par le travail du flux gazeux mélangé chauffé (74) dans une machine de détente (75) et- le chauffage complet du flux gazeux mélangé détendu (76) dans l'échangeur de chaleur principal (9),caractérisé en ce que
le flux supérieur (29, 31, 71) ayant une teneur en azote plus élevée est retiré de l'espace d'évaporation du condenseur supérieur d'argon (21). - Procédé selon la revendication 1, caractérisé en ce que- une fraction d'azote gazeux (64, 65) de la colonne basse pression (13) est utilisée en tant que gaz de recyclage,- le gaz de recyclage est chauffé dans l'échangeur de chaleur principal (9),- le gaz de recyclage chauffé (66) est comprimé dans un compresseur d'azote (67),- le gaz de recyclage comprimé (70) est refroidi dans l'échangeur de chaleur principal (9), et retiré de l'échangeur de chaleur principal (9) sous forme gazeuse et- au moins une première part du gaz de recyclage refroidi (89) est introduite soit sous forme gazeuse soit sous forme liquéfiée dans le système de colonne de séparation, en particulier dans la colonne haute pression (12) et/ou la colonne basse pression (13).
- Procédé selon la revendication 2, caractérisé en ce que au moins une part du gaz de recyclage refroidi (89) est introduite (36, 40 41) dans la colonne haute pression (12) par le biais de l'espace de liquéfaction du condenseur principal (14).
- Procédé selon les revendications 1 à 3, caractérisé en ce que- le système de colonne de séparation comprend en outre une colonne d'argon pur (19),- un flux d'argon brut (58) est retiré de la colonne d'argon brut (18) ou du condenseur supérieur d'argon (21),- le flux d'argon brut (58) est introduit dans la colonne d'argon pur (19),- un flux d'argon pur liquide (59) est retiré de la colonne d'argon pur (19),- le flux d'argon pur liquide (59) est mis sous pression (61) dans l'état liquide,- le flux d'argon pur sous pression (62) est chauffé dans l'échangeur de chaleur principal (9) et- finalement récupéré en tant que produit d'argon sous pression (63).
- Procédé selon les revendications 1 à 4, caractérisé en ce que la colonne d'argon brut est divisée en une première partie (118) et une seconde partie (218), le condenseur supérieur d'argon (21) étant agencé sur la partie supérieure de la seconde partie (218), moyennant quoi une fraction gazeuse (190) provenant de la partie supérieure de la première partie (118) est introduite dans la partie inférieure de la seconde partie (218) et au moins une première part (193) du liquide inférieur (191) de la seconde partie est introduite dans la partie supérieure de la première partie (118).
- Procédé selon la revendication 5, caractérisé en ce que- le système de colonne de séparation comprend en outre une colonne d'oxygène pur (16),- une fraction liquide (49, 149) de la colonne d'argon brut (18, 118) est introduite dans la partie supérieure de la colonne d'oxygène pur (16) et- une fraction d'oxygène pur liquide (50) est retirée de la partie inférieure de la colonne d'oxygène pur (16).
- Procédé selon la revendication 6, caractérisé en ce que la colonne d'oxygène pur (16) est agencée immédiatement au-dessous d'une colonne de rejet de méthane (17) n'ayant qu'une seule plaque inférieure/supérieure entre elles.
- Procédé selon la revendication 6 ou 7, caractérisé en ce que la colonne d'oxygène pur (16) présente un bouilleur inférieur (20), qui est un condenseur-évaporateur ayant un espace de liquéfaction et un espace d'évaporation.
- Procédé selon les revendications 2 et 8, caractérisé en ce que une seconde part (37) du gaz de recyclage refroidi (89) est introduite dans l'espace de liquéfaction du bouilleur inférieur de colonne d'oxygène pur (20).
- Procédé selon les revendications 1 à 9, caractérisé en ce que, au moins temporairement, un mélange d'argon-oxygène (81) est retiré de la colonne d'argon brute (18, 118) par le biais d'une sortie de gaz intermédiaire et le mélange d'argon-oxygène est chauffé dans l'échangeur de chaleur principal (9).
- Procédé selon les revendications 1 à 10, caractérisé en ce que- la colonne basse pression est divisée en une partie inférieure (113) et une partie supérieure (213),- un flux de liaison gazeux (194, 195) est retiré de la partie supérieure de la section inférieure (113),- le flux de liaison gazeux (195) est introduit dans la partie supérieure de la section supérieure (213),- un flux de liaison liquide (196, 197, 199) est retiré de la partie inférieure de la section supérieure (213) et- le flux de liaison liquide est introduit dans la partie supérieure de la section inférieure (113).
- Procédé selon les revendications 1 ou 4 à 11, caractérisé en ce que- une part (300) du gaz supérieur de la colonne haute pression (12) est chauffée dans l'échangeur de chaleur principal (9) et- le gaz chauffé (301) est retiré (302) en tant que produit d'azote gazeux sous pression.
- Procédé selon les revendications 1 ou 4 à 12, caractérisé en ce que- un gaz supérieur (64, 65) de la colonne basse pression (13, 113/213) est chauffé dans l'échangeur de chaleur principal (9),- le gaz chauffé (66) est comprimé dans un compresseur d'azote (67) et- le gaz comprimé (369) est retiré (302) en tant que produit d'azote gazeux sous pression, en particulier en le mélangeant au gaz supérieur chauffé de la colonne haute pression (12).
- Procédé selon les revendications 1 à 13, caractérisé en ce que le gaz de recyclage refroidi (89) est introduit dans la colonne haute pression (12) sous forme gazeuse.
- Appareil de séparation cryogénique d'air comprenant un système de colonne de séparation comprenant une colonne haute pression (12), une colonne basse pression (13), un condenseur principal (14), qui est un condenseur-évaporateur ayant un espace de liquéfaction et un espace d'évaporation et est configuré pour amener la partie supérieure de colonne haute pression et la partie inférieure de colonne basse pression en relation d'échange de chaleur, et une colonne d'argon brut (18) ayant un condenseur supérieur d'argon (21), qui est un condenseur-évaporateur ayant un espace de liquéfaction et un espace d'évaporation, et comprenant en outre- un compresseur d'air principal (3) pour comprimer un flux d'air d'alimentation total (1),- un échangeur de chaleur principal (9) pour refroidir l'air d'alimentation comprimé (8),- un moyen (19) pour introduire au moins une part de l'air d'alimentation dans la colonne haute pression (12),- un moyen d'introduction d'au moins une fraction (24, 26) de la colonne haute pression (12) directement ou indirectement à la colonne basse pression (13),- une ligne de transition d'argon pour introduire une fraction de transition d'argon (46, 48) de la colonne basse pression (13) à la colonne d'argon brut (18),- un moyen d'introduction d'une fraction de refroidissement liquide (27) de la colonne haute pression (12) dans l'espace d'évaporation du condenseur supérieur d'argon (21),- un moyen de retrait d'un flux d'oxygène gazeux (72) à partir de la colonne basse pression (13),- un moyen de mélange du flux d'oxygène gazeux (72) avec un autre flux gazeux ayant une teneur en azote plus élevée que le flux d'oxygène gazeux pour former un flux gazeux mélangé (73),- un moyen d'introduction du flux gazeux mélangé dans l'échangeur de chaleur principal (9) pour chauffer,- une machine de détente (75) pour détendre par le travail le flux gazeux mélangé chauffé (74) et- un moyen de chauffage complet du flux gazeux mélangé détendu (76) dans l'échangeur de chaleur principal (9),caractérisé en ce que
un moyen (29, 31, 71) de mélange du flux d'oxygène gazeux (72) avec un autre flux gazeux ayant une teneur en azote plus élevée sont reliés à l'espace d'évaporation du condenseur supérieur d'argon (21).
Applications Claiming Priority (2)
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EP20020419 | 2020-09-17 | ||
PCT/EP2021/025333 WO2022058043A1 (fr) | 2020-09-17 | 2021-09-09 | Procédé et appareil de séparation cryogénique d'air, à turbine à gaz mixte |
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EP4214456A1 EP4214456A1 (fr) | 2023-07-26 |
EP4214456C0 EP4214456C0 (fr) | 2024-05-08 |
EP4214456B1 true EP4214456B1 (fr) | 2024-05-08 |
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EP21777405.8A Active EP4214456B1 (fr) | 2020-09-17 | 2021-09-09 | Procédé et appareil de séparation cryogénique de l'air à l'aide d'une turbine à gaz mixte |
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US (1) | US20230358468A1 (fr) |
EP (1) | EP4214456B1 (fr) |
KR (1) | KR20230069966A (fr) |
CN (1) | CN116171366A (fr) |
IL (1) | IL300773A (fr) |
TW (1) | TW202227766A (fr) |
WO (1) | WO2022058043A1 (fr) |
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Publication number | Priority date | Publication date | Assignee | Title |
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US11933541B2 (en) | 2021-08-11 | 2024-03-19 | Praxair Technology, Inc. | Cryogenic air separation unit with argon condenser vapor recycle |
CN117980678A (zh) * | 2021-09-01 | 2024-05-03 | 林德有限责任公司 | 用于空气的低温分馏的设施和方法 |
WO2023030679A1 (fr) * | 2021-09-01 | 2023-03-09 | Linde Gmbh | Procédé de séparation à basse température de l'air et station de séparation d'air |
JP2024024800A (ja) | 2022-08-10 | 2024-02-26 | 日本エア・リキード合同会社 | 空気分離装置 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1988001037A1 (fr) * | 1986-08-01 | 1988-02-11 | Erickson Donald C | Ameliorations a la distillation de l'air pour l'obtention d'oxygene de grande purete |
EP0269342A2 (fr) * | 1986-11-24 | 1988-06-01 | The BOC Group plc | Séparation de l'air |
DE19543953C1 (de) * | 1995-11-25 | 1996-12-19 | Linde Ag | Verfahren und Vorrichtung zur Gewinnung von Sauerstoff und Stickstoff unter überatmosphärischem Druck |
EP0881446A1 (fr) * | 1997-05-30 | 1998-12-02 | The BOC Group plc | Procédé cryogénique avec double colonne et condenseur-reboilleur externe pour liquide riche |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5129932A (en) * | 1990-06-12 | 1992-07-14 | Air Products And Chemicals, Inc. | Cryogenic process for the separation of air to produce moderate pressure nitrogen |
US5137559A (en) * | 1990-08-06 | 1992-08-11 | Air Products And Chemicals, Inc. | Production of nitrogen free of light impurities |
US5469710A (en) * | 1994-10-26 | 1995-11-28 | Praxair Technology, Inc. | Cryogenic rectification system with enhanced argon recovery |
EP3193114B1 (fr) | 2016-01-14 | 2019-08-21 | Linde Aktiengesellschaft | Procédé de production d'un produit d'air dans une installation de séparation d'air et installation de séparation d'air |
JP6440232B1 (ja) * | 2018-03-20 | 2018-12-19 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | 製品窒素ガスおよび製品アルゴンの製造方法およびその製造装置 |
JP7355978B2 (ja) * | 2019-04-08 | 2023-10-04 | レール・リキード-ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | 深冷空気分離装置 |
-
2021
- 2021-09-09 US US18/044,858 patent/US20230358468A1/en active Pending
- 2021-09-09 CN CN202180062897.9A patent/CN116171366A/zh active Pending
- 2021-09-09 IL IL300773A patent/IL300773A/en unknown
- 2021-09-09 WO PCT/EP2021/025333 patent/WO2022058043A1/fr active Application Filing
- 2021-09-09 EP EP21777405.8A patent/EP4214456B1/fr active Active
- 2021-09-09 KR KR1020237012420A patent/KR20230069966A/ko unknown
- 2021-09-17 TW TW110134752A patent/TW202227766A/zh unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1988001037A1 (fr) * | 1986-08-01 | 1988-02-11 | Erickson Donald C | Ameliorations a la distillation de l'air pour l'obtention d'oxygene de grande purete |
EP0269342A2 (fr) * | 1986-11-24 | 1988-06-01 | The BOC Group plc | Séparation de l'air |
DE19543953C1 (de) * | 1995-11-25 | 1996-12-19 | Linde Ag | Verfahren und Vorrichtung zur Gewinnung von Sauerstoff und Stickstoff unter überatmosphärischem Druck |
EP0881446A1 (fr) * | 1997-05-30 | 1998-12-02 | The BOC Group plc | Procédé cryogénique avec double colonne et condenseur-reboilleur externe pour liquide riche |
Also Published As
Publication number | Publication date |
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CN116171366A (zh) | 2023-05-26 |
EP4214456A1 (fr) | 2023-07-26 |
EP4214456C0 (fr) | 2024-05-08 |
TW202227766A (zh) | 2022-07-16 |
WO2022058043A1 (fr) | 2022-03-24 |
KR20230069966A (ko) | 2023-05-19 |
US20230358468A1 (en) | 2023-11-09 |
IL300773A (en) | 2023-04-01 |
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