EP0504029B1 - Process for the production of gaseous pressurised oxygen - Google Patents
Process for the production of gaseous pressurised oxygen Download PDFInfo
- Publication number
- EP0504029B1 EP0504029B1 EP92400600A EP92400600A EP0504029B1 EP 0504029 B1 EP0504029 B1 EP 0504029B1 EP 92400600 A EP92400600 A EP 92400600A EP 92400600 A EP92400600 A EP 92400600A EP 0504029 B1 EP0504029 B1 EP 0504029B1
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- EP
- European Patent Office
- Prior art keywords
- pressure
- air
- oxygen
- turbine
- column
- 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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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 72
- 239000001301 oxygen Substances 0.000 title claims description 72
- 229910052760 oxygen Inorganic materials 0.000 title claims description 72
- 238000000034 method Methods 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 57
- 238000009434 installation Methods 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 26
- 238000009834 vaporization Methods 0.000 claims description 23
- 230000008016 vaporization Effects 0.000 claims description 23
- 238000009833 condensation Methods 0.000 claims description 21
- 230000005494 condensation Effects 0.000 claims description 15
- 230000006835 compression Effects 0.000 claims description 6
- 238000007906 compression Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012263 liquid product Substances 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000013459 approach Methods 0.000 claims 1
- 239000007792 gaseous phase Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 238000010586 diagram Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 210000003127 knee Anatomy 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- 238000003303 reheating Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010792 warming 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
- F25J3/04151—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
- F25J3/04236—Integration of different exchangers in a single core, so-called integrated cores
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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
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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
- F25J3/04084—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 nitrogen
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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
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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
- F25J3/04006—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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- F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
- F25J3/04163—Hot end purification of the feed air
- F25J3/04169—Hot end purification of the feed air by adsorption of the impurities
- F25J3/04175—Hot end purification of the feed air by adsorption of the impurities at a pressure of substantially more than the highest pressure column
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- F25J3/04284—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams
- F25J3/0429—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams of feed air, e.g. used as waste or product air or expanded into an auxiliary column
- F25J3/04296—Claude expansion, i.e. expanded into the main or high pressure column
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- F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
- F25J3/04284—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams
- F25J3/0429—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams of feed air, e.g. used as waste or product air or expanded into an auxiliary column
- F25J3/04303—Lachmann expansion, i.e. expanded into oxygen producing or low pressure column
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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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- F25J3/04406—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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- 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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- 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
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- Y10S62/00—Refrigeration
- Y10S62/939—Partial feed stream expansion, air
- Y10S62/94—High pressure column
Definitions
- the present invention relates to a process for the production of gaseous oxygen under a high oxygen pressure by air distillation in a double column installation, pumping of liquid oxygen withdrawn from the bottom of the low pressure column, and vaporization of liquid oxygen compressed by heat exchange, in the heat exchange line of the installation, with air brought to a high air pressure, in which all of the air is compressed at high air pressure the air to be distilled; at an intermediate cooling temperature, a fraction of this air is expanded in a turbine, at the pressure of the medium pressure column.
- the pressures discussed below are absolute pressures.
- the pressures in the medium pressure column and the low pressure column will be referred to as “medium pressure” and “low pressure”, respectively.
- Pump processes make it possible to eliminate any gaseous oxygen compressor. To obtain a competitive energy expenditure, it is necessary to compress a large air flow, of the order of 1.5 times the flow of oxygen to be vaporized, to a sufficient pressure allowing it to liquefy against -current oxygen.
- EP-A-0.024.962 describes a process for vaporizing liquid oxygen, using a Claude turbine with production of liquid nitrogen.
- EP-A-0.042.676 describes a process for vaporizing liquid oxygen by heat exchange with nitrogen. The process frigories are supplied only by nitrogen expansion.
- the invention aims to provide a "pump" process requiring only a reduced investment.
- the process according to the invention is characterized in that the air fraction is in excess with respect to the refrigerating needs of the heat exchange line, the turbine is braked by an air booster and the temperature difference at the hot end of the exchange line by evacuating at least one liquid product from the installation.
- the abovementioned small temperature differences are obtained, and therefore a low specific energy expenditure, while avoiding the appearance of liquid at the inlet of the wheel of the expansion turbine.
- the invention also relates to a process for producing gaseous oxygen under a high oxygen pressure of at least Approximately 13 bar by air distillation in a double column installation comprising a low pressure column and a medium pressure column, pumping of liquid oxygen withdrawn from the bottom of the low pressure column, and vaporization of the compressed liquid oxygen by exchange of heat with air brought to a high pressure markedly higher than the medium pressure, in which all of the air to be distilled is compressed to a first high pressure markedly higher than the medium pressure, and a first fraction of this is cooled air under the first high pressure and, at an intermediate cooling temperature, at least part of it is relieved at medium pressure in a turbine before introducing it into the double column, characterized in that the rest of the air is boosted at a second high pressure under the first high pressure, at least part of the compressed air, the flow rate of which is lower than the flow rate of liquid oxygen to be vaporized, being cooled and liquefied then, after expansion, introduced into the double column, the second high pressure being on the one hand
- the air distillation installation shown in FIG. 1 essentially comprises: an air compressor 1, an apparatus 2 for purifying the compressed air into water and CO 2 by adsorption, this apparatus comprising two bottles of adsorption 2A, 2B, one of which operates in adsorption while the other is being regenerated; a turbine-booster assembly 3 comprising an expansion turbine 4 and a booster 5 whose shafts are coupled; a heat exchanger 6 constituting the heat exchange line of the installation; a double distillation column 7 comprising a medium pressure column 8 surmounted by a low pressure column 9, with a vaporizer-condenser 10 putting the overhead vapor (nitrogen) from column 8 in heat exchange relation with the tank liquid (oxygen) from column 9; a liquid oxygen tank 11, the bottom of which is connected to a liquid oxygen pump 12; and a liquid nitrogen tank 13, the bottom of which is connected to a liquid nitrogen pump 14.
- This installation is intended to supply, via a pipe 15, gaseous oxygen under a predetermined high pressure, which can be between a few bars and a few tens of bars (in the present specification, the pressures considered are absolute pressures).
- liquid oxygen withdrawn from the tank of the column 9 via a pipe 16 and stored in the tank 11, is brought to high pressure by the pump 12 in the liquid state, then vaporized and heated --- under this high pressure in passages 17 of exchanger 6.
- the heat necessary for this vaporization and this reheating, as well as for the reheating and possibly for the vaporization of other fluids drawn from the double column, is supplied by the air to be distilled, under the following conditions.
- All of the air to be distilled is compressed by compressor 1 at a pressure higher than the medium pressure of column 8 but lower than the high pressure. Then the air, precooled in 18 and cooled to around ambient temperature in 19, is purified in one, 2A for example, of the adsorption bottles, and entirely pressurized at high pressure by the booster 5, which is driven by the turbine 4.
- the air is then introduced at the hot end of the exchanger 6 and completely cooled to an intermediate temperature. At this temperature, a fraction of the air continues to cool and is liquefied in passages 20 of the exchanger, then is expanded at low pressure in an expansion valve 21 and introduced at an intermediate level into column 9. The rest of the air, or excess air, is expanded to medium pressure in the turbine 4 and then sent directly, via a pipe 22, to the base of the column 8.
- the low-pressure nitrogen is heated in passages 28 of the exchanger 6 and then discharged via a line 29, while the residual gas, after heating in passages 30 of the exchanger, is used to regenerate an adsorption bottle, the bottle 2B in the example considered, before being evacuated via a pipe 31.
- part of the medium pressure liquid nitrogen is, after expansion in an expansion valve 32, stored in the reservoir 13, and a production of liquid nitrogen and / or liquid oxygen is supplied via a line 33 (for nitrogen) and / or 34 (for oxygen).
- this air pressure is the pressure of condensation of the air by heat exchange with the oxygen being vaporized under the high pressure, i.e. - say the pressure for which the knee G of air liquefaction, on the heat exchange diagram (temperatures on the abscissa, quantities of heat exchanged on the ordinate) is located slightly to the right of the vertical stage P of vaporization of oxygen under high pressure ( Figure 3).
- the temperature difference at the hot end of the exchange line is adjusted by means of the turbine, the suction temperature of which is indicated in A. The irreversibility of the heat exchange is thus minimal.
- Such air pressure is worn depending on the high pressure, on the left portion C1 of the curve in Figure 2.
- a high pressure of around 13 bars corresponds in this way to an air pressure of around 30 bars (more precisely, around 28.5 bars).
- an air pressure of the order of 30 bars is chosen, whatever this high pressure, as indicated on the straight portion C2 of the curve of FIG. 2.
- nitrogen gas under pressure can, in addition, be produced in an analogous manner, by bringing liquid nitrogen to the desired pressure, by drawing off at the top of the column 8 or by means of a pump such as 14 sucking the liquid nitrogen there or in the reservoir 13, and passing this liquid nitrogen through suitable vaporization-heating passages for the exchanger 6.
- part of the gaseous oxygen produced can be produced under a different high pressure, by vaporizing it under this pressure in other suitable passages of the exchanger 6.
- the two high pressures are one less than approximately 13 bars and the other greater than approximately 13 bars
- all of the air is preferably compressed to approximately 30 bars (or above as explained above), and in any case so that the liquefaction knee G is opposite the vaporization level P1 of the oxygen at the lowest high pressure, and the suction temperature of the turbine (point A) is higher than that of the stage P2 for vaporizing the oxygen at the highest high pressure.
- a tight heat exchange diagram is obtained, which is very favorable from an energy point of view.
- a second turbine (not shown) can be provided, de-energizing a fraction of the medium pressure to the low pressure. in the order of 10 to 25% of the treated air flow, the low pressure air thus obtained being blown into column 9. If the high oxygen pressure is less than approximately 13 bars, this fraction can be taken with exhaust of the turbine 4, the temperature of which is sufficiently high. In the opposite case, said fraction is taken from the bottom of the column 8, or taken from the exhaust of the turbine 4 and separated from its liquid phase, and reheated before expansion.
- This variant makes it possible to increase the production of liquid while slightly reducing the production of liquid at medium pressure, and consequently the operating pressure of the installation, that is to say the high air pressure.
- the turbine 4 can also be braked by a device other than a booster.
- the booster 5 is eliminated, and the compressor 1 directly compresses all of the air at the high air pressure defined above.
- the installation shown in Figure 6 is intended to produce gaseous oxygen at a pressure at least equal to about 13 bars and, in this example, 35 bars. It essentially comprises a double distillation column 41, a main heat exchange line 42, a sub-cooler 43, a compressor single air 44, a blower 45 for air overpressure, an expansion turbine 46 whose wheel is mounted on the same shaft as that of the booster 45, an additional blower 47 driven by an electric motor 48, and a pump liquid oxygen 49.
- the double column consists, in a conventional manner, of a medium pressure column 50 operating at about 6 bars and surmounted by a low pressure column 51 operating slightly above atmospheric pressure, with, in tank from the latter, a vaporizer-condenser 52 which brings the liquid oxygen from the bottom of the low pressure column into heat exchange relation with the nitrogen at the head of the medium pressure column.
- the first stream is cooled under this first high pressure in passages 53 of the exchange line 42. Part of this first stream continues to cool, and is liquefied, until the cold end of the exchange line, then is expanded at medium pressure and at low pressure in expansion valves 54 and 55 respectively and distributed between columns 50 and 51. The rest of the first stream left the exchange line at an intermediate temperature T1, expanded in the turbine 46 at medium pressure and introduced at the base of column 50.
- the second stream of pressurized air is again pressurized, up to a second high pressure of the order of 35 to 40 bars, by the blower 47, then cooled and liquefied in passages 56 of the exchange line, up to 'at the cold end of it.
- the liquid thus obtained is expanded in an expansion valve 57 and sent to the base of the column 50.
- blower or "blower” is understood here to mean a single-wheel compressor whose energy expenditure, by the flow rate of treated gas and the compression ratio, is considerably lower than that of the main compressor 44 of the installation. , and for example of the order of 2 to 3% of the latter.
- the compression ratio of such a blower is generally less than 2.
- Each of the blowers in question here comprises at its outlet a water or atmospheric air refrigerant, not shown.
- Liquid oxygen withdrawn from the tank of the column 51 is brought by the pump 49 to the desired production pressure, then vaporized and heated in passages 58 of the exchange line before being evacuated from the installation via a pipe. of production 59.
- the temperature T1 of turbine inlet 46 is lower than the temperature of the stage 69 of vaporization of oxygen under the production pressure, and the refrigeration balance of the installation is balanced, in order to maintain a small temperature difference at hot end of the exchange line, by drawing off via the lines 64 and / or 65 certain quantities of liquid nitrogen and / or liquid oxygen, as explained above with reference to FIGS. 1 to 5.
- the pressure of the air at the discharge of compressor 44 is of the order of 23 bars, this equilibrium is obtained for a withdrawal of liquid of the order of 5% of the treated air flow.
- the aforementioned second high pressure is on the one hand lower than the condensation pressure of the air by heat exchange with the oxygen being vaporized under the production pressure, and on the other hand chosen so that the air brought to this second high pressure begins to condense at a temperature close to T1.
- This ensures a significant supply of calories in the vicinity of this temperature T1 and allows the turbine 46 to operate in good conditions, that is to say without producing liquid at the entrance of its wheel, while maintaining gaps optimal temperatures, of the order of 2 to 3 ° C, at the two ends of the exchange line as well as at the location of the vaporization bearing 69.
- the air compressor 44 of the installation directly compresses all of the air at the first high pressure of the order of 23 bars, and a first stream of this air is treated as previously in the passages 53, the turbine 46 and the expansion valve 54 then sent to the base of the column 50.
- a first blower 70 which, like the blower 45 in Figure 6, is directly coupled to the turbine 46, and a second blower 71 directly coupled to a second expansion turbine 72.
- the air boosted at 70 passes entirely through the blower 71 then through the passages 56 of the exchange line 42, and part of this air is exited from the exchange line at a temperature T2 higher than the temperature T1 in order to be expanded in the turbine 72.
- the exhaust of the latter at medium pressure, is connected to the base of the column 50 like that of the turbine 46.
- the air at the highest pressure which is not expanded in the turbine 72 continues to cool and is liquefied in the passages 56 to the cold end of the exchange line, then is expanded in expansion valves 57 and 57A and distributed between the two columns 50 and 51.
- the valve 57A replaces the valve 55 in FIG. 6.
- the temperature T2 can be chosen slightly above the stage 69 of oxygen vaporization. Taking into account the relatively low flow rate of the expanded air in the turbine 72, an air cooling curve is obtained which is roughly parallel to the warming curve for liquid oxygen and nitrogen gas at the temperature T2 knee 73 of condensation or pseudo-condensation of the air under the highest pressure.
- an air flow taken between the two blowers 70 and 71, is cooled and liquefied in additional passages 74 of the exchange line, until the cold end thereof, then expanded to the medium pressure in an expansion valve 75 and sent to the base of the column 50.
- the turbine 72 can be supplied with air flowing in the passages 74, which are then interrupted at the temperature T2.
- the expansion valve 75 is then eliminated, and it is the air circulating in the passages 56 which is entirely liquefied in the passages 56 and then expanded at medium pressure in the expansion valve 57.
- the highest air pressure can be increased by passing the air coming from the blower 71 into an additional blower 76 driven by an electric motor 77.
- the installation represented in FIG. 11 is a variant of that of FIG. 8. It differs from it only in that the exhaust of the two turbines 46 and 72 opens into a phase separator 78 of which the liquid and a part of the vapor phase are sent to the bottom of the column 50 while the rest of the vapor phase, after partial reheating in passages 79 of the exchange line, is expanded at low pressure in an additional turbine 80 braked by an appropriate brake 81. The low pressure air leaving the turbine 80 is blown into the column 51 via a pipe 82.
- This solution is applicable when the oxygen product gas under pressure is of low purity (less than 99.5%).
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Description
La présente invention est relative à un procédé de production d'oxygène gazeux sous une haute pression d'oxygène par distillation d'air dans une installation à double colonne, pompage d'oxygène liquide soutiré en cuve de la colonne basse pression, et vaporisation de l'oxygène liquide comprimé par échange de chaleur, dans la ligne d'échange thermique de l'installation, avec de l'air porté à une haute pression d'air, dans lequel on comprime à la haute pression d'air la totalité de l'air à distiller; à une température intermédiaire de refroidissement, on détend dans une turbine, à la pression de la colonne moyenne pression, une fraction de cet air.The present invention relates to a process for the production of gaseous oxygen under a high oxygen pressure by air distillation in a double column installation, pumping of liquid oxygen withdrawn from the bottom of the low pressure column, and vaporization of liquid oxygen compressed by heat exchange, in the heat exchange line of the installation, with air brought to a high air pressure, in which all of the air is compressed at high air pressure the air to be distilled; at an intermediate cooling temperature, a fraction of this air is expanded in a turbine, at the pressure of the medium pressure column.
Les pressions dont il est question ci-dessous sont des pressions absolues. Les pressions de la colonne moyenne pression et de la colonne basse pression seront appelées "moyenne pression" et "basse pression", respectivement.The pressures discussed below are absolute pressures. The pressures in the medium pressure column and the low pressure column will be referred to as "medium pressure" and "low pressure", respectively.
Les procédés de ce type, dits procédés "à pompe" permettent de supprimer tout compresseur d'oxygène gazeux. Pour obtenir une dépense d'énergie compétitive, il est nécessaire de comprimer un débit d'air important, de l'ordre de 1,5 fois le débit d'oxygène à vaporiser, jusqu'à une pression suffisante permettant de le liquéfier à contre-courant de l'oxygène.Processes of this type, called "pump" processes, make it possible to eliminate any gaseous oxygen compressor. To obtain a competitive energy expenditure, it is necessary to compress a large air flow, of the order of 1.5 times the flow of oxygen to be vaporized, to a sufficient pressure allowing it to liquefy against -current oxygen.
Des exemples de procédés de ce type se retrouvent dans US-A-3.648.471, GB-A-929.798, EP-A-0.024.962 et EP-A-0.042.676Examples of such processes are found in US-A-3,648,471, GB-A-929,798, EP-A-0.024.962 and EP-A-0.042.676
US-A-3.648.471 et GB-A-929.798 décrivent un procédé de vaporisation d'oxygène liquide, utilisant une turbine Claude sans aucune production de liquide comme produit final.US-A-3,648,471 and GB-A-929,798 describe a process for vaporizing liquid oxygen, using a Claude turbine without any production of liquid as final product.
EP-A-0.024.962 décrit un procédé de vaporisation d'oxygène liquide, utilisant une turbine Claude avec production d'azote liquide.EP-A-0.024.962 describes a process for vaporizing liquid oxygen, using a Claude turbine with production of liquid nitrogen.
EP-A-0.042.676 décrit un procédé de vaporisation d'oxygène liquide par échange de chaleur avec de l'azote. Les frigories du procédé sont fournies uniquement par détente d'azote.EP-A-0.042.676 describes a process for vaporizing liquid oxygen by heat exchange with nitrogen. The process frigories are supplied only by nitrogen expansion.
Il est connu que la dépense d'énergie des installations correspondantes n'est inférieure ou égale à celle des installations munies d'un compresseur que pour des pressions de vaporisation d'oxygène inférieures à 10 bar environ, et que cette dépense d'énergie augmente progressivement avec cette pression. De plus, dans le domaine où la dépense d'énergie est acceptable, la technique habituelle utilise deux compresseurs en série, le second ne traitant que la fraction de l'air destinée à la vaporisation de l'oxygène liquide, ce qui accroît considérablement l'investissement de l'installation.It is known that the energy expenditure of the corresponding installations is less than or equal to that of the installations provided with a compressor only for oxygen vaporization pressures of less than approximately 10 bar, and that this energy expenditure increases gradually with this pressure. In addition, in the field where the energy expenditure is acceptable, the usual technique uses two compressors in series, the second only treating the fraction of the air intended to the vaporization of liquid oxygen, which considerably increases the investment of the installation.
L'invention a pour but de fournir un procédé "à pompe" ne nécessitant qu'un investissement réduit.The invention aims to provide a "pump" process requiring only a reduced investment.
A cet effet, le procédé suivant l'invention est caractérisé en ce que la fraction d'air est excédentaire par rapport aux besoins frigorifiques de la ligne d'échange thermique, la turbine est freinée par un surpresseur d'air et on réduit l'écart de température au bout chaud de la ligne d'échange en évacuant de l'installation au moins un produit liquide.To this end, the process according to the invention is characterized in that the air fraction is in excess with respect to the refrigerating needs of the heat exchange line, the turbine is braked by an air booster and the temperature difference at the hot end of the exchange line by evacuating at least one liquid product from the installation.
Suivant des modes de réalisation préférés de l'invention:
- pour une haute pression d'oxygène inférieure à 13 bar environ, on choisit comme haute pression d'air la pression de condensation de l'air par échange de chaleur avec l'oxygène en cours de vaporisation sous la haute pression d'oxygène ;
- pour une haute pression d'oxygène supérieure à 13 bar environ, on choisit comme haute pression d'air, quelle que soit la haute pression d'oxygène, une pression inférieure à la pression de condensation de l'air par échange de chaleur avec l'oxygène en cours de vaporisation sous la haute pression d'oxygène et au moins égale à 30 bar environ.
- for a high oxygen pressure of less than about 13 bar, the condensation pressure of the air is chosen as the high air pressure by heat exchange with the oxygen being vaporized under the high oxygen pressure;
- for a high oxygen pressure higher than approximately 13 bar, one chooses as high air pressure, whatever the high oxygen pressure, a pressure lower than the pressure of condensation of the air by heat exchange with l oxygen being vaporized under the high oxygen pressure and at least equal to approximately 30 bar.
Une étude approfondie des phénomènes mis en jeu dans le procédé défini ci-dessus montre que, dans certains cas, la turbine de détente risque de voir du liquide se former à l'entrée de sa roue si l'on veut maintenir des écarts de température réduits à l'emplacement du palier de vaporisation de l'oxygène et au bout chaud de la ligne d'échange. C'est le cas lorsque la pression d'oxygène est supérieure à 13 bar environ, lorsque l'installation comprend une seule turbine de détente (c'est-à-dire ne comporte pas de turbine détente d'air en basse pression) et lorsque la presque totalité de l'oxygène liquide soutiré de la double colonne est vaporisé sous pression.An in-depth study of the phenomena involved in the process defined above shows that, in certain cases, the expansion turbine risks seeing liquid forming at the inlet of its wheel if it is desired to maintain temperature differences reduced at the location of the oxygen vaporization bearing and at the hot end of the exchange line. This is the case when the oxygen pressure is greater than approximately 13 bar, when the installation comprises a single expansion turbine (that is to say does not include an air expansion turbine at low pressure) and when almost all of the liquid oxygen withdrawn from the double column is vaporized under pressure.
Suivant un développement de l'invention, on obtient les faibles écarts de température précités, et donc une faible dépense d'énergie spécifique, tout en évitant l'apparition de liquide à l'entrée de la roue de la turbine de détente.According to a development of the invention, the abovementioned small temperature differences are obtained, and therefore a low specific energy expenditure, while avoiding the appearance of liquid at the inlet of the wheel of the expansion turbine.
A cet effet, l'invention a également pour objet un procédé de production d'oxygène gazeux sous une haute pression d'oxygène d'au moins 13 bar environ par distillation d'air dans une installation à double colonne comprenant une colonne basse pression et une colonne moyenne pression, pompage d'oxygène liquide soutiré en cuve de la colonne basse pression, et vaporisation de l'oxygène liquide comprimé par échange de chaleur avec de l'air porté à une haute pression nettement supérieure à la moyenne pression, dans lequel on comprime la totalité de l'air à distiller à une première haute pression nettement supérieure à la moyenne pression, et on refroidit une première fraction de cet air sous la première haute pression et, à une température intermédiaire de refroidissement, on en détend au moins une partie à la moyenne pression dans une turbine avant de l'introduire dans la double colonne ,
caractérisé en ce qu'on surpresse à une seconde haute pression le reste de l'air sous la première haute pression, une partie au moins de l'air surpressé, dont le débit est inférieur au débit d'oxygène liquide à vaporiser, étant refroidie et liquéfiée puis, après détente, introduite dans la double colonne, la seconde haute pression étant d'une part inférieure à la pression de condensation ou de pseudo-condensation de l'air par échange de chaleur avec l'oxygène en cours de vaporisation sous la haute pression d'oxygène et au moins égale à 30 bar environ et, d'autre part, choisie de façon que la condensation ou la pseudo-condensation de l'air sous cette seconde haute pression ait lieu au voisinage de la température d'admission de la turbine et on réduit l'écart de température au bout chaud d'une ligne d'échange thermique en évacuant de l'installation au moins un produit liquide.To this end, the invention also relates to a process for producing gaseous oxygen under a high oxygen pressure of at least Approximately 13 bar by air distillation in a double column installation comprising a low pressure column and a medium pressure column, pumping of liquid oxygen withdrawn from the bottom of the low pressure column, and vaporization of the compressed liquid oxygen by exchange of heat with air brought to a high pressure markedly higher than the medium pressure, in which all of the air to be distilled is compressed to a first high pressure markedly higher than the medium pressure, and a first fraction of this is cooled air under the first high pressure and, at an intermediate cooling temperature, at least part of it is relieved at medium pressure in a turbine before introducing it into the double column,
characterized in that the rest of the air is boosted at a second high pressure under the first high pressure, at least part of the compressed air, the flow rate of which is lower than the flow rate of liquid oxygen to be vaporized, being cooled and liquefied then, after expansion, introduced into the double column, the second high pressure being on the one hand lower than the pressure of condensation or pseudo-condensation of the air by heat exchange with oxygen being vaporized under the high oxygen pressure and at least equal to approximately 30 bar and, on the other hand, chosen so that the condensation or pseudo-condensation of the air under this second high pressure takes place in the vicinity of the temperature inlet of the turbine and the temperature difference at the hot end of a heat exchange line is reduced by removing at least one liquid product from the installation.
Des exemples de mise en oeuvre de l'invention vont maintenant être décrits en regard des dessins annexés sur lesquels :
- la figure 1 représente schématiquement une installation de production d'oxygène gazeux pour mettre en oeuvre un procédé conforme à l'invention ;
- la figure 2 est un diagramme montrant l'évolution de la pression de vaporisation d'oxygène, suivant l'invention, en fonction de la haute pression de l'oxygène ;
- les figures 3 à 5 sont des diagrammes d'échange thermique correspondant à trois utilisations différentes du procédé suivant l'invention ;
- la figure 6 représente schématiquement une autre installation de production d'oxygène gazeux pour mettre en oeuvre un procédé conforme à l'invention ;
- la figure 7 est un diagramme d'échange thermique correspondant à cette installation, avec en abscisses la température en degrés Celsius et en ordonnées les enthalpies échangées dans la ligne d'échange thermique ;
- les figures 8 et 9 sont des vues analogues respectivement aux figures 6 et 7 mais relatives à un autre mode de réalisation de l'installation suivant l'invention ; et
- les figures 10 et 11 représentent schématiquement plusieurs variantes de l'installation.
- FIG. 1 schematically represents an installation for producing gaseous oxygen for implementing a method according to the invention;
- Figure 2 is a diagram showing the evolution of the oxygen vaporization pressure, according to the invention, as a function of the high oxygen pressure;
- Figures 3 to 5 are heat exchange diagrams corresponding to three different uses of the method according to the invention;
- FIG. 6 schematically represents another installation for producing gaseous oxygen for implementing a method in accordance with the invention;
- FIG. 7 is a heat exchange diagram corresponding to this installation, with the temperature in degrees Celsius on the abscissa and the enthalpies exchanged in the heat exchange line on the ordinate;
- Figures 8 and 9 are views similar to Figures 6 and 7 respectively but relating to another embodiment of the installation according to the invention; and
- Figures 10 and 11 schematically represent several variants of the installation.
L'installation de distillation d'air représentée à la figure 1 comprend essentiellement : un compresseur d'air 1, un appareil 2 d'épuration de l'air comprimé en eau et en CO2 par adsorption, cet appareil comprenant deux bouteilles d'adsorption 2A, 2B, dont l'une fonctionne en adsorption pendant que l'autre est en cours de régénération ; un ensemble turbine-surpresseur 3 comprenant une turbine de détente 4 et un surpresseur 5 dont les arbres sont couplés ; un échangeur de chaleur 6 constituant la ligne d'échange thermique de l'installation ; une double colonne de distillation 7 comprenant une colonne moyenne pression 8 surmontée d'une colonne basse pression 9, avec un vaporiseur-condenseur 10 mettant la vapeur de tête (azote) de la colonne 8 en relation d'échange thermique avec le liquide de cuve (oxygène) de la colonne 9 ; un réservoir d'oxygène liquide 11 dont le fond est relié à une pompe d'oxygène liquide 12 ; et un réservoir d'azote liquide 13 dont le fond est relié à une pompe d'azote liquide 14.The air distillation installation shown in FIG. 1 essentially comprises: an
Cette installation est destinée à fournir, via une conduite 15, de l'oxygène gazeux sous une haute pression prédéterminée, qui peut être comprise entre quelques bars et quelques dizaines de bars (dans le présent mémoire, les pressions considérées sont des pressions absolues).This installation is intended to supply, via a
Pour cela, de l'oxygène liquide soutiré de la cuve de la colonne 9 via une conduite 16 et stocké dans le réservoir 11, est amené à la haute pression par la pompe 12 à l'état liquide, puis vaporisé et réchauffé --- sous cette haute pression dans des passages 17 de l'échangeur 6.For this, liquid oxygen withdrawn from the tank of the
La chaleur nécessaire à cette vaporisation et à ce réchauffage, ainsi qu'au réchauffage et éventuellement à la vaporisation d'autres fluides soutirés de la double colonne, est fournie par l'air à distiller, dans les conditions suivantes.The heat necessary for this vaporization and this reheating, as well as for the reheating and possibly for the vaporization of other fluids drawn from the double column, is supplied by the air to be distilled, under the following conditions.
La totalité de l'air à distiller est comprimée par le compresseur 1 à une pression supérieure à la moyenne pression de la colonne 8 mais inférieure à la haute pression. Puis l'air, prérefroidi en 18 et refroidi au voisinage de la température ambiante en 19, est épuré dans l'une, 2A par exemple, des bouteilles d'adsorption, et surpressé en totalité à la haute pression par le surpresseur 5, lequel est entraîné par la turbine 4.All of the air to be distilled is compressed by
L'air est alors introduit au bout chaud de l'échangeur 6 et refroidi en totalité jusqu'à une température intermédiaire. A cette température, une fraction de l'air poursuit son refroidissement et est liquéfié dans des passages 20 de l'échangeur, puis est détendu à la basse pression dans une vanne de détente 21 et introduit à un niveau intermédiaire dans la colonne 9. Le reste de l'air, ou air excédentaire, est détendu à la moyenne pression dans la turbine 4 puis envoyé directement, via une conduite 22, à la base de la colonne 8.The air is then introduced at the hot end of the
On reconnait par ailleurs sur la Figure 1 les conduites habituelles des installations à double colonne, celle représentée étant du type dit "à minaret", c'est-à-dire avec production d'azote sous la basse pression : les conduites 23 à 25 d'injection dans la colonne 9, à des niveaux croissants, de "liquide riche" (air enrichi en oxygène) détendu, de "liquide pauvre inférieur" (azote impur) détendu et de "liquide pauvre supérieur" (azote pratiquement pur) détendu, respectivement, ces trois fluides étant respectivement soutirés à la base, en un point intermédiaire et au sommet de la colonne 8; et les conduites 26 de soutirage d'azote gazeux partant du sommet de la colonne 9 et 27 d'évacuation du gaz résiduaire (azote impur) partant du niveau d'injection du liquide pauvre inférieur. L'azote basse pression est réchauffé dans des passages 28 de l'échangeur 6 puis évacué via une conduite 29, tandis que le gaz résiduaire, après réchauffement dans des passages 30 de l'échangeur, est utilisé pour régénérer une bouteille d'adsorption, la bouteille 2B dans l'exemple considéré, avant d'être évacué via une conduite 31.We also recognize in Figure 1 the usual lines of double column installations, that shown being of the type called "minaret", that is to say with nitrogen production under low pressure:
On voit encore sur la Figure 1 qu'une partie de l'azote liquide moyenne pression est, après détente dans une vanne de détente 32, stockée dans le réservoir 13, et une production d'azote liquide et/ou d'oxygène liquide est fournie via une conduite 33 (pour l'azote) et/ou 34 (pour l'oxygène).It can also be seen in FIG. 1 that part of the medium pressure liquid nitrogen is, after expansion in an
Pour le choix de la pression de l'air surpressé, on distingue deux cas.For the choice of the pressure of the compressed air, there are two cases.
Lorsque la haute pression d'oxygène est inférieure à 13 bars environ, cette pression d'air est la pression de condensation de l'air par échange de chaleur avec l'oxygène en cours de vaporisation sous la haute pression, c'est-à-dire la pression pour laquelle le genou G de liquéfaction de l'air, sur le diagramme d'échange thermique (températures en abscisses, quantités de chaleur échangées en ordonnées) est situé légèrement à droite du palier vertical P de vaporisation de l'oxygène sous la haute pression (Figure 3). L'écart de température au bout chaud de la ligne d'échange est ajusté au moyen de la turbine, dont la température d'aspiration est indiquée en A. L'irréversibilité de l'échange thermique est ainsi minimale. Une telle pression d'air est portée en fonction de la haute pression, sur la portion gauche C1 de la courbe de la Figure 2.When the high oxygen pressure is less than approximately 13 bars, this air pressure is the pressure of condensation of the air by heat exchange with the oxygen being vaporized under the high pressure, i.e. - say the pressure for which the knee G of air liquefaction, on the heat exchange diagram (temperatures on the abscissa, quantities of heat exchanged on the ordinate) is located slightly to the right of the vertical stage P of vaporization of oxygen under high pressure (Figure 3). The temperature difference at the hot end of the exchange line is adjusted by means of the turbine, the suction temperature of which is indicated in A. The irreversibility of the heat exchange is thus minimal. Such air pressure is worn depending on the high pressure, on the left portion C1 of the curve in Figure 2.
Comme on le voit sur la Figure 2, une haute pression de l'ordre de 13 bars correspond de cette manière à une pression d'air de l'ordre de 30 bars (plus précisément, environ 28,5 bars). Lorsque la haute pression est supérieure à 13 bars, on choisit une pression d'air de l'ordre de 30 bars, quelle que soit cette haute pression, comme indiqué sur la portion droite C2 de la courbe de la Figure 2.As seen in Figure 2, a high pressure of around 13 bars corresponds in this way to an air pressure of around 30 bars (more precisely, around 28.5 bars). When the high pressure is greater than 13 bars, an air pressure of the order of 30 bars is chosen, whatever this high pressure, as indicated on the straight portion C2 of the curve of FIG. 2.
Dans le premier cas (haute pression inférieure à 13 bars environ), la production d'oxygène et/ou d'azote sous forme liquide a pour conséquence un déficit de produits gazeux froids dans l'échangeur 6, d'où une température d'aspiration relativement élevée de la turbine 4. Ce phénomène a pour conséquence une production frigorifique importante par cette turbine, ce qui permet à l'installation de produire une quantité importante d'oxygène et/ou d'azote sous forme liquide, ceci dans des conditions d'investissement particulièrement avantageuses.In the first case (high pressure less than about 13 bars), the production of oxygen and / or nitrogen in liquid form results in a deficit of cold gaseous products in the
Dans le second cas (haute pression supérieure à 13 bars environ), en considérant la Figure 2, la pression d'air ne se trouve plus sur le prolongement C3 de la courbe C1; par suite, le genou G de liquéfaction de l'air (Figure 4) se décale vers la gauche par rapport au palier P de vaporisation de l'oxygène, et la température d'aspiration de la turbine devient inférieure à celle du palier P. Par suite, une fraction importante de l'air turbiné se trouve en moyenne pression sous forme liquide, et le bilan frigorifique de l'installation est équilibré, avec un écart de température au bout chaud de l'ordre de 3°C, en soutirant de l'installation au moins un produit (oxygène et/ou azote) sous forme liquide via les conduites 33 et/ou 34. Lorsque la pression de l'air est de l'ordre de 30 bars, cet équilibre s'obtient pour un soutirage de liquide de l'ordre de 25% de la production d'oxygène gazeux sous haute pression.In the second case (high pressure greater than about 13 bars), considering Figure 2, the air pressure is no longer on the extension C3 of the curve C1; as a result, the knee G of air liquefaction (Figure 4) shifts to the left relative to the stage P of vaporization of oxygen, and the suction temperature of the turbine becomes lower than that of the stage P. As a result, a large fraction of the turbined air is at medium pressure in liquid form, and the refrigeration balance of the installation is balanced, with a temperature difference at the hot end of the order of 3 ° C., by withdrawing of the installation at least one product (oxygen and / or nitrogen) in liquid form via
En variante, on peut choisir une pression d'air comprise entre 30 bars environ et la courbe C3, c'est-à-dire dans la région B de la Figure 2. Il faut alors évacuer une plus grande quantité de liquide pour atteindre l'équilibre précité.As a variant, it is possible to choose an air pressure between approximately 30 bars and the curve C3, that is to say in region B of FIG. above balance.
Ainsi, sur toute la gamme de pressions d'oxygène, on utilise une installation à un seul compresseur, ce qui constitue un investissement réduit, et le surcoût d'énergie résultant de la compression de la totalité de l'air à la pression de vaporisation d'oxygène sert à produire du liquide.Thus, over the whole range of oxygen pressures, an installation with a single compressor is used, which constitutes a reduced investment, and the additional energy cost resulting from the compression of all the air at the vaporization pressure. oxygen is used to produce liquid.
Dans une variante non représentée, dans des gammes de pression et de débit aisément déterminables par le calcul, de l'azote gazeux sous pression peut, en supplément, être produit de manière analogue, en portant de l'azote liquide à la pression désirée, par soutirage au sommet de la colonne 8 ou au moyen d'une pompe telle que 14 aspirant l'azote liquide à cet endroit ou dans le réservoir 13, et en faisant passer cet azote liquide dans des passages appropriés de vaporisation-réchauffement de l'échangeur 6.In a variant not shown, in pressure and flow ranges easily determinable by calculation, nitrogen gas under pressure can, in addition, be produced in an analogous manner, by bringing liquid nitrogen to the desired pressure, by drawing off at the top of the
Dans une autre variante, illustrée uniquement par le diagramme d'échange thermique de la Figure 5, une partie de l'oxygène gazeux produit peut l'être sous une haute pression différente, en la vaporisant sous cette pression dans d'autres passages appropriés de l'échangeur 6. Si les deux hautes pressions sont l'une inférieure à 13 bars environ et l'autre supérieure à 13 bars environ, la totalité de l'air est de préférence comprimée à 30 bars environ (ou au-dessus comme expliqué plus haut), et en tout cas de manière que le genou de liquéfaction G se trouve en regard du palier de vaporisation P1 de l'oxygène sous la haute pression la plus faible, et la température d'aspiration de la turbine (point A) est supérieure à celle du palier P2 de vaporisation de l'oxygène sous la haute pression la plus élevée. On obtient dans ce cas un diagramme d'échange thermique bien resserré, très favorable du point de vue énergétique.In another variant, illustrated only by the heat exchange diagram in FIG. 5, part of the gaseous oxygen produced can be produced under a different high pressure, by vaporizing it under this pressure in other suitable passages of the
En variante encore, si l'oxygène produit est à faible pureté (de l'ordre de 90 à 98%), on peut prévoir une deuxième turbine (non représentée) détendant de la moyenne pression à la basse pression une fraction, de l'ordre de 10 à 25%, du débit d'air traité, l'air basse pression ainsi obtenu étant insufflé dans la colonne 9. Si la haute pression d'oxygène est inférieure à 13 bars environ, cette fraction peut être prise à l'échappement de la turbine 4, dont la température est suffisamment élevée. Dans le cas inverse, ladite fraction est prélevée en cuve de la colonne 8, ou prise à l'échappement de la turbine 4 et séparée de sa phase liquide, et réchauffée avant la détente.As a further variant, if the oxygen produced is of low purity (of the order of 90 to 98%), a second turbine (not shown) can be provided, de-energizing a fraction of the medium pressure to the low pressure. in the order of 10 to 25% of the treated air flow, the low pressure air thus obtained being blown into
Cette variante permet d'augmenter la production de liquide tout en diminuant légèrement la production de liquide en moyenne pression, et par suite la pression de marche de l'installation, c'est-à-dire la haute pression d'air.This variant makes it possible to increase the production of liquid while slightly reducing the production of liquid at medium pressure, and consequently the operating pressure of the installation, that is to say the high air pressure.
On comprend par ailleurs que la turbine 4 peut également être freinée par un appareil autre qu'un surpresseur. Dans ce cas, le surpresseur 5 est supprimé, et le compresseur 1 comprime directement la totalité de l'air à la haute pression d'air définie plus haut.It is also understood that the turbine 4 can also be braked by a device other than a booster. In this case, the
L'installation représentée à la Figure 6 est destinée à produire de l'oxygène gazeux sous une pression au moins égale à 13 bars environ et, dans cet exemple, de 35 bars. Elle comprend essentiellement une double colonne de distillation 41, une ligne d'échange thermique principale 42, un sous-refroidisseur 43, un compresseur d'air unique 44, une soufflante 45 de surpression d'air, une turbine de détente 46 dont la roue est montée sur le même arbre que celle du surpresseur 45, une soufflante additionnelle 47 entraînée par un moteur électrique 48, et une pompe d'oxygène liquide 49. La double colonne est constituée, de manière classique, d'une colonne moyenne pression 50 fonctionnant sous environ 6 bars et surmontée d'une colonne basse pression 51 fonctionnant légèrement au-dessus de la pression atmosphérique, avec, en cuve de cette dernière, un vaporiseur-condenseur 52 qui met en relation d'échange thermique l'oxygène liquide de cuve de la colonne basse pression avec l'azote de tête de la colonne moyenne pression.The installation shown in Figure 6 is intended to produce gaseous oxygen at a pressure at least equal to about 13 bars and, in this example, 35 bars. It essentially comprises a
En fonctionnement, l'air à distiller, comprimé en totalité par le compresseur 44 à une pression de l'ordre de 23 bars et épuré dans un adsorbeur 44A, est surpressé en totalité par le surpresseur 45 à une première haute pression de l'ordre de 28 bars, puis divisé en deux courants.In operation, the air to be distilled, fully compressed by the
Le premier courant est refroidi sous cette première haute pression dans des passages 53 de la ligne d'échange 42. Une partie de ce premier courant poursuit son refroidissement, et est liquéfié, jusqu'au bout froid de la ligne d'échange, puis est détendu à la moyenne pression et à la basse pression dans des vannes de détente 54 et 55 respectivement et réparti entre les colonnes 50 et 51. Le reste du premier courant est sorti de la ligne d'échange à une température intermédiaire T1, détendu dans la turbine 46 à la moyenne pression et introduit à la base de la colonne 50.The first stream is cooled under this first high pressure in
Le second courant d'air surpressé est à nouveau surpressé, jusqu'à une seconde haute pression de l'ordre de 35 à 40 bars, par la soufflante 47, puis refroidi et liquéfié dans des passages 56 de la ligne d'échange, jusqu'au bout froid de celle-ci. Le liquide ainsi obtenu est détendu dans une vanne de détente 57 et envoyé à la base de la colonne 50.The second stream of pressurized air is again pressurized, up to a second high pressure of the order of 35 to 40 bars, by the
On entend ici par "surpresseur" ou "soufflante" un compresseur à une seule roue dont la dépense d'énergie, de par le débit de gaz traité et le taux de compression, est considérablement inférieure à celle du compresseur principal 44 de l'installation, et par exemple de l'ordre de 2 à 3% de cette dernière. Le taux de compression d'une telle soufflante est généralement inférieur à 2. Chacune des soufflantes dont il est question ici comporte à sa sortie un réfrigérant à eau ou à air atmosphérique non représenté.The term "booster" or "blower" is understood here to mean a single-wheel compressor whose energy expenditure, by the flow rate of treated gas and the compression ratio, is considerably lower than that of the
L'oxygène liquide soutiré en cuve de la colonne 51 est amené par la pompe 49 à la pression de production désirée, puis vaporisé et réchauffé dans des passages 58 de la ligne d'échange avant d'être évacué de l'installation via une conduite de production 59.Liquid oxygen withdrawn from the tank of the
On retrouve par ailleurs dans l'installation de la Figure 6 les conduites et accessoires habituels des installations à double colonne : une conduite 60 de remontée dans la colonne 51 du "liquide riche" (air enrichi en oxygène) recueilli en cuve de la colonne 50, avec sa vanne de détente 61, une conduite 62 de remontée en tête de la colonne 51 du "liquide pauvre" (azote à peu près pur) soutiré en tête de la colonne 50, avec sa vanne de détente 63, ainsi qu'une conduite 64 de production d'oxygène liquide, piquée en cuve de la colonne 51, qu'une conduite 65 de production d'azote liquide, piquée sur la conduite 62, et qu'une conduite 66 de soutirage d'azote impur, constituant le gaz résiduaire de l'installation, piquée en tête de la colonne 51, cet azote impur étant réchauffé dans le sous-refroidisseur 43 puis dans des passages 67 de la ligne d'échange avant d'être évacué via une conduite 68.In the installation in FIG. 6, we also find the usual pipes and accessories for double column installations: a
Comme on le voit sur la Figure 7, la température T1 d'admission de la turbine 46 est inférieure à la température du palier 69 de vaporisation de l'oxygène sous la pression de production, et l'on équilibre le bilan frigorifique de l'installation, afin de maintenir un faible écart de température au bout chaud de la ligne d'échange, en soutirant via les conduites 64 et/ou 65 certaines quantités d'azote liquide et/ou d'oxygène liquide, comme expliqué plus haut en regard des Figures 1 à 5. Lorsque la pression de l'air au refoulement du compresseur 44 est de l'ordre de 23 bars, cet équilibre s'obtient pour un soutirage de liquide de l'ordre de 5% du débit d'air traité.As seen in Figure 7, the temperature T1 of
De plus, la seconde haute pression précitée est d'une part inférieure à la pression de condensation de l'air par échange thermique avec l'oxygène en cours de vaporisation sous la pression de production, et d'autre part choisie de façon que l'air porté à cette seconde haute pression commence à se condenser à une température voisine de T1. Ceci assure un important apport de calories au voisinage de cette température T1 et permet à la turbine 46 de fonctionner dans de bonnes conditions, c'est-à-dire sans production de liquide à l'entrée de sa roue, tout en maintenant des écarts de température optimaux, de l'ordre de 2 à 3°C, au deux bouts de la ligne d'échange ainsi qu'à l'emplacement du palier de vaporisation 69.In addition, the aforementioned second high pressure is on the one hand lower than the condensation pressure of the air by heat exchange with the oxygen being vaporized under the production pressure, and on the other hand chosen so that the air brought to this second high pressure begins to condense at a temperature close to T1. This ensures a significant supply of calories in the vicinity of this temperature T1 and allows the
Il est à noter que le débit d'air surpressé qui est liquéfié dans les passages 56 est très inférieur à celui nécessaire pour vaporiser l'oxygène. Ce débit d'air liquéfié est en effet inférieur au débit d'oxygène à vaporiser et est juste suffisant pour éviter l'apparition de liquide à l'entrée de la roue de la turbine 46.It should be noted that the flow of compressed air which is liquefied in the
Si les paramètres de l'installation sont tels que la seconde haute pression de l'air est super-critique, c'est la pseudo-condensation de l'air qui doit intervenir au voisinage de la température T1.If the installation parameters are such that the second high air pressure is super-critical, it is the pseudo-condensation of the air which must intervene in the vicinity of temperature T1.
Dans le mode de réalisation de la Figure 8, le compresseur d'air 44 de l'installation comprime directement la totalité de l'air à la première haute pression de l'ordre de 23 bars, et un premier courant de cet air est traité comme précédemment dans les passages 53, la turbine 46 et la vanne de détente 54 puis envoyé à la base de la colonne 50.In the embodiment of Figure 8, the
En revanche, le reste de cet air est surpressé en deux étapes, par deux soufflantes montées en série : une première soufflante 70 qui, comme la soufflante 45 de la Figure 6, est couplée directement à la turbine 46, et une deuxième soufflante 71 directement couplée à une deuxième turbine de détente 72. L'air surpressé en 70 passe en totalité dans la soufflante 71 puis dans les passages 56 de la ligne d'échange 42, et une partie de cet air est sorti de la ligne d'échange à une température T2 supérieure à la température T1 pour être détendu dans la turbine 72. L'échappement de cette dernière, à la moyenne pression, est relié à la base de la colonne 50 comme celui de la turbine 46.However, the rest of this air is boosted in two stages, by two blowers connected in series: a
L'air à la plus haute pression non détendu dans la turbine 72 poursuit son refroidissement et est liquéfié dans les passages 56 jusqu'au bout froid de la ligne d'échange, puis est détendu dans des vannes de détente 57 et 57A et réparti entre les deux colonnes 50 et 51. La vanne 57A remplace la vanne 55 de la Figure 6.The air at the highest pressure which is not expanded in the
Comme on le voit sur la Figure 9, on peut choisir la température T2 légèrement au-dessus du palier 69 de vaporisation de l'oxygène. Compte-tenu du débit relativement faible de l'air détendu dans la turbine 72, on obtient une courbe de refroidissement d'air à peu près parallèle à la courbe de réchauffement de l'oxygène liquide et de l'azote gazeux de la température T2 au genou 73 de condensation ou de pseudo-condensation de l'air sous la plus haute pression.As can be seen in FIG. 9, the temperature T2 can be chosen slightly above the
L'installation de la Figure 10 diffère de la précédente par les points suivants.The installation of Figure 10 differs from the previous one in the following points.
D'une part, la totalité de l'air refroidi sous la première haute pression est détendu dans la turbine 46, c'est-à-dire que les passages 53 sont interrompus au niveau de température T1 et que la vanne de détente 54 est supprimée.On the one hand, all of the air cooled under the first high pressure is expanded in the
D'autre part, un débit d'air, prélevé entre les deux soufflantes 70 et 71, est refroidi et liquéfié dans des passages supplémentaires 74 de la ligne d'échange, jusqu'au bout froid de celle-ci, puis détendu à la moyenne pression dans une vanne de détente 75 et envoyé à la base de la colonne 50.On the other hand, an air flow, taken between the two
En variante, comme indiqué en trait mixte, la turbine 72 peut être alimentée par l'air circulant dans les passages 74, lesquels sont alors interrompus à la température T2. La vanne de détente 75 est alors supprimé, et c'est l'air circulant dans les passages 56 qui est en totalité liquéfié dans les passages 56 puis détendu à la moyenne pression dans la vanne de détente 57.As a variant, as indicated in phantom, the
Bien entendu, on peut envisager une combinaison des deux variantes ci-dessus.Of course, one can envisage a combination of the two variants above.
En variante encore, comme indiqué en trait interrompu sur la Figure 10, la pression d'air la plus haute peut être accrue en faisant passer l'air issu de la soufflante 71 dans une soufflante additionnelle 76 entraînée par un moteur électrique 77.In another variant, as indicated in broken lines in FIG. 10, the highest air pressure can be increased by passing the air coming from the
L'installation représentée à la Figure 11 est une variante de celle de la Figure 8. Elle n'en diffère que par le fait que l'échappement des deux turbines 46 et 72 débouche dans un séparateur de phases 78 dont le liquide et une partie de la phase vapeur sont envoyés en cuve de la colonne 50 tandis que le reste de la phase vapeur, après réchauffement partiel dans des passages 79 de la ligne d'échange, est détendu à la basse pression dans une turbine additionnelle 80 freinée par un frein approprié 81. L'air basse pression sortant de la turbine 80 est insufflé dans la colonne 51 via une conduite 82. Cette solution est applicable lorsque l'oxygène produit gazeux sous pression est à faible pureté (moins de 99,5%).The installation represented in FIG. 11 is a variant of that of FIG. 8. It differs from it only in that the exhaust of the two
Claims (17)
- Process for producing gaseous oxygen at a high oxygen pressure by distilling air in a double column installation (7), pumping (12) liquid oxygen withdrawn from the vessel of the low pressure column (9), and vaporizing (6) the compressed liquid oxygen by heat exchange, in a heat exchange line (6) of the installation, with air raised to a high air pressure, wherein the entirety of the air to be distilled is compressed to a high air pressure; a fraction of this air is expanded in a turbine (4) to the pressure of the medium pressure column (8), at an intermediate cooling temperature, characterized in that the air fraction is in excess in relation to the cooling requirements of the heat exchange line, the turbine (4) is retarded by an air compressor (5) and the temperature difference is reduced at the warm end of the exchange line by removing at least part of a liquid product from the installation.
- Process according to claim 1, characterized in that, for a high oxygen pressure less than about 13 bar, the high air pressure is selected to be the pressure for the condensation of air by heat exchange with oxygen during vaporisation at the high oxygen pressure.
- Process according to claim 1, characterized in that, for a high oxygen pressure greater than about 13 bar, a high air pressure is selected, whatever the high oxygen pressure, to be a pressure less than the pressure for the condensation of air by heat exchange with oxygen during vaporisation at the high oxygen pressure and equal to at least about 30 bar.
- Process according to claim 3, characterized in that the said high air pressure approaches 30 bar, the flow rate of the liquid product removed being of the order of 25 % of the production of gaseous oxygen at the high oxygen pressure.
- Process according to claim 1, characterized in that, for the production of gaseous oxygen at two different high oxygen pressures, less than and greater than about 13 bar respectively, the two streams of compressed liquid oxygen are vaporized by heat exchange with air compressed to a single high air pressure which is on the one hand less than the pressure for the condensation of air by heat exchange with oxygen during vaporisation at the higher oxygen pressure and, on the other hand, equal to at least about 30 bar, in particular to a high air pressure approaching 30 bar, and in any case greater than the pressure for the condensation of air by heat exchange with oxygen during vaporisation at the lower oxygen pressure.
- Process according to any one of claims 1 to 5, characterized in that the air is compressed in two stages, the final stage being carried out by means of the compressor (5) driven by the turbine (4).
- Process according to any one of claims 1 to 6, characterized in that liquid nitrogen under pressure, withdrawn from the double column (7) and possibly compressed by a pump (14), is also vaporized, in the heat exchange line (6), by heat exchange with air at the high air pressure.
- Process according to any one of claims 1 to 7, characterized in that part of the medium pressure air is, possibly after separation from its liquid phase, expanded to the low pressure in a second turbine and injected into the low pressure column (9).
- Process according to claim 8, characterized in that air expanded to the low pressure is bled from the vessel of the medium pressure column (8).
- Process for producing gaseous oxygen at a high oxygen pressure of at least about 13 bar by distilling air in a double column installation comprising a low pressure column (51) and a medium pressure column (50), pumping (49) liquid oxygen withdrawn from the vessel of the low pressure column (51), and vaporizing (42) compressed liquid oxygen by heat exchange with air raised to a high pressure markedly greater than the medium pressure, wherein the entirety of the air to be distilled is compressed to a first high pressure markedly greater than the medium pressure, and a first fraction of this air at the first high pressure is cooled (53) and, at an intermediate cooling temperature, at least part is expanded to the medium pressure in a turbine (46) before being introduced into the double column (41),
characterized in that the remainder of the air at the first high pressure is compressed to a second high pressure, at least part of the compressed air, the flow rate of which is less than the flow rate of liquid oxygen to be vaporized, being cooled and liquefied (56) and then, after expansion (57, 57A), introduced into the double column (41), the second high pressure being on the one hand less than the pressure for condensation or pseudo-condensation of the air by heat exchange with oxygen during vaporization at the high oxygen pressure and at least equal to about 30 bar and, on the other hand, chosen so that condensation or pseudo-condensation of air at this second high pressure occurs close to the entry temperature of the turbine (46) and the temperature difference is reduced at the warm end of a heat exchange line (6) by removing at least part of the liquid product (64, 65) from the installation. - Process according to claim 10, characterized in that the said increase in pressure is carried out by a blower (47) having a compression ratio less than 2.
- Process according to claim 11, characterized in that the blower (47) is driven by an external energy source (48) (figure 6).
- Process according to claim 10, characterized in that the said compression is carried out by two blowers (70, 71) in series, each coupled to an expansion turbine (46, 72), the first blower (70) being coupled to a second turbine (46) for expanding air at the first high pressure and the second blower (71) being coupled to the turbine (72) for expanding part of the compressed air, the entry temperature of the second turbine (72) being greater than that of the first turbine (46) (figures 8, 10 and 11).
- Process according to claim 13, characterized in that a stream of air is bled off between the two blowers (70, 71) and, at least in part, cooled and liquefied (74) and then, after expansion (75), introduced into the double column (41) (figure 10).
- Process according to claim 10, characterized in that the said compression is carried out by a blower (70) coupled to the turbine (46) for expanding air at the first high pressure, a first part of the compressed air being expanded in a second turbine (72) coupled to a second blower (71) fed by the remainder of the compressed air, the air coming from the second blower (71) being cooled and liquefied and then, after expansion (in 57) introduced into the double column (41) (figure 10).
- Process according to any one of claims 13 to 15, characterized in that the air coming from the second blower (71) is once again compressed by a third blower (76) driven by an external energy source (77) (figure 10).
- Process according to any one of claims 10 to 16, characterized in that part of the gaseous phase of the air coming from the, or each turbine (46, 72) is expanded to the low pressure in an additional turbine (80), and then injected into the low pressure column (51).
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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FR9102917 | 1991-03-11 | ||
FR9102917A FR2674011B1 (en) | 1991-03-11 | 1991-03-11 | PROCESS AND PLANT FOR PRODUCING PRESSURE GAS OXYGEN. |
FR9115935A FR2685460B1 (en) | 1991-12-20 | 1991-12-20 | PROCESS AND PLANT FOR THE PRODUCTION OF GASEOUS OXYGEN UNDER PRESSURE BY AIR DISTILLATION |
FR9115935 | 1991-12-20 |
Publications (2)
Publication Number | Publication Date |
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EP0504029A1 EP0504029A1 (en) | 1992-09-16 |
EP0504029B1 true EP0504029B1 (en) | 1996-10-23 |
Family
ID=26228561
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP92400600A Revoked EP0504029B1 (en) | 1991-03-11 | 1992-03-09 | Process for the production of gaseous pressurised oxygen |
Country Status (9)
Country | Link |
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US (1) | US5329776A (en) |
EP (1) | EP0504029B1 (en) |
JP (1) | JP2909678B2 (en) |
KR (1) | KR100210532B1 (en) |
AU (1) | AU655630B2 (en) |
CA (1) | CA2062506C (en) |
DE (1) | DE69214693T2 (en) |
ES (1) | ES2093799T3 (en) |
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US7197894B2 (en) | 2004-02-13 | 2007-04-03 | L'air Liquide, Societe Anonyme A' Directorie Et Conseil De Survelliance Pour L'etude Et, L'exploltation Des Procedes Georges, Claude | Integrated process and air separation process |
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- 1992-03-05 JP JP4048528A patent/JP2909678B2/en not_active Expired - Lifetime
- 1992-03-09 CA CA002062506A patent/CA2062506C/en not_active Expired - Lifetime
- 1992-03-09 DE DE69214693T patent/DE69214693T2/en not_active Expired - Lifetime
- 1992-03-09 EP EP92400600A patent/EP0504029B1/en not_active Revoked
- 1992-03-09 ES ES92400600T patent/ES2093799T3/en not_active Expired - Lifetime
- 1992-03-10 KR KR1019920003937A patent/KR100210532B1/en not_active IP Right Cessation
- 1992-03-10 AU AU12157/92A patent/AU655630B2/en not_active Expired
- 1992-03-10 ZA ZA921777A patent/ZA921777B/en unknown
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1993
- 1993-11-17 US US08/153,794 patent/US5329776A/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6038885A (en) * | 1997-07-30 | 2000-03-21 | Linde Aktiengesellschaft | Air separation process |
US7076971B2 (en) | 2003-02-13 | 2006-07-18 | L'Air Liquide, Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et l'Expolitation des Procédés Georges Claude | Method and installation for producing, in gaseous form and under high pressure, at least one fluid chosen from oxygen, argon and nitrogen by cryogenic distillation of air |
US7197894B2 (en) | 2004-02-13 | 2007-04-03 | L'air Liquide, Societe Anonyme A' Directorie Et Conseil De Survelliance Pour L'etude Et, L'exploltation Des Procedes Georges, Claude | Integrated process and air separation process |
DE102012017488A1 (en) | 2012-09-04 | 2014-03-06 | Linde Aktiengesellschaft | Method for building air separation plant, involves selecting air separation modules on basis of product specification of module set with different air pressure requirements |
Also Published As
Publication number | Publication date |
---|---|
AU1215792A (en) | 1992-09-17 |
KR100210532B1 (en) | 1999-07-15 |
ZA921777B (en) | 1992-11-25 |
CA2062506A1 (en) | 1992-09-12 |
JP2909678B2 (en) | 1999-06-23 |
DE69214693T2 (en) | 1997-02-20 |
JPH0579753A (en) | 1993-03-30 |
CA2062506C (en) | 2004-07-20 |
ES2093799T3 (en) | 1997-01-01 |
AU655630B2 (en) | 1995-01-05 |
KR920017943A (en) | 1992-10-21 |
DE69214693D1 (en) | 1996-11-28 |
EP0504029A1 (en) | 1992-09-16 |
US5329776A (en) | 1994-07-19 |
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