EP0982554A1 - Process and plant for producing impure oxygen by distillation - Google Patents
Process and plant for producing impure oxygen by distillation Download PDFInfo
- Publication number
- EP0982554A1 EP0982554A1 EP99402116A EP99402116A EP0982554A1 EP 0982554 A1 EP0982554 A1 EP 0982554A1 EP 99402116 A EP99402116 A EP 99402116A EP 99402116 A EP99402116 A EP 99402116A EP 0982554 A1 EP0982554 A1 EP 0982554A1
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- EP
- European Patent Office
- Prior art keywords
- oxygen
- column
- impure
- nitrogen
- impure oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000001301 oxygen Substances 0.000 title claims abstract description 54
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims description 23
- 238000004821 distillation Methods 0.000 title claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 19
- 229910052786 argon Inorganic materials 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000002407 reforming Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004401 flow injection analysis Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229940095054 ammoniac Drugs 0.000 description 1
- 150000001485 argon Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
- F25J3/04563—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating
- F25J3/04587—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating for the NH3 synthesis, e.g. for adjusting the H2/N2 ratio
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
- F25J3/04078—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression
- F25J3/04084—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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
- F25J3/04284—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams
- F25J3/0429—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams of feed air, e.g. used as waste or product air or expanded into an auxiliary column
- F25J3/04296—Claude expansion, i.e. expanded into the main or high pressure column
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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
- F25J3/04248—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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- 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
- F25J3/0446—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 the heat generated by mixing two different phases
- F25J3/04466—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 the heat generated by mixing two different phases for producing oxygen as a mixing column overhead gas by mixing gaseous air feed and liquid 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
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
- F25J3/04527—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general
- F25J3/04539—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general for the H2/CO synthesis by partial oxidation or oxygen consuming reforming processes of fuels
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/04—Processes or apparatus using separation by rectification in a dual pressure main column system
- F25J2200/06—Processes or apparatus using separation by rectification in a dual pressure main column system in a classical double column flow-sheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- 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
- F25J2215/00—Processes characterised by the type or other details of the product stream
- F25J2215/50—Oxygen or special cases, e.g. isotope-mixtures or low purity O2
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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
- F25J2235/50—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being oxygen
Definitions
- the present invention relates to a method and an installation for production of impure oxygen by air distillation.
- the impure oxygen typically contains from 1 to 5 mol% of argon. This argon accumulates in the synthesis loop and can cause losses of ammonia production and possible pollution during purges.
- J-B-74023997 describes the use of an air separation device for supply oxygen and nitrogen to an ammonia production unit.
- EP-A-0562893 describes a process using a double column to produce nitrogen containing less than 10 ppm in moles of oxygen for a medium to high purity ammonia and oxygen manufacturing unit, or 95 to 99.5 mol% for the production of hydrogen by reaction of oxygen on heavy hydrocarbons, hydrogen being intended to supply the same ammonia manufacturing unit.
- EP-A-0636845 describes a process in which oxygen pumped a double column is sent at the head of a mixing column.
- the process uses an intermediate pressure column of the so-called column type Etienne supplied with rich liquid from the medium pressure column and produces oxygen at 30 bar with 95% by mole of oxygen, 2% by mole nitrogen and 3% by mole of argon.
- EP-A-0531182 discloses a process using a mixing column operating at a pressure different from that of the medium pressure column to produce oxygen having a purity between 80 and 97 mol% oxygen.
- US-A-5490391 describes a process using a double column and a mixing column with a Claude turbine to provide cold to the device.
- a method of supplying of impure oxygen to a syngas production unit including synthesis is separated into a part enriched in hydrogen intended for a unit of ammonia synthesis characterized in that the impure oxygen comes from a air separation device by cryogenic distillation and contains from 70 to 98% in moles of oxygen and less than 2% in moles of argon.
- the impure oxygen contains from 1 to 30 mol% of nitrogen.
- the impure oxygen contains between 75 and 85 mol% of oxygen, it contains 15 to 25 mol% of nitrogen and less than 2 mol% of argon.
- the synthesis gas production unit can be a device for reforming or partial oxidation.
- a method of supply of impure oxygen to a syngas production unit including the synthesis gas is separated into a part enriched in hydrogen intended for an ammonia synthesis and nitrogen supply unit to the ammonia synthesis characterized in that impure oxygen and nitrogen come from an air separation device by cryogenic distillation and impure oxygen contains 70 to 98% in moles of oxygen and less than 2% in moles of argon.
- the syngas production unit produces synthesis gas which is separated into a part enriched in hydrogen intended for the synthesis of ammonia.
- the impurities in impure oxygen are essentially nitrogen which will take part in the synthesis reaction ammonia.
- the air is compressed to 6 bars in a compressor 1, is cooled in 3 and purified in water and carbon dioxide and hydrocarbons in the beds adsorbent 5. The air is then divided into three fractions. The first fraction 6 is cooled to its dew temperature in the exchanger 13 and sent to the medium pressure column 15 of a double column 14.
- the second fraction 8 is boosted by the booster 7 at 11 bars, cools in exchanger 13 and is sent to the bottom of a column of mixture 19.
- the third fraction 10 is boosted by the booster 9 to 8 bars, is cooled in 13 and expanded in the blowing turbine 11 before to be sent to the low pressure column 17 of the double column.
- the mixing column can be supplied to the tank by a flow withdrawn from the medium pressure column.
- a flow rate of 99 mol% of oxygen is withdrawn from the bottom of the low pressure column 14, pressurized to 11.8 bar by pump 21 and sent at the head of the mixing column 19.
- Impure oxygen gas flow 23 to 95 mol% oxygen, 4% nitrogen molars and 1 mol% argon is withdrawn at the top of the mixture and a flow 22 is drawn off at an intermediate level thereof and returned to the low pressure column.
- a flow of liquid nitrogen is drawn off at the top of the middle column pressure, pressurized by the pump 25 and sent (at 26) to the exchanger 13 where it vaporizes.
- Nitrogen can be compressed by a compressor.
- the process also produces low pressure nitrogen 33 withdrawn at the head of the minaret in column 17. This nitrogen flow can be sent at the ammonia synthesis unit.
- Impure nitrogen at low pressure is used to regenerate the beds adsorbents 5.
- a liquid flow 31 is sent from the mixing column to the column low pressure 17 a few trays above the flow injection point 22 and the flow injection point 10.
- FIG. 3 shows the steps of an ammonia production process according to the invention.
- An apparatus for air separation by cryogenic distillation 1 produces oxygen containing less than 1% argon and pure nitrogen.
- Oxygen is sent to unit 3 where hydrocarbons undergo a stage reforming or partial oxidation.
- the synthesis gas mixture is separated in a PSA 5 and the hydrogen by 6 is sent to the synthesis of ammonia 7 produced in 8 using the nitrogen 9 produced by the separation 1.
- Fraction 6 is sent to the medium pressure column 15 and the fraction 8 is compressed by compressor 7 with n stages.
- Fraction 10 is compressed by at most n-1 compressor stages 8 and then by booster 49, cooled in 13 and slackened in a Claude 41 turbine before being sent to the column medium pressure.
- the turbine 11, 41 can produce a flow which is at least partially liquid.
- the mixing column can operate at between 2 and 30 bar. She can operate at the same pressure as the low pressure column or at a pressure above or below this value.
- Figures 1, 2 and 4 can obviously include a argon column fed from the low pressure column.
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Separation By Low-Temperature Treatments (AREA)
Abstract
De l'oxygène impur contenant de 70 à 98% molaires d'oxygène et moins de 2% molaires d'argon est fourni à une unité de production de gaz de synthèse (3) qui fournit de l'hydrogène à une unité de production d'ammoniac (7). Le même appareil de séparation d'air (1) peut fournir l'azote (9) à l'unité de production d'ammoniac et de l'oxygène impur (2) à l'unité de production de gaz de synthèse. <IMAGE>Impure oxygen containing 70 to 98 mol% of oxygen and less than 2 mol% of argon is supplied to a synthesis gas production unit (3) which supplies hydrogen to a production unit d 'ammonia (7). The same air separation device (1) can supply nitrogen (9) to the ammonia production unit and impure oxygen (2) to the synthesis gas production unit. <IMAGE>
Description
La présente invention est relative à un procédé et une installation de production d'oxygène impur par distillation d'air.The present invention relates to a method and an installation for production of impure oxygen by air distillation.
De l'oxygène impur est souvent utilisé pour la production de gaz de synthèse par oxydation partielle ou reformage. Le gaz de synthèse est séparé par PSA pour produire de l'hydrogène qui est mélangé avec de l'azote pour la synthèse d'ammoniac.Unclean oxygen is often used for the production of synthesis by partial oxidation or reforming. Synthesis gas is separated by PSA to produce hydrogen which is mixed with nitrogen for the ammonia synthesis.
L'oxygène impur contient typiquement de 1 à 5 % en moles d'argon. Cet argon s'accumule dans la boucle de synthèse et peut entraíner des pertes de production d'ammoniac et des pollutions éventuelles à l'occasion des purges.The impure oxygen typically contains from 1 to 5 mol% of argon. This argon accumulates in the synthesis loop and can cause losses of ammonia production and possible pollution during purges.
J-B-74023997 décrit l'usage d'un appareil de séparation d'air pour fournir de l'oxygène et de l'azote à une unité de production d'ammoniac.J-B-74023997 describes the use of an air separation device for supply oxygen and nitrogen to an ammonia production unit.
EP-A-0562893 décrit un procédé utilisant une double colonne pour produire de l'azote contenant moins de 10 ppm en moles d'oxygène pour une unité de fabrication d'ammoniac et de l'oxygène de pureté moyenne à haute, soit 95 à 99,5 % en moles pour la production d'hydrogène par réaction de l'oxygène sur des hydrocarbures lourdes, l'hydrogène étant destiné à alimenter la même unité de fabrication d'ammoniac.EP-A-0562893 describes a process using a double column to produce nitrogen containing less than 10 ppm in moles of oxygen for a medium to high purity ammonia and oxygen manufacturing unit, or 95 to 99.5 mol% for the production of hydrogen by reaction of oxygen on heavy hydrocarbons, hydrogen being intended to supply the same ammonia manufacturing unit.
Evidemment le problème lié à la présence d'argon en moles d'oxygène contenant moins de 1 % en moles d'argon mais ceci augmente les coûts de production.Obviously the problem linked to the presence of argon in moles of oxygen containing less than 1% by mole of argon but this increases the costs of production.
Un procédé de ce genre est décrit dans la demande FR 97 04083 au nom de la demanderesse qui n'a pas encore été publiée.A process of this kind is described in application FR 97 04083 in name of the applicant which has not yet been published.
Il est connu de produire de l'oxygène impur utilisant une double colonne et une colonne de mélange.It is known to produce impure oxygen using a double column and a mixing column.
EP-A-0636845 décrit un procédé dans lequel de l'oxygène pompé d'une double colonne est envoyé en tête d'une colonne de mélange. Le procédé utilise une colonne à pression intermédiaire du type dit colonne Etienne alimentée par du liquide riche de la colonne moyenne pression et produit de l'oxygène à 30 bar avec 95 % en moles d'oxygène, 2 % en moles d'azote et 3 % en moles d'argon.EP-A-0636845 describes a process in which oxygen pumped a double column is sent at the head of a mixing column. The process uses an intermediate pressure column of the so-called column type Etienne supplied with rich liquid from the medium pressure column and produces oxygen at 30 bar with 95% by mole of oxygen, 2% by mole nitrogen and 3% by mole of argon.
EP-A-0531182 divulgue un procédé utilisant une colonne de mélange opérant à une pression différente de celle de la colonne moyenne pression pour produire de l'oxygène ayant une pureté entre 80 et 97 % en moles d'oxygène.EP-A-0531182 discloses a process using a mixing column operating at a pressure different from that of the medium pressure column to produce oxygen having a purity between 80 and 97 mol% oxygen.
US-A-5490391 décrit un procédé utilisant une double colonne et une colonne de mélange avec une turbine Claude pour fournir du froid à l'appareil.US-A-5490391 describes a process using a double column and a mixing column with a Claude turbine to provide cold to the device.
Selon un objet de l'invention, il est prévu un procédé de fourniture d'oxygène impur à une unité de production de gaz de synthèse dont le gaz de synthèse est séparé en une partie enrichie en hydrogène destinée à une unité de synthèse d'ammoniac caractérisé en ce que l'oxygène impur provient d'un appareil de séparation d'air par distillation cryogénique et contient de 70 à 98 % en moles d'oxygène et moins de 2 % en moles d'argon.According to an object of the invention, there is provided a method of supplying of impure oxygen to a syngas production unit including synthesis is separated into a part enriched in hydrogen intended for a unit of ammonia synthesis characterized in that the impure oxygen comes from a air separation device by cryogenic distillation and contains from 70 to 98% in moles of oxygen and less than 2% in moles of argon.
De préférence l'oxygène impur contient de 1 à 30 % en moles d'azote.Preferably the impure oxygen contains from 1 to 30 mol% of nitrogen.
Si l'oxygène impur contient entre 75 et 85 % en moles d'oxygène, il contient de 15 à 25 % en moles d'azote et moins de 2% en moles d'argon.If the impure oxygen contains between 75 and 85 mol% of oxygen, it contains 15 to 25 mol% of nitrogen and less than 2 mol% of argon.
Dans un procédé de séparation d'air pour produire l'oxygène impur, on envoie de l'air dans une colonne moyenne pression d'une double colonne de l'appareil de séparation d'air, on envoie un liquide enrichi en oxygène et un liquide enrichi en azote de la colonne moyenne pression à une colonne basse pression de la double colonne, on envoie de l'air en cuve d'une colonne de mélange, on envoie un liquide enrichi en oxygène de la colonne basse pression à la tête de la colonne de mélange et on soutire l'oxygène impur comme produit en tête de la colonne de mélange.In an air separation process to produce impure oxygen, we sends air into a medium pressure column from a double column of the air separation device, we send an oxygen-enriched liquid and a liquid enriched in nitrogen from the medium pressure column to a low column pressure of the double column, we send air to the tank of a column of mixture, we send an oxygen-enriched liquid from the lower column pressure at the head of the mixing column and the impure oxygen is drawn off as product at the top of the mixing column.
L'unité de production de gaz de synthèse peut être un appareil à reformage ou à oxydation partielle.The synthesis gas production unit can be a device for reforming or partial oxidation.
Selon un autre objet de l'invention, il est prévu un procédé de fourniture d'oxygène impur à une unité de production de gaz de synthèse dont le gaz de synthèse est séparé en une partie enrichie en hydrogène destinée à une unité de synthèse d'ammoniac et de fourniture d'azote à l'unité de synthèse d'ammoniac caractérisé en ce que l'oxygène impur et l'azote proviennent d'un appareil de séparation d'air par distillation cryogénique et l'oxygène impur contient de 70 à 98 % en moles d'oxygène et moins de 2 % en moles d'argon.According to another object of the invention, there is provided a method of supply of impure oxygen to a syngas production unit including the synthesis gas is separated into a part enriched in hydrogen intended for an ammonia synthesis and nitrogen supply unit to the ammonia synthesis characterized in that impure oxygen and nitrogen come from an air separation device by cryogenic distillation and impure oxygen contains 70 to 98% in moles of oxygen and less than 2% in moles of argon.
L'invention sera maintenant décrite plus en détails avec des références aux figures dans lesquelles
- les Figures 1, 2 et 4 sont des diagrammes schématiques de procédés de fourniture d'oxygène impur selon l'invention ;
- la Figure 3 est un schéma simplifié d'un procédé de synthèse d'ammoniac comprenant un procédé de fourniture d'oxygène impur selon l'invention.
- Figures 1, 2 and 4 are schematic diagrams of methods for supplying impure oxygen according to the invention;
- Figure 3 is a simplified diagram of a process for synthesizing ammonia comprising a process for supplying impure oxygen according to the invention.
Préférablement, l'unité de production de gaz de synthèse produit du gaz de synthèse qui est séparé en une partie enrichie en hydrogène destiné à la synthèse d'ammoniac. Les impuretés contenues dans l'oxygène impur sont essentiellement de l'azote qui va prendre part à la réaction de synthèse d'ammoniac.Preferably, the syngas production unit produces synthesis gas which is separated into a part enriched in hydrogen intended for the synthesis of ammonia. The impurities in impure oxygen are essentially nitrogen which will take part in the synthesis reaction ammonia.
Un exemple de mise en oeuvre de l'invention va maintenant être décrit en regard du dessin annexé, dont la figure représente schématiquement une installation de production d'oxygène impur pour réaliser un procédé conforme à l'invention.An example of implementation of the invention will now be described. opposite the appended drawing, the figure of which schematically represents a installation for the production of impure oxygen to carry out a process in accordance with the invention.
Tout l'air est comprimé à 6 bars dans un compresseur 1, est refroidi en
3 et épuré en eau et en dioxyde de carbone et hydrocarbures dans les lits
d'adsorbant 5. L'air est ensuite divisé en trois fractions. La première fraction 6
est refroidie à sa température de rosée dans l'échangeur 13 et envoyée à la
colonne moyenne pression 15 d'une double colonne 14.All the air is compressed to 6 bars in a compressor 1, is cooled in
3 and purified in water and carbon dioxide and hydrocarbons in the beds
adsorbent 5. The air is then divided into three fractions. The first fraction 6
is cooled to its dew temperature in the
La deuxième fraction 8 est surpressée par le surpresseur 7 à 11 bars,
se refroidit dans l'échangeur 13 et est envoyée en cuve d'une colonne de
mélange 19. La troisième fraction 10 est surpressée par le surpresseur 9 à 8
bars, est refroidie en 13 et détendue dans la turbine d'insufflation 11 avant
d'être envoyée à la colonne basse pression 17 de la double colonne.
Alternativement la colonne de mélange peut être alimentée en cuve par un
débit soutiré de la colonne moyenne pression.The
Un débit de 99 % en moles d'oxygène est soutiré en cuve de la
colonne basse pression 14, pressurisé à 11,8 bars par la pompe 21 et envoyé
en tête de la colonne de mélange 19.A flow rate of 99 mol% of oxygen is withdrawn from the bottom of the
Un débit gazeux d'oxygène impur 23 à 95 % molaires d'oxygène, 4 %
molaires d'azote et 1 % molaire d'argon est soutiré en tête de la colonne de
mélange et un débit 22 est soutiré à un niveau intermédiaire de celle-ci et
renvoyé à la colonne basse pression.Impure oxygen gas flow 23 to 95 mol% oxygen, 4%
nitrogen molars and 1 mol% argon is withdrawn at the top of the
mixture and a
Un débit d'azote liquide est soutiré en tête de la colonne moyenne
pression, pressurisé par la pompe 25 et envoyé (en 26) à l'échangeur 13 où il
se vaporise.A flow of liquid nitrogen is drawn off at the top of the middle column
pressure, pressurized by the
Il va de soi que cette vaporisation n'est pas essentielle au procédé. L'azote peut être comprimé par un compresseur.It goes without saying that this vaporization is not essential to the process. Nitrogen can be compressed by a compressor.
Le procédé permet également de produire de l'azote basse pression 33
soutiré en tête du minaret de la colonne 17. Ce débit d'azote peut être envoyé
à l'unité de synthèse d'ammoniac.The process also produces low pressure nitrogen 33
withdrawn at the head of the minaret in
De l'azote impur à la basse pression sert à régénérer les lits
d'adsorbants 5.Impure nitrogen at low pressure is used to regenerate the
Un débit liquide 31 est envoyé de la colonne de mélange à la colonne
basse pression 17 quelques plateaux au-dessus du point d'injection du débit
22 et du point d'injection du débit 10.A
Il peut être avantageux de renvoyer le débit de cuve de la colonne de mélange plutôt à la colonne moyenne pression si la colonne de mélange opère à une pression supérieure à celle à laquelle opère la colonne moyenne pression (voir Figure 2, débit 30).It may be advantageous to return the tank flow from the mix rather with the medium pressure column if the mixing column operates at a pressure higher than that at which the middle column operates pressure (see Figure 2, flow 30).
La figure 3 montre les étapes d'un procédé de production d'ammoniac
selon l'invention. Un appareil de séparation d'air par distillation cryogénique 1
produit de l'oxygène contenant moins de 1 % d'argon et de l'azote pur.
L'oxygène est envoyé à une unité 3 où des hydrocarbures subissent une étape
de reforming ou d'oxydation partielle. Le mélange de gaz de synthèse est
séparé dans un PSA 5 et l'hydrogène par 6 est envoyé au synthèse
d'ammoniac 7 produit en 8 en utilisant l'azote 9 produit par l'appareil de
séparation 1.Figure 3 shows the steps of an ammonia production process
according to the invention. An apparatus for air separation by cryogenic distillation 1
produces oxygen containing less than 1% argon and pure nitrogen.
Oxygen is sent to
Dans la figure 4, le débit d'air à 6 bars est divisé en trois. La fraction 6
est envoyée à la colonne moyenne pression 15 et la fraction 8 est comprimé
par le compresseur 7 à n étages. La fraction 10 est comprimée par au plus n-1
étages du compresseur 8 et ensuite par le booster 49, refroidie en 13 et
détendue dans une turbine Claude 41 avant être envoyée à la colonne
moyenne pression.In Figure 4, the air flow at 6 bar is divided into three. Fraction 6
is sent to the
La turbine 11, 41 peut produire un débit qui est au moins partiellement
liquide.The
La colonne de mélange peut opérer à entre 2 et 30 bar. Elle peut fonctionner à la même pression que la colonne basse pression ou à une pression au-dessus ou au-dessous de cette valeur.The mixing column can operate at between 2 and 30 bar. She can operate at the same pressure as the low pressure column or at a pressure above or below this value.
L'installation des figures 1, 2 et 4 peut évidemment comprendre une colonne argon alimentée à partir de la colonne basse pression.The installation of Figures 1, 2 and 4 can obviously include a argon column fed from the low pressure column.
Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9810813A FR2782787B1 (en) | 1998-08-28 | 1998-08-28 | PROCESS AND PLANT FOR PRODUCING IMPURED OXYGEN BY AIR DISTILLATION |
FR9810813 | 1998-08-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0982554A1 true EP0982554A1 (en) | 2000-03-01 |
Family
ID=9529954
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99402116A Withdrawn EP0982554A1 (en) | 1998-08-28 | 1999-08-25 | Process and plant for producing impure oxygen by distillation |
Country Status (4)
Country | Link |
---|---|
US (1) | US6247333B1 (en) |
EP (1) | EP0982554A1 (en) |
JP (1) | JP2000203827A (en) |
FR (1) | FR2782787B1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7238215B2 (en) | 2000-12-27 | 2007-07-03 | L'Air Liquide, Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procédés Georges Claude | Integrated process and installation for the production of synthesis gas |
EP3557166A1 (en) | 2018-04-19 | 2019-10-23 | Linde Aktiengesellschaft | Method for the low-temperature decomposition of air and air separation plant |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2861841B1 (en) * | 2003-11-04 | 2006-06-30 | Air Liquide | METHOD AND APPARATUS FOR AIR SEPARATION BY CRYOGENIC DISTILLATION |
FR2862128B1 (en) * | 2003-11-10 | 2006-01-06 | Air Liquide | PROCESS AND INSTALLATION FOR SUPPLYING HIGH-PURITY OXYGEN BY CRYOGENIC AIR DISTILLATION |
Citations (6)
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EP0367428A1 (en) * | 1988-10-15 | 1990-05-09 | The BOC Group plc | Air separation |
EP0531182A1 (en) * | 1991-08-07 | 1993-03-10 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and plant for distilling air and application in the feeding of gas to steel plants |
EP0562893A1 (en) * | 1992-03-24 | 1993-09-29 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and apparatus for the production of high pressure nitrogen and oxygen |
EP0636845A1 (en) * | 1993-04-30 | 1995-02-01 | The BOC Group plc | Air separation |
US5704228A (en) * | 1995-03-15 | 1998-01-06 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and device for the evaporation of a liquid flow |
US5775128A (en) * | 1997-05-02 | 1998-07-07 | Praxair Technology, Inc. | Process for producing ammonia and recovering argon using low purity oxygen |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4863707A (en) * | 1982-09-30 | 1989-09-05 | Engelhard Corporation | Method of ammonia production |
US5740673A (en) * | 1995-11-07 | 1998-04-21 | Air Products And Chemicals, Inc. | Operation of integrated gasification combined cycle power generation systems at part load |
US5666823A (en) * | 1996-01-31 | 1997-09-16 | Air Products And Chemicals, Inc. | High pressure combustion turbine and air separation system integration |
-
1998
- 1998-08-28 FR FR9810813A patent/FR2782787B1/en not_active Expired - Fee Related
-
1999
- 1999-08-25 EP EP99402116A patent/EP0982554A1/en not_active Withdrawn
- 1999-08-27 JP JP11241791A patent/JP2000203827A/en active Pending
- 1999-08-30 US US09/384,981 patent/US6247333B1/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0367428A1 (en) * | 1988-10-15 | 1990-05-09 | The BOC Group plc | Air separation |
EP0531182A1 (en) * | 1991-08-07 | 1993-03-10 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and plant for distilling air and application in the feeding of gas to steel plants |
EP0562893A1 (en) * | 1992-03-24 | 1993-09-29 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and apparatus for the production of high pressure nitrogen and oxygen |
EP0636845A1 (en) * | 1993-04-30 | 1995-02-01 | The BOC Group plc | Air separation |
US5704228A (en) * | 1995-03-15 | 1998-01-06 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and device for the evaporation of a liquid flow |
US5775128A (en) * | 1997-05-02 | 1998-07-07 | Praxair Technology, Inc. | Process for producing ammonia and recovering argon using low purity oxygen |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7238215B2 (en) | 2000-12-27 | 2007-07-03 | L'Air Liquide, Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procédés Georges Claude | Integrated process and installation for the production of synthesis gas |
EP3557166A1 (en) | 2018-04-19 | 2019-10-23 | Linde Aktiengesellschaft | Method for the low-temperature decomposition of air and air separation plant |
US11602713B2 (en) | 2018-04-19 | 2023-03-14 | Linde Aktiengesellschaft | Method for cryogenic separation of air, and air separation plant |
Also Published As
Publication number | Publication date |
---|---|
FR2782787B1 (en) | 2000-09-29 |
JP2000203827A (en) | 2000-07-25 |
FR2782787A1 (en) | 2000-03-03 |
US6247333B1 (en) | 2001-06-19 |
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