EP0562893A1 - Verfahren und Apparat zur Herstellung von Hochdruck-Stickstoff und Sauerstoff - Google Patents

Verfahren und Apparat zur Herstellung von Hochdruck-Stickstoff und Sauerstoff Download PDF

Info

Publication number
EP0562893A1
EP0562893A1 EP93400522A EP93400522A EP0562893A1 EP 0562893 A1 EP0562893 A1 EP 0562893A1 EP 93400522 A EP93400522 A EP 93400522A EP 93400522 A EP93400522 A EP 93400522A EP 0562893 A1 EP0562893 A1 EP 0562893A1
Authority
EP
European Patent Office
Prior art keywords
nitrogen
pressure
oxygen
compressor
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.)
Granted
Application number
EP93400522A
Other languages
English (en)
French (fr)
Other versions
EP0562893B1 (de
EP0562893B2 (de
Inventor
Yves Koeberle
Jean-Pierre Tranier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=9427994&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0562893(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP0562893A1 publication Critical patent/EP0562893A1/de
Publication of EP0562893B1 publication Critical patent/EP0562893B1/de
Application granted granted Critical
Publication of EP0562893B2 publication Critical patent/EP0562893B2/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • F25J3/04109—Arrangements of compressors and /or their drivers
    • F25J3/04145—Mechanically coupling of different compressors of the air fractionation process to the same driver(s)
    • 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
    • F25J3/04012—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of warm gaseous streams; details of intake or interstage cooling
    • F25J3/04018—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of warm gaseous streams; details of intake or interstage cooling of main feed air
    • 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
    • F25J3/04012—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of warm gaseous streams; details of intake or interstage cooling
    • F25J3/0403—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of warm gaseous streams; details of intake or interstage cooling of nitrogen
    • 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
    • F25J3/0409—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
    • 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
    • F25J3/04109—Arrangements of compressors and /or their drivers
    • F25J3/04115—Arrangements of compressors and /or their drivers characterised by the type of prime driver, e.g. hot gas expander
    • F25J3/04121—Steam turbine as the prime mechanical driver
    • 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
    • F25J3/04309—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 nitrogen
    • F25J3/04315—Lowest pressure or impure nitrogen, so-called waste nitrogen expansion
    • 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
    • F25J3/04333—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using quasi-closed loop internal vapor compression refrigeration cycles, e.g. of intermediate or oxygen enriched (waste-)streams
    • F25J3/04351—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using quasi-closed loop internal vapor compression refrigeration cycles, e.g. of intermediate or oxygen enriched (waste-)streams of nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04406—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system
    • F25J3/04412—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system in a classical double column flowsheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
    • 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
    • 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
    • F25J3/04545—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 for the gasification of solid or heavy liquid fuels, e.g. integrated gasification combined cycle [IGCC]
    • 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
    • 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
    • F25J2200/20—Processes or apparatus using separation by rectification in an elevated pressure multiple column system wherein the lowest pressure column is at a pressure well above the minimum pressure needed to overcome pressure drop to reject the products to atmosphere
    • 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
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/50—Processes or apparatus involving steps for increasing the pressure of gaseous process streams the fluid being oxygen
    • 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
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/12—Particular process parameters like pressure, temperature, ratios

Definitions

  • the present invention relates to the production of nitrogen and oxygen by air distillation. It relates firstly to a process for the simultaneous production on the one hand of pure nitrogen under a high nitrogen pressure greater than about 25 bar absolute, and on the other hand of oxygen, by air distillation in a double column distillation comprising a medium pressure column and a low pressure column of the "minaret" type producing pure nitrogen at the head.
  • a particular application of the invention is the simultaneous production of a share of high purity nitrogen, containing less than 10 ppm of oxygen, in large quantity (that is to say representing at least 20% and typically more 30% of the treated air flow), under 50 to 60 bars, for a unit for manufacturing ammonia, and on the other hand oxygen of medium to high purity, ie 95 to 99.5% in moles, at a pressure of the order of 65 bars and with a high extraction yield, for the production of hydrogen by reaction of oxygen with heavy hydrocarbons, the hydrogen being intended to supply the same production unit for ammonia.
  • Low pressure column of the minaret type is understood to mean a low pressure column, forming part of a double air distillation column, the upper end part of which is supplied at the top with “upper lean liquid” (nitrogen practically pure) withdrawn at the head of the medium pressure column and relaxed, and produces pure nitrogen at the head at low pressure.
  • the object of the invention is to provide a process allowing the production, in addition to oxygen, of nitrogen under high pressure in large quantity, that is to say representing at least 20% of the flow of treated air, with a reduced investment.
  • the method according to the invention is characterized in that after heating the nitrogen from the low pressure column, it is compressed at high pressure by means of a single nitrogen compressor of centrifugal type having at most six compression wheels, and the low pressure column is operated under a pressure of the order of P N / ⁇ N or P N denotes the high nitrogen pressure and ⁇ N the compression ratio of said compressor d 'nitrogen.
  • the invention also relates to an installation intended for the implementation of such a method.
  • This installation comprises an air compressor adapted to bring the air to be treated at a medium pressure greater than 6 bar absolute, and a single nitrogen compressor body of the centrifugal type having at most six compression wheels and the suction of the first wheel is connected to the head of the minaret of the low pressure column, this column operating under low pressure of the order of P N / ⁇ N , or P N denotes the high nitrogen pressure and ⁇ N the compression ratio of said nitrogen compressor.
  • the nitrogen compressor and the air compressor can in particular be connected to a common power source.
  • the installation shown in the drawings is intended to produce on the one hand, under 55 bars, high purity nitrogen gas (typically containing less than 10 ppm of oxygen), in a flow rate at least equal to 20% of the flow rate of treated air, and on the other hand, at 65 bars, oxygen having a purity of 95 to 99.5%, with a high extraction yield.
  • high purity nitrogen gas typically containing less than 10 ppm of oxygen
  • oxygen having a purity of 95 to 99.5% oxygen having a purity of 95 to 99.5%
  • the installation essentially comprises an air compressor 1, an apparatus 2 for purifying the air by adsorption, a heat exchange line 3 of the counter-current type, a double distillation column 4, an expansion turbine. 5, a liquid oxygen pump 6, a nitrogen compressor 7, an oxygen compressor 8 and an energy source 9 constituted for example by a steam turbine.
  • the double column 4 comprises a medium pressure column 10 surmounted by a low pressure column 11 whose upper end part forms a minaret 11A for producing pure nitrogen under low pressure.
  • a condenser-vaporizer 12 puts the overhead vapor (practically pure nitrogen) from column 10 into heat exchange relationship with the tank liquid (oxygen from determined purity) of column 11.
  • a pipe fitted with an expansion valve 13 makes it possible to raise the "rich liquid” (oxygen-enriched air) from the tank of the column 10 to an intermediate point of the column 11;
  • a pipe fitted with an expansion valve 14 makes it possible to raise "lower lean liquid” (impure nitrogen) from an intermediate point of the column 10 at the base of the minaret 11A;
  • a pipe fitted with an expansion valve 15 makes it possible to raise "upper lean liquid” (practically pure nitrogen) from the head of the column 10 to the top of the minaret.
  • the nitrogen compressor 7 consists of a single three-stage compressor.
  • the first two stages each include two compression wheels and have average compression ratios per wheel of 2 and 1.73 respectively, while the third stage comprises a single compression wheel having a compression ratio of 1.83.
  • the overall compression ratio of the compressor is therefore 22.
  • Each wheel has a coolant at its outlet.
  • the oxygen compressor 8 also consists of a single compressor. This compressor has six wheels with an average compression ratio per wheel of 1.37. The overall compression ratio is therefore 6.5.
  • the shaft 16 of the compressor 7 is coupled to the shaft 17 of the compressor 1 by a coupling 18, and the assembly is driven by the common energy source 9.
  • the shaft 16 can drive the different stages of the compressor 7 by means of speed multipliers suitable for each stage.
  • the compressor 8 is driven by a separate energy source 19.
  • the low pressure is chosen so that, multiplied by the compression ratio of the compressor 7, it provides the desired high production pressure for nitrogen.
  • this corresponds to an average pressure of the order of 11 bars.
  • the incoming air is compressed to 11 bars in the compressor 1, purified in 2, cooled from the hot end to the cold end of the exchange line 3, and introduced in the vicinity of its dew point in the tank of the column 10
  • the low pressure pure nitrogen leaving the gaseous top of the minaret 11A and warmed to room temperature from the cold end to the hot end of the exchange line is introduced at the suction of the first stage of the compressor 7, with the possible exception of a flow of nitrogen produced at low pressure via a pipe 20.
  • the high pressure nitrogen is produced at the outlet of the third stage of the compressor and discharged via a pipe 21.
  • Compressor 7 is also used as a nitrogen cycle compressor. Indeed, medium pressure nitrogen is drawn off at the top of the column 10, via a line 22, warmed to ambient temperature in the exchange line and introduced via a line 23 at the suction of the second stage of the compressor 7 Nitrogen at high cycle pressure is discharged at the outlet of this second stage via a line 24, cooled, liquefied and sub-cooled in the exchange line, expanded to medium pressure in an expansion valve 25 and introduced at the top of column 10.
  • the nitrogen flow circulating in line 24 is greater by a predetermined amount than the nitrogen flow circulating in line 23.
  • the difference constitutes an additional liquid nitrogen flow, said rectification support, introduced in reflux at the top of column 10. This flow rate is taken from the low pressure nitrogen stream sucked in by the first stage of the compressor 7.
  • Impure nitrogen constituting the residual gas of the installation, is drawn off at the base of the minaret 11A via a pipe 25, heated to an intermediate temperature in the exchange line, taken out of the latter, expanded to atmospheric pressure in a turbine 5 which keeps the installation cold, then reintroduced into the exchange line, warmed up to room temperature, and finally used to regenerate the adsorption bottles of the device 2 and evacuated from installation via a pipe 26.
  • Oxygen at 65 bar is produced as follows.
  • the desired liquid oxygen flow rate is withdrawn from the bottom of the column 11, brought by the pump 6 to an intermediate pressure of oxygen, vaporized and warmed to room temperature in the exchange line 3, then compressed to the pressure of compressor production 8.
  • the vaporization of the liquid oxygen under the intermediate oxygen pressure is effected by condensation of the nitrogen under the high cycle pressure, with a subcritical value for this high pressure, for example 30 bars. This value corresponds to a vaporization of liquid oxygen at about 11 bars, which is therefore the pressure supplied by the pump 6.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Separation By Low-Temperature Treatments (AREA)
EP93400522A 1992-03-24 1993-03-02 Verfahren zur Herstellung von Hochdruck-Stickstoff und Sauerstoff Expired - Lifetime EP0562893B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9203501A FR2689224B1 (fr) 1992-03-24 1992-03-24 Procede et installation de production d'azote sous haute pression et d'oxygene.
FR9203501 1992-03-24

Publications (3)

Publication Number Publication Date
EP0562893A1 true EP0562893A1 (de) 1993-09-29
EP0562893B1 EP0562893B1 (de) 1997-05-07
EP0562893B2 EP0562893B2 (de) 2000-12-20

Family

ID=9427994

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93400522A Expired - Lifetime EP0562893B2 (de) 1992-03-24 1993-03-02 Verfahren zur Herstellung von Hochdruck-Stickstoff und Sauerstoff

Country Status (7)

Country Link
US (1) US5341647A (de)
EP (1) EP0562893B2 (de)
CA (1) CA2092140C (de)
DE (1) DE69310429T3 (de)
ES (1) ES2101256T5 (de)
FR (1) FR2689224B1 (de)
ZA (1) ZA932796B (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0834712A2 (de) * 1996-10-01 1998-04-08 Air Products And Chemicals, Inc. Verfahren zur Herstellung von Hochdruck-Stickstoff mit Hilfe einer Kolonne unter höherem Druck und ein oder mehrere Kolonnen unter niedrigerem Druck
EP0982554A1 (de) * 1998-08-28 2000-03-01 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Verfahren und Anlage zur Herstellung von unreinem Sauerstoff durch Rektifikation
EP1120616A2 (de) * 2000-01-28 2001-08-01 The BOC Group plc Verfahren zur Luftzerlegung
WO2003016676A1 (en) 2001-08-15 2003-02-27 Shell Internationale Research Maatschappij B.V. Tertiary oil recovery combined with gas conversion process
US6871513B2 (en) 2000-10-30 2005-03-29 L'Air Liquide, Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procédés Georges Claude Process and installation for separation of air by cryogenic distillation integrated with an associated process
EP3059536A1 (de) * 2015-02-19 2016-08-24 Linde Aktiengesellschaft Verfahren und Vorrichtung zur Gewinnung eines Druckstickstoffprodukts
CN106489059A (zh) * 2014-07-05 2017-03-08 林德股份公司 以可变能耗低温分离空气的方法和设备

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2703140B1 (fr) * 1993-03-23 1995-05-19 Air Liquide Procédé et installation de production d'oxygène gazeux et/ou d'azote gazeux sous pression par distillation de l'air.
US5471843A (en) * 1993-06-18 1995-12-05 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process and installation for the production of oxygen and/or nitrogen under pressure at variable flow rate
FR2706595B1 (fr) * 1993-06-18 1995-08-18 Air Liquide Procédé et installation de production d'oxygène et/ou d'azote sous pression à débit variable.
US5460003A (en) * 1994-06-14 1995-10-24 Praxair Technology, Inc. Expansion turbine for cryogenic rectification system
US5689975A (en) * 1995-10-11 1997-11-25 The Boc Group Plc Air separation
US5600970A (en) * 1995-12-19 1997-02-11 Praxair Technology, Inc. Cryogenic rectification system with nitrogen turboexpander heat pump
GB9618576D0 (en) * 1996-09-05 1996-10-16 Boc Group Plc Air separation
GB9618577D0 (en) * 1996-09-05 1996-10-16 Boc Group Plc Air separation
GB9619717D0 (en) * 1996-09-20 1996-11-06 Boc Group Plc Air separation
GB9619718D0 (en) * 1996-09-20 1996-11-06 Boc Group Plc Air separation
GB9810587D0 (en) * 1998-05-15 1998-07-15 Cryostar France Sa Pump
GB9903908D0 (en) * 1999-02-19 1999-04-14 Boc Group Plc Air separation
US6192707B1 (en) * 1999-11-12 2001-02-27 Praxair Technology, Inc. Cryogenic system for producing enriched air
DE10013075A1 (de) * 2000-03-17 2001-09-20 Linde Ag Verfahren zur Gewinnung von gasförmigem und flüssigem Stickstoff mit variablem Anteil des Flüssigprodukts
EP1678275A1 (de) * 2003-10-29 2006-07-12 Shell Internationale Researchmaatschappij B.V. Verfahren zur förderung methanols oder eines kohlenwasserstoffs
FR2863348B1 (fr) * 2003-12-05 2006-12-22 Air Liquide Compresseur de gaz, appareil de separation d'un melange gazeux incorporant un tel compresseur et procede de separation d'un melange gazeux incorporant un tel compresseur
US7225637B2 (en) * 2004-12-27 2007-06-05 L'Air Liquide Société Anonyme á´ Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procédés Georges Claude Integrated air compression, cooling, and purification unit and process
US7712331B2 (en) * 2006-06-30 2010-05-11 Air Products And Chemicals, Inc. System to increase capacity of LNG-based liquefier in air separation process
DE102010056570A1 (de) 2010-12-30 2012-07-05 Linde Aktiengesellschaft Verfahren und Vorrichtung zur Gewinnung von Drucksauerstoff und Druckstickstoff durch Tieftemperaturzerlegung von Luft
WO2021204424A2 (de) * 2020-04-09 2021-10-14 Linde Gmbh Verfahren zur tieftemperaturzerlegung von luft, luftzerlegungsanlage und verbund aus wenigstens zwei luftzerlegungsanlagen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2982108A (en) * 1955-12-15 1961-05-02 Air Liquide Separation of air
SU739316A1 (ru) † 1977-08-22 1980-06-05 Предприятие П/Я А-3605 Способ разделени воздуха
EP0042676A1 (de) * 1980-06-17 1981-12-30 Air Products And Chemicals, Inc. Verfahren zur Herstellung gasförmigen Sauerstoffs und kryogenische Anlage zur Durchführung dieses Verfahrens
EP0384483A2 (de) † 1989-02-23 1990-08-29 Linde Aktiengesellschaft Verfahren und Vorrichtung zur Luftzerlegung durch Rektifikation

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1112997B (de) * 1960-08-13 1961-08-24 Linde Eismasch Ag Verfahren und Einrichtung zur Gaszerlegung durch Rektifikation bei tiefer Temperatur
US3123457A (en) * 1960-12-22 1964-03-03 E smith
DE1263037B (de) * 1965-05-19 1968-03-14 Linde Ag Verfahren zur Zerlegung von Luft in einer Rektifikationssaeule und damit gekoppelterZerlegung eines Wasserstoff enthaltenden Gasgemisches
US4869741A (en) * 1988-05-13 1989-09-26 Air Products And Chemicals, Inc. Ultra pure liquid oxygen cycle

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2982108A (en) * 1955-12-15 1961-05-02 Air Liquide Separation of air
SU739316A1 (ru) † 1977-08-22 1980-06-05 Предприятие П/Я А-3605 Способ разделени воздуха
EP0042676A1 (de) * 1980-06-17 1981-12-30 Air Products And Chemicals, Inc. Verfahren zur Herstellung gasförmigen Sauerstoffs und kryogenische Anlage zur Durchführung dieses Verfahrens
EP0384483A2 (de) † 1989-02-23 1990-08-29 Linde Aktiengesellschaft Verfahren und Vorrichtung zur Luftzerlegung durch Rektifikation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Prospectus de l'entreprise Atlas Copco: "Process-Engineered Centrifugal Compressors", 1991, pages 1 à 24 †
Rohde, W., "Plants with Molecular Sieve Absorbers, Comparison with other Processes and Operational Advantages", LINDE-Symposium "Air Separation Plats", juin 1986, pages 1 à 20 †
Springmann, H., "Die Gewinnung von Hochdruck-Sauerstoff", LINDE-Berichte aus Wissenschaft und Technik, 46/1979 †

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0834712A3 (de) * 1996-10-01 1998-10-21 Air Products And Chemicals, Inc. Verfahren zur Herstellung von Hochdruck-Stickstoff mit Hilfe einer Kolonne unter höherem Druck und ein oder mehrere Kolonnen unter niedrigerem Druck
EP0834712A2 (de) * 1996-10-01 1998-04-08 Air Products And Chemicals, Inc. Verfahren zur Herstellung von Hochdruck-Stickstoff mit Hilfe einer Kolonne unter höherem Druck und ein oder mehrere Kolonnen unter niedrigerem Druck
EP0982554A1 (de) * 1998-08-28 2000-03-01 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Verfahren und Anlage zur Herstellung von unreinem Sauerstoff durch Rektifikation
US6247333B1 (en) 1998-08-28 2001-06-19 L'air Liquide, Societe Anonyme Pour L'etrude Et L'exploitation Des Procedes Georges Claude Process for supplying impure oxygen to a synthesis-gas production unit
EP1120616A2 (de) * 2000-01-28 2001-08-01 The BOC Group plc Verfahren zur Luftzerlegung
EP1120616A3 (de) * 2000-01-28 2002-08-28 The BOC Group plc Verfahren zur Luftzerlegung
US6871513B2 (en) 2000-10-30 2005-03-29 L'Air Liquide, Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procédés Georges Claude Process and installation for separation of air by cryogenic distillation integrated with an associated process
US7100692B2 (en) 2001-08-15 2006-09-05 Shell Oil Company Tertiary oil recovery combined with gas conversion process
WO2003016676A1 (en) 2001-08-15 2003-02-27 Shell Internationale Research Maatschappij B.V. Tertiary oil recovery combined with gas conversion process
CN106489059A (zh) * 2014-07-05 2017-03-08 林德股份公司 以可变能耗低温分离空气的方法和设备
CN106662394A (zh) * 2014-07-05 2017-05-10 林德股份公司 以可变能耗低温分离空气的方法和设备
RU2691210C2 (ru) * 2014-07-05 2019-06-11 Линде Акциенгезелльшафт Способ и устройство для низкотемпературного разделения воздуха с переменным потреблением энергии
CN106662394B (zh) * 2014-07-05 2019-11-05 林德股份公司 以可变能耗低温分离空气的方法和设备
CN106489059B (zh) * 2014-07-05 2019-11-05 林德股份公司 以可变能耗低温分离空气的方法和设备
EP3059536A1 (de) * 2015-02-19 2016-08-24 Linde Aktiengesellschaft Verfahren und Vorrichtung zur Gewinnung eines Druckstickstoffprodukts
WO2016131545A1 (de) * 2015-02-19 2016-08-25 Linde Aktiengesellschaft Verfahren und vorrichtung zur gewinnung eines druckstickstoffprodukts
CN108207113A (zh) * 2015-02-19 2018-06-26 林德股份公司 获得压缩氮产品的方法及设备

Also Published As

Publication number Publication date
ES2101256T3 (es) 1997-07-01
EP0562893B1 (de) 1997-05-07
FR2689224B1 (fr) 1994-05-06
EP0562893B2 (de) 2000-12-20
DE69310429T3 (de) 2001-08-23
DE69310429D1 (de) 1997-06-12
US5341647A (en) 1994-08-30
CA2092140C (fr) 1998-08-18
DE69310429T2 (de) 1997-12-11
FR2689224A1 (fr) 1993-10-01
CA2092140A1 (fr) 1993-09-25
ES2101256T5 (es) 2001-03-16
ZA932796B (en) 1993-09-30

Similar Documents

Publication Publication Date Title
EP0562893B1 (de) Verfahren zur Herstellung von Hochdruck-Stickstoff und Sauerstoff
EP0576314B2 (de) Verfahren und Apparat zur Herstelling von gasförmigem Sauerstoff unter Druck
EP0689019B1 (de) Verfahren und Einrichtung zur Herstellung von gasförmigem Drucksauerstoff
CA2062506C (fr) Procede et installation de production d'oxygene gazeux sous pression
EP0628778B2 (de) Verfahren und Hochdruckgasversorgungseinheit für eine ein Luftbestandteil verbrauchende Anlage
EP0618415B1 (de) Verfahren und Vorrichtung zur Herstellung von gasförmigem Sauerstoff und/oder gasförmigem Stickstoff unter Druck durch Zerlegung von Luft
EP0789208A1 (de) Verfahren und Einrichtung zur Herstellung von gasförmigem Sauerstoff unter hohe Druck
EP0605262A1 (de) Druckgassauerstoffherstellungsverfahren und Apparat
FR2690982A1 (fr) Procédé et installation de production d'oxygène gazeux impur par distillation d'air.
FR2711778A1 (fr) Procédé et installation de production d'oxygène et/ou d'azote sous pression.
EP0430803B1 (de) Verfahren und Einrichtung zur Luftdestillierung mit Argongewinnung
FR2701313A1 (fr) Procédé et installation de production d'azote ultra-pur par distillation d'air.
EP0641983B1 (de) Verfahren und Einrichtung zur Herstellung von gasförmigem Sauerstoff und/oder Stickstoff unter Druck
FR2688052A1 (fr) Procede et installation de production d'oxygene et/ou d'azote gazeux sous pression par distillation d'air.
EP0611218B2 (de) Verfahren und Anlage zur Herstellung von Drucksauerstoff
EP0641982B1 (de) Verfahren und Einrichtung zur Herstellung von wenigstens einem durch Zerlegung von Luft gewonnenem Gas unter Druck
FR2702040A1 (fr) Procédé et installation de production d'oxygène et/ou d'azote sous pression.
CA2109148A1 (fr) Procede et installation de production d'azote et d'oxygene
FR2862004A1 (fr) Procede et installation d'enrichissement d'un flux gazeux en l'un de ses constituants
FR2674011A1 (fr) Procede et installation de production d'oxygene gazeux sous pression.
EP3913310A1 (de) Verfahren und gerät zur trennung von luft durch kryogene destillation
EP0017538A1 (de) Verfahren und Vorrichtung zum Erhalten substantiell reinen Argons
FR2685460A1 (fr) Procede et installation de production d'oxygene gazeux sous pression par distillation d'air.

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19930305

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES IT NL

17Q First examination report despatched

Effective date: 19950714

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES IT NL

REF Corresponds to:

Ref document number: 69310429

Country of ref document: DE

Date of ref document: 19970612

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2101256

Country of ref document: ES

Kind code of ref document: T3

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: LINDE AKTIENGESELLSCHAFT

Effective date: 19980206

NLR1 Nl: opposition has been filed with the epo

Opponent name: LINDE AKTIENGESELLSCHAFT

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20001220

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): DE ES IT NL

NLR2 Nl: decision of opposition
ITF It: translation for a ep patent filed

Owner name: ING. A. GIAMBROCONO & C. S.R.L.

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Kind code of ref document: T5

Effective date: 20010219

NLR3 Nl: receipt of modified translations in the netherlands language after an opposition procedure
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20060215

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20060217

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20060302

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20060331

Year of fee payment: 14

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20071001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20071001

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20071002

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20070303

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070303

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070302