US20060254311A1 - Process and installation for supplying gaseous carbon monoxide and/or a gaseous mixture containing at least 10% carbon monoxide - Google Patents

Process and installation for supplying gaseous carbon monoxide and/or a gaseous mixture containing at least 10% carbon monoxide Download PDF

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Publication number
US20060254311A1
US20060254311A1 US10/557,013 US55701305A US2006254311A1 US 20060254311 A1 US20060254311 A1 US 20060254311A1 US 55701305 A US55701305 A US 55701305A US 2006254311 A1 US2006254311 A1 US 2006254311A1
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Prior art keywords
carbon monoxide
column
methane
separation unit
liquid
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Inventor
Jean Billy
Natacha Haik-Beraud
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA a Directoire et Conseil de Surveillance pour lEtude et lExploitation des Procedes Georges Claude
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Assigned to L'AIR LIQUIDE, SOCIETE ANONYME A DIRECTORIE ET CONSEIL DE SURVEILLANCE POUR I'ETUDE ET L'EXPLOITATION DES PROCEDES GEORGES CLAUDE reassignment L'AIR LIQUIDE, SOCIETE ANONYME A DIRECTORIE ET CONSEIL DE SURVEILLANCE POUR I'ETUDE ET L'EXPLOITATION DES PROCEDES GEORGES CLAUDE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BILLY, JEAN, HAIK-BERAUD, NATACHA
Publication of US20060254311A1 publication Critical patent/US20060254311A1/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/506Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/40Carbon monoxide
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes 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
    • F25J3/0204Processes 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 characterised by the feed stream
    • F25J3/0223H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes 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
    • F25J3/0228Processes 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 characterised by the separated product stream
    • F25J3/0252Processes 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 characterised by the separated product stream separation of hydrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes 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
    • F25J3/0228Processes 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 characterised by the separated product stream
    • F25J3/0261Processes 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 characterised by the separated product stream separation of carbon monoxide
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes 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
    • F25J3/0228Processes 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 characterised by the separated product stream
    • F25J3/0271Processes 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 characterised by the separated product stream separation of H2/CO mixtures, i.e. of synthesis gas
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/046Purification by cryogenic separation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/047Composition of the impurity the impurity being carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/048Composition of the impurity the impurity being an organic compound
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00Processes or apparatus using separation by rectification
    • F25J2200/70Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00Processes or apparatus using separation by rectification
    • F25J2200/76Refluxing the column with condensed overhead gas being cycled in a quasi-closed loop refrigeration cycle
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00Processes or apparatus using separation by rectification
    • F25J2200/90Details relating to column internals, e.g. structured packing, gas or liquid distribution
    • F25J2200/94Details relating to the withdrawal point
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00Processes or apparatus using other separation and/or other processing means
    • F25J2205/30Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00Processes characterised by the type or other details of the feed stream
    • F25J2210/42Nitrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00Processes characterised by the type or other details of the product stream
    • F25J2215/02Mixing or blending of fluids to yield a certain product
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00Processes characterised by the type or other details of the product stream
    • F25J2215/04Recovery of liquid products
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2235/00Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/02Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams using a pump in general or hydrostatic pressure increase
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00Processes or apparatus involving steps for recycling of process streams
    • F25J2245/02Recycle of a stream in general, e.g. a by-pass stream
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2250/00Details related to the use of reboiler-condensers
    • F25J2250/30External or auxiliary boiler-condenser in general, e.g. without a specified fluid or one fluid is not a primary air component or an intermediate fluid
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/02Internal refrigeration with liquid vaporising loop
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/04Internal refrigeration with work-producing gas expansion loop
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/08Internal refrigeration by flash gas recovery loop
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/24Quasi-closed internal or closed external carbon monoxide refrigeration cycle
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00Refrigeration techniques used
    • F25J2270/90External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/904External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by liquid or gaseous cryogen in an open loop
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2280/00Control of the process or apparatus
    • F25J2280/02Control in general, load changes, different modes ("runs"), measurements
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/62Details of storing a fluid in a tank

Definitions

  • This invention concerns processes and installations for providing gaseous carbon monoxide and/or a mixture containing at least 10% carbon monoxide.
  • it concerns the supply of carbon monoxide by vaporisation of liquid carbon monoxide when an industrial installation, such as a separation unit, cannot provide all or part of the gaseous carbon monoxide product.
  • the beds may contain adsorbents such as alumina or zeolites, such as molecular sieves.
  • the purification cycle can be adapted so that following the regeneration step, only a limited amount of feed gas is sent to the bed at the beginning of the adsorption step (around 5% of the normal feed flow).
  • EP-A-0837031 and EP-A-1245533 show a liquid carbon monoxide storage vessel incorporated at the top of a carbon monoxide-methane separation column, the liquid carbon monoxide being used to provide reflux for the column and to provide cooling for the methane wash column and, in the case of EP-A-0837031 for the main heat exchanger wherein the synthesis gas is used to its distillation temperature.
  • independent vessels collect liquid carbon monoxide used in the carbon monoxide cycle used in the methane wash process.
  • an installation for supplying gaseous carbon monoxide and/or a gaseous mixture containing at least 10% carbon monoxide by vaporisation of liquid carbon monoxide including
  • FIG. 1 shows an apparatus for separating a mixture containing principally methane, carbon monoxide and hydrogen.
  • the mixture may also contain small amounts of nitrogen, carbon dioxide, humidity, higher hydrocarbons etc.
  • This mixture is generally synthesis gas produced by a partial oxidation unit, a steam methane reformer or an autothermal reformer.
  • the mixture 1 is purified in a front end purification unit 3 at around ambient temperature to removed water and carbon dioxide. Then the mixture is cooled to a cryogenic temperature in a heat exchanger 5 and sent to the bottom of a methane wash column 7 operating at a pressure between 10 and 60 bars. A methane wash stream 9 is fed to the top of column 7 and a hydrogen enriched stream 11 is removed from the top of the column. From the bottom of the column is removed a liquid stream 13 enriched in carbon monoxide.
  • Stream 13 is further treated before being sent to the stripping column 19 which operates at between 4 and 17 bars, at least one feed stream formed from stream 13 being sent to the top of stripping column 19 .
  • the feed stream is feed thereto at a lower point.
  • the gas 21 from the top of the stripping column is warmed in the exchanger 5 and is used as fuel or burnt.
  • the liquid stream 23 from the bottom of the stripping column 19 is further treated before being sent to the column 27 .
  • several feeds (liquid, dual phase, gaseous) at different levels may be provided to the column 27 .
  • Column 27 operates at between 1 and 10 bars, often around 2.5 bars.
  • methane rich liquid 29 at the bottom of the column and a carbon monoxide rich gas 31 at the top of the column.
  • Part of the methane rich liquid is pumped and sent to the top of the methane washing column and the rest is removed as a purge stream.
  • the two portions of the methane rich liquid may be removed separately from the column.
  • the methane rich liquid is pumped by pump 33 and sent in part to the top of the methane washing column 7 and the remaining purge stream is mixed with stream 21 .
  • the part to be mixed with stream 21 need not be pumped.
  • the carbon monoxide rich product stream 31 is compressed in a compressor 35 and is removed as a compressed product gas 37 .
  • Refrigeration for the system is provided by a carbon monoxide cycle of which the compressor 35 forms part.
  • the carbon monoxide is compressed in compressor 35 to a pressure of between 10 and 60 bars.
  • Part of the compressed carbon monoxide 39 is cooled in exchanger 5 to an intermediate temperature of the exchanger and then expanded in turbine 41 .
  • the expanded carbon monoxide gas is warmed in the exchanger 5 and recycled to the compressor 35 at the entry thereof or an intermediate pressure thereof.
  • the unexpanded carbon monoxide 43 serves to reboil columns 19 and 27 and the thereby cooled carbon monoxide is expanded in valve 45 and sent to storage vessel 47 .
  • the storage vessel 47 forms an integral part of the column 27 and additionally serves to provide reflux to the top of column 27 , to supply liquid carbon monoxide to cool the methane wash column 7 and to supply liquid carbon monoxide directly to the main heat exchanger 5 where it is vaporised to balance the heat exchange diagram at the cold end of the heat exchanger 5 .
  • This independent storage vessel could be placed within or outside the cold box (not shown) which encloses the columns 7 , 19 , 27 , the exchanger 5 and the turbine 41 , optionally turbine 89 which expands part 87 of gas 71 .
  • the storage vessel may be pressurised so that the carbon monoxide is stored at between above 1 and below 60 bars. Ideally the storage vessel should be at a pressure which is substantially the product pressure of the carbon monoxide gas 37 or the carbon monoxide mixture 73 , allowing for pressure drop in the conduits and vaporiser 53 . Alternatively the carbon monoxide may be stored at atmospheric pressure and then, if required, pumped in liquid form and/or compressed in gaseous form to its final pressure.
  • Flash gas 49 produced by the expansion is mixed with the carbon monoxide rich gas 31 prior to compression.
  • a stream of liquid carbon monoxide 57 is vaporised in exchanger 59 against the gas streams within the methane wash column 7 and forms part of the gaseous carbon monoxide cycle.
  • a further stream of liquid carbon monoxide 61 withdrawn from the vessel 47 is vaporised in exchanger 5 .
  • liquid 51 from the storage vessel 47 is withdrawn when required and vaporised in the vaporiser 53 .
  • the vaporiser may either allow heat exchange with ambient air, water or steam if it is outside the cold box or may be within the cold box and may be constituted by the exchanger 5 or another heat exchanger.
  • the vaporised carbon monoxide produced 55 is sent to the compressor 35 to form all or part of the product gas.
  • the liquid to be vaporised 51 is available at high pressure, for example following a pumping process upstream of the vaporiser 53 or where the liquid is stored at high pressure, the gas produced can be directly mixed with the product gas 37 .
  • the withdrawal and vaporisation of the carbon monoxide may take place
  • the level in the storage vessel will remain constant or will rise. The level will fall whenever one of the conditions is fulfilled and the vessel will need to be replenished, for example when the amount of feed gas increases and/or when the adsorbers are saturated with carbon monoxide and/or when the product requirement is less than the maximum capacity of the separation unit.
  • the carbon monoxide turbine needs to be overdimensioned to replenish the vessel or else a cryogenic liquid from an outside source can be added.
  • This cryogenic liquid may be liquid carbon monoxide from an outside source or liquid nitrogen which is then used to liquefy gaseous carbon monoxide by heat exchange in a heat exchanger.
  • the adsorbers are operated as described in FR01/06041 (incorporated by reference) such that the amount of feed sent to the adsorbers does not reach its full amount until the adsorber bed to which it is sent is saturated with carbon monoxide.
  • the flow starts at 5% mol. of the normal flow, then is increased to 50% mol. and finally is increased to 100%.
  • the liquid carbon monoxide may begin to be sent to the vaporiser for example when the flow is at its smallest or alternatively may begin a few minutes before the flow is at its smallest.
  • the liquid carbon monoxide is no longer sent to the vaporiser once the flow has increased to 50%.
  • Gaseous and liquid carbon monoxide are defined to be respectively a gas and a liquid containing at least 85% carbon monoxide, preferably at least 95% carbon monoxide.
  • the process may also be used to produce a mixture containing at least 10% carbon monoxide 73 , for example an oxogas used in the production of oxoalcohols.
  • This mixture is produced by withdrawing a gaseous mixture 71 from one of the columns of the system, warming it in exchanger 5 and enriching it by adding gaseous carbon monoxide 72 to achieve a desired concentration of carbon monoxide. Where the gaseous carbon monoxide is insufficient, part of the requirement may be provided by vaporising part of the carbon monoxide liquid from storage 47 .
  • cryogenic separation processes for mixtures containing carbon monoxide and at least one of hydrogen, nitrogen and methane as principal components, for example processes to separate mixtures of hydrogen, carbon monoxide and methane such as the partial condensation process or processes for separating mixtures containing carbon monoxide and nitrogen only as principal components.
  • the separation unit shown here as a cryogenic distillation unit could of course operated by permeation in a membrane system or by adsorption.
  • the liquid carbon monoxide could be imported from an external source or could be produced by liquefying part of the gaseous carbon monoxide product at times of low demand.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Separation Of Gases By Adsorption (AREA)
US10/557,013 2003-05-19 2004-05-06 Process and installation for supplying gaseous carbon monoxide and/or a gaseous mixture containing at least 10% carbon monoxide Abandoned US20060254311A1 (en)

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EP03291159A EP1479989B1 (en) 2003-05-19 2003-05-19 Process and installation for providing gaseous carbon monoxide and/or a mixture containing carbon monoxide
EP03291159.6 2003-05-19
PCT/IB2004/001403 WO2004102094A1 (en) 2003-05-19 2004-05-06 Process and installation for supplying gaseous carbon monoxide and/or a gaseous mixture containing at least 10% carbon monoxide

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US20060254311A1 true US20060254311A1 (en) 2006-11-16

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US (1) US20060254311A1 (es)
EP (1) EP1479989B1 (es)
JP (1) JP2007504433A (es)
CN (1) CN100434848C (es)
AT (1) ATE504791T1 (es)
DE (1) DE60336638D1 (es)
ES (1) ES2364242T3 (es)
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WO (1) WO2004102094A1 (es)

Cited By (7)

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US20080245101A1 (en) * 2005-04-08 2008-10-09 Richard Dubettier-Grenier Integrated Method and Installation for Cryogenic Adsorption and Separation for Producing Co2
WO2008142349A2 (fr) * 2007-05-21 2008-11-27 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Capacite de stockage, appareil et procede de production de monoxyde de carbone et/ou d'hydrogene par separation cryogenique integrant une telle capacite
US20110056239A1 (en) * 2008-04-18 2011-03-10 L'air Liquide Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method And Device For Cryogenically Separating A Mixture of Hydrogen And Carbon Monoxide
US20120031143A1 (en) * 2009-01-08 2012-02-09 Helmar Van Santem Process and appartus for removing gaseous contaminants from gas stream comprising gaseous contaminants
US20120279254A1 (en) * 2009-11-24 2012-11-08 L'Air Liquide Societe Annonyme Pour L'Etude Et L'Exploitation Des Procedes Georges Claud Method for cryogenically separating a mixture of nitrogen and carbon monoxide
CN108332510A (zh) * 2018-03-22 2018-07-27 上海华林工业气体有限公司 一种提高HyCO冷箱CO回收率的系统及方法
US11999662B2 (en) 2017-05-17 2024-06-04 SABIC Agri-Nutrients Company Anti-caking fertilizer compositions

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FR2881063B1 (fr) 2005-01-25 2007-04-20 Air Liquide Procede et installation de production de monoxyde de carbone par distillation cryogenique
DE102006051759A1 (de) * 2006-11-02 2008-05-08 Linde Ag Verfahren und Vorrichtung zur Zerlegung von Synthesegas mittels Methanwäsche
EP2562502A1 (en) * 2011-06-24 2013-02-27 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process and installation for supplying gaseous carbon monoxide by cryogenic distillation
EP2662652A1 (en) * 2012-05-07 2013-11-13 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process and apparatus for the separation by cryogenic distillation of a mixture of methane, carbon dioxide and hydrogen
CN103868324B (zh) * 2014-03-07 2015-10-14 上海交通大学 小型撬装式混合制冷剂天然气液化和ngl回收一体系统
FR3058996B1 (fr) * 2016-11-18 2022-01-07 Air Liquide Procede et installation de separation cryogenique d’un melange gazeux par lavage au methane
CN108131896A (zh) * 2017-12-28 2018-06-08 上海华林工业气体有限公司 Hyco冷箱双液态co罐切换积液和外供气体的系统和方法

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080245101A1 (en) * 2005-04-08 2008-10-09 Richard Dubettier-Grenier Integrated Method and Installation for Cryogenic Adsorption and Separation for Producing Co2
WO2008142349A3 (fr) * 2007-05-21 2013-07-18 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Capacite de stockage, appareil et procede de production de monoxyde de carbone et/ou d'hydrogene par separation cryogenique integrant une telle capacite
WO2008142349A2 (fr) * 2007-05-21 2008-11-27 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Capacite de stockage, appareil et procede de production de monoxyde de carbone et/ou d'hydrogene par separation cryogenique integrant une telle capacite
FR2916523A1 (fr) * 2007-05-21 2008-11-28 Air Liquide Capacite de stockage, appareil et procede de production de monoxyde de carbone et/ou d'hydrogene par separation cryogenique integrant une telle capacite.
US20100199718A1 (en) * 2007-05-21 2010-08-12 Alain Briglia Storage Enclosure, Method And Apparatus For Producing Carbon Monoxide And/Or Hydrogen By Means Of Cryogenic Separation, Including One Such Enclosure
US8783062B2 (en) 2007-05-21 2014-07-22 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Storage enclosure, method and apparatus for producing carbon monoxide and/or hydrogen by means of cryogenic separation, including one such enclosure
US8869553B2 (en) * 2008-04-18 2014-10-28 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method and device for cryogenically separating a mixture of hydrogen and carbon monoxide
US20110056239A1 (en) * 2008-04-18 2011-03-10 L'air Liquide Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method And Device For Cryogenically Separating A Mixture of Hydrogen And Carbon Monoxide
US20120031143A1 (en) * 2009-01-08 2012-02-09 Helmar Van Santem Process and appartus for removing gaseous contaminants from gas stream comprising gaseous contaminants
US20120279254A1 (en) * 2009-11-24 2012-11-08 L'Air Liquide Societe Annonyme Pour L'Etude Et L'Exploitation Des Procedes Georges Claud Method for cryogenically separating a mixture of nitrogen and carbon monoxide
US9625209B2 (en) * 2009-11-24 2017-04-18 L'Air Liquide Société Anonyme Pour L'Étude Et L'Exploitation Des Procedes Georges Claude Method for cryogenically separating a mixture of nitrogen and carbon monoxide
US11999662B2 (en) 2017-05-17 2024-06-04 SABIC Agri-Nutrients Company Anti-caking fertilizer compositions
CN108332510A (zh) * 2018-03-22 2018-07-27 上海华林工业气体有限公司 一种提高HyCO冷箱CO回收率的系统及方法

Also Published As

Publication number Publication date
PT1479989E (pt) 2011-07-08
DE60336638D1 (de) 2011-05-19
EP1479989A1 (en) 2004-11-24
CN100434848C (zh) 2008-11-19
ES2364242T3 (es) 2011-08-29
EP1479989B1 (en) 2011-04-06
JP2007504433A (ja) 2007-03-01
WO2004102094A1 (en) 2004-11-25
CN1791780A (zh) 2006-06-21
ATE504791T1 (de) 2011-04-15

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