WO2011086345A1 - Separation de gaz - Google Patents

Separation de gaz Download PDF

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Publication number
WO2011086345A1
WO2011086345A1 PCT/GB2011/000024 GB2011000024W WO2011086345A1 WO 2011086345 A1 WO2011086345 A1 WO 2011086345A1 GB 2011000024 W GB2011000024 W GB 2011000024W WO 2011086345 A1 WO2011086345 A1 WO 2011086345A1
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WO
WIPO (PCT)
Prior art keywords
gas
carbon dioxide
shifted
pressure
shift reaction
Prior art date
Application number
PCT/GB2011/000024
Other languages
English (en)
Inventor
Richard James Beavis
Jonathan Alec Forsyth
Original Assignee
Bp Alternative Energy International Limited
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
Priority claimed from GBGB1001193.0A external-priority patent/GB201001193D0/en
Application filed by Bp Alternative Energy International Limited filed Critical Bp Alternative Energy International Limited
Publication of WO2011086345A1 publication Critical patent/WO2011086345A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
    • 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
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/0605—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the feed stream
    • F25J3/0625—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • 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
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/0655—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of hydrogen
    • 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
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/067—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C01B2203/0288—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing two CO-shift steps
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/046—Purification by cryogenic separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/84—Energy production
    • 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
    • F25J2215/04—Recovery of liquid products
    • 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
    • F25J2230/20—Integrated compressor and process expander; Gear box arrangement; Multiple compressors on a common shaft
    • 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
    • F25J2230/30—Compression of the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/04—Internal refrigeration with work-producing gas expansion loop
    • F25J2270/06—Internal refrigeration with work-producing gas expansion loop with multiple gas expansion loops
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry

Definitions

  • pressures and/or temperature ranges may be used.
  • higher pressures may be employed for the shift reaction, for example pressures up to about 250 bar.
  • lower reaction temperatures may be used, for example greater than 145 degrees C, for example 155 degrees C or more.
  • the exact composition of the raw synthesis gas treated will depend upon how it is manufactured but in general it will consist of carbon monoxide, carbon dioxide, hydrogen and steam together with the un-reacted components of air (oxygen, nitrogen and the like) and, if sour, sulphurous impurities such as hydrogen sulphide, carbonyl sulphide and the lower mercaptans.
  • Suitable sources of raw synthesis gas include those produced by the autothermal or steam reforming of natural gas or methane and the gasification or partial oxidation of carbonaceous sources such as heavy oil, shale oil coal, lignite, coke or petroleum coke.
  • the raw synthesis gas may further contain impurities such as methane and ethane.
  • the raw synthesis gas is generated by these processes at a pressure in the range up to 60bar.
  • the high temperature shift stage will generate a wet partially shifted synthesis gas containing an equilibrium amount of carbon monoxide of the order of 1 to 8 mol%. Thereafter the partially shifted synthesis gas is cooled before being further treated in a second or 'low temperature shift' stage. In some cases, water might be removed from the partially shifted gas at this stage.
  • the cooled partially shifted gas and steam is passed though a bed of a second Water Gas Shift reaction catalyst operating at a temperature in the range 175 to 320°C and at a lower partial pressure of steam.
  • this is likewise typically a transition metal oxide catalyst it may be different from that used in the high temperature shift in which case it is suitably formulated to be more active at lower temperatures.
  • Working at this lower temperature such a catalyst is able to reduce the carbon monoxide level further generating a wet fully shifted synthesis (the shifted gas) gas containing an equilibrium amount of typically less than 4 mol% carbon monoxide.
  • the raw synthesis gas needs to be compressed in accordance with one or other of two strategies. Under the first it is compressed to the desired pressure upstream of the high temperature stage of the Water Gas shift reaction unit so that consequently both the high temperature and low temperature stages are carried out high pressure. Since increasing pressure has no significant on the Water Gas Shift reaction equilibrium but does increase the rate of the reaction this has the advantage that lower catalyst contact times and smaller vessels can be used in both stages. Also since the steam can be added to the inlet of the high temperature stage in the form of pumped water, which may be later evaporated, the amount of gas to be compressed can be kept to a minimum.
  • the high temperature stage can be operated at a conventional pressure and the partially shifted gas compressed after cooling, possibly with water removal before being treated in the low temperature stage.
  • This has the further advantages of there being less material to compress (since much of the steam has been removed) and therefore being less energy intensive.
  • compression of this wet stream may also introduce its own dew point problems and in any event compression increases the temperature of the partially shifted synthesis gas. For this reason it may be desirable to condense out the majority of the water in the partially shifted synthesis gas before compression and feeding the required amount of condensate back into the inlet of the low temperature shift stage. In doing the condensate can be used to remove any excess heat generated during the compression whilst at the same time providing steam for the low temperature shift reaction.
  • the shifted gas leaving the low temperature shift stage may still contain significant amounts of steam and therefore may need to be dried before being subjected to stage (3) of the process. This may be effected by cooling the shifted gas significantly below the dew point temperature of the stream at the relevant pressure and recovering the water in a separator.
  • the separator suitably consists of one or more condensers or knock-out pots arranged in series which remove most of the water followed by polishers containing e.g. molecular sieves or equivalent desiccants. Thereafter the dried shifted gas may be further compressed to bring it to the pressure required to carry out stage (3). As mentioned previously this is not however essential and depending upon the efficiency of carbon dioxide removal required in stage (4) it may be possible to use the shifted gas in stage (3) without any further compression whatsoever.
  • the dried shifted gas is compressed to a pressure in the range 80 to 250 bar, preferably 100 to 200 bar before it is cooled in stage (3).
  • Such compression can be effected by a single compressor or a series thereof for example with interstage heat exchangers designed to remove the heat generated by the compression.
  • the gases will at some stage usually need to be desulphurised.
  • the shifted gas may now be at a pressure in the range 50 to 250 bar in some examples, and may then be cooled until some preferably most of the carbon dioxide contained therein liquefies.
  • this involves passing the shifted gas though at least one heat exchanger in which the shifted gas enters into heat exchange relationship with the cold separated liquid carbon dioxide and/or hydrogen rich fractions generated in stage (4) below thereby allowing these latter fractions to be warmed back towards their final desired temperature.
  • the flows of the shifted gas, the cold separated liquid carbon dioxide and the hydrogen rich fractions are configured so as to flow though at least one or at least one array of multichannel diffusion bonded and/or micro-channel heat exchangers thereby cooling the shifted gas mixture to the operating temperature of the fractionation unit.
  • heat exchangers are described for example in EP 0212878 and WO 2004/017008 the contents of which are incorporated by reference herein.
  • the cooled shifted gas (now a two-phase mixture of liquid carbon dioxide and a non-condensable hydrogen rich gas) may be separated into its component parts in a fractionation unit.
  • thermodynamic constraints referred to above relate to ideal systems and that the shifted gases being treated herein may exhibit significant deviation from ideality potentially giving rise to an elevation of the triple point temperature.
  • the temperature of the fractionation unit should be at least 3°C preferably at least 5°C above the theoretical triple point temperature of carbon dioxide. In practical terms and for the mixtures described herein this generally means operating the fractionation unit at a temperature in the range -25 to -53°C and preferably in the range -40 to -50°C.
  • the pressure should preferably be in the range 50 to 250bar, preferably 100 to 200bar as mentioned above.
  • the fractionation unit used in the process of the present invention may be for example a conventional gas-liquid separator adapted to work at the high pressures and low temperatures set out above. In such vessels the gaseous hydrogen rich fraction is typically taken off overhead and the liquid carbon dioxide removed at or near the bottom. The pressure drop across the fractionator is typically no more than between 0.1 and 0.5bar.
  • the hydrogen rich fraction may optionally be fed to a scrubber where it is contacted with preferably a continuously fed and continuously removed stream of cold alcohol in order to extract residual carbon dioxide therefrom.
  • a scrubber where it is contacted with preferably a continuously fed and continuously removed stream of cold alcohol in order to extract residual carbon dioxide therefrom.
  • This is typically effected by continuously contacting a stream of the hydrogen rich fraction with the cold alcohol stream under conditions which cause intimate and turbulent mixing of the two for example by counter-current mixing or by sparging the hydrogen rich fraction through the solvent. Under these conditions the residual carbon dioxide dissolves in the alcohol and is removed from the system by way of the effluent from the scrubber.
  • the alcohol solvent used is selected from methanol, ethanol, the isomers of propanol and low molecular weight glycols and glycol ethers formed by oligomerisation of ethylene or propylene glycol.
  • the alcohol solvent chosen should be one which will not freeze under the operating conditions of the scrubber. Since it is preferred that this scrubbing is conducted immediately after stage (4) with no intermediate treatment of the hydrogen rich fraction the operating temperature and pressure of the scrubber should preferably be the same as or substantially the same as those of the fractionation unit. However the temperature and pressure ranges disclosed above for the fractionation unit are applicable mutatis mutandis to the scrubber irrespective of whether any treatment of the hydrogen rich fraction has occurred between the fractionation unit and the scrubber. It will be appreciated however that the scrubber may work most efficiently when the cold alcohol solvent is fed to the scrubber at or close to the latter' s operating temperature.
  • the effluent solvent from the scrubber may be passed to a treater where fresh solvent may be regenerated by distillation and overhead removal of carbon dioxide in gaseous form. Thereafter the regenerated solvent can be cooled and recycled to the scrubber.
  • the gaseous carbon dioxide so liberated can thereafter be either disposed of or liquefied and combined with the main carbon dioxide stream before doing so.
  • stage (5) of the process of the present invention the hydrogen rich fraction is warmed and decompressed in order to restore it to the temperature and pressure required for its further utilisation.
  • this stage is preferably effected by passing this fraction through a plurality of turboexpanders and associated interstage heat exchangers arranged in series.
  • the hydrogen rich fraction is expanded isentropically progressively reducing its pressure and progressively releasing expansion energy which in turn drives a turbine capable of recovering this energy as mechanical work.
  • the process of the present invention may suitably employ from two to eight turboexpanders arranged in series preferably from two to six.
  • turbo expanders themselves are preferably arranged so that they drive a common shaft.
  • the mechanical work generated can if desired be used elsewhere in the process thereby minimising overall energy usage.
  • the expansion of the hydrogen rich fraction causes it to cool and the cooling capacity generated can be used in the interstage coolers to cool warmer streams especially those involved in stage (3).
  • these interstage coolers are integrated into a single or array of multichannel heat exchangers though which the incoming shifted gas of stage (3) also flows in order to manage the cooling capacity of the whole system as efficiently as possible.
  • Subsequent treatment of the liquid carbon dioxide recovered in stage (4) will depend to a certain extent on what is to be done with it. It may for example be piped or tankered offsite for underground storage. In this case it may be desirable to liquefy any further gaseous carbon dioxide recovered in the optional scrubbing stage and combine it with the material recovered in stage (4).
  • the liquid carbon dioxide may if desired be warmed by passing it through the multichannel heat exchanger to utilise its cooling capacity too. It is preferred some examples that little or no expansion of the liquid carbon dioxide occurs downstream of the fractionation unit so that its pressure is maintained at or above 50 bar after the fractionation unit.
  • a gas shift and separation plant for converting raw synthesis gas into separate streams consisting of respectively liquid carbon dioxide and a hydrogen rich fraction which plant comprises;
  • an expansion system for warming and expanding the separated gaseous hydrogen rich fraction comprising a plurality of turboexpanders for progressively recovering energy from the gaseous hydrogen rich fraction as mechanical work and at least one means for supplying cooling capacity to at least one of the heat exchangers in the cooling system.
  • the shift and separation plant described above may typically form part of a larger integrated complex for example an Integrated Gasification Combined Cycle (IGCC) or similar hydrogen power plants which include the additional step of burning the hydrogen (preferably diluted with nitrogen) in the burners of a gas turbine.
  • IGCC Integrated Gasification Combined Cycle
  • similar hydrogen power plants which include the additional step of burning the hydrogen (preferably diluted with nitrogen) in the burners of a gas turbine.
  • a further aspect of the invention provides a process for decarbonising a gas stream comprising carbon monoxide, which process comprises:
  • the process may further include the step of removing water from the shifted gas prior to the condensing of the carbon dioxide.
  • the pressure of the gas stream may be selected in dependence on system parameters. In some systems, it may be advantageous for a high pressure to be used.
  • the gas stream may be compressed to a pressure of more than 100 bar, for example 150 bar or more, or 250 bar or more.
  • the gas stream may for example be compressed to a pressure in the range 50 to 150 bar, for example in the range 50 to 100 bar before treatment with the Water Gas Shift reaction catalyst.
  • the compression may occur upstream of all of the Water Gas Shift reaction catalysts, and/or between catalysts of a multi-step Water Gas Shift reaction.
  • the gas stream may be compressed to a pressure of at least 50 bar, preferably in the range 50 to 100 bar, before treatment with the low temperature Water Gas Shift reaction catalyst.
  • the gas stream may include sulphurous impurities, and sulphurous impurities may be removed downstream of the Water Gas Shift reaction catalyst.
  • a Water Gas Shift reactor for receiving the gas stream and for reacting the gas stream in the presence of at least one Water Gas Shift reaction catalyst to generate a shifted gas comprising carbon dioxide and hydrogen having a pressure of at least 50 bar;
  • Figure 1 shows a schematic view of stages (1) and (2) of the process of the present invention.
  • the raw synthesis gas is compressed upstream of the high temperature shift unit.
  • a stream of wet shifted gas containing less than 3% carbon monoxide is then removed via line 12 and cooled to 40°C in heat exchanger E5 after which any condensed water is removed in a knock-out pot (not shown).
  • the effluent from E5 is then fed via line 13 to a desulphurisation unit A4 (typically a Selexol unit) where sulphurous impurities are removed by solvent extraction and taken away via line 14.
  • A4 typically a Selexol unit
  • a series of compressors C2, C3 and C4 and associated interstage heat exchangers E2,E3 and E4 where the dry shifted gas is compressed and cooled to a pressure of 175 bar and 40°C before being passed via line SI
  • This stream is warmed yet again to -30°C in LNG- 100 before being expanded one last time in turboexpander EX4 to a pressure of 31 bar and a temperature of -50°C. Finally the gas stream is passed through LNG-100 one last time and optionally a series of other heat exchangers (not shown) where it is warmed to a final temperature of 25°C. The warm hydrogen-rich gas stream then leaves the plant via line 29.

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  • Engineering & Computer Science (AREA)
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  • Thermal Sciences (AREA)
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Abstract

L'invention concerne un procédé pour décarboniser un flux gazeux contenant du monoxyde de carbone. Le procédé consiste à : (a) mettre à réagir le flux gazeux contenant du monoxyde de carbone en présence d'au moins un catalyseur de conversion du gaz à l'eau pour générer un gaz converti contenant du dioxyde de carbone et de l'hydrogène à une pression d'au moins 50 bars ; (b) refroidir le gaz converti au moyen d'au moins un échangeur de chaleur, de telle sorte que le dioxyde de carbone se condense à partir du gaz converti et qu'un mélange de gaz-liquide à deux phases est formé ; (c) séparer le mélange à deux phases en dioxyde de carbone liquide séparé et en fractions gazeuses riches en hydrogène ; et (d) chauffer et dilater la fraction riche en hydrogène au moyen d'au moins un échangeur de chaleur pour échanger de la chaleur avec le gaz converti et d'une pluralité de turbo-détenteurs capables de récupérer progressivement l'énergie provenant de la fraction riche en hydrogène en tant que travail mécanique. Des exemples décrivent un procédé intégré pour convertir un flux de gaz de synthèse brut et séparer par cryogénie le produit converti en un composant riche en hydrogène et un flux de dioxyde de carbone liquide. Le procédé précité est spécialement approprié pour traiter un gaz de synthèse brut produit par un gazéifieur, un reformeur à vapeur de méthane ou un reformeur auto-thermique dont l'objet est de récupérer un flux sans carbone riche en hydrogène à brûler dans une centrale à hydrogène. Le dioxyde de carbone récupéré sous forme liquide peut être commodément acheminé hors site par pipeline pour être stocké en sous-sol dans des formations géologiques appropriées (par exemple, dans des puits de pétrole appauvris). Le procédé permet de former, par exemple, de manière appropriée un cycle combiné de gazéification intégrée (IGCC).
PCT/GB2011/000024 2010-01-12 2011-01-10 Separation de gaz WO2011086345A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP10250045 2010-01-12
EP10250045.1 2010-01-12
GB1001193.0 2010-01-25
GBGB1001193.0A GB201001193D0 (en) 2010-01-25 2010-01-25 Separation of gases

Publications (1)

Publication Number Publication Date
WO2011086345A1 true WO2011086345A1 (fr) 2011-07-21

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN108952861A (zh) * 2018-06-07 2018-12-07 上海柯来浦能源科技有限公司 液化工质中氢气升压床回收余热发电的装置和方法

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US3614872A (en) 1967-12-22 1971-10-26 Texaco Inc Synthesis gas separation process
EP0212878A1 (fr) 1985-08-08 1987-03-04 Heatric Pty. Limited Echangeur de chaleur à plaques et à courant croisé
WO2004017008A1 (fr) 2002-08-15 2004-02-26 Velocys, Inc. Procede de refroidissement d'un produit dans un echangeur thermique comportant des microcanaux
US20060228284A1 (en) * 2005-04-11 2006-10-12 Schmidt Craig A Integration of gasification and ammonia production
WO2010012981A2 (fr) 2008-07-31 2010-02-04 Bp Alternative Energy International Limited Séparation du dioxyde de carbone et de l’hydrogène

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3614872A (en) 1967-12-22 1971-10-26 Texaco Inc Synthesis gas separation process
EP0212878A1 (fr) 1985-08-08 1987-03-04 Heatric Pty. Limited Echangeur de chaleur à plaques et à courant croisé
WO2004017008A1 (fr) 2002-08-15 2004-02-26 Velocys, Inc. Procede de refroidissement d'un produit dans un echangeur thermique comportant des microcanaux
US20060228284A1 (en) * 2005-04-11 2006-10-12 Schmidt Craig A Integration of gasification and ammonia production
WO2010012981A2 (fr) 2008-07-31 2010-02-04 Bp Alternative Energy International Limited Séparation du dioxyde de carbone et de l’hydrogène

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108952861A (zh) * 2018-06-07 2018-12-07 上海柯来浦能源科技有限公司 液化工质中氢气升压床回收余热发电的装置和方法

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