WO2009088971A1 - Reformage à la vapeur avec séparation des gaz de queue de psa - Google Patents

Reformage à la vapeur avec séparation des gaz de queue de psa Download PDF

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Publication number
WO2009088971A1
WO2009088971A1 PCT/US2009/000022 US2009000022W WO2009088971A1 WO 2009088971 A1 WO2009088971 A1 WO 2009088971A1 US 2009000022 W US2009000022 W US 2009000022W WO 2009088971 A1 WO2009088971 A1 WO 2009088971A1
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Prior art keywords
stream
psa
reformer
combustion
burner
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PCT/US2009/000022
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English (en)
Inventor
Jonathan Jay Feinstein
Michael P. Ralston
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Tribute Creations, Llc
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Publication of WO2009088971A1 publication Critical patent/WO2009088971A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • 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
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • 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
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • 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
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • 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
    • C01B2203/0495—Composition of the impurity the impurity being water
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/146—At least two purification steps in series
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
    • 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

Definitions

  • the present invention relates generally to the field of gas separation.
  • a "PSA unit” as used herein shall mean a pressure swing adsorption bed or group of beds working in parallel such that high and low pressure effluent flows from each of the parallel beds in the PSA unit to the next process unit or use point. Process gases may flow symmetrically back and fourth between multiple beds of a PSA unit without exiting the PSA unit. Multiple PSA units or the like shall describe the use of more than one bed or groups of beds such that a given high or low pressure effluent stream from one bed or group of beds subsequently passes unilaterally to a second bed or group of beds.
  • a steam-to-carbon ratio or S/C ratio is defined herein as the ratio of water molecules in the steam to the carbon atoms in the hydrocarbon feedstock of the steam and hydrocarbon mixture that are reformed in a reformer.
  • Unrecovered H 2 is defined herein as all H 2 exiting a PSA unit not contained in the product or high purity H 2 stream.
  • High purity H 2 is defined herein as gas containing at least 90% H 2 and preferably at least 99% H 2 .
  • SMR Steam methane reforming
  • H 2 O + CO H 2 + CO 2 at temperatures of 200° to 400° C.
  • a large portion of the unreacted steam is then removed by cooling the syngas and passing it through a liquid phase water separator.
  • the resulting syngas is often next separated by a PSA unit into a high purity hydrogen stream and a tail gas stream of the remaining species of CO 2 , CH 4 , CO, unrecovered H 2 , some H 2 O, and contaminants such as N 2 or Ar.
  • Tail gas containing a limited amount of methane slip can be utilized as fuel for the burners in the reformer.
  • SMR operation at S/C ratios of less than 2.8 referred to herein as steam lean reforming, causes greater methane slip to exit the reformer and water gas shift reactor than at higher S/C ratios in which the methane slip can be fully utilized as a fuel for the burners in the reformer.
  • S/C ratios less than about 2.8 to 1 and particularly below 2 to 1 the increased methane slip causes the combustion energy content of the tail gas to exceed the heating requirements of the burners in the reformer.
  • parallel reforming consist of a first stream of a hydrocarbon and steam being heated and reformed in a combustion heated first reformer and a second stream of a hydrocarbon and steam being heated and reformed with heat from the outlet reformed gas or from the flue gas from the first reformer. Because parallel reforming reforms more hydrocarbon and steam for a given amount of combustion heat compared to practices in which all of the hydrocarbon and steam are heated and reformed in a combustion heated reformer, the energy content of the resulting downstream PSA tail gas for parallel reforming is increased and may be in excess of the heat required by the combustion heated reformer.
  • the gas energy content of the PSA tail gas downstream of parallel reforming or steam lean reforming which is in excess of the combustion heated reformer requirements could be used to generate steam export from the SMR plant, but in many situations the steam may not be needed. If used in a gas turbine for driving compressors, the excess energy units may or may not be competitive to the alternative use of an electric motor. Further, the tail gas may contain sufficient quantities of CO, CO 2 , and/or H 2 as to prohibit its use as an export fuel, gas turbine fuel or in other applications. It may therefore be necessary to consume all of the tail gas energy within the SMR plant to monetize the energy savings that result from lowering the amount of fuel needed for combustion heating of the reformer in lean steam or parallel reforming practices.
  • wet scrubbing by physical or chemical absorption OfCO 2 into an amine or carbonate solution to extract CO 2 from syngas is known.
  • Use of wet scrubbing in combination with PSA is known to enable co-production of H 2 and CO 2 .
  • US Patent 5,669,960 incorporated herein by reference in its entirety, teaches the use of a single PSA unit to separate syngas from an SMR reformer and water gas shift unit into a high purity hydrogen stream, a combustible-rich tail gas stream, and a third stream that is combustible-lean and carbon dioxide-rich.
  • the purpose is to concentrate the energy content of the tail gas into a smaller volume of gas. This in turn permits the use of this tail gas as a burner fuel which produces a stable flame or as a recycled feedstock to the reformer.
  • the prior art solves a problem related to conventional SMR reforming in which the tail gas may have insufficient combustion energy content to support a stable flame.
  • US Patent 6,500,241 teaches co- production of H 2 and CO 2 from syngas evolved from a reformer or partial oxidation unit followed by a water gas shift reactor.
  • a wet scrubbing unit is used in combination with a H 2 PSA unit and a liquefaction unit.
  • the patent teaches the use of a CO 2 PSA unit, a H 2 PSA unit, and a liquefaction unit. The recycling of an intermediate stream to the H 2 PSA for increased H 2 yield is taught.
  • Use of either of the disclosed combinations of three separation process units requires substantially more capital equipment investment.
  • Steam and a hydrocarbon feedstock are reformed in a combustion heated reformer in such a way that the fuel requirements for reforming are less than the energy content of the downstream PSA tail gas, preferably by employing at least one of reformer at a S/C ratio of less than 2.8 and more prefereably less than 2 to 1 or by employing parallel reforming.
  • the syngas is separated in one or more PSA units into at least a stream containing high purity hydrogen, at least one process gas recycle stream containing tail gas energy units which together with the burner stream exceed the energy units required for heating the reformer, and a burner stream containing the balance of the PSA inlet gases and preferably containing no more energy units than are required for heating the reformer.
  • the recycle streams are recycled as process gas to the reformer, the PSA, or both, and the burner stream is used for heating the reformer.
  • FIG. 1 is a schematic representation of the present invention according to a first embodiment.
  • FIG. 2 is a schematic representation of the present invention according to a second embodiment.
  • FIG. 3 is a schematic representation of the present invention according to a third embodiment.
  • FIG. 4 is a schematic representation of the present invention according to a preferred fourth embodiment.
  • FIG. 5 is a schematic representation of the present invention according to a fifth embodiment.
  • FIG. 6 is a schematic representation of the present invention according to a sixth embodiment.
  • a hydrocarbon feedstock such as methane is combined with steam at a S/C ratio of less than 2.8 and preferably less than 2, or steam and a hydrocarbon are parallel reformed. Reforming preferably takes place at a pressure in excess of 10 bar and the mixture is introduced together via line 1 into one or more reformers 2 wherein the reactants are heated and reacted to form a syngas in the presence of a suitable catalyst. While one reformer 2 is shown in Fig. 1 , it is foreseen that more than one reformer may be employed.
  • Use of a reforming catalytic reactor with high effective catalyst loading and high axial heat transfer enables reforming to take place at low S/C ratios without forming coke deposits in the reforming catalytic reactor.
  • US patent application 2006/0008399A 1 and WIPO patent application WO2006/058060A2 which are incorporated herein by reference in their entirety, teach examples of suitable reforming catalytic reactors.
  • the outlet syngas from the reformers is conveyed by line 3 to heat exchanger 4 in which the syngas is cooled to a temperature of around 200 0 C.
  • the syngas is preferably conveyed by line 5 to optional water gas shift reactor 6 in which the H 2 O and CO contents of the syngas are reduced and the H 2 and CO 2 contents are increased.
  • the syngas is preferably conveyed by line 7 to optional heat exchanger 8 in which the syngas is further cooled.
  • the syngas is preferably then conveyed by line 9 to optional water separation unit 10 in which water condensate is removed.
  • the partially dried syngas is then conveyed by line 1 1 to a PSA unit 12 in which the syngas is separated into various product and tail gas streams.
  • the PSA unit is a conventional H 2 PSA unit as is typically used in an SMR plant.
  • the PSA unit is fitted with valves to separate the inlet gas, which is provided to the PSA unit, into a high purity H 2 stream designated the product stream, and two tail gas streams designated the burner stream and the feedstock stream, respectively.
  • the product stream containing high purity H 2 exits the PSA unit via line 13.
  • a feedstock stream exits the PSA unit via line 14, is subsequently compressed in compressor 15, and is recycled to the process gas inlet line 1 of the reformer via line 16.
  • a burner stream exits the PSA unit via line 17, which conveys the burner stream to the reformer burners (not shown) providing at least part of the burner fuel requirements.
  • Line 17 may contain a blower or compressor (not shown).
  • the product stream provided in line 13 contains most of the inlet H 2 to the PSA unit in the form of high purity H 2 .
  • the product stream exits the product or high pressure outlet end of each bed in the PSA unit.
  • the feedstock stream contains CH 4 , most of the H 2 O and CO 2 , and some of the unrecovered hydrogen.
  • the feedstock stream preferably contains at least all tail gas energy units in excess of the energy units required for the reformer burner fuel requirements, with as much of those excess energy units as possible being in the form Of CH 4 and as few as possible being in the form of H 2 .
  • the burner stream contains the balance of the inlet gas to the PSA unit and preferably contains no more energy units than are required for heating the reformer. All tail gas streams of each embodiment exit the opposite end of each bed from the product stream. The method and apparatus for separating the tail gas into multiple streams of different compositions from each other are described below.
  • a second embodiment is illustrated in which all components corresponding to Figure 1 have the same numbering as in Fig. 1.
  • all of the components of the first embodiment are employed, and an additional tail gas stream designated the CO 2 stream is conveyed from PSA unit 12 via line 18.
  • the CO 2 stream contains most of the H 2 O and CO 2 from the inlet gas to the PSA unit.
  • the product stream contains high purity hydrogen, and the feedstock stream contains at least some of the energy units exceeding the energy units required for heating the reformer.
  • the burner stream contains the balance of the inlet gas to the PSA unit, including most of the unrecovered H 2 and preferably contains no more energy units than are required for heating the reformer.
  • the CO 2 stream is vented, beneficiated into a useful product, or sequestered from the atmosphere. CO 2 beneficiation may be by means of compression, further purification, or both.
  • a third embodiment is illustrated in which all components corresponding to Fig. 1 have the same numbering as in Fig. 1.
  • all of the components of the first embodiment are employed, and an additional tail gas stream designated the PSA recycle stream is conveyed from PSA unit 12 via line 19, which is compressed in compressor 20 and is then returned via line 21 to the inlet line of PSA unit 12 or is equivalently returned to PSA unit 12.
  • the product and feedstock stream gas contents are as defined above in connection with the first embodiment.
  • the PSA recycle stream contains a substantial portion of the unrecovered H 2 .
  • the PSA recycle stream preferably contains only as much H 2 as is possible consistent with a suitable H 2 concentration so as to make its compression and recovery via PSA unit 12 economically attractive in view of its effect on net capital and energy costs.
  • the burner stream contains the balance of the inlet gas to PSA unit 12 and preferably contains no more energy units than are required for heating the reformer.
  • a preferred fourth embodiment is illustrated in which all components corresponding to Fig. 3 have the same numbering as in Fig. 3.
  • all of the components of the third embodiment are employed, and an additional tail gas stream designated the CO 2 stream is conveyed from PSA unit 12 via line 18.
  • the product and PSA recycle stream gas contents are as defined in the third embodiment
  • the feedstock stream contains at least some of the energy units in excess of the energy requirements for heating the reformer
  • the CO 2 stream contains most of the H 2 O and CO 2 from the inlet gas to the PSA unit
  • the burner stream contains the balance of the inlet gas to the PSA unit and preferably contains no more energy units than are required for heating the reformer.
  • a fifth embodiment is illustrated in which all components corresponding to Fig. 1 have the same numbering as in Fig. 1.
  • all of the components of the first embodiment are employed except that items 14, 15, and 16 for conveying a feedstock stream to the reformer inlet line are not included, and an additional tail gas stream designated the PSA recycle stream is conveyed from PSA unit 12 via line 19. is compressed in compressor 20 and returned via line 21 to PSA inlet line 1 1 or is equivalently returned to PSA unit 12.
  • the product stream gas content is high purity H 2 .
  • the PSA recycle stream contains a substantial portion of the unrecovered H 2 .
  • the PSA recycle stream preferably contains only as much H 2 as is possible consistent with a suitable H 2 concentration so as to make its compression and recovery via the PSA unit economically attractive in view of its effect on net capital and energy costs.
  • the burner stream contains the balance of the inlet gas to the PSA unit and preferably contains no more energy units than are required for heating the reformer. No tail gas is separated or recirculated as feedstock to the reformer inlet.
  • the energy units in excess of those required for use in the reformer burners is separated from the tail gas in the form of H 2 for recirculation to the PSA unit, as opposed to in all other embodiments in which the excess energy units are at least partly separated in the form of CH 4 for recirculation to the reformer.
  • the tail gas streams are separated from each other as required in each embodiment by timing the opening and closing of valves at the tail gas outlet end of each PSA bed to allow the gas exiting each bed at particular times to be directed to the respective tail gas outlet lines described in the respective embodiments. While not being held to this explanation or sequence, it is understood that molecular sieves used in PSA units for separating a high purity H 2 product have different adsorptive affinities for H 2 O, CO 2 , CH 4 , CO, and H 2 , such that these respective gases exit PSA beds as tail gas in this approximate and overlapping sequence during the collective depressurization and purge portions of a complete PSA process cycle.
  • the CO 2 stream, followed by the feedstock stream followed by the burner stream followed by the PSA recycle stream are diverted from a given bed by opening only valves to lines 18, 17, 14, and 19, respectively, while all other valves to outlet lines are closed, to the extent that each of these respective tail gas streams is employed in the respective embodiments.
  • Any or all outlet lines 18, 17, 14, and 19, respectively may contain a surge tank.
  • the various molecular sieves are preferably layered from the gas inlet end to the H 2 product outlet end in such sequence as to accentuate H 2 recovery and separation of the tail gas stream compositions from each other.
  • different molecular sieves are preferably used in the sequence of PSA units as to accentuate H 2 recovery and separation of the tail gas stream compositions from each other.
  • a sixth embodiment is illustrated in which all components corresponding to Fig. 3 have the same numbering as in Fig. 3.
  • syngas is conveyed from water separator 10 via line 22 to PSA unit 23, in which the syngas is separated into a first stream and a CO 2 stream.
  • the first stream is conveyed via line 11 to PSA unit 12, which corresponds to PSA unit 12 in Figure 3.
  • All outlet lines from PSA unit 12 correspond to those of like numbering exiting unit 12 in Figure 3.
  • the CO 2 stream is exported from PSA unit 23 and from the system via line 24.
  • PSA unit 23 contains a molecular sieve for separating H 2 O and CO 2 from syngas.
  • the CO 2 stream exported via line 24 contains most of the H 2 O and CO 2 entering PSA unit 23, and preferably contains less than 10% CH 4 and yet smaller volume percentages of CO and H 2
  • the balance of the syngas entering PSA unit 23 is conveyed to PSA unit 12 via line 1 1.
  • a PSA recycle stream exits PSA unit 12 via line 19 and preferably contains only as much H 2 as is possible consistent with a suitable H 2 concentration so as to make its compression and recovery via PSA unit 12 economically attractive in view of its effect on net capital and energy costs.
  • a feedstock stream exits PSA unit 12 via line 14 and contains at least some of the energy units exceeding the energy requirements needed for heating the reformer.
  • a burner stream exits PSA unit 12 via line 14 and contains the balance of the inlet gas to PSA unit 12. The burner stream preferably contains no more energy units than are required for heating in the reformer.

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  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

L'invention concerne de la vapeur et une matière première d'hydrocarbure qui sont reformés dans un reformeur chauffé par combustion d'une manière selon laquelle la teneur énergétique du gaz de queue de PSA en aval dépasse les exigences de chauffage du reformeur. Le gaz de synthèse est séparé dans une ou plusieurs unités de PSA dans au moins un flux d'hydrogène haute pureté, au moins un flux de recyclage de gaz de traitement contenant des unités énergétiques de gaz de queue dépassant les unités énergétiques nécessaires pour chauffer le reformeur, et un flux de brûleur contenant le reste des gaz d'entrée de PSA et ne contenant de préférence pas plus d'unités énergétiques que nécessaires pour chauffer le reformeur. Les flux de recyclage sont recyclés sous la forme de gaz de traitement vers le reformeur, le PSA ou les deux, et le flux de brûleur est utilisé pour chauffer le reformeur.
PCT/US2009/000022 2008-01-04 2009-01-05 Reformage à la vapeur avec séparation des gaz de queue de psa WO2009088971A1 (fr)

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WO2013131916A1 (fr) * 2012-03-08 2013-09-12 Shell Internationale Research Maatschappij B.V. Procédé de production d'hydrogène
US20150175417A1 (en) * 2012-06-25 2015-06-25 Sk Innovation Co., Ltd. Method for modifying carbon dioxide using carbon black catalyst
US9067169B2 (en) 2013-05-28 2015-06-30 Uop Llc Methods of preparing an impurity-depleted hydrogen stream, methods of analyzing content of an impurity-depleted hydrogen stream, and pressure swing adsorption apparatuses
WO2018127388A1 (fr) * 2017-01-05 2018-07-12 Solvay Sa Unité de séparation de gaz à grande echelle comprenant un rotor avec une pluralité de secteurs et un stator
CN112203973A (zh) * 2018-06-29 2021-01-08 普莱克斯技术有限公司 Psa缓冲罐内的尾气加热
CN112897462A (zh) * 2019-12-03 2021-06-04 现代自动车株式会社 使用废气作为冷却介质的重整系统和重整方法
GB2592695A (en) * 2020-03-06 2021-09-08 Reinertsen New Energy As Hydrogen and/or ammonia production process
WO2022040677A1 (fr) * 2020-08-17 2022-02-24 Jonathan Jay Feinstein Reformage à la vapeur à capture de carbone
WO2023164500A3 (fr) * 2022-02-23 2023-10-26 Jonathan Jay Feinstein Reformage avec capture de carbone

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US6183628B1 (en) * 1999-03-19 2001-02-06 Membrane Technology And Research, Inc. Process, including PSA and membrane separation, for separating hydrogen from hydrocarbons
US20050066813A1 (en) * 2003-09-25 2005-03-31 Dunn Graeme John High recovery carbon monoxide production process
US20060156921A1 (en) * 2003-07-24 2006-07-20 Christian Monereau Adsorption method for producing hydrogen and device for carrying out said method
US20070264186A1 (en) * 2004-09-09 2007-11-15 Dybkjaer Ib Process for Production of Hydrogen and/or Carbon Monoxide

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US6183628B1 (en) * 1999-03-19 2001-02-06 Membrane Technology And Research, Inc. Process, including PSA and membrane separation, for separating hydrogen from hydrocarbons
US20060156921A1 (en) * 2003-07-24 2006-07-20 Christian Monereau Adsorption method for producing hydrogen and device for carrying out said method
US20050066813A1 (en) * 2003-09-25 2005-03-31 Dunn Graeme John High recovery carbon monoxide production process
US20070264186A1 (en) * 2004-09-09 2007-11-15 Dybkjaer Ib Process for Production of Hydrogen and/or Carbon Monoxide

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013131916A1 (fr) * 2012-03-08 2013-09-12 Shell Internationale Research Maatschappij B.V. Procédé de production d'hydrogène
US20150175417A1 (en) * 2012-06-25 2015-06-25 Sk Innovation Co., Ltd. Method for modifying carbon dioxide using carbon black catalyst
US9067169B2 (en) 2013-05-28 2015-06-30 Uop Llc Methods of preparing an impurity-depleted hydrogen stream, methods of analyzing content of an impurity-depleted hydrogen stream, and pressure swing adsorption apparatuses
WO2018127388A1 (fr) * 2017-01-05 2018-07-12 Solvay Sa Unité de séparation de gaz à grande echelle comprenant un rotor avec une pluralité de secteurs et un stator
CN112203973A (zh) * 2018-06-29 2021-01-08 普莱克斯技术有限公司 Psa缓冲罐内的尾气加热
CN112203973B (zh) * 2018-06-29 2023-10-27 普莱克斯技术有限公司 Psa缓冲罐内的尾气加热
CN112897462A (zh) * 2019-12-03 2021-06-04 现代自动车株式会社 使用废气作为冷却介质的重整系统和重整方法
CN112897462B (zh) * 2019-12-03 2024-04-02 现代自动车株式会社 使用废气作为冷却介质的重整系统和重整方法
GB2592695A (en) * 2020-03-06 2021-09-08 Reinertsen New Energy As Hydrogen and/or ammonia production process
GB2592695B (en) * 2020-03-06 2022-08-31 Reinertsen New Energy As Hydrogen and/or ammonia production process
WO2022040677A1 (fr) * 2020-08-17 2022-02-24 Jonathan Jay Feinstein Reformage à la vapeur à capture de carbone
WO2023164500A3 (fr) * 2022-02-23 2023-10-26 Jonathan Jay Feinstein Reformage avec capture de carbone

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