WO2002068092A1 - Reacteur a membrane pour l'extraction de gaz - Google Patents

Reacteur a membrane pour l'extraction de gaz Download PDF

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Publication number
WO2002068092A1
WO2002068092A1 PCT/US2002/005717 US0205717W WO02068092A1 WO 2002068092 A1 WO2002068092 A1 WO 2002068092A1 US 0205717 W US0205717 W US 0205717W WO 02068092 A1 WO02068092 A1 WO 02068092A1
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WO
WIPO (PCT)
Prior art keywords
reactor
gas
purification system
membrane
gas purification
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PCT/US2002/005717
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English (en)
Inventor
Robert E. Buxbaum
Original Assignee
Buxbaum Robert E
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.)
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Publication date
Application filed by Buxbaum Robert E filed Critical Buxbaum Robert E
Priority to JP2002567444A priority Critical patent/JP4278984B2/ja
Priority to US10/469,276 priority patent/US20040136883A1/en
Publication of WO2002068092A1 publication Critical patent/WO2002068092A1/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
    • B01D53/22—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 diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/006—Baffles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2475—Membrane reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/2485—Monolithic reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
    • 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
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • 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
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/108—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/18—Specific valves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/22—Cooling or heating elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/22—Cooling or heating elements
    • B01D2313/221—Heat exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/42—Catalysts within the flow path
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/0009—Coils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00159—Controlling the temperature controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761—Details of the reactor
    • B01J2219/00763—Baffles
    • B01J2219/00765—Baffles attached to the reactor wall
    • B01J2219/0077—Baffles attached to the reactor wall inclined
    • B01J2219/00774—Baffles attached to the reactor wall inclined in the form of cones
    • 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
    • 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
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • 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
    • C01B2203/0405—Purification by membrane separation
    • C01B2203/041—In-situ membrane purification during hydrogen production
    • 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
    • C01B2203/0833—Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
    • 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
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1023—Catalysts in the form of a monolith or honeycomb
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • 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
    • C01B2203/1217—Alcohols
    • C01B2203/1223—Methanol
    • 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
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the present invention relates to an apparatus for the generation of a gas and the separation and purification of the generated gas from a mixed gas flow; and, more particularly, the generation of hydrogen by steam reforming liquid fuel and the purification of hydrogen from a mixture of gases using a hydrogen selective membrane.
  • a purifier either using membranes or pressure swing absorption often is used in-line after the reactor, but a better solution for many applications is a membrane reactor, a device that combines a hydrogen generating reactor and a hydrogen extracting membrane.
  • Membrane reactors combine in one vessel a reaction, that often is catalyzed with a membrane that extracts a product or introduces a reactant. Such reactors have advantages over conventional reactors especially for applications like converting liquid hydrocarbon fuels to hydrogen for use in fuel cells or for chemical applications.
  • Membrane reactors of this type are illustratively described in U.S. Patent Nos. 4,810,485; 5,888,273; 6,183,543 and 5,931,987.
  • an appropriate feedstock material such as methane-water, methanol-water or ammonia is heated to boiling outside of the reactor and reacted in the presence of a reaction catalyst. Hydrogen as well as undesirable gases are produced, but only the hydrogen is extracted through the membranes.
  • the catalyst is distributed within the reactor housing such that catalyst is in contact with a membrane making horizontal orientation of the reactor apparatus difficult because reaction catalyst displacement causes lower efficiency gas collection.
  • the hydrogen output of the reactor is determined in large part by heat transfer to the reaction catalyst and to a much lesser extent by permeation in the membrane or specific activity in the reaction catalyst. Heat transfer is increased temporarily by using higher temperature heating gases, for example, and reaction rates rise as expected, but this solution often harms the reaction catalyst and can reduce the overall thermal efficiency as well. Thus, there exists a need for a membrane reactor that achieves better thermal integration between a heat source and a reaction catalyst.
  • a gas purification system includes a reactor having a wall with both interior and exterior sides and a communicating portal therebetween for a mixed gas flow.
  • the system includes a heat conduit within the reactor volume.
  • the heat conduit has a wall having an interior side in contact with a heated material and an exterior side facing a gas selective membrane.
  • a reaction catalyst coating is in contact with the exterior side of the conduit wall.
  • a gas selective membrane resides within the reactor volume in contact with the mixed gas flow and selectively passes a constituent gas of the mixed gas flow therethrough with a raffinate of the mixed gas flow retained in contact with the membrane.
  • An outlet channel for removing the raffinate from contact with the membrane is provided, and a passageway for the removal of the constituent gas from the interior of said reactor is also provided.
  • the gas purification system optionally includes any of a combustion catalyst, preferably in contact with the interior side of the conduit wall, a flow distributor and a heat transfer element.
  • a fuel cell system is also provided herein.
  • An inventive fuel cell system includes a reactor having a volume and a wall, the wall has an interior side and an exterior side and a communicating portal therebetween for a mixed gas flow.
  • a gas selective membrane within the reactor volume is in contact with the mixed gas flow and selectively passes a constituent gas of the mixed gas flow therethrough whereby a raffinate of the mixed gas flow is retained in contact with the membrane.
  • An outlet channel is provided for removing the raffinate from contact with the membrane.
  • a raffinate compressor is disposed in a raffinate removal channel.
  • a passageway for removal of the constituent gas from the interior of the reactor is also provided.
  • the raffinate compressor is a venturi.
  • the fuel cell system includes a fuel cell powered by the constituent gas.
  • an inventive system in another embodiment, includes a reactor having a volume and a wall, the wall has an interior side and an exterior side and a communicating portal therebetween for a mixed gas flow.
  • a feed conduit is provided for delivering the mixed gas flow.
  • the feed conduit is in contact with the communicating portal so as to deliver the mixed gas to the inside of the reactor.
  • a gas selective membrane within the reactor volume is in contact with the mixed gas flow and selectively passes a constituent gas of the mixed gas flow therethrough whereby a raffinate of the mixed gas flow is retained in contact with the membrane.
  • An outlet channel is provided for removing the raffinate from contact with the membrane. The passageway for the removal of the constituent gas is in thermal contact with the feed conduit.
  • a passageway for removal of the constituent gas from the interior of the reactor is also provided.
  • the passageway for the removal of the constituent gas is brazed to the feed conduit.
  • an inventive system includes a reactor having a volume and a wall, the wall has an interior side and an exterior side and a communicating portal therebetween for a mixed gas flow.
  • a gas selective membrane within the reactor volume is in contact with the mixed gas flow and selectively passes a constituent gas of the mixed gas flow therethrough whereby a raffinate of the mixed gas flow is retained in contact with the membrane.
  • An outlet channel is provided for removing the raffinate from contact with the membrane.
  • a passageway for removal of the constituent gas from the interior of the reactor is also provided.
  • the system optionally includes any of the following: a raffinate burner, a feed pump, a feed pump controller, a feed:water ratio controller, a raffinate compressor, a back pressure regulator, a needle valve, a raffmate:air mix controller and an oxygen sensor.
  • an inventive system in another embodiment, includes a reactor that optionally includes multiple reaction catalysts within the reaction volume. In a further option, the reaction catalysts are differentially distributed within the reaction volume along a temperature gradient.
  • Figure 1 is a schematic-cross sectional view of a membrane reactor apparatus including a reaction catalyst coated on the external wall of the reactor according to the present invention.
  • Figure 2 is a perspective view of a membrane reactor of the present invention having a multichannel monolith.
  • Figure 3 is a perspective view of a membrane reactor having a coiled feed tube coated with combustion catalyst according to the present invention.
  • Figure 4 is an exploded view of a membrane reactor having fins inside the reactor volume.
  • FIG. 5 is a flow diagram illustrating a process for controlling a membrane reactor. Detailed Description of the Invention
  • Thermal integration of a heat source and a reaction catalyst is achieved by providing an apparatus to allow heat to transfer through a solid component to the reaction catalyst.
  • the reaction catalyst is coated on the interior of the reactor body and/or on the interior of a feed tube.
  • a coated feed tube functions as a pre-reactor.
  • the feed tube is coiled.
  • Further thermal integration is achieved by coating a combustion catalyst on an exterior surface of the reactor and/or feed tube ceramic support.
  • a reaction taking place in the reactor of the present invention illustratively includes a cracking reaction and an aromatization reaction.
  • the reactor includes a membrane selective for specific materials, such as a desired gas.
  • a hydrogen selective membrane is included.
  • a hydrogen selective membrane includes a hydrogen selective material such as palladium-coated refractory metals, or alloys of refractory metals, polymers, palladium-silver, palladium-copper, porous metals, silica and ceramics.
  • the desired gas generated by the reactor is a synthetic gas where an oxygen-containing gas mixture, such as air, contacts the oxygen selective membrane causing oxygen ions to diffuse through the membrane.
  • an oxygen-containing gas mixture such as air
  • a mixed gas containing a low molecular weight hydrocarbon, such as methane is brought into contact with the oxygen to form synthesis gas and higher hydrocarbons.
  • Catalysts for conversion of hydrocarbons to synthesis gas and membranes selective for oxygen are well known in the art as illustratively detailed in Nataraj et al., U.S. Patent 6,214,066.
  • a membrane included in the reactor of the present invention is preferably tubular and has a diameter ranging from 0.02 to 0.25 inches.
  • One or more membranes are included in the reactor.
  • Reaction catalyst coating Heat transfer by gas phase thermal conduction is less efficient than solid state thermal conduction.
  • the present invention provides solid state thermal conduction in a gas generating membrane reactor where the reaction catalyst 28 is coated on the interior side of the wall of a reactor, shown generally at 10 in Figure 1.
  • a feed tube for mixed gases having a wall with an interior side 12 and an exterior side 14 conducts gases into the reactor 10.
  • the reactor has a wall having an exterior side 16 and an interior side 18 coated with reaction catalyst.
  • a tube 20 has a selective membrane allows the passage of a desired gas through a purified gas outlet 26 for collection. Raffinate gas exits through a passage 24.
  • Suitable reaction catalysts include but are not limited to promoted nickel on alumina, nickel, copper-zinc oxide (G-66), and a mixture thereof.
  • a high level of gas production, such as hydrogen production, is observed with a mixture of catalysts.
  • a high temperature catalyst remains stable in the higher temperature reactor zones, while a low temperature catalyst maintains activity in the lower temperature zones.
  • a "high temperature catalyst” is defined to include materials that retain catalytic activity for at least one week at an operating temperature of over 300°C.
  • lower temperature catalyst includes material that retains catalytic activity for at least one week at an operating temperature below 300°C. This mixed catalyst effect is also achieved by initially distributing catalyst so that a high temperature or reforming catalyst goes into a high temperature zone, and a low temperature or water gas catalyst is initially placed into a lower temperature zone.
  • space is left unfilled between the reaction catalyst coated wall and the membrane.
  • the space between the reaction catalyst coated wall and the membrane optimally ranges from 0.05 to 1.0 inches. More preferably, the space ranges from 0.3 to 0.6 inches.
  • the space between the membrane and the catalyst on interior side of the wall is occupied by a flow distributor.
  • a flow distributor is composed of a suitable material illustratively including packing, particulate, mesh wire, wool, granule, pellet, or fluidized catalyst where the reactor is operated in a flow up mode with a proper distribution plate. Illustrative examples of appropriate packing are described in U.S. Patent No. 5,931 ,987.
  • a fluidized bed membrane reactor is illustratively described in U.S. Patent Nos. 5,326,550; 6,183,169; and 6,212,794.
  • the space between the catalyst on interior side of the wall and the membrane is filled by a multichannel monolith.
  • FIG. 2 specifically shows a configuration for generation of a syngas or higher hydrocarbon.
  • the reactor 30 encloses a monolith 34 containing a channel 36 coated with a selective membrane and reaction catalyst.
  • the monolith is sealed against the interior reactor wall using a gasket 38.
  • An air inlet 40 is present on one side of the monolith 34 while a lower hydrocarbon inlet valve 42 is present on an opposing side of the monolith. Exit passages for a desired gas and a waste gas are present at 44 and 46 respectively.
  • a suitable porous multichannel monolith substrate of this type is generated by techniques known to those skilled in the art.
  • a porous multichannel monolith suitable for inclusion in a reactor of the present invention has channels or pores of diameter ranging from 10 micrometers to 1 millimeter.
  • a monolith substrate, once cast, is coated with reaction catalyst.
  • the coating of the monolith substrate is achieved by a suitable method illustratively including dip coating.
  • the channels present in the monolith substrate are coated with a selective coating illustratively including palladium, palladium- copper or perovskite oxides and others described in U.S. Patent 5,458,857, so that the channels are gas transport selective.
  • a sintered filter is wash coated such that a layer of alumina ranging from 1 to 100 micrometers in thickness is deposited.
  • a wash coat of a selective membrane material such as palladium is then applied followed by a coating of a reaction catalyst such as Cu or Ce 2 O 3 .
  • the edges of the monolith substrate are then sealed, by methods for example including using a gasket.
  • monolith substrates as described in U.S. Patent No. 6,239,064 are operative herein. Appropriate selective coating processes are known for single channel monoliths and catalytically inactive porous substrates.
  • the monolith substrate is used in autothermal reforming or syngas production where the heat is generated within the channels as well as in endothermic reactions for which external heat is supplied.
  • the monolith substrate membrane reactor is used for an endothermic reaction such as that in which hydrogen is produced by methanol reforming or ammonia cracking
  • good thermal contact between the coated monolith substrate and the wall is preferred for efficient heat transfer.
  • the monolith is attached to the exterior wall of the reactor by any appropriate known method illustratively including using a ceramic paste.
  • the monolith is attached in a way that allows differential thermal expansion illustratively including use of a ceramic felt gasket. Felt gaskets are well known in the manufacture of automotive catalytic converters.
  • the selective membrane layer is coated on the interior surface of the monolith channels.
  • the reactor of the present invention is oriented in any desired direction including horizontal and vertical.
  • a heat source external to the reactor is required to drive the hydrogen-generation reaction. Heat is transferred to the reactor via a liquid or gas. Hot gases produced by combustion of the less desirable gases, or waste products of the reactor, are brought to the external surface of the reactor wall by a suitable method illustratively including free convection and low pressure forced convection.
  • a suitable method illustratively including free convection and low pressure forced convection.
  • the external thermal resistance is typically significant resulting in inefficient heat transfer from the hot gases external to the reactor to the internal reactor. Therefore, in a preferred embodiment, external heat is transferred by coating a combustion catalyst on an exterior wall of a reactor and driving the combustion gases and air over that surface, reducing external gas phase heat transfer resistance.
  • Application techniques for combustion catalysts are known to those skilled in the art of automotive catalytic converters.
  • the reactor wall is formed of a suitable material illustratively including metal such as aluminized stainless steel, stainless steel metal felt or reticulated metal or ceramic or mixtures such as platinum supported on a porous alumina ceramic and one of skill in the art will recognize the appropriate combination of reactor wall material and combustion catalyst material.
  • a combustion catalyst illustratively includes mixed oxides of platinum, palladium, chromium, nickel and rhodium.
  • heat is transferred from combustion gases to the reactor wall more effectively by increasing the surface area of the exterior surface of the reactor wall.
  • the surface area of the exterior surface is increased in any of a number of ways illustratively including adding an element such as bumps or packing to the exterior surface of the reactor wall or adding extended surface reactor vessel such as a fin tube.
  • a fin tube is oriented radially, axially or helically in direction with respect to the reactor wall.
  • An element of the reactor wall added to increase surface area is optionally coated with combustion catalyst.
  • the element of the reactor wall added to increase surface area is optionally a tubular feed for mixed gases. Also optionally, the tubular feed is coated with reaction catalyst on an interior aspect to function as a pre-reactor.
  • a heat transfer element is placed inside the reforming zone providing solid state heat transfer to the reforming catalyst.
  • a fin is used to conduct heat within the reforming zone from a heat conduit along a reactor wall.
  • a heat conduit runs internal to the reactor and defines a space between the conduit wall and the membrane, the catalytic reaction volume.
  • a fin optionally runs radially and axially along the conduit exterior wall thus extending into the catalytic reaction volume.
  • a fin is in contact with the conduit exterior wall and, optionally, in contact with the membrane.
  • the heat transfer element may provide structural support to the membrane.
  • a fin is brazed to the membrane, providing support thereto.
  • Further examples of a heat transfer element illustratively include a wire mesh, particulate, and others as listed herein.
  • heat is recovered from the purified gas and recycled for another purpose such as heating the feed.
  • an output tube containing hot purified gas is placed in close proximity to a feed tube containing relatively cooler material.
  • the output tube and the feed tube are oriented such that the materials moving through the tubes are flowing in a direction counter to each other.
  • the feed tube may be a tube for delivery of fuel or impure gas such as air, water to a hydrogen generator or delivery of an impure gas, such as hydrogen, to a hydrogen purifier.
  • the output tube is in contact with the feed tube and, more preferably, may be brazed to the feed tube. For example, silver braze is used to connect the output tube and the feed tube.
  • a relatively cool feed is in thermal contact with that portion of the reactor where a water gas reaction takes place.
  • a low pressure drop flow disruptor is added to the external gas flow channel of the reactor in order to disrupt a stagnant gas layer next to a reactor wall.
  • An illustrative example of low pressure drop gas flow disruptor is found in home hot water heaters where the designs are typically helical. It will be appreciated by those skilled in the art that other flow disruptor conformations may be desirable depending on the design of a particular reactor of the present invention.
  • the flow disruptor illustratively takes the form of bumps, protrusions, baffles or another shape such as a fin which generates turbulence in a stream of gas contacting the disruptor.
  • the exterior surface of a reactor is increased as described and combined with flow disrupting means in order to increase heat transfer efficiency.
  • the feed tube is coiled into a helix and brazed to the reactor as shown generally at 60 in Figure 3.
  • a feed tube for mixed gases 62 is helically coiled around the external wall of the reactor 64 leading into the reactor via a conduit 66. Inside the reactor the mixed gases react to produce a desired gas which passes through a selective membrane and exits through a purified gas outlet 68. Raffinate gas exits through passage 70.
  • a plug 76 is optionally included in the raffinate exit passage where necessary to hold reaction catalyst in place. This is particularly important where the gas flows upward.
  • a fitting 78 is optionally used to add or remove catalyst.
  • Heat is provided to the reactor in part by a heat source 72 and conducted through a chimney 74 enclosing the reactor. This combination provides additional surface area such that the feed tube surface area is almost as large as that of the original reactor, and the flow of combustion gases is disrupted from below at minimal pressure drop.
  • pellets of reaction catalyst, G66 are placed within the coiled feed tube to enhance internal heat transfer to the reactor and provide a pre-reactor with a large ratio of surface to volume.
  • a feed tube 82 leads into the reactor shown generally at 80.
  • Heat is provided to the reactor in part by a heat source (not shown) and conducted through a heat conduit 84.
  • the heat conduit 84 has an interior side 102 and an exterior side 108.
  • a fin 86 including a passageway 88 is present inside the reactor.
  • a desired gas passes through a selective membrane 90 to a space between the membrane 90 and the outer shell 92. Purified gas exits through an outlet 94.
  • a top plate 98 and a bottom plate 100 are adjacent to the top and bottom of the reactor respectively. The top and bottom plates aid in maintaining pressure within the reformer zone.
  • the top plate has an opening 104 to allow the feed in.
  • the top plate also includes a heat conduit 106.
  • the bottom plate has an aperture 110 for evacuation of raffinate and a heat conduit 112.
  • a heat transfer element may include a passage, such as that shown at 88, to allow reactant circulation contributing to flow disruption as described above. It is appreciated that curved membranes, dimples, protrusions, packing, mesh wire, wool, granulate, palletized catalyst and fluidized catalyst are operative herein as flow disruptors.
  • a passage has a diameter ranging from 10 micrometers to 1 centimeter. It is appreciated that variations and accessories are readily coupled to the inventive system, illustratively including placement of heat transfer material or combustion catalysts on a heat transfer surface of the reactor, coating reforming catalyst on an interior surface of the reactor body, adding a coiled feed tube, optionally coating a combustion catalyst on the exterior surface of the reactor or feed tube. Heat transfer within channels
  • external heat transfer enhancement occurs through heated channels within the reactor.
  • a hot purge gas, or sweep gas flows through the same channel as the membrane purified hydrogen and exits with the hydrogen.
  • a still more preferred embodiment includes a straight tube hydrogen permeable membrane with a catheter to allow the purge gas to be introduced and withdrawn.
  • the hydrogen produced flows through a shell provided with an inlet and an outlet and a sweep gas flows through the catheter and annular space of a tube, exiting with the formed hydrogen.
  • This configuration is useful in reactors converting methane or similar light hydrocarbons to benzene and similar higher hydrocarbons. For example, where 6CH - benzene + 9H 2 .
  • a method of enhancing heat transfer from the outside of the reactor to the inside can be combined with another , method of enhancing heat transfer or used alone.
  • a method or combination of methods for enhancing heat transfer from the outside of the reactor to the inside is combined with a method for enhanced heat transfer within the reactor such as coating a reaction catalyst on an interior wall of the reactor and placing a catalyst-coated monolith within the reactor. Sweep gas flow to lower partial pressure
  • a sweep gas is directed through a catheter to the inside of the hydrogen permeable tubes to decrease a partial pressure gradient across the membrane wall.
  • a suitable sweep gas for this application is an inexpensive, readily available, non-toxic gas that is readily separated from the hydrogen, such as steam.
  • a sweep gas is optionally an inert gas such as neon, argon, or nitrogen.
  • the feed liquid entering an inventive reactor is compressed using pressure energy in the raffinate.
  • raffinate gas is expanded against a piston and the liquid feed compressed using the other end of the piston turned smaller than the first piston end, or a second smaller piston attached by a rocker to the first piston.
  • a membrane reactor including a compressor optionally also includes a secondary pressure release for the expanding raffinate gases.
  • the mixed gas feed is controlled by provided valves. Compressor designs of this sort are known to those skilled in the art of steam locomotion. Suitable designs are shown in the book, "LBSC's shop, shed and road", by
  • a process for controlling a membrane reactor includes regulation of a number of variables of the reactor system including the amount of air sent to the burner, how much raffinate is sent to the burner, how much raffinate is sent to an optional mechanical energy recovery device, the fuel to water feed ratio and the feed pumping rate. Methods for control of any or all of these variables may be included in a process for controlling a membrane reactor as shown in generally in Figure 5 at 200.
  • a source of air 202 may be mixed with raffinate at a point before entering a burner 204 and the amount of air may be controlled by a mix controller 206.
  • the heated exhaust gas 210 which exits the burner 208 is preferably analyzed using an oxygen sensor 212 which provides electronic feedback at 214 to the mix controller in order to adjust the amount of air mixed with raffinate before entering the burner.
  • the range of oxygen to raffinate is in the range of 5:1 to 0.5:1.
  • the oxygen-raffmate mixture enters the burner at a 1 : 1 ratio. In general, slightly more oxygen is included to assure complete combustion. With too little air, energy is lost and carbon monoxide pollutants emerge from the reactor. With too much air, thermal energy is dissipated.
  • the amount of raffinate sent to the burner is regulated.
  • the present invention optionally uses a combination of a back-pressure regulator 232 and a needle valve 234 in parallel in order to regulate the amount of raffinate sent to the burner.
  • a safety pressure vent to air is incorporated (not shown).
  • a needle valve should be an adjustable constant flow valve such that flow is relatively insensitive to downstream pressure.
  • a common valve or frit may be used rather than a needle valve.
  • the fuel to water feed ratio is controlled to prevent coking among other problems.
  • Optimum mixes are determined by one skilled in the art. For example, an optimal ratio of water to methanol is in the range of 2:1 to 0.5:1 with a preferred ratio of about 1.1 :1.
  • the feed pumping rate is adjusted to control hydrogen output. Desirable hydrogen output pressure is typically determined by downstream uses. Feed pump rate control will also be important in controlling reactor temperature.
  • a feed pump rate controller used in a process of the present invention is preferably programmable to coordinate the optimal hydrogen output pressure with the optimal or desired reactor temperature.
  • a process for controlling a membrane reactor optionally comprises a fuel-water ratio controller shown at 216 to adjust the fuel-water mix which is fed into the reactor 222 by a feed pump shown at 218. The feed pump rate is controlled by a regulator shown at 220.
  • Further controls may include a secondary control and a shutoff (not shown). Where the temperature goes too low, as often occurs during startup, raw fuel may be diverted from the reactor to the burner. Alternatively, where the reactor temperature goes too high, as for example during periods where the catalyst or membrane has deactivated, the pump may be shut down.
  • Mechanisms used in combining these two effects in the controller illustratively include fuzzy logic programming.
  • any of these methods for controlling a membrane reactor may be used in combination with any other method for controlling a membrane reactor or alone.
  • a hydrogen consuming fuel cell may be combined with a hydrogen generator or purifier of the present invention as a fuel cell system.
  • an inventive reactor system allows a fuel cell to operate at sub-atmospheric pressure. Operation of a fuel cell at sub-atmospheric pressures is more efficient and allows an operator to use a greater proportion of the hydrogen generated as desired.
  • a preferred method of optimizing a reactor system operation is to create a vacuum to draw a small flow of low pressure bleed from the fuel cell.
  • a vacuum is created by exhausting the raffinate to the burner section through a venturi or pump 228.
  • a vacuum is created in the throat of the venturi, the vacuum can be used to draw a small flow of low pressure bleed from the fuel cell at sub-atmospheric pressure.
  • the resultant mixture of hydrogen, impurities, and raffinate is then communicated to the burner, e.g. to provide heat for the membrane reactor.
  • raffinate gases exit the reactor as shown at 226 and are optionally fed through a venturi shown at 228.
  • Purified hydrogen or a purified desired gas exits the reactor as shown at 224 and to an exemplary usage device shown herein as fuel cell 230.
  • the raffinate gas pressure may be regulated optionally by a back-pressure regulator 232 or a needle valve 234, preferably both in parallel. It is typically advantageous that a needle valve should be set so that most of the flow exits through the needle valve, even at maximum output.
  • this method of increasing the efficiency of the inventive reactor system may be used in combination with a heat transfer method, a method of feed liquid compression, with any other component or process of a membrane reactor as disclosed or alone.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

Le réacteur à membrane de la présente invention génère un gaz voulu tel que de l'hydrogène produit par reformage à la vapeur de combustibles liquides. Ce réacteur à membrane prévoit une intégration thermique entre la source de chauffage et le catalyseur de réaction par conduction thermique à travers un milieu solide. Un système de purification de gaz extrait de l'énergie des gaz résiduels pour chauffer le réacteur à membrane.
PCT/US2002/005717 2001-02-27 2002-02-27 Reacteur a membrane pour l'extraction de gaz WO2002068092A1 (fr)

Priority Applications (2)

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JP2002567444A JP4278984B2 (ja) 2001-02-27 2002-02-27 ガス抽出用メンブレン反応器
US10/469,276 US20040136883A1 (en) 2002-02-27 2002-02-27 Membrane reactor for gas extraction

Applications Claiming Priority (4)

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US27188301P 2001-02-27 2001-02-27
US60/271,883 2001-02-27
US33873701P 2001-12-05 2001-12-05
US60/338,737 2001-12-05

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009028145A1 (de) 2009-07-31 2011-02-03 Evonik Degussa Gmbh Keramische Membranen mit Polyaramid-Faser haltigen Supportmaterialien und Verfahren zur Herstellung dieser Membranen
DE102012202111A1 (de) * 2012-02-13 2013-08-14 Krones Ag Verfahren zur Steuerung und/oder Regelung von Filteranlagen zur Ultrafiltration

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5024674B2 (ja) * 2007-03-09 2012-09-12 日産自動車株式会社 水素分離装置
JP2015064306A (ja) * 2013-09-26 2015-04-09 日立Ｇｅニュークリア・エナジー株式会社 使用済核燃料集合体の輸送方法および使用済核燃料集合体の輸送容器

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US5746985A (en) * 1994-05-23 1998-05-05 Ngk Insulators, Ltd. Reforming reactor
US5938800A (en) * 1997-11-13 1999-08-17 Mcdermott Technology, Inc. Compact multi-fuel steam reformer
US20020006369A1 (en) * 2000-07-07 2002-01-17 Buxbaum Robert E. Membrane reactor for gas extraction

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US5746985A (en) * 1994-05-23 1998-05-05 Ngk Insulators, Ltd. Reforming reactor
US5938800A (en) * 1997-11-13 1999-08-17 Mcdermott Technology, Inc. Compact multi-fuel steam reformer
US20020006369A1 (en) * 2000-07-07 2002-01-17 Buxbaum Robert E. Membrane reactor for gas extraction

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009028145A1 (de) 2009-07-31 2011-02-03 Evonik Degussa Gmbh Keramische Membranen mit Polyaramid-Faser haltigen Supportmaterialien und Verfahren zur Herstellung dieser Membranen
DE102012202111A1 (de) * 2012-02-13 2013-08-14 Krones Ag Verfahren zur Steuerung und/oder Regelung von Filteranlagen zur Ultrafiltration

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