US20060029541A1 - Method and apparatus for obtaining enhanced production rate of thermal chemical reactions - Google Patents

Method and apparatus for obtaining enhanced production rate of thermal chemical reactions Download PDF

Info

Publication number
US20060029541A1
US20060029541A1 US11236125 US23612505A US2006029541A1 US 20060029541 A1 US20060029541 A1 US 20060029541A1 US 11236125 US11236125 US 11236125 US 23612505 A US23612505 A US 23612505A US 2006029541 A1 US2006029541 A1 US 2006029541A1
Authority
US
Grant status
Application
Patent type
Prior art keywords
catalyst
reaction
reaction chamber
heat
porous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11236125
Inventor
Anna Tonkovich
Yong Wang
Robert Wegeng
Yufei Gao
Original Assignee
Tonkovich Anna L Y
Yong Wang
Wegeng Robert S
Yufei Gao
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093Microreactors, e.g. miniaturised or microfabricated reactors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J12/00Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/007Chemical 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24Stationary reactors without moving elements inside
    • B01J19/248Reactors comprising multiple separated flow channels
    • B01J19/249Plate-type reactors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0285Heating or cooling the reactor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067Heating or cooling the reactor
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06Production 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
    • C01B3/12Production 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
    • C01B3/16Production 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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
    • C01B3/384Production 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/48Production 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
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28DHEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D7/00Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00168Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00194Tubes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00168Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212Plates; Jackets; Cylinders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00309Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781Aspects relating to microreactors
    • B01J2219/00783Laminate assemblies, i.e. the reactor comprising a stack of plates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781Aspects relating to microreactors
    • B01J2219/00788Three-dimensional assemblies, i.e. the reactor comprising a form other than a stack of plates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781Aspects relating to microreactors
    • B01J2219/00819Materials of construction
    • B01J2219/00822Metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781Aspects relating to microreactors
    • B01J2219/00819Materials of construction
    • B01J2219/00835Comprising catalytically active material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781Aspects relating to microreactors
    • B01J2219/00851Additional features
    • B01J2219/00858Aspects relating to the size of the reactor
    • B01J2219/0086Dimensions of the flow channels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781Aspects relating to microreactors
    • B01J2219/00873Heat exchange
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781Aspects relating to microreactors
    • B01J2219/0095Control aspects
    • B01J2219/00984Residence time
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24Stationary reactors without moving elements inside
    • B01J2219/2401Reactors comprising multiple separate flow channels
    • B01J2219/245Plate-type reactors
    • B01J2219/2451Geometry of the reactor
    • B01J2219/2453Plates arranged in parallel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24Stationary reactors without moving elements inside
    • B01J2219/2401Reactors comprising multiple separate flow channels
    • B01J2219/245Plate-type reactors
    • B01J2219/2451Geometry of the reactor
    • B01J2219/2454Plates arranged concentrically
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24Stationary reactors without moving elements inside
    • B01J2219/2401Reactors comprising multiple separate flow channels
    • B01J2219/245Plate-type reactors
    • B01J2219/2451Geometry of the reactor
    • B01J2219/2456Geometry of the plates
    • B01J2219/2458Flat plates, i.e. plates which are not corrugated or otherwise structured, e.g. plates with cylindrical shape
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24Stationary reactors without moving elements inside
    • B01J2219/2401Reactors comprising multiple separate flow channels
    • B01J2219/245Plate-type reactors
    • B01J2219/2461Heat exchange aspects
    • B01J2219/2465Two reactions in indirect heat exchange with each other
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24Stationary reactors without moving elements inside
    • B01J2219/2401Reactors comprising multiple separate flow channels
    • B01J2219/245Plate-type reactors
    • B01J2219/2476Construction materials
    • B01J2219/2477Construction materials of the catalysts
    • B01J2219/2481Catalysts in granular from between plates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24Stationary reactors without moving elements inside
    • B01J2219/2401Reactors comprising multiple separate flow channels
    • B01J2219/245Plate-type reactors
    • B01J2219/2491Other constructional details
    • B01J2219/2497Size aspects, i.e. concrete sizes are being mentioned in the classified document
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0283Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/0495Composition of the impurity the impurity being water
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06Integration with other chemical processes
    • C01B2203/066Integration with other chemical processes with fuel cells
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0833Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005Arrangement or shape of catalyst
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005Arrangement or shape of catalyst
    • C01B2203/1023Catalysts in the form of a monolith or honeycomb
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005Arrangement or shape of catalyst
    • C01B2203/1029Catalysts in the form of a foam
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1047Group VIII metal catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1047Group VIII metal catalysts
    • C01B2203/1052Nickel or cobalt catalysts
    • C01B2203/1058Nickel catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1047Group VIII metal catalysts
    • C01B2203/1064Platinum group metal catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1082Composition of support materials
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235Hydrocarbons
    • C01B2203/1241Natural gas or methane
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235Hydrocarbons
    • C01B2203/1247Higher hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288Evaporation of one or more of the different feed components
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16Controlling the process
    • C01B2203/1614Controlling the temperature
    • C01B2203/1619Measuring the temperature
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16Controlling the process
    • C01B2203/1628Controlling the pressure
    • C01B2203/1633Measuring the pressure
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16Controlling the process
    • C01B2203/1642Controlling the product
    • C01B2203/1647Controlling the amount of the product
    • C01B2203/1652Measuring the amount of product
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16Controlling the process
    • C01B2203/1642Controlling the product
    • C01B2203/1671Controlling the composition of the product
    • C01B2203/1676Measuring the composition of the product
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16Controlling the process
    • C01B2203/169Controlling the feed
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

Abstract

Reactors and processes are disclosed that can utilize high heat fluxes to obtain fast, steady-state reaction rates. Porous catalysts used in conjunction with microchannel reactors to obtain high rates of heat transfer are also disclosed. Reactors and processes that utilize short contact times, high heat flux and low pressure drop are described. Improved methods of steam reforming are also provided.

Description

    RELATED APPLICATIONS
  • This application is a continuation-in-part of U.S. Ser. No. 09/123,779 which are incorporated by reference.
  • This invention was made with Government support under Contract DE-AC0676RLO1830 awarded by the U.S. Department of Energy. The Government has certain rights in the invention.
  • FIELD OF THE INVENTION
  • The present invention relates to a method and apparatus for thermal chemical reactions. The method and apparatus can provide an enhanced reaction rates for thermal chemical reactions.
  • BACKGROUND OF THE INVENTION
  • Thermal chemical reactions are those chemical reactions that produce (exothermic) or consume (endothermic) heat. Examples of thermal chemical reactions include hydrocarbon conversion reactions such as steam reforming, water-gas shift reactions and combustion. These well-known reactions are usually carried out in the presence of a catalyst at temperatures up to about 1300° C. Because the intrinsic kinetics of a thermal chemical reaction can be much faster than the heat transfer rate between the reaction vessel and the thermal sink, source or environment, the actual rate of product production (i.e., the observed rate) is slower than the intrinsic rate. Intrinsic kinetics means the rate at which products could theoretically be formed at the catalyst surface.
  • Limited production rates may result from longer residence time which is typically seconds to minutes in conventional thermal chemical reaction vessels. As it is conventionally defined, residence time is equal to the volume of the reaction zone divided by the inlet volumetric flow rate of reactants at the reaction system's temperature and pressure. The reaction zone is the total volume of the catalyst and surrounding area through which reactants and products flow.
  • An example of these limited production rates can be seen in the water gas shift reaction which is conventionally carried out in fixed bed reactors. In the water gas shift reaction, carbon monoxide and water are converted to carbon dioxide and hydrogen. Conventionally, this reaction suffers from multiple-second residence times (a kinetic impediment) when carried out in fixed bed reactors. Theoretical kinetics suggests that residence times on the order of milliseconds could, theoretically, be obtained. There are two kinetic retarding aspects to conventional reactors. The first is a diffusion limitation as reactants diffuse into and out of a catalyst-bearing porous pellet and the second is a heat transfer limitation which is a combination of heat transfer parameters (thermal conductivity and length) of catalyst supports and overall reactor geometry (shape, size, and distance to the external heat exchanger). Because the water gas shift reaction is critical to a multi-reactor fuel processing system that supports distributed energy production through the use of a fuel cell, there is a need for a smaller, faster water gas shift reactor.
  • Another example of a thermal chemical reaction is in the conventional methane steam reforming reactor which produces synthesis gas at an average residence time of several seconds and with an effectiveness factor of 0.01 to 0.05 as reported by Adris, A., Pruden, B., Lim, C., J. Grace, 1996, “On the reported attempts to radically improve the performance of the steam methane reforming reactor,” Canadian Journal of Chemical Engineering, 74, 177-186. In a typical industrial operation, the methane to steam ratio is run at 3:1 to prevent coke formation. Efforts to improve heat transfer between the reaction vessel for this endothermic reaction and the thermal source have made only modest improvements in product production rate.
  • Thermal reactions have long been, and continue to be, conducted in huge volumes on production scales requiring very large capital investments, typically greater than $100 million. Not surprisingly, there have been extensive efforts, over a long period of time, aimed at improving the speed and efficiency of these reactions. Despite these attempts, there remains a need for a method and apparatus that increase the heat transfer rate between the reaction vessel and the thermal sink or source and thereby approach the theoretical intrinsic kinetic rate of reaction and production.
  • SUMMARY OF THE INVENTION
  • The present invention provides methods and apparatuses for obtaining an enhanced production rate per reaction chamber volume of a reaction chamber with an inlet and an outlet for a thermal chemical reaction, wherein a ratio of the enhanced production rate per reaction chamber volume to a conventional production rate per conventional reaction chamber volume for the thermal chemical reaction is at least 2. For example, for conventional steam reforming, residence time is on the order of seconds whereas with the present invention, residence time is less by a factor of 2, on the order of milliseconds to tens or hundreds of milliseconds. In one aspect, the invention includes:
      • (a) a porous insert within the reaction chamber volume, wherein a reactant flow substantially completely passes through the porous insert wherein the reaction chamber volume with the porous insert has a mean porosity less than 1 and a mass transport distance of reactants to a catalyst site of no greater than 3 mm;
      • (b) the reaction chamber volume with a length parallel to a bulk reactant flow, the length less than or equal to 6 inches, and with a height (a thermal distance from the heat sink to the heat source) less than or equal to 2 inches, thereby transferring reaction heat at an enhanced heat transfer rate through the porous insert; and
      • (c) a heat transfer chamber in thermal contact with the reaction chamber volume, serving as a heat sink or heat source, the heat transfer chamber transferring heat at said enhanced heat transfer rate across a wall between the heat transfer chamber and the reaction chamber, thereby obtaining the enhanced production rate per reaction chamber volume for the thermal chemical reaction wherein a ratio of the enhanced production rate per reaction chamber volume to a conventional production rate per conventional reaction chamber volume for the thermal chemical reaction is at least 2.
  • These features have been found to cooperate with the reaction kinetics in terms of transferring heat at a rate sufficient to avoid substantial impediment of the kinetics. These features are effective for both catalytic and non-catalytic thermal chemical reactions. For catalytic chemical reactions, addition of a thin catalyst layer (<150 microns, μm, more preferably less than 50 μm) upon the porous insert substantially reduces the diffusion pathways of reactants to catalyst sites compared with more severe limitations of reactant diffusion within ceramic pellets (>1 mm) as in conventional systems. Thus, according to the present invention, for catalytic thermal chemical reactions, both kinetic impediments are substantially reduced permitting realization of theoretical or near theoretical reaction kinetics. More specifically, a water gas shift reactor made according to the present invention has 1/10th to 1/100th the size of conventional processing hardware for the same production output.
  • The present invention further provides a method and apparatus (vessel) for providing a heat transfer rate from a reaction chamber through a wall to a heat transfer chamber (exothermic reaction) or providing heat from a heat transfer chamber through a wall to a reaction chamber (endothermic reaction) substantially matching a local heat transfer requirement of a catalytic thermal chemical reaction. An important aspect of this invention is the thermal distance defined on a cross sectional plane through the vessel inclusive of a heat transfer chamber, reaction chamber and a wall between the chambers. The cross sectional plane is perpendicular to a bulk flow direction of the reactant stream, and the thermal distance is a distance between a coolest position and a hottest position on the cross sectional plane. The thermal distance is of a length wherein the heat transfer rate from (or to) the reaction chamber to (or from) a heat transfer chamber (heat exchanger) substantially matches the local heat transfer rate.
  • The invention includes a process for the catalytic conversion of at least one reactant in a thermal chemical reaction, in which at least one reactant is passed into at least one reaction chamber; heat is transferred to or from the reaction chamber into at least one heat exchanger; and at least one product is obtained. The reaction chamber contains a catalyst that catalyzes the reaction of the reactant or reactants. In preferred embodiments, the process has one or more of the following characteristics: at steady state, at least 0.6 W/(cc of total reactor volume) of heat is transferred, where total reactor volume is defined as the sum of the volume of the reaction chamber(s) and heat exchanger chamber(s) including the volume of chamber walls; the contact time of the reactant with the catalyst is less than about 0.3 seconds; and the pressure drop through the reaction chamber is less than about 15 psig.
  • One example of a thermal chemical reaction that can be conducted using methods and reactors of the present invention is steam reforming of a hydrocarbon. In this process a feed stream comprising hydrocarbon gas and steam is passed into a reaction chamber which contains a catalyst that catalyzes the reaction of hydrocarbon gas and steam to produce a gaseous mixture comprising at least carbon monoxide and hydrogen gas. This process can produce more than 0.01 SLPM of hydrogen gas per cubic centimeter of total reactor volume.
  • The present invention also provides a reactor for the catalytic conversion of at least one reactant in a thermal chemical reaction, comprising: at least one reaction chamber containing a porous catalyst insert; and at least one heat exchanger that is in thermal contact with the reaction chamber. The reaction chamber has a length less than or equal to 6 inches and a height less than or equal to 2 inches. The porous catalyst insert comprises a porous metal foam having open cells ranging from about 20 ppi to about 3000 ppi.
  • The invention also includes a reactor in which the reaction chamber has a height less than or equal to 2 inches; and wherein at least one heat exchanger and at least one reaction chamber are configured such that, during steady-state operation, at least 0.6 W of heat per cc of total reactor volume can be transferred between the heat exchanger and the reaction chamber.
  • The invention also includes a process for the catalytic conversion of at least one reactant in a thermal chemical reaction in which at least one reactant is passed into at least one reaction chamber that contains a catalyst that catalyzes the reaction of the at least one reactant; transferring heat to or from said at least one reaction chamber from or into said at least one heat exchanger; and obtaining at least one product from the reaction chamber; where the step of transferring heat, at steady-state, transfers at least 0.6 W of heat per cc of total reactor volume, such that, at steady state, the catalyst is maintained within a temperature range that reduces the formation of at least one undesirable chemical reaction product. Alternatively, the formation of undesirable chemical product(s) can be reduced by utilizing a contact time of less than about 0.3 seconds, thereby suppressing slow reactions that may form an undesirable chemical reaction product. Undesired chemical products can result from secondary reactions or slow parallel reactions. In the water-gas shift reaction, desirable products include carbon dioxide and water, and an undesirable product is methane. In steam reforming of a hydrocarbon, desirable products include hydrogen and carbon monoxide and/or carbon dioxide, and an undesirable product is coke.
  • The subject matter of the present invention is particularly pointed out and distinctly claimed in the concluding portion of this specification. However, both the organization and method of operation, together with further advantages and objects thereof, may best be understood by reference to the following description taken in connection with accompanying drawings wherein like reference characters refer to like elements.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 a is a cross section of a stacked reaction chamber with heat exchanger chamber.
  • FIG. 1 b is an isometric of a nested reaction chamber with heat exchanger chamber.
  • FIG. 2 a is a graph of percent selectivity versus residence time for long contact time water gas shift with a powder catalytic porous insert.
  • FIG. 2 b is a graph of percent selectivity versus residence time for short contact time water gas shift with a powder catalytic porous insert.
  • FIG. 3 is a graph of percent selectivity versus temperature for various contact times for water gas shift with a coated metal foam porous insert.
  • FIG. 4 is a graph of methane conversion versus temperature for various contact times for a steam to methane ratio of 2.5:1.
  • FIG. 5 a is a graph of conversion and selectivity versus time for n-butane steam reforming with a porous catalyst insert.
  • FIG. 5 b is a graph of conversion and selectivity versus time for n-butane steam reforming with a regenerated porous catalyst insert.
  • FIG. 6 illustrates design features of a microchannel reactor having multiple reaction chambers and heat exchangers.
  • FIG. 7 illustrates front (top) and side (bottom) views of a reactor design having porous catalyst inserts within a reaction chamber.
  • FIG. 8 illustrates a cross-sectional view of a reactor design having cylindrical reaction chambers and heat exchangers.
  • FIG. 9 is a graph showing conversion %, H2 selectivity and % H2 in effluent of an isooctane steam reforming process.
  • FIG. 10 is a bar graph showing conversion %, H2 selectivity and % H2 in effluent of an isooctane steam reforming process at varying steam to carbon ratios.
  • DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
  • Referring to FIGS. 1 a and 1 b, a vessel 100 for thermal chemical reactions having two chambers 102 and 104 with a wall 106 therebetween. Either of the two chambers 102, 104 may be the reaction chamber. Bulk flow of reactants within the reaction chamber 102 is substantially perpendicular to a cross section plane 108. The vessel 100 may have stacked chambers as in FIG. 1 a or nested chambers as in FIG. 1 b. The reaction in the reaction chamber may be endothermic or exothermic.
  • In a thermal chemical reaction, the steady-state rate of production (reaction kinetics) is limited by the rate of heat transfer either to (endothermic) or from (exothermic) the reaction site. In the case of exothermic reactions, low rates of heat removal may promote undesired side reactions, or cause thermal hot spots or thermal runaway in the reactor. Commercial exothermic reactors are often operated with low conversion per pass to prevent hot spots and thermal excursions. Enhanced heat removal would safely permit operating at a higher production rate per unit reactor hardware volume. In order to obtain an enhanced heat transfer rate and thereby an enhanced production rate, the reaction chamber preferably has a porous insert (not shown) within the reaction chamber volume wherein the porous insert within the reaction chamber volume has a mean porosity less than 1, a transport distance of the reactant(s) to the catalyst site no greater than 3 mm, and a height (a thermal transport distance from heat source to heat sink, no greater than 2 inches, thereby transferring reaction heat at an enhanced heat transfer rate through the porous insert.
  • The porous insert may be a powder, a porous monolith (including but not limited to metal or ceramic foam, felt, honeycomb, tube bank, stacked microchannel assembly, and combinations thereof), fibers, wad (e.g. steel wool), or combinations thereof. In view of the cost of replacing spent catalyst, for catalytic reactors, it is preferred that the porous insert be removable from the reaction chamber. The porous insert may be arranged to provide single or multiple flow passages for reactants through the reaction chamber volume.
  • Preferably, the reaction chamber volume has a length parallel to a bulk reactant flow, the length less than or equal to 6 inches, and has a height, a thermal distance from heat sink to heat source, less than or equal to 2 inches. The limited length and height provide short distances permitting faster heat transfer. Moreover, the short length reduces overall pressure drop through the reaction chamber.
  • The heat transfer chamber (heat exchanger) is in thermal contact with the reaction chamber volume, the heat transfer chamber transferring heat at the enhanced heat transfer rate across the wall 106 between the heat transfer chamber and the reaction chamber, thereby obtaining the enhanced production rate per reaction chamber volume for the thermal chemical reaction.
  • For catalytic thermal chemical reactions, a preferred catalyst has a porous support, a solution deposited interfacial layer thereon, and a catalyst material on the interfacial layer. A more preferred catalyst has a porous support, a buffer layer, an interfacial layer, and a catalyst material. Any layer may be continuous or discontinuous as in the form of spots or dots, or in the form of a layer with gaps or holes.
  • The porous support may be a porous ceramic or a metal foam. Other porous supports suitable for use in the present invention include carbides, nitrides, and composite materials. Prior to depositing the layers, the porous support has a porosity of at least 5% as measured by mercury porosimetry and an average pore size (sum of pore diameters/number of pores) of from 1 μm to 1000 μm as measured by optical and scanning electron microscopy. Preferably, the porous support has a porosity of about 30% to about 99%, more preferably 60% to 98%. Preferred forms of porous supports are foams, felts, wads and combinations thereof. Foam is a structure with continuous walls defining pores throughout the structure. Felt is a structure of fibers with interstitial spaces therebetween. Wad is a structure of tangled strands, like steel wool. Less preferably, porous supports may also include other porous media such as pellets and honeycombs, provided that they have the aforementioned porosity and pore size characteristics. The open cells of a metal foam preferably range from about 20 pores per inch (ppi) to about 3000 ppi and more preferably about 20 to about 1000 ppi, still more preferably about 40 to about 120 ppi. PPI is defined as the largest number of pores per inch (in isotropic materials the direction of the measurement is irrelevant; however, in anisotropic materials, the measurement is done in the direction that maximizes pore number). In the present invention, ppi is measured by scanning electron microscopy. It has been discovered that a porous support provides several advantages in the present invention including low pressure drop, enhanced thermal conductivity over conventional ceramic pellet supports, and ease of loading/unloading in chemical reactors.
  • The buffer layer, if present, has different composition and/or density than both the support and the interfacial layers, and preferably has a coefficient of thermal expansion that is intermediate the thermal expansion coefficients of the porous support and the interfacial layer. Preferably, the buffer layer is a metal oxide or metal carbide. Applicants discovered that vapor-deposited layers are superior because they exhibit better adhesion and resist flaking even after several thermal cycles. More preferably, the buffer layer is Al2O31, TiO2, SiO2, and ZrO2 or combinations thereof. More specifically, the Al2O3 is α-Al2O3, γ-Al2O3 and combinations thereof. α-Al2O3 is more preferred because of its excellent resistance to oxygen diffusion. Therefore, it is expected that resistance against high temperature oxidation can be improved with alumina coated on the porous support. The buffer layer may also be formed of two or more compositionally different sublayers. When the porous support is metal, for example a stainless steel foam, a preferred embodiment has a buffer layer formed of two compositionally different sub-layers (not shown). The first sublayer (in contact with the porous support) is preferably TiO2 because it exhibits good adhesion to the porous metal support. The second sublayer is preferably α-Al2O3 which is placed upon the TiO2. In a preferred embodiment, the α-Al2O3 sublayer is a dense layer that provides excellent protection of the underlying metal surface. A less dense, high surface area interfacial layer such as alumina may then be deposited as support for a catalytically active layer.
  • Typically the porous support has a thermal coefficient of expansion different from that of the interfacial layer. Accordingly, for high temperature catalysis (T>150° C.) a buffer layer is needed to transition between the two coefficients of thermal expansion. The thermal expansion coefficient of the buffer layer can be tailored by controlling the composition to obtain an expansion coefficient that is compatible with the expansion coefficients of the porous support and interfacial layers. Another advantage of the buffer layer is that it provides resistance against side reactions such as coking or cracking caused by a bare metal foam surface. For chemical reactions which do not require large surface area supports such as catalytic combustion, the buffer layer stabilizes the catalyst metal due to strong metal to metal-oxide interaction. In chemical reactions which require large surface area supports, the buffer layer provides stronger bonding to the high surface area interfacial layer. Preferably, the buffer layer is free of openings and pin holes—this provides superior protection of the underlying support. More preferably, the buffer layer is nonporous. The buffer layer has a thickness that is less than one half of the average pore size of the porous support. Preferably, the buffer layer is between about 0.05 and about 10 μm thick, more preferably, less than 5 μm thick. The buffer layer should exhibit thermal and chemical stability at elevated temperatures.
  • In some embodiments of the present invention, adequate adhesion and chemical stability can be obtained without a buffer layer, so the buffer layer can be omitted, thus saving cost, providing extra volume and further enhancing heat transfer from the catalyst.
  • The interfacial layer can be comprised of nitrides, carbides, sulfides, halides, metal oxides, carbon and combinations thereof. The interfacial layer provides high surface area and/or provides a desirable catalyst-support interaction for supported catalysts. The interfacial layer can be comprised of any material that is conventionally used as a catalyst support. Preferably, the interfacial layer is a metal oxide. Examples of metal oxides include, but are not limited, to γ-Al2O3, SiO2, ZrO2, TiO2, tungsten oxide, magnesium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, nickel oxide, cobalt oxide, copper oxide, zinc oxide, molybdenum oxide, tin oxide, calcium oxide, aluminum oxide, lanthanum series oxide(s), zeolite(s) and combinations thereof. The interfacial layer may serve as a catalytically active layer without any further catalytically active material deposited thereon. Usually, however, the interfacial layer is used in combination with catalytically active layer. The interfacial layer may also be formed of two or more compositionally different sublayers. The interfacial layer has a thickness that is less than one half of the average pore size of the porous support. Preferably, the interfacial layer thickness ranges from about 0.5 to about 100 μm, more preferably from about 1 to about 50 μm. The interfacial layer can be either crystalline or amorphous and preferably has a BET surface area of at least 1 m2/g.
  • The catalytically active material (when present) can be deposited on the interfacial layer. Alternatively, a catalytically active material can be simultaneously deposited with the interfacial layer. The catalytically active layer (when present) is typically intimately dispersed on the interfacial layer. That the catalytically active layer is “disposed on” or “deposited on” the interfacial layer includes the conventional understanding that microscopic catalytically active particles are dispersed: on the support layer (i.e., interfacial layer) surface, in crevices in the support layer, and in open pores in the support layer. The catalytically active layer may include: catalyst metals, including but not limited to, noble metal, transition metal and combinations thereof; metal oxides, including but not limited to, oxides of alkali elements, alkaline earth elements, boron, gallium, germanium, arsenic, selenium, tellurium, thallium, lead, bismuth, polonium, magnesium, titanium, vanadium, chromium, manganese, iron, nickel, cobalt, copper, zinc, zirconium, molybdenum, tin, calcium, aluminum, silicon, lanthanum series element(s), and combinations thereof; composites; zeolite(s); nitrides; carbides; sulfides; halides; phosphates; and combinations of any of the above.
  • In order to mitigate the mass transfer limitation of the catalyst structure, the catalyst impregnation preferably forms a porous interfacial layer having a depth less than 50 μm, preferably less than 20 μm. Therefore, the diffusion path length is at least a factor of 5 shorter than for standard catalyst particles. The thinner impregnated catalyst structure also enhances heat transfer, due to a shorter heat transfer pathway.
  • The catalyst structure may be any geometric configuration. Preferably, the catalyst is a porous structure such as a foam, felt, wad and combinations thereof. The catalyst (including the support and catalytic material), preferably is sized to fit within a reaction chamber. The catalyst may be a single piece of porous contiguous material, or many pieces in physical contact. The catalyst is preferred to have contiguous material and contiguous porosity such that molecules can diffuse through the catalyst. In this preferred embodiment, the catalyst can be disposed in a reaction chamber such that gases will flow substantially through the catalyst (single or multiple pieces) rather than around it. In a preferred embodiment, the cross-sectional area of the catalyst occupies at least 80%, more preferably at least 95% of the cross-sectional area of the reaction chamber. In preferred embodiments, the catalytically active metal is distributed on surfaces throughout catalyst such that reactants passing through the catalyst can react anywhere along the passage through the catalyst; this is a significant advantage over pellet-type catalysts that have a large volume of unused space or catalytically ineffectively used space in the pellet's interior. The porous catalyst is also superior over powders because packed powders may cause a severe pressure drop. The catalyst preferably has a surface area, as measured by BET, of greater than about 0.5 m2/g, more preferably greater than about 2.0 m2/g.
  • Catalysts of the present invention can also be characterized by the properties they exhibit. Factors that can be controlled to effect these properties include: selection of the porous support, buffer, interfacial, and catalytically active layers; gradation of thermal expansion coefficients, crystallinity, metal-support interactions, catalyst size, thermal conductivity of the support, porosity, thermal conductance from reaction chamber, deposition techniques and other factors as are apparent in view of the descriptions herein. Certain preferred embodiments of the catalysts of the present invention exhibit one or more of the following properties: adhesion—after 3 thermal cycles in air, the catalyst exhibits less than 2% (by area) of flaking as viewed by SEM (scanning electron microscope) analysis; oxidation resistance, conversion of reactant(s), contact/residence times, product selectivity, pressure drop and production rates.
  • A preferred method of making the inventive catalyst has the steps of selecting a porous support, depositing a buffer layer on the porous support and depositing an interfacial layer thereover. Optionally a catalyst layer may be deposited onto the interfacial layer, or both the interfacial layer and the catalyst layer may be simultaneously deposited on the buffer layer.
  • Because metal has web surfaces that are nonporous and smooth, deposition of the buffer layer may be impeded. One way to mitigate this problem is to rough the metal surface via chemical etching. The adhesion of high surface area gamma-alumina supported metal catalysts to metal foam is significantly improved when metal foam is roughed via chemical etching using mineral acid solutions, for example 0.1 to 1 M HCl. Roughed web surface also shows improved resistance to the spalling of catalyst layer under thermal cyclings. In a preferred embodiment, wherein a metal foam is used as the porous support, the metal foam is etched prior to vapor depositing the buffer layer. Etching is preferably with an acid, for example HCl.
  • Deposition of the buffer layer is preferably by vapor deposition including but not limited to chemical vapor deposition, physical vapor deposition or combinations thereof. Surprisingly, it has been found that vapor deposition, which is typically conducted at high temperatures, results in polycrystalline or amorphous phases that provide good adhesion of the buffer layer to the surface of the porous support. The method is particularly advantageous for adhering a metal oxide buffer layer to a metal porous support. Alternatively, the buffer layer may be obtained by solution coating. For example, the solution coating has the steps of metal surface functionalization via exposing the metal surface to water vapor to form surface hydroxyls, followed by surface reaction and hydrolysis of alkoxides to obtain a coating of metal oxide. This solution coating may be preferred as a lower cost method of depositing the buffer layer.
  • The interfacial layer is preferably formed by vapor or solution deposition using precursors as are known for these techniques. Suitable precursors include organometallic compounds, halides, carbonyls, acetonates, acetates, metals, colloidal dispersions of metal oxides, nitrates, slurries, etc. For example, a porous alumina interfacial layer can be wash-coated with PQ alumina (Nyacol Products, Ashland, Mass.) colloidal dispersion followed by drying in a vacuum oven overnight and calcining at 500° C. for 2 hours.
  • The catalytically active material can be deposited by any suitable method. For example, catalyst precursors can be deposited on colloidal metal oxide particles and slurry coated on a buffer-coated porous support, then dried and reduced.
  • Certain embodiments of the present invention can be characterized in terms of residence or contact time. These terms have well-defined meanings in the art. Contact time is the total volume of the catalyst chambers divided by the total flowrate (defined as F-total) of inlet reactants assuming they are an ideal gas corrected to standard conditions (i.e., the volume of the catalyst chamber/F-total at STP where STP is 273K and 1 atm). The volume of the catalyst chambers includes the volume in immediate proximity and surrounding the catalyst zone. As an example, if one were to pack one quarter of the channels with powders, then the volume of the catalyst chamber would only include that region where gas can flow and where it can contact the catalyst, i.e. only one quarter of the total channel volume would be included in this calculation. The volume of dead space, i.e., headers, footers, etc. is ignored in this calculation. Residence time (meaning average residence time) is the total volume of the catalyst chambers divided by the total flowrate of inlet reactants, corrected to the actual temperature and pressure of the reactants in the reactor (i.e., the volume of the catalyst chamber/F-total corrected to actual conditions). F-total at STP is the total volumetric flowrate of reactants (includes all reactants, and diluents if present). Inlet gases are typically metered with mass flow controllers set to standard conditions, i.e. the user presets the desired STP flowrate. F-total corrected to actual conditions=F-total-STP×(Temperature in K)/273×1 atm/(P actual in atm): this value is used to calculate the residence time or the ‘true time’ within a reactor. Most practitioners prefer to use contact time, because it is a convenient method to keep the time variable fixed while stepping through 10 degree C. increments in reaction temperature etc.
  • The invention further provides a catalytic process comprising passage of at least one reactant into a reaction chamber comprising the inventive catalyst, conversion of said at least one reactant into at least one product, and passage of the product out of the reaction chamber. In a preferred embodiment, the catalytic process is conducted in an apparatus having microchannels. Microchannels have at least one dimension of about 1 mm or less. Examples of suitable microchannel apparatus and various process related factors are described in U.S. Pat. Nos. 5,611,214, 5,811,062, 5,534,328, and U.S. patent application Ser. Nos. 08/883,643, 08/938,228, 09/375,610, 09/123,781, cofiled U.S. patent application Ser. No. ______ (attorney docket no. E-1666A-CIP), Ser. No. 09/375,614 (filed Aug. 17, 1999) and Ser. No. 09/265,227 (filed Mar. 8, 1999), all of which are incorporated by reference as if reproduced in full below. In another preferred embodiment, the catalyst is a monolith—a single contiguous, yet porous, piece of catalyst or several contiguous pieces that are stacked together (not a bed of packed powder or pellets or a coating on the wall of a microchannel) that can easily be inserted and extracted from a reaction chamber. The piece or stack of catalyst pieces preferably have a width of 0.1 mm to about 2 cm, with a preferred thickness of less than 1 cm, more preferably, about 1 to about 3 mm. The inventive catalyst may provide numerous advantages to catalytic processes such as: chemical stability, stability to repeated thermal cycling, thermal stability, efficient loading and unloading of catalysts, high rates of heat transfer and mass transfer, and maintenance of desired catalytic activity.
  • In constructing preferred embodiments of the heat exchanger, thin sheets or tubes can be used to obtain high heat duties and short contact times. The thickness of the web between the reaction channel and the heat exchange channel can vary, but is preferably between about 0.01 inches and about 0.25 inches. The preferred thickness for the heat exchange channel (meaning the thickness of the smallest dimension of the heat transfer channel) preferably ranges from 100 microns to 10 millimeters. In some preferred embodiments, this smallest dimension may be channel width, in other embodiments, channel height. The preferred thickness is 250 microns to 3 millimeter. Flow of the heat transfer fluid may be either counter-current, cross-current, or co-current to the direction of the flow of reactants. Preferred heat transfer fluids include: a combustion stream (for endothermic reactions), oil (lower temperature reactions), and steam.
  • The metal surfaces within microchannel apparatus can be coated with either or both the buffer and the interfacial layers. This can be done using any of the processes described herein, preferably by vapor deposition. Preferred coating materials include titania and and 5-10% SiO2/Al2O3. The interior surfaces of the reaction chamber, heat exchanger and other surfaces of microchannel apparatus may be coated. In some embodiments, the walls of a reaction chamber can be coated with an optional buffer layer, an interfacial layer, and a catalytically active material—typically the catalytically active material and the interfacial layer combine to form a supported catalyst. Coatings can also be applied to metal walls in tubes and pipes that form connections to or within microchannel apparatus.
  • The inventive method is preferably carried out in a reaction chamber in which the catalyst has a thickness of about 2 cm or less and is touching or in close proximity (within about 1 mm) of a reaction chamber wall, where the reaction chamber wall is in thermal contact with a heat exchanger. Heat transfer from (or to) the reaction chamber is preferably enhanced by addition of microchannels on at least one chamber wall through which heat is transferred, preferably, on the side of the reaction chamber wall opposite the catalyst structure. The catalyst preferably has contiguous and relatively large pores, such as in a foam, to avoid large pressure drops. Preferably the pore size of the large pores in the catalyst is between about 10 μm and about 300 μm.
  • Catalytic processes of the present invention include: acetylation, addition reactions, alkylation, dealkylation, hydrodealkylation, reductive alkylation, amination, aromatization, arylation, autothermal reforming, carbonylation, decarbonylation, reductive carbonylation, carboxylation, reductive carboxylation, reductive coupling, condensation, cracking, hydrocracking, cyclization, cyclooligomerization, dehalogenation, dimerization, epoxidation, esterification, exchange, Fischer-Tropsch, halogenation, hydrohalogenation, homologation, hydration, dehydration, hydrogenation, dehydrogenation, hydrocarboxylation, hydroformylation, hydrogenolysis, hydrometallation, hydrosilation, hydrolysis, hydrotreating, hydrodesulferization/hydrodenitrogenation (HDS/HDN), isomerization, methanation, methanol synthesis, methylation, demethylation, metathesis, nitration, oxidation, partial oxidation, polymerization, reduction, steam and carbon dioxide reforming, sulfonation, telomerization, transesterification, trimerization, water gas shift (WGS), and reverse water gas shift (RWGS).
  • The reaction process or processes of the present invention can be conducted in parallel, with tens, hundreds, thousands, or millions of small reaction chambers, each chamber having an internal diameter less than about 2 inches, preferably less than about 2 cm, more preferably ranging from about 1 mm to about 5 mm. The reaction process or processes can also be run in series. For example, products from one reaction chamber can be fed to another reaction chamber having the same or a different catalyst. A series of reactions could also be conducted by placing a series of different catalysts within the same reaction chamber. Reaction products can be collected and stored, for example in tanks, or immediately consumed in subsequent reactions.
  • Reactors and methods of the present invention can be characterized by various properties that they exhibit. Heat flux is a particularly important characteristic in the present invention. For the sum of the volume of the reaction chamber(s) and heat exchanger chamber(s) including the volume of chamber walls, the present invention preferably exhibits a heat flux during steady-state operation of at least about 0.6 W/cc, more preferably above about 1 W/cc still more preferably between about 5 and about 250 W/cc, and in another preferred range, between about 10 and 100 W/cc. These heat fluxes can be obtained at short contact times and low pressure drops through the reaction chamber. The contact time is preferably less than about 0.3 seconds, more preferably, less than about 0.1 seconds, still more preferably, less than about 0.05 seconds and yet more preferably, less than about 0.01 seconds. The pressure drop through the reaction chamber is preferably less than about 15 psig (pounds per square inch gauge), more preferably less than about 10 psig, still more preferably less than about 5 psig, and yet more preferably less than about 1 psig. In the apparatus and methods of the present invention, these high fluxes can be obtained in a wide variety of catalyzed reactions and is not limited to the highly exothermic, deep oxidation (combustion) reactions.
  • It has been surprisingly discovered that the aforementioned short contact times and high heat fluxes can be obtained in steady-state, catalyzed thermal reactions. Factors that can contribute to shorter contact times and higher heat flux include: catalysts with fast intrinsic kinetics, porous catalysts, thermally conductive supports, the use of microchannel apparatus, short distances for thermal transport in the reaction chamber and/or heat exchanger; short mass transfer distances in the reaction chamber; and selection of heat transfer fluid(s). The transfer of a sufficiently high heat flux is an important aspect of the present invention. The selection of various process factors can depend on the particulars of a given thermal chemical reaction; precise control of all factors is not required in every case. Guided by the descriptions herein, persons skilled in this technological area can, without undue experimentation, control these factors to obtain the desired level of flux.
  • The reactors and methods of the present invention can also be characterized by their high rates of production per unit reactor volume. For example, in a steady-state process for steam reforming of a gaseous or liquid hydrocarbon, the inventive process preferably produces more than 0.01 standard liter per minute (SLPM) of hydrogen gas per cubic centimeter (cc) of reactor hardware (the sum of the volume of the reaction chamber(s) and heat exchanger chamber(s) including the volume of chamber walls), more preferably more than 0.1 SLPM of hydrogen gas per cc of reactor hardware. Typically, the production rate of hydrogen case can range up to about 0.5 SLPM or more of hydrogen gas per cubic centimeter of reactor hardware. In the more general case, the reactors and methods of the present invention can consume more than about 0.01 SLPM of reactant gas per cubic centimeter of reactor hardware. By building multiple reaction chambers and heat exchangers operating in parallel, reactors and methods of the present invention can produce thousands or millions or more of liters of product per day.
  • The invention also provides a method of suppressing undesirable chemical reactions, especially coke formation. The reactors and methods of the present invention can be characterized by their ability to suppress chemical products that are slower forming, kinetically, or which are more likely to form within a reactor that has a lesser degree of temperature control. For example, in the steady-state process for a water-gas shift reactor, methanation is a common side reaction that does not take place as quickly as the reaction of interest, for the conversion of carbon monoxide to carbon dioxide. Likewise, coke is a slower forming by-product in steam reforming reactions, with the prevalence for the reaction is also a function of the temperature of the catalyst surface. In these cases, the reactors and methods of the present invention can support the primary reactions of interest (e.g., water-gas shift and steam reforming) while enhancing the ability of the system to avoid or suppress the formation of certain undesirable secondary products (e.g., methane and coke). More generally, the reactors and methods of the present invention can be used for suppressing other undesirable byproducts where their formation can be avoided through short contact times and/or enhanced temperature control.
  • EXAMPLE 1
  • An experiment was conducted to demonstrate a chemical thermal reactor according to the present invention using the water gas shift reaction.
  • A first porous insert was made with a catalyst material of a pre-reduced and stabilized 5-wt % Ru/ZrO2 catalyst (⅛-inch extrudates) obtained from Degussa Corporation. The catalyst material was ground and sieved to 65 to 100 mesh.
  • A second porous insert was made with Ni metal foam with 80 pores per inch (ppi) machined to fit in a 7 mm ID quartz tube, ranging from 0.5 to 2.5 cm in length. The metal foam was washed in a sonicator with acetone, chloroform, and water successively over 10-minute intervals. It was also etched in a 1 M HCl solution at 60° C. for 30 min. The etched metal foam was saturated with a zirconium n-propoxide/1-propanol solution (Aldrich), followed by ambient hydrolysis with water vapor for 72 h, then calcined at 450° C. for 4 h to form the interfacial layer. The ZrO2-coated metal foam was saturated with a dilute aqueous RuCl3 solution (RuCl3 hydrate, Aldrich). The saturation process was repeated several times until the desired Ru loading was achieved. The coated metal foam supported Ru catalyst was finally dried at 100° C. in vacuum overnight, followed by calcination at 350° C. for 1 h. Prior to testing, the catalyst was activated with a 10% H2/He mixture at 350° C. for at least 1 h.
  • A catalytic plug flow reactor (PFR) system was used to test both porous inserts. The PFR was configured in a single-zone furnace as the heat transfer chamber. The reactor system included a steam generator placed directly prior to the reactor inlet, a PFR housed within the furnace, and a condenser located at the reactor outlet. The porous insert was packed in a 7 mm ID quartz tube, which was necked at the center. The feed water was fed to the steam generator using a Cole Parmer syringe pump. Carbon monoxide and nitrogen (a diluent) were fed to the system using Matheson mass flow controllers. The mixed feed stream flowed through the steam generator before entering the PFR in a downflow fashion. The product gases were directed through the condenser and sent to an on-line gas chromatograph, where the product stream was analyzed.
  • Two thermocouples were placed inside the catalytic PFR system. One thermocouple was located above the porous insert. The second thermocouple was placed adjacent to the porous insert outside of the quartz tube to measure the furnace temperature. A pressure gauge at the reactor inlet was used to measure the differential pressure across the porous insert.
  • The product gases were analyzed immediately upon exit from the reactor with a Microsensor Technology Inc., (MTI) M200 Gas Chromatograph. Using a 10-m molecular sieve column (argon carrier gas, 100° C., 34.1 psig) and an 8-m PoraplotU column (helium carrier gas, 65° C., 26.9 psig) in parallel, the GC analyzes for hydrogen, nitrogen, oxygen, methane, carbon monoxide, air, carbon dioxide, ethane, and ethylene in 75 sec. The M200 used a vacuum pump to draw a small sample from the product stream with a 40-sec purge and a 100-millisecond injection time. Water was removed from the gas stream prior to entering the M200.
  • Carbon monoxide conversion was calculated based on the moles of material in the inlet and outlet gas stream, as shown in equation 1. The selectivity to carbon dioxide (and hydrogen) or methane was calculated in equations 2 and 3, respectively.
    X CO=100*(n CO-in −n CO-out)/n CO-in  (1)
    S CO2=100*n CO2/(n CO2 +n CH4)  (2)
    S CH4=100−S CO2  (3)
  • Using the first porous insert, fine catalyst powders (65 to 100 mesh), the intrinsic reaction kinetics were approximately measured. The contact time varied from 10 milliseconds to 1 sec. FIGS. 2 a and 2 b show the performance for long and short contact times. At 300° C. and a steam to carbon ratio of 3:1, 25 milliseconds on the Ru-based catalyst was sufficient to convert greater than 98% of the carbon monoxide to carbon dioxide and hydrogen. At 50 milliseconds, a CO conversion of 99.8% was measured with a selectivity of 100% to the desired products (CO2 and H2). The equilibrium conversion of CO at 300° C. and a steam to carbon ratio of 3:1 was 99.93%.
  • Tests with longer contact times (>100 milliseconds) showed the formation of methane, which has an equilibrium selectivity of 22.82%. The equilibrium selectivity line for carbon dioxide and hydrogen is shown on FIG. 2 a. As the contact time increased, the formation of methane also increased. A software package, FACT™, was used for all equilibrium calculations.
  • The results with the second porous insert (coated metal foam) are shown in FIG. 3. At 300° C., the CO conversion was less than 10%. However, at 500° C. and a steam to carbon ratio of 3:1, the measured carbon monoxide conversion reached 94% with a contact time of 50 milliseconds. The equilibrium conversion was 94.53% at these conditions. With a contact time as short as 10 milliseconds, the carbon monoxide conversion exceeded 90% and 100% selectivity to carbon dioxide and hydrogen was observed. The equilibrium CO2 selectivity was 93.52% at 500° C.
  • At the contact times of 10, 50, and 100 milliseconds, the measured selectivity remained near 100%, with methane below the detectability limit of the GC. These findings showed that desired non-equilibrium chemistry was exploited in the coated metal foam. Unwanted series and slow parallel reaction pathways, such as the formation of methane, were effectively shut down.
  • The second porous insert of the coated metal foam had a higher activation temperature than the first porous insert of catalyst powder for two reasons. First, the catalyst washcoat had a slightly different composition and structure than the catalyst powders. Independent catalyst tests with powders made from the same washcoat verified the higher required activation temperature. The other distinction between the two porous inserts was a reduced weight of active catalyst (approximately 10%) on the coated metal foam.
  • EXAMPLE 2
  • An experiment was conducted to demonstrate hydrocarbon steam reforming according to the present invention.
  • Using the first porous insert (powder) as in Example 1, methane steam reforming was achieved with 100% conversion at 850° C. in 25 milliseconds on a 5% Rh/gamma-Al2O3 catalyst (FIG. 4). Using the second porous insert (coated metal foam) as in Example 1, with a 5% Rh/Al2O3 catalyst/interfacial layers on 80 ppi stainless steel metal foam reduced the operating temperature by 100° C. to achieve the same performance at 750° C.
  • No coke formation was observed during any of the millisecond residence time experiments with lower steam to methane ratios (2.5:1).
  • Results for other hydrocarbons are shown in Table E2-1 wherein “time” is residence time. The data on butane, gasoline and kerosene were obtained using a powder catalyst while the data on isooctane were obtained using a foam catalyst.
  • Table E2-1: Preliminary Hydrocarbon Reforming Data Based on 5% Rh/Al2O3 Catalyst Screening Tests
    Temperature
    Hydrocarbon (C.) Time (ms) Conversion % H2 Sel. %
    Butane 600 25 100 96
    Gasoline 800 50 95 ˜95
    Iso-octaneA 700 25 100 89.5
    Kerosene 600 50 95 ˜98

    ACatalyst material included a titania buffer layer
  • Further data for an n-butane steam reforming experiment are shown in FIG. 5 a. A porous insert consisted of 80 ppi stainless steel with an interfacial layer of alumina and a catalyst material of rhodium (15.6 wt % Rh on 17.1 wt % alumina, balance stainless steel foam, no buffer layer). Conditions were 650° C. at 95 ms residence time with a steam to carbon ratio of 3.58:1. The pressure drop increased from negligible to over 7 psig, attributed to cracking and spalling of the interfacial and catalyst layers. The catalyst was regenerated in air to remove deposited carbon. FIG. 5 b shows poorer performance. Pressure drop increased to over 7 psig after only 5 operating hours in two days.
  • EXAMPLE 3
  • A preferred, contemplated, embodiment of the invention is shown in FIG. 6. The distance from the heat source to heat sink is about 1 centimeter or less. This distance is a function of the heat duty, the selection of heat transfer fluid(s), and the effective thermal conductivity of the porous catalyst insert. The porous catalyst insert may have a porosity greater than 95%, which creates an effective thermal conductivity roughly two orders of magnitude below the pure metal or alloy forming the porous support.
  • Thin sheets or tubes can be used to obtain high heat duties and short contact times. The thickness of the web between the reaction channel and the heat exchange channel can vary, but is preferably between about 0.01 inches and about 0.25 inches. The preferred thickness for the heat exchange channel preferably ranges from 100 microns to 10 millimeters. The preferred thickness is 250 microns to 3 millimeter. Flow of the heat transfer fluid may be either counter-current, cross-current, or co-current to the direction of the flow of reactants.
  • The thickness for the catalyst preferably ranges from 100 microns to 10 millimeters. The preferred thickness is 250 microns to 1 millimeter. The catalyst may be comprised of a single contiguous porous monolithic catalyst, or may be created by placing multiple porous monoliths adjacent to each other. The porous monoliths may also be inserted with a gap between the porous monolith catalysts, or with a smaller monolith (as shown in FIG. 7) adjacent to and/or between larger monoliths. Preferably, one or several equal sized monoliths are adjacent to each other; this design option will favor contact of the reactants with the catalyst surface.
  • The volumetric heat flux using short contact time reactions within a device that can facilitate a high heat duty should easily exceed 0.6 W/cc. It has been shown that heat duties in the range of 1 to 10 W/cc are well within the range of this catalyst and reactor. Higher heat duties, up to 100 W/cc, can also be achieved if the contact time is less than 25 milliseconds and if the distance between the heat source and sink is on the order of one millimeter (about 0.5 to about 5 mm).
  • EXAMPLE 4
  • A compact reactor that transferred roughly 10 W/cc to 16 W/cc was demonstrated for the steam reforming of isooctane. The steam reforming reaction uses steam to transform hydrocarbons into CO and H2. For the case of isooctane steam reforming, the reaction stoichiometry is:
    iso-C8H18+8H2O→8CO+17H2,
    and the standard heat of reaction is strongly endothermic (ΔHr°=+1275 kJ/mole of isooctane). Isooctane was chosen to simulate gasoline because it represents the mid-range molecular weight of gasoline's hydrocarbon mixture. The steam reforming reaction is often run at steam concentrations higher than the reaction stoichiometry shown above to avoid coke formation and to improve conversion. The steam concentration is usually given in the form of the steam to carbon ratio (S:C), the ratio of steam molecules per carbon atom in the reactant feed. A ratio greater than one points to a greater than stoichiometric steam concentration, and under those conditions the water gas shift reaction also takes place as a secondary reaction.
  • A microchannel isooctane steam reformer was built, with a total volume of roughly 30 cubic centimeters. This reactor has integrated heat exchange to add the heat needed for this highly endothermic reaction. The heat exchange fluid used to heat the reactor zone was combustion gas set at 750° C. and a total flowrate of roughly 100 SLPM. This design was built to process a hydrogen gas stream large enough to produce 1.0 kilowatt equivalent electric (kWe) power in a PEM fuel cell. The reactor configuration is shown in FIG. 6. There were 12 reactant channels interspersed between 13 heat exchange channels. The reaction channels had a thickness of roughly 0.03 inches, a length of 1.1 inch, and a channel height of 1 inch. The heat exchange channels had an identical length and height. The thickness of the heat exchange channels was roughly 0.02 inches. The web thickness between the reaction and heat exchange channel was roughly 0.19 inches.
  • The catalyst was a 15 wt % Rh2O3 on an aluminum containing spinel coated on a porous stainless steel foam. The specific details of catalyst preparation are as follows. Gamma alumina support (Strem) was calcined at 500° C. for 5 hours. The incipient wetness method was used to impregnate magnesium nitrate solution on the alumina support to achieve 5 wt % MgO. The modified support was dried at 110° C. in vacuum for 4 hours followed by calcination at 900° C. for 2 hours to form the aluminum containing spinel support. The spinel support was impregnated with a rhodium nitrate solution (Engelhard) using the incipient wetness technique to reach the desired Rh2O3 loading. After drying at 110° C. in vacuum for 4 hours, supported Rh powder catalyst was calcined at 500° C. for 3 hours. The powdered catalyst was ball milled overnight and slurry dip-coated on a 80 ppi (Astromet, Cincinnati, Ohio) stainless steel foam. Prior to the dip-coating, the stainless steel foam was coated with the titania and alumina buffer layer using CVD.
  • The data from the microchannel isooctane steam reformer's first hour of operation is shown in FIG. 9. The inlet flowrate of liquid isooctane was 2.54 mL/min. The reactor zone was operated at 650° C. and one atmosphere. The reactants had a 6:1 steam to carbon ratio, which created a total contact time of roughly 22 milliseconds within the sum of the total reaction channels. The reactor was able to reach isooctane conversions ranging from 86.5% to 95%, thus requiring roughly 300 W of thermal energy. The hydrogen selectivity was in the 85 to 90% range. The results show that the microchannel isooctane steam reformer reactor can supply the heat necessary to sustain this reaction with a high processing rate per unit reactor volume. The reactant side pressure drop through this device was roughly 6.9 kPa (1.0 p.s.i). The expected fuel cell output under these conditions was sufficient to produce 0.5-kWe electrical output from a PEM fuel cell. This demonstration was continued for another hour and then shut down. The volumetric heat flux of the reactor was roughly 10 W/cc.
  • Another three demonstrations were run using this device, putting the device through four thermal cycles. These four thermal cycles put the device through over 12 total hours of on-line service. The results of the final three thermal cycles in bar chart form in FIG. 10. All of the results in FIG. 10 are at one atmosphere, a 630 to 670° C. temperature range and a 22 millisecond contact time within the sum of the total reaction channels. The results for the equivalent 0.5-kWe power output and the 6:1 steam to carbon ratio for these tests are consistent with the values shown in FIG. 9. As the steam to carbon ratio is lowered from 6-1 to 5.7:1, 5:1, 4.06:1, and finally to 2.98:1, the isooctane conversion decreases, but the hydrogen selectivity remains steady. At constant residence time, the effect of reducing the steam to carbon ratio is the same as increasing the isooctane flow rate. So while the conversion percentage decreases with decreasing steam to carbon ratio, the amount of isooctane being converted increases, resulting in a net increase in the actual rate at which hydrogen is generated. This is seen in the higher equivalent electrical power output listed with these values. The last set of bar data on the far right side of FIG. 10 are the results acquired with a 5.7:1 steam to carbon ratio and roughly half the originating contact time, resulting in a 1.0-kWe equivalent power output. Under these conditions, nearly 500 W of thermal energy were required to convert roughly 75% of the inlet isooctane stream set at 5.04 mL/min. This device demonstrated a volumetric heat flux greater than 16 W/cc.
  • CLOSURE
  • While a preferred embodiment of the present invention has been shown and described, it will be apparent to those skilled in the art that many changes and modifications may be made without departing from the invention in its broader aspects. The appended claims are therefore intended to cover all such changes and modifications as fall within the true spirit and scope of the invention.

Claims (3)

  1. 1. (canceled)
  2. 2. A process for the steam reforming of a hydrocarbon comprising:
    passing a feed stream comprising hydrocarbon gas and steam into a reaction chamber;
    said reaction chamber comprising a catalyst that catalyzes the reaction of said hydrocarbon gas and water gas to produce a gaseous mixture comprising at least carbon monoxide and hydrogen gas;
    wherein said process produces more than 0.01 SLPM of hydrogen gas per cubic centimeter of reactor volume, where reactor volume is defined as the sum of the volume of the reaction chamber(s) and heat exchanger chamber(s) including the volume of chamber walls.
  3. 3-12. (canceled)
US11236125 1998-07-27 2005-09-26 Method and apparatus for obtaining enhanced production rate of thermal chemical reactions Abandoned US20060029541A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US09123779 US6540975B2 (en) 1998-07-27 1998-07-27 Method and apparatus for obtaining enhanced production rate of thermal chemical reactions
US09492246 US6616909B1 (en) 1998-07-27 2000-01-27 Method and apparatus for obtaining enhanced production rate of thermal chemical reactions
US10610282 US7045114B2 (en) 1998-07-27 2003-07-01 Method and apparatus for obtaining enhanced production rate of thermal chemical reactions
US11236125 US20060029541A1 (en) 1998-07-27 2005-09-26 Method and apparatus for obtaining enhanced production rate of thermal chemical reactions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11236125 US20060029541A1 (en) 1998-07-27 2005-09-26 Method and apparatus for obtaining enhanced production rate of thermal chemical reactions

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US10610282 Division US7045114B2 (en) 1998-07-27 2003-07-01 Method and apparatus for obtaining enhanced production rate of thermal chemical reactions

Publications (1)

Publication Number Publication Date
US20060029541A1 true true US20060029541A1 (en) 2006-02-09

Family

ID=23955534

Family Applications (3)

Application Number Title Priority Date Filing Date
US09492246 Expired - Lifetime US6616909B1 (en) 1998-07-27 2000-01-27 Method and apparatus for obtaining enhanced production rate of thermal chemical reactions
US10610282 Expired - Lifetime US7045114B2 (en) 1998-07-27 2003-07-01 Method and apparatus for obtaining enhanced production rate of thermal chemical reactions
US11236125 Abandoned US20060029541A1 (en) 1998-07-27 2005-09-26 Method and apparatus for obtaining enhanced production rate of thermal chemical reactions

Family Applications Before (2)

Application Number Title Priority Date Filing Date
US09492246 Expired - Lifetime US6616909B1 (en) 1998-07-27 2000-01-27 Method and apparatus for obtaining enhanced production rate of thermal chemical reactions
US10610282 Expired - Lifetime US7045114B2 (en) 1998-07-27 2003-07-01 Method and apparatus for obtaining enhanced production rate of thermal chemical reactions

Country Status (7)

Country Link
US (3) US6616909B1 (en)
EP (3) EP1251949B2 (en)
JP (2) JP5265833B2 (en)
CA (1) CA2396083C (en)
DE (1) DE60141809D1 (en)
ES (1) ES2344447T3 (en)
WO (1) WO2001054807A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060008399A1 (en) * 2004-07-07 2006-01-12 Feinstein Jonathan J Reactor with primary and secondary channels
US20080286177A1 (en) * 2007-05-18 2008-11-20 Tribute Creations, Llc Reactor with differentially distributed catalytic activity
US20100305911A1 (en) * 2009-05-27 2010-12-02 King Fahd University Of Petroleum & Minerals Method for modeling fluid flow over porous blocks
US20110166304A1 (en) * 2008-08-29 2011-07-07 Horst-Werner Zanthoff Use of foam bodies in oxidation reactors for preparing unsaturated aldehydes or carboxylic acids
US9950305B2 (en) 2011-07-26 2018-04-24 Battelle Memorial Institute Solar thermochemical processing system and method

Families Citing this family (148)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6440895B1 (en) 1998-07-27 2002-08-27 Battelle Memorial Institute Catalyst, method of making, and reactions using the catalyst
US6616909B1 (en) * 1998-07-27 2003-09-09 Battelle Memorial Institute Method and apparatus for obtaining enhanced production rate of thermal chemical reactions
US6800269B2 (en) * 1999-07-30 2004-10-05 Conocophillips Company Short contact time catalytic sulfur recovery system for removing H2S from a waste gas stream
US7357908B2 (en) * 2000-12-18 2008-04-15 Conocophillips Company Apparatus and catalytic partial oxidation process for recovering sulfur from an H2S-containing gas stream
US7326397B2 (en) * 2000-12-18 2008-02-05 Conocophillips Company Catalytic partial oxidation process for recovering sulfur from an H2S-containing gas stream
US6946111B2 (en) * 1999-07-30 2005-09-20 Conocophilips Company Short contact time catalytic partial oxidation process for recovering sulfur from an H2S containing gas stream
US7122170B2 (en) * 2000-07-25 2006-10-17 Conocophillips Company Catalysts for SPOC™ enhanced synthesis gas production
US6403051B1 (en) * 1999-07-30 2002-06-11 Conoco Inc. Recovery of sulfur from H2S and concurrent production of H2 using short contact time CPOX
US6451864B1 (en) * 1999-08-17 2002-09-17 Battelle Memorial Institute Catalyst structure and method of Fischer-Tropsch synthesis
US6488838B1 (en) * 1999-08-17 2002-12-03 Battelle Memorial Institute Chemical reactor and method for gas phase reactant catalytic reactions
US6969506B2 (en) * 1999-08-17 2005-11-29 Battelle Memorial Institute Methods of conducting simultaneous exothermic and endothermic reactions
JP2003507161A (en) * 1999-08-17 2003-02-25 バッテル・メモリアル・インスティチュート Catalyst structure and method of Fischer-Tropsch synthesis
CA2381154C (en) * 1999-08-17 2009-02-03 Battelle Memorial Institute Chemical reactor and method for catalytic gas phase reactions
US6872919B2 (en) * 2000-08-29 2005-03-29 Maytag Corporation Multi-stage catalyst for a cooking appliance
US6921518B2 (en) * 2000-01-25 2005-07-26 Meggitt (Uk) Limited Chemical reactor
FR2807746B1 (en) * 2000-04-13 2002-12-13 Air Liquide Method for producing a mixture comprising hydrogen and CO
US7125540B1 (en) * 2000-06-06 2006-10-24 Battelle Memorial Institute Microsystem process networks
DK1320712T3 (en) * 2000-07-28 2007-01-15 Honda Motor Co Ltd Micro component with the micro-channels and multi-purpose
US7118917B2 (en) * 2001-03-07 2006-10-10 Symyx Technologies, Inc. Parallel flow reactor having improved thermal control
US7201883B2 (en) * 2001-10-12 2007-04-10 Compactgtl Plc Catalytic reactor
GB0124999D0 (en) * 2001-10-18 2001-12-05 Accentus Plc Catalytic reactor
GB0125295D0 (en) * 2001-10-22 2001-12-12 Lattice Intellectual Property Shift reaction
EP1442263A2 (en) * 2001-10-29 2004-08-04 CHART HEAT EXCHANGERS Limited Partnership Heat exchangers
DE10153935A1 (en) * 2001-11-06 2003-05-22 Viessmann Werke Kg Apparatus for generating hydrogen
US6746657B2 (en) * 2002-03-12 2004-06-08 Precision Combustion, Inc. Method for reduced methanation
GB0210794D0 (en) * 2002-05-10 2002-06-19 Chart Heat Exchangers Ltd Heat exchangers
US7402719B2 (en) 2002-06-13 2008-07-22 Velocys Catalytic oxidative dehydrogenation, and microchannel reactors for catalytic oxidative dehydrogenation
US6969505B2 (en) * 2002-08-15 2005-11-29 Velocys, Inc. Process for conducting an equilibrium limited chemical reaction in a single stage process channel
US9192929B2 (en) 2002-08-15 2015-11-24 Velocys, Inc. Integrated combustion reactor and methods of conducting simultaneous endothermic and exothermic reactions
US7014835B2 (en) 2002-08-15 2006-03-21 Velocys, Inc. Multi-stream microchannel device
US6622519B1 (en) 2002-08-15 2003-09-23 Velocys, Inc. Process for cooling a product in a heat exchanger employing microchannels for the flow of refrigerant and product
US7250151B2 (en) * 2002-08-15 2007-07-31 Velocys Methods of conducting simultaneous endothermic and exothermic reactions
US7404936B2 (en) * 2002-10-22 2008-07-29 Velocys Catalysts, in microchannel apparatus, and reactions using same
US6652627B1 (en) 2002-10-30 2003-11-25 Velocys, Inc. Process for separating a fluid component from a fluid mixture using microchannel process technology
US7459224B1 (en) * 2002-11-26 2008-12-02 General Motors Corporation Methods, apparatus, and systems for producing hydrogen from a fuel
US7105148B2 (en) * 2002-11-26 2006-09-12 General Motors Corporation Methods for producing hydrogen from a fuel
US7405338B2 (en) * 2003-04-07 2008-07-29 Velocys Dehydrogenation reactions in narrow reaction chambers and integrated reactors
US7294734B2 (en) * 2003-05-02 2007-11-13 Velocys, Inc. Process for converting a hydrocarbon to an oxygenate or a nitrile
WO2004103539A3 (en) 2003-05-16 2005-05-19 Velocys Inc Process for forming an emulsion using microchannel process technology
US7220390B2 (en) 2003-05-16 2007-05-22 Velocys, Inc. Microchannel with internal fin support for catalyst or sorption medium
US7485671B2 (en) 2003-05-16 2009-02-03 Velocys, Inc. Process for forming an emulsion using microchannel process technology
US7208136B2 (en) * 2003-05-16 2007-04-24 Battelle Memorial Institute Alcohol steam reforming catalysts and methods of alcohol steam reforming
US7153334B2 (en) * 2003-05-21 2006-12-26 General Motors Corporation Fuel reforming system and method of operation
EP1651562A2 (en) * 2003-06-25 2006-05-03 Velocys, Inc. Catalysts, systems and methods of steam reforming, and methods of making steam reforming catalysts
US8277773B2 (en) 2004-02-13 2012-10-02 Velocys Corp. Steam reforming method
GB0314790D0 (en) * 2003-06-25 2003-07-30 Accentus Plc Catalytic reactor and process
WO2005004257A3 (en) * 2003-06-27 2005-05-19 Ultracell Corp Efficient micro fuel cell systems and methods
US20050207953A1 (en) * 2003-07-22 2005-09-22 The Regents Of The University Of California High aspect ratio chemical microreactor
US20050203195A1 (en) * 2003-08-05 2005-09-15 Yong Wang Tailored Fischer-Tropsch synthesis product distribution
US7029647B2 (en) * 2004-01-27 2006-04-18 Velocys, Inc. Process for producing hydrogen peroxide using microchannel technology
US7084180B2 (en) 2004-01-28 2006-08-01 Velocys, Inc. Fischer-tropsch synthesis using microchannel technology and novel catalyst and microchannel reactor
US9023900B2 (en) 2004-01-28 2015-05-05 Velocys, Inc. Fischer-Tropsch synthesis using microchannel technology and novel catalyst and microchannel reactor
US8747805B2 (en) * 2004-02-11 2014-06-10 Velocys, Inc. Process for conducting an equilibrium limited chemical reaction using microchannel technology
US20050189097A1 (en) * 2004-03-01 2005-09-01 The Boeing Company Formed sheet heat exchanger
JP4971975B2 (en) * 2004-03-23 2012-07-11 ヴェロシス インコーポレイテッド Catalysis method using a catalyst, and it has a catalytic material applied directly to the thermal growth of alumina; improved oxidative dehydrogenation methods
CA2560834C (en) 2004-03-23 2014-05-27 Velocys, Inc. Tailored and uniform coatings in microchannel apparatus
US8378163B2 (en) * 2004-03-23 2013-02-19 Velocys Corp. Catalysts having catalytic material applied directly to thermally-grown alumina and catalytic methods using same, improved methods of oxidative dehydrogenation
GB0408896D0 (en) * 2004-04-20 2004-05-26 Accentus Plc Catalytic reactor
US7304198B2 (en) 2004-05-14 2007-12-04 Battelle Memorial Institute Staged alkylation in microchannels
US7305850B2 (en) 2004-07-23 2007-12-11 Velocys, Inc. Distillation process using microchannel technology
CA2574113C (en) 2004-07-23 2014-02-18 Anna Lee Tonkovich Distillation process using microchannel technology
KR100786703B1 (en) * 2004-07-24 2007-12-21 삼성전자주식회사 Device and method for measuring physical exercise using acceleration sensor
JP5731092B2 (en) * 2004-08-12 2015-06-10 ヴェロシス,インク. Method using microchannel reactor for converting ethylene to ethylene oxide and it using microchannel process technology
US7129194B2 (en) * 2004-09-23 2006-10-31 Corning Incorporated Catalyst system with improved corrosion resistance
EP1804964A1 (en) 2004-10-01 2007-07-11 Velocys Inc. Multiphase mixing process using microchannel process technology
US7955504B1 (en) 2004-10-06 2011-06-07 State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University Microfluidic devices, particularly filtration devices comprising polymeric membranes, and method for their manufacture and use
US20060110311A1 (en) * 2004-11-03 2006-05-25 Dimascio Felice Catalyst composite and methods of making and using
US7468455B2 (en) * 2004-11-03 2008-12-23 Velocys, Inc. Process and apparatus for improved methods for making vinyl acetate monomer (VAM)
CA2586971C (en) * 2004-11-12 2013-07-23 Velocys Inc. Process using microchannel technology for conducting alkylation or acylation reaction
EP1819435A1 (en) 2004-11-16 2007-08-22 Velocys Inc. Multiphase reaction process using microchannel technology
CA2587412C (en) * 2004-11-17 2013-03-26 Velocys Inc. Emulsion process using microchannel process technology
FR2879474B1 (en) * 2004-12-16 2008-06-13 Air Liquide Process for purifying an incoming mixture comprising carbon dioxide (CO2) and carbon monoxide (co) for the elimination of carbon monoxide (CO) contained in this mixture
US7485161B2 (en) * 2005-01-04 2009-02-03 Air Products And Chemicals, Inc. Dehydrogenation of liquid fuel in microchannel catalytic reactor
JP2008528938A (en) * 2005-02-02 2008-07-31 キャリア コーポレイションCarrier Corporation Parallel flow heat exchanger incorporating a porous insert
US7507274B2 (en) * 2005-03-02 2009-03-24 Velocys, Inc. Separation process using microchannel technology
JP2006248814A (en) * 2005-03-09 2006-09-21 Hitachi Ltd Apparatus and method for feeding hydrogen
US7871578B2 (en) * 2005-05-02 2011-01-18 United Technologies Corporation Micro heat exchanger with thermally conductive porous network
EP1890802A2 (en) * 2005-05-25 2008-02-27 Velocys, Inc. Support for use in microchannel processing
JP2008546533A (en) * 2005-06-28 2008-12-25 ミレニアム セル インコーポレイテッド Hydrogen generating catalyst and hydrogen generating system
JP2007008731A (en) * 2005-06-28 2007-01-18 Dainippon Printing Co Ltd Hydrogen producing apparatus and method for producing the same
US20070004810A1 (en) * 2005-06-30 2007-01-04 Yong Wang Novel catalyst and fischer-tropsch synthesis process using same
WO2007008495A3 (en) * 2005-07-08 2007-04-12 Velocys Inc Catalytic reaction process using microchannel technology
KR100658684B1 (en) * 2005-09-28 2006-12-11 삼성에스디아이 주식회사 Catalyst for reforming fuel and fuel cell system comprising the same
US8957259B2 (en) * 2005-09-30 2015-02-17 Battelle Memorial Institute Dimethyl ether production from methanol and/or syngas
US20070154377A1 (en) * 2005-12-22 2007-07-05 Rekers Dominicus M Process for the removal of combustible volatile contaminant materials from a process stream
KR20080080372A (en) * 2005-12-22 2008-09-03 셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이 Producing alkylene glycols in microchannel apparatus
US7750170B2 (en) 2005-12-22 2010-07-06 Shell Oil Company Process for mixing an oxidant having explosive potential with a hydrocarbon
US7226572B1 (en) 2006-03-03 2007-06-05 Conocophillips Company Compact sulfur recovery plant and process
WO2007111997A3 (en) * 2006-03-23 2008-01-24 Velocys Inc Process for making styrene using microchannel process technology
US8048383B2 (en) * 2006-04-20 2011-11-01 Velocys, Inc. Process for treating and/or forming a non-Newtonian fluid using microchannel process technology
US7501111B2 (en) 2006-08-25 2009-03-10 Conoco Phillips Company Increased capacity sulfur recovery plant and process for recovering elemental sulfur
US20080108122A1 (en) * 2006-09-01 2008-05-08 State of Oregon acting by and through the State Board of Higher Education on behalf of Oregon Microchemical nanofactories
US7999144B2 (en) 2006-09-01 2011-08-16 Velocys Microchannel apparatus and methods of conducting catalyzed oxidative dehydrogenation
EP2104755A4 (en) * 2006-10-26 2011-01-12 Symyx Solutions Inc High pressure parallel fixed bed reactor and method
US7923592B2 (en) 2007-02-02 2011-04-12 Velocys, Inc. Process for making unsaturated hydrocarbons using microchannel process technology
DE102007020888A1 (en) * 2007-05-04 2008-11-06 Micro Systems Engineering Gmbh & Co. Kg Ceramic substrate material, methods of making and using the same antenna or antenna array, and
US7626063B2 (en) * 2007-05-11 2009-12-01 Conocophillips Company Propane utilization in direct hydrotreating of oils and/or fats
US20090093555A1 (en) * 2007-07-09 2009-04-09 Range Fuels, Inc. Methods and apparatus for producing syngas
US20090018371A1 (en) * 2007-07-09 2009-01-15 Range Fuels, Inc. Methods and apparatus for producing alcohols from syngas
US8142530B2 (en) * 2007-07-09 2012-03-27 Range Fuels, Inc. Methods and apparatus for producing syngas and alcohols
US9227895B2 (en) * 2007-07-09 2016-01-05 Albemarle Corporation Methods and apparatus for producing alcohols from syngas
US20090014689A1 (en) * 2007-07-09 2009-01-15 Range Fuels, Inc. Methods and apparatus for producing syngas and alcohols
US8153027B2 (en) * 2007-07-09 2012-04-10 Range Fuels, Inc. Methods for producing syngas
CA2698140A1 (en) 2007-10-02 2009-04-09 Compactgtl Plc Gas-to-liquid plant using parallel units
DE102007049172A1 (en) * 2007-10-13 2009-04-16 Micro Systems Engineering Gmbh & Co. Kg Micro-reactor and process for the preparation of such and methods of making a substrate for a micro-reactor
US8101140B2 (en) * 2008-02-26 2012-01-24 Battelle Memorial Institute Structured catalyst bed and method for conversion of feed materials to chemical products and liquid fuels
US9908093B2 (en) * 2008-04-09 2018-03-06 Velocys, Inc. Process for converting a carbonaceous material to methane, methanol and/or dimethyl ether using microchannel process technology
US8100996B2 (en) * 2008-04-09 2012-01-24 Velocys, Inc. Process for upgrading a carbonaceous material using microchannel process technology
US20100081577A1 (en) * 2008-09-30 2010-04-01 Symyx Technologies, Inc. Reactor systems and methods
JP5715568B2 (en) 2008-10-10 2015-05-07 ヴェロシス,インク. Process and apparatus for using microchannel process technology
DE102008043352A1 (en) 2008-10-31 2010-05-06 Micro Systems Engineering Gmbh Ceramic substrate material, methods of making and using the same antenna or antenna array, and
US9623393B2 (en) * 2008-10-31 2017-04-18 Asemblon, Inc. Dehydrogenation of cyclic thioethers
US8933285B2 (en) * 2008-11-26 2015-01-13 Elevance Renewable Sciences, Inc. Methods of producing jet fuel from natural oil feedstocks through metathesis reactions
CN102227489B (en) * 2008-11-26 2015-04-15 埃莱文斯可更新科学公司 Methods of producing jet fuel from natural oil feedstocks through oxygen-cleaved reactions
EP2260937A1 (en) * 2009-06-12 2010-12-15 DSM IP Assets B.V. Device for processing and conditioning of material transported through the device
US8801922B2 (en) * 2009-06-24 2014-08-12 State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University Dialysis system
US20100326914A1 (en) * 2009-06-24 2010-12-30 State of Oregon acting by and through the State Board of Higher Education on behalf of Oregon Microfluidic devices
US20100143755A1 (en) * 2009-06-24 2010-06-10 Fischer Bernhard A Multi-Channel Fuel Reformer with Augmented Heat Transfer
US8765070B2 (en) * 2009-09-22 2014-07-01 Lockheed Martin Corporation System and method for rejecting heat from equipment via endothermic isomerization
US20110083997A1 (en) * 2009-10-09 2011-04-14 Silva Laura J Process for treating heavy oil
US9365487B2 (en) 2009-10-12 2016-06-14 Elevance Renewable Sciences, Inc. Methods of refining and producing dibasic esters and acids from natural oil feedstocks
US9000246B2 (en) 2009-10-12 2015-04-07 Elevance Renewable Sciences, Inc. Methods of refining and producing dibasic esters and acids from natural oil feedstocks
US9169447B2 (en) 2009-10-12 2015-10-27 Elevance Renewable Sciences, Inc. Methods of refining natural oils, and methods of producing fuel compositions
US9051519B2 (en) 2009-10-12 2015-06-09 Elevance Renewable Sciences, Inc. Diene-selective hydrogenation of metathesis derived olefins and unsaturated esters
US9388098B2 (en) 2012-10-09 2016-07-12 Elevance Renewable Sciences, Inc. Methods of making high-weight esters, acids, and derivatives thereof
US9222056B2 (en) 2009-10-12 2015-12-29 Elevance Renewable Sciences, Inc. Methods of refining natural oils, and methods of producing fuel compositions
US9175231B2 (en) 2009-10-12 2015-11-03 Elevance Renewable Sciences, Inc. Methods of refining natural oils and methods of producing fuel compositions
US9382502B2 (en) 2009-10-12 2016-07-05 Elevance Renewable Sciences, Inc. Methods of refining and producing isomerized fatty acid esters and fatty acids from natural oil feedstocks
US8735640B2 (en) 2009-10-12 2014-05-27 Elevance Renewable Sciences, Inc. Methods of refining and producing fuel and specialty chemicals from natural oil feedstocks
US8753515B2 (en) 2009-12-05 2014-06-17 Home Dialysis Plus, Ltd. Dialysis system with ultrafiltration control
US8580161B2 (en) 2010-05-04 2013-11-12 State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University Fluidic devices comprising photocontrollable units
US8501009B2 (en) 2010-06-07 2013-08-06 State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University Fluid purification system
US8710106B2 (en) * 2010-07-29 2014-04-29 Precision Combustion, Inc. Sabatier process and apparatus for controlling exothermic reaction
KR101297597B1 (en) 2011-04-19 2013-08-19 한국화학연구원 Reactor system for producing hydrocarbons from synthetic gas
KR101249204B1 (en) 2011-04-29 2013-04-09 한국과학기술원 Electrochemical reaction device and method for electrochemical reaction
WO2013052680A3 (en) 2011-10-07 2013-07-11 Home Dialysis Plus, Ltd. Heat exchange fluid purification for dialysis system
US9169174B2 (en) 2011-12-22 2015-10-27 Elevance Renewable Sciences, Inc. Methods for suppressing isomerization of olefin metathesis products
US9139493B2 (en) 2011-12-22 2015-09-22 Elevance Renewable Sciences, Inc. Methods for suppressing isomerization of olefin metathesis products
US9133416B2 (en) 2011-12-22 2015-09-15 Elevance Renewable Sciences, Inc. Methods for suppressing isomerization of olefin metathesis products
WO2013117948A1 (en) 2012-02-06 2013-08-15 Helbio Societé Anonyme Hydrogen And Energy Production Systems Heat integrated reformer with catalytic combustion for hydrogen production
CA2862538A1 (en) 2012-03-08 2013-09-12 Helbio Societe Anonyme Hydrogen And Energy Production Systems Catalytically heated fuel processor with replaceable structured supports bearing catalyst for fuel cell
GB201214122D0 (en) 2012-08-07 2012-09-19 Oxford Catalysts Ltd Treating of catalyst support
RU2535826C2 (en) * 2012-12-04 2014-12-20 Открытое акционерное общество "Тольяттиазот" Method of producing synthesis gas by steam conversion of hydrocarbons
US9676623B2 (en) 2013-03-14 2017-06-13 Velocys, Inc. Process and apparatus for conducting simultaneous endothermic and exothermic reactions
EP3137128A4 (en) 2014-04-29 2018-01-03 Outset Medical, Inc. Dialysis system and methods
FR3023494A1 (en) * 2014-07-09 2016-01-15 Air Liquide Exchanger and / or reactor-exchanger manufactured by additive method
US9943819B2 (en) 2014-11-03 2018-04-17 Singh Instrument LLC Small-scale reactor having improved mixing
GB2543849A (en) * 2015-11-02 2017-05-03 Johnson Matthey Plc Oxidation catalyst

Citations (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3545926A (en) * 1963-06-06 1970-12-08 Texaco Inc Production of synthesis gas and hydrogen
US3885063A (en) * 1973-06-15 1975-05-20 Battelle Memorial Institute Process for protecting a metallic surface against corrosion and wear
US4863712A (en) * 1986-09-10 1989-09-05 Imperial Chemical Industries Plc Catalysts for reforming hydrocarbon feedstocks
US4906176A (en) * 1983-07-01 1990-03-06 Hitachi, Ltd. High temperature stable catalyst, process for preparing same, and process for conducting chemical reaction using same
US4985230A (en) * 1987-08-27 1991-01-15 Haldor Topsoe A/S Method of carrying out heterogeneous catalytic chemical processes
US5047381A (en) * 1988-11-21 1991-09-10 General Electric Company Laminated substrate for catalytic combustor reactor bed
US5300275A (en) * 1990-01-08 1994-04-05 Imperial Chemical Industries Plc Steam reforming
US5324452A (en) * 1992-07-08 1994-06-28 Air Products And Chemicals, Inc. Integrated plate-fin heat exchange reformation
US5354547A (en) * 1989-11-14 1994-10-11 Air Products And Chemicals, Inc. Hydrogen recovery by adsorbent membranes
US5364824A (en) * 1992-12-08 1994-11-15 Huntsman Specialty Chemicals Corporation Catalysis for the production of maleic anhydride containing vanadium-phosphorus oxide with selected promoter elements
US5366719A (en) * 1989-09-08 1994-11-22 Veg-Gasinstituut N.V. Method of performing a chemical reaction and a reactor for use therewith
US5417938A (en) * 1988-09-02 1995-05-23 Sulzer Brothers Limited Device for carrying out catalyzed reactions
US5440872A (en) * 1988-11-18 1995-08-15 Pfefferle; William C. Catalytic method
US5512250A (en) * 1994-03-02 1996-04-30 Catalytica, Inc. Catalyst structure employing integral heat exchange
US5552360A (en) * 1993-03-04 1996-09-03 Engelhard Corporation Substrate configuration for catalytic combustion systems
US5609834A (en) * 1994-07-05 1997-03-11 Ishikawajima-Harima Heavy Industries Co., Ltd. Plate reformer
US5637283A (en) * 1993-07-16 1997-06-10 Thermatrix, Inc. Method and afterburner apparatus for control of highly variable flows
US5648582A (en) * 1993-08-20 1997-07-15 Regents Of The University Of Minnesota Stable, ultra-low residence time partial oxidation
US5725756A (en) * 1995-04-18 1998-03-10 Center For Research, Inc. In situ mitigation of coke buildup in porous catalysts with supercritical reaction media
US5811062A (en) * 1994-07-29 1998-09-22 Battelle Memorial Institute Microcomponent chemical process sheet architecture
US5846494A (en) * 1992-04-30 1998-12-08 Gaiser; Gerd Reactor for catalytically processing gaseous fluids
US5855676A (en) * 1997-05-01 1999-01-05 Virginia Tech Intellectual Properties, Inc. Tube lining apparatus
US5858314A (en) * 1996-04-12 1999-01-12 Ztek Corporation Thermally enhanced compact reformer
US5866734A (en) * 1996-09-05 1999-02-02 Aktiengesellschaft Hydrogenation process
US5888456A (en) * 1996-01-19 1999-03-30 Ngk Insulators, Ltd. Catalytic converter
US5914028A (en) * 1997-01-10 1999-06-22 Chevron Chemical Company Reforming process with catalyst pretreatment
US5976472A (en) * 1997-10-15 1999-11-02 Eastman Kodak Company Integrated micro-ceramic chemical plant with insertable catalytic reaction chambers
US6040266A (en) * 1994-02-22 2000-03-21 Ultramet Foam catalyst support for exhaust purification
US6056932A (en) * 1996-12-21 2000-05-02 Degussa-Huls Aktiengesellschaft Reactor for performing endothermic catalytic reactions
US6059961A (en) * 1998-04-27 2000-05-09 Uop Llc Method to alleviate thermal cycles in moving bed radial flow reactor
US6063342A (en) * 1994-11-15 2000-05-16 Babcock-Hitachi Kabushiki Kaisha Catalyst unit and gas purifying apparatus
US6129973A (en) * 1994-07-29 2000-10-10 Battelle Memorial Institute Microchannel laminated mass exchanger and method of making
US6143943A (en) * 1998-09-08 2000-11-07 Uop Llc Process using plate exchanger with high thermal density heat transfer fluid and simultaneous reaction
US6168765B1 (en) * 1998-09-08 2001-01-02 Uop Llc Process and apparatus for interbed injection in plate reactor arrangement
US6180846B1 (en) * 1998-09-08 2001-01-30 Uop Llc Process and apparatus using plate arrangement for combustive reactant heating
US6200536B1 (en) * 1997-06-26 2001-03-13 Battelle Memorial Institute Active microchannel heat exchanger
US6203587B1 (en) * 1999-01-19 2001-03-20 International Fuel Cells Llc Compact fuel gas reformer assemblage
US6228341B1 (en) * 1998-09-08 2001-05-08 Uop Llc Process using plate arrangement for exothermic reactions
US6241875B1 (en) * 1997-02-01 2001-06-05 Bg Plc Method of providing heat
US6254807B1 (en) * 1998-01-12 2001-07-03 Regents Of The University Of Minnesota Control of H2 and CO produced in partial oxidation process
US6274101B1 (en) * 1998-09-08 2001-08-14 Uop Llc Apparatus for in-situ reaction heating
US6274113B1 (en) * 1994-01-04 2001-08-14 Chevron Phillips Chemical Company Lp Increasing production in hydrocarbon conversion processes
US20020031471A1 (en) * 1998-07-27 2002-03-14 Anna Lee Y. Tonkovich Method and apparatus for obtaining enhanced production rate of thermal chemical reactions
US20020038062A1 (en) * 1999-12-24 2002-03-28 Diego Carmello Metallic monolith catalyst support for selective gas phase reactions in tubular fixed bed reactors
US20020168308A1 (en) * 2000-10-06 2002-11-14 Loffler Daniel A. Catalytic separator plate reactor and method of catalytic reforming of fuel to hydrogen
US6488838B1 (en) * 1999-08-17 2002-12-03 Battelle Memorial Institute Chemical reactor and method for gas phase reactant catalytic reactions
US6537506B1 (en) * 2000-02-03 2003-03-25 Cellular Process Chemistry, Inc. Miniaturized reaction apparatus
US6616909B1 (en) * 1998-07-27 2003-09-09 Battelle Memorial Institute Method and apparatus for obtaining enhanced production rate of thermal chemical reactions

Family Cites Families (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL279655A (en) * 1961-06-19
US3829888A (en) * 1971-01-08 1974-08-13 Hitachi Ltd Semiconductor device and the method of making the same
US3944504A (en) * 1974-03-25 1976-03-16 Olin Corporation Catalyst for the diminution of automobile exhaust gases
GB1537822A (en) * 1975-01-22 1979-01-04 Shell Int Research Process for the production of normally gaseous olefins
US4006102A (en) * 1975-08-25 1977-02-01 Ford Motor Company Stabilized rhenium catalyst
US4131643A (en) * 1975-09-05 1978-12-26 Kobe Steel Limited Catalyst for converting nitrogen oxides and method for converting nitrogen oxides in exhaust gases by using said catalyst
US4196099A (en) 1978-02-10 1980-04-01 Matthey Bishop, Inc. Catalyst comprising a metal substrate
US4316882A (en) * 1978-04-20 1982-02-23 Levine Bernard B Compositions for testing to predict and/or diagnose allergy to penicillins
EP0025308B1 (en) * 1979-09-06 1984-07-11 Imperial Chemical Industries Plc A process and apparatus for catalytically reacting steam with a hydrocarbon in endothermic conditions
CA1137962A (en) * 1980-05-20 1982-12-21 Martin Moskovits Heterogeneous catalyst and process for its manufacture
NL8200544A (en) 1982-02-12 1983-09-01 Veg Gasinstituut Nv Process for the preparation of methane from gas mixtures containing carbon monoxide with the aid of nickel-containing catalysts.
US4422961A (en) 1982-03-01 1983-12-27 Olin Corporation Raney alloy methanation catalyst
US5023276A (en) 1982-09-30 1991-06-11 Engelhard Corporation Preparation of normally liquid hydrocarbons and a synthesis gas to make the same, from a normally gaseous hydrocarbon feed
US4601999A (en) * 1983-11-09 1986-07-22 William B. Retallick Metal support for a catalyst
DE3435319A1 (en) * 1984-09-26 1986-04-03 Michael Laumen Catalytic steam generators
JPH0510133B2 (en) 1984-11-06 1993-02-08 Toyoda Chuo Kenkyusho Kk
DE3526383C1 (en) 1985-07-24 1986-12-11 Didier Werke Ag A process for the production of catalysts for the reduction of nitrogen oxides from exhaust gases and chemical air purification processes
US4742038A (en) * 1985-11-26 1988-05-03 Toyota Jidoshi Kabushiki Kaisha Monolithic catalyst support and catalyst deposited on the support
US5227407A (en) 1985-12-30 1993-07-13 Exxon Research And Engineering Company Water addition for increased CO/H2 hydrocarbon synthesis activity over catalysts comprising cobalt, ruthenium and mixtures thereof which may include a promoter metal
JPH0422827Y2 (en) 1987-09-25 1992-05-26
DE3810761C2 (en) 1988-03-30 1990-10-25 Didier-Werke Ag, 6200 Wiesbaden, De
DE3813946A1 (en) * 1988-04-26 1989-11-09 Asea Brown Boveri A method for applying a precious metal from and / or noble metal compounds existing catalyst layer on a support made of a ceramic material
US5051241A (en) * 1988-11-18 1991-09-24 Pfefferle William C Microlith catalytic reaction system
US5102851A (en) 1988-12-28 1992-04-07 Den Norske Stats Oljeselskap A.S. Supported catalyst for hydrocarbon synthesis
US4945116A (en) 1988-12-29 1990-07-31 Uop Fischer-Tropsch synthesis process employing a moderated ruthenium catalyst
DE69007885D1 (en) * 1989-07-13 1994-05-11 Seco Tools Ab Fagersta With more oxides coated carbide body and process for its preparation.
US5366717A (en) * 1989-10-02 1994-11-22 Research Triangle Institute Method for producing elemental sulfur from sulfur-containing gases
RU2093261C1 (en) 1991-05-12 1997-10-20 Татьяна Николаевна Довбышева Method of preparing solid block catalyst for afterburning of hydrogen in presence of water vapor
DE4207905A1 (en) * 1992-03-12 1993-09-16 Bayer Ag Fixed bed reactors with short catalyst bed in stroemungsrichtung
US5461022A (en) 1992-12-31 1995-10-24 Sandia Corporation Thin film hydrous metal oxide catalysts
US5534328A (en) 1993-12-02 1996-07-09 E. I. Du Pont De Nemours And Company Integrated chemical processing apparatus and processes for the preparation thereof
US5422331A (en) * 1994-02-25 1995-06-06 Engelhard Corporation Layered catalyst composition
JP3599370B2 (en) * 1994-05-23 2004-12-08 日本碍子株式会社 Hydrogen production system
JPH0812302A (en) * 1994-06-30 1996-01-16 Toyota Motor Corp Reforming reactor
US5480622A (en) * 1994-07-05 1996-01-02 Ford Motor Company Electrically heatable catalyst device using electrically conductive non-metallic materials
US6126723A (en) * 1994-07-29 2000-10-03 Battelle Memorial Institute Microcomponent assembly for efficient contacting of fluid
US5611214A (en) 1994-07-29 1997-03-18 Battelle Memorial Institute Microcomponent sheet architecture
NL1000146C2 (en) * 1995-04-13 1996-10-15 Gastec Nv A method for performing a chemical reaction.
DE19524158A1 (en) * 1995-07-03 1997-01-09 Degussa A process for preparing hydrocyanic acid
FR2736650B1 (en) * 1995-07-13 1997-09-05 Inst Francais Du Petrole Method for converting the liquid phase synthesis gas
EP0761308A1 (en) * 1995-09-12 1997-03-12 Basf Aktiengesellschaft Shell catalyst for instationary reactions
GB2322633A (en) 1997-02-28 1998-09-02 Norske Stats Oljeselskap Fischer-Tropsch reactor
JPH10273304A (en) * 1997-03-28 1998-10-13 Sekiyu Sangyo Kasseika Center Heat exchange type reformer
US5883138A (en) * 1997-04-25 1999-03-16 Exxon Research And Engineering Company Rapid injection catalytic partial oxidation process and apparatus for producing synthesis gas (law 562)
DE19719375A1 (en) * 1997-05-07 1998-11-12 Linde Ag Method and reactor for the production of ethylene oxide
RU2193917C2 (en) * 1997-07-03 2002-12-10 Е.И.Дюпон Де Немур Энд Компани Catalytic reactor with induction heating
US6479428B1 (en) * 1998-07-27 2002-11-12 Battelle Memorial Institute Long life hydrocarbon conversion catalyst and method of making
US6440895B1 (en) * 1998-07-27 2002-08-27 Battelle Memorial Institute Catalyst, method of making, and reactions using the catalyst
US6140266A (en) * 1999-02-18 2000-10-31 International Fuel Cells, Co., Llc Compact and light weight catalyst bed for use in a fuel cell power plant and method for forming the same
WO2001012753A1 (en) 1999-08-17 2001-02-22 Battelle Memorial Institute Catalyst structure and method of fischer-tropsch synthesis
CA2381154C (en) 1999-08-17 2009-02-03 Battelle Memorial Institute Chemical reactor and method for catalytic gas phase reactions
US6265451B1 (en) * 1999-09-21 2001-07-24 Hydrocarbon Technologies, Inc. Skeletal iron catalyst and its preparation for Fischer-Tropsch synthesis processes

Patent Citations (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3545926A (en) * 1963-06-06 1970-12-08 Texaco Inc Production of synthesis gas and hydrogen
US3885063A (en) * 1973-06-15 1975-05-20 Battelle Memorial Institute Process for protecting a metallic surface against corrosion and wear
US4906176A (en) * 1983-07-01 1990-03-06 Hitachi, Ltd. High temperature stable catalyst, process for preparing same, and process for conducting chemical reaction using same
US4863712A (en) * 1986-09-10 1989-09-05 Imperial Chemical Industries Plc Catalysts for reforming hydrocarbon feedstocks
US4985230A (en) * 1987-08-27 1991-01-15 Haldor Topsoe A/S Method of carrying out heterogeneous catalytic chemical processes
US5417938A (en) * 1988-09-02 1995-05-23 Sulzer Brothers Limited Device for carrying out catalyzed reactions
US5440872A (en) * 1988-11-18 1995-08-15 Pfefferle; William C. Catalytic method
US5047381A (en) * 1988-11-21 1991-09-10 General Electric Company Laminated substrate for catalytic combustor reactor bed
US5366719A (en) * 1989-09-08 1994-11-22 Veg-Gasinstituut N.V. Method of performing a chemical reaction and a reactor for use therewith
US5354547A (en) * 1989-11-14 1994-10-11 Air Products And Chemicals, Inc. Hydrogen recovery by adsorbent membranes
US5300275A (en) * 1990-01-08 1994-04-05 Imperial Chemical Industries Plc Steam reforming
US5846494A (en) * 1992-04-30 1998-12-08 Gaiser; Gerd Reactor for catalytically processing gaseous fluids
US5324452A (en) * 1992-07-08 1994-06-28 Air Products And Chemicals, Inc. Integrated plate-fin heat exchange reformation
US5364824A (en) * 1992-12-08 1994-11-15 Huntsman Specialty Chemicals Corporation Catalysis for the production of maleic anhydride containing vanadium-phosphorus oxide with selected promoter elements
US5552360A (en) * 1993-03-04 1996-09-03 Engelhard Corporation Substrate configuration for catalytic combustion systems
US5637283A (en) * 1993-07-16 1997-06-10 Thermatrix, Inc. Method and afterburner apparatus for control of highly variable flows
US5648582A (en) * 1993-08-20 1997-07-15 Regents Of The University Of Minnesota Stable, ultra-low residence time partial oxidation
US6274113B1 (en) * 1994-01-04 2001-08-14 Chevron Phillips Chemical Company Lp Increasing production in hydrocarbon conversion processes
US6040266A (en) * 1994-02-22 2000-03-21 Ultramet Foam catalyst support for exhaust purification
US5512250A (en) * 1994-03-02 1996-04-30 Catalytica, Inc. Catalyst structure employing integral heat exchange
US5609834A (en) * 1994-07-05 1997-03-11 Ishikawajima-Harima Heavy Industries Co., Ltd. Plate reformer
US5670269A (en) * 1994-07-05 1997-09-23 Ishikawajima-Harima Heavy Industries, Co., Ltd. Molten carbonate power generation system with plate reformer
US5811062A (en) * 1994-07-29 1998-09-22 Battelle Memorial Institute Microcomponent chemical process sheet architecture
US6129973A (en) * 1994-07-29 2000-10-10 Battelle Memorial Institute Microchannel laminated mass exchanger and method of making
US6063342A (en) * 1994-11-15 2000-05-16 Babcock-Hitachi Kabushiki Kaisha Catalyst unit and gas purifying apparatus
US5725756A (en) * 1995-04-18 1998-03-10 Center For Research, Inc. In situ mitigation of coke buildup in porous catalysts with supercritical reaction media
US5888456A (en) * 1996-01-19 1999-03-30 Ngk Insulators, Ltd. Catalytic converter
US5858314A (en) * 1996-04-12 1999-01-12 Ztek Corporation Thermally enhanced compact reformer
US5866734A (en) * 1996-09-05 1999-02-02 Aktiengesellschaft Hydrogenation process
US6056932A (en) * 1996-12-21 2000-05-02 Degussa-Huls Aktiengesellschaft Reactor for performing endothermic catalytic reactions
US5914028A (en) * 1997-01-10 1999-06-22 Chevron Chemical Company Reforming process with catalyst pretreatment
US6241875B1 (en) * 1997-02-01 2001-06-05 Bg Plc Method of providing heat
US5855676A (en) * 1997-05-01 1999-01-05 Virginia Tech Intellectual Properties, Inc. Tube lining apparatus
US6200536B1 (en) * 1997-06-26 2001-03-13 Battelle Memorial Institute Active microchannel heat exchanger
US5976472A (en) * 1997-10-15 1999-11-02 Eastman Kodak Company Integrated micro-ceramic chemical plant with insertable catalytic reaction chambers
US6254807B1 (en) * 1998-01-12 2001-07-03 Regents Of The University Of Minnesota Control of H2 and CO produced in partial oxidation process
US6059961A (en) * 1998-04-27 2000-05-09 Uop Llc Method to alleviate thermal cycles in moving bed radial flow reactor
US20020031471A1 (en) * 1998-07-27 2002-03-14 Anna Lee Y. Tonkovich Method and apparatus for obtaining enhanced production rate of thermal chemical reactions
US6616909B1 (en) * 1998-07-27 2003-09-09 Battelle Memorial Institute Method and apparatus for obtaining enhanced production rate of thermal chemical reactions
US6180846B1 (en) * 1998-09-08 2001-01-30 Uop Llc Process and apparatus using plate arrangement for combustive reactant heating
US6143943A (en) * 1998-09-08 2000-11-07 Uop Llc Process using plate exchanger with high thermal density heat transfer fluid and simultaneous reaction
US6274101B1 (en) * 1998-09-08 2001-08-14 Uop Llc Apparatus for in-situ reaction heating
US6168765B1 (en) * 1998-09-08 2001-01-02 Uop Llc Process and apparatus for interbed injection in plate reactor arrangement
US6228341B1 (en) * 1998-09-08 2001-05-08 Uop Llc Process using plate arrangement for exothermic reactions
US6869578B1 (en) * 1998-09-08 2005-03-22 Uop Llc Apparatus using plate arrangement for exothermic reactions
US6203587B1 (en) * 1999-01-19 2001-03-20 International Fuel Cells Llc Compact fuel gas reformer assemblage
US6488838B1 (en) * 1999-08-17 2002-12-03 Battelle Memorial Institute Chemical reactor and method for gas phase reactant catalytic reactions
US20020038062A1 (en) * 1999-12-24 2002-03-28 Diego Carmello Metallic monolith catalyst support for selective gas phase reactions in tubular fixed bed reactors
US6537506B1 (en) * 2000-02-03 2003-03-25 Cellular Process Chemistry, Inc. Miniaturized reaction apparatus
US20020168308A1 (en) * 2000-10-06 2002-11-14 Loffler Daniel A. Catalytic separator plate reactor and method of catalytic reforming of fuel to hydrogen

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060008399A1 (en) * 2004-07-07 2006-01-12 Feinstein Jonathan J Reactor with primary and secondary channels
US7566487B2 (en) 2004-07-07 2009-07-28 Jonathan Jay Feinstein Reactor with primary and secondary channels
US20080286177A1 (en) * 2007-05-18 2008-11-20 Tribute Creations, Llc Reactor with differentially distributed catalytic activity
WO2008143851A1 (en) * 2007-05-18 2008-11-27 Tribute Creations, Llc Reactor with differentially distributed catalytic activity
US20110166304A1 (en) * 2008-08-29 2011-07-07 Horst-Werner Zanthoff Use of foam bodies in oxidation reactors for preparing unsaturated aldehydes or carboxylic acids
US8841481B2 (en) 2008-08-29 2014-09-23 Evonik Degussa Gmbh Use of foam bodies in oxidation reactors for preparing unsaturated aldehydes or carboxylic acids
US20100305911A1 (en) * 2009-05-27 2010-12-02 King Fahd University Of Petroleum & Minerals Method for modeling fluid flow over porous blocks
US8165855B2 (en) 2009-05-27 2012-04-24 King Fahd University Of Petroleum & Minerals Method for modeling fluid flow over porous blocks
US9950305B2 (en) 2011-07-26 2018-04-24 Battelle Memorial Institute Solar thermochemical processing system and method

Also Published As

Publication number Publication date Type
JP2010131595A (en) 2010-06-17 application
EP1632282A2 (en) 2006-03-08 application
ES2344447T3 (en) 2010-08-27 grant
CA2396083C (en) 2009-05-19 grant
EP2208525A3 (en) 2012-04-25 application
CA2396083A1 (en) 2001-08-02 application
EP1251949B1 (en) 2010-04-14 grant
EP2208525A2 (en) 2010-07-21 application
US7045114B2 (en) 2006-05-16 grant
EP1251949B2 (en) 2018-02-21 grant
JP5474508B2 (en) 2014-04-16 grant
WO2001054807A1 (en) 2001-08-02 application
JP5265833B2 (en) 2013-08-14 grant
US6616909B1 (en) 2003-09-09 grant
JP2003520674A (en) 2003-07-08 application
US20040013606A1 (en) 2004-01-22 application
EP1251949A1 (en) 2002-10-30 application
DE60141809D1 (en) 2010-05-27 grant

Similar Documents

Publication Publication Date Title
Reuse et al. Hydrogen production for fuel cell application in an autothermal micro-channel reactor
US4927857A (en) Method of methanol production
US6680044B1 (en) Method for gas phase reactant catalytic reactions
US6607678B2 (en) Catalyst and method of steam reforming
US4863707A (en) Method of ammonia production
Song et al. Tri-reforming of methane: a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO ratios
US7288231B2 (en) Chemical reactor and method for gas phase reactant catalytic reactions
EP0303438A2 (en) Production of synthesis gas from hydrocarbonaceous feedstock
US6436363B1 (en) Process for generating hydrogen-rich gas
US20020028171A1 (en) Production of hydrogen by autothermic decomposition of ammonia
Pino et al. Catalytic partial-oxidation of methane on a ceria-supported platinum catalyst for application in fuel cell electric vehicles
US4522894A (en) Fuel cell electric power production
US20040266615A1 (en) Catalyst support and steam reforming catalyst
US20080210596A1 (en) Process and apparatus for converting natural gas to higher molecular weight hydrocarbons using microchannel process technology
US7029647B2 (en) Process for producing hydrogen peroxide using microchannel technology
US6447745B1 (en) Catalytic oxidation process
Lindström et al. Combined methanol reforming for hydrogen generation over monolithic catalysts
US7084180B2 (en) Fischer-tropsch synthesis using microchannel technology and novel catalyst and microchannel reactor
Görke et al. Highly selective methanation by the use of a microchannel reactor
US20050013769A1 (en) Catalytic reactor
Cai et al. Hydrogen production from ethanol steam reforming in a micro-channel reactor
US6491880B1 (en) Catalyst structure and method of fischer-tropsch synthesis
Aartun et al. Catalytic conversion of propane to hydrogen in microstructured reactors
US20040223908A1 (en) Microcombustors, microreformers, and methods involving combusting or reforming fluids
US20040258587A1 (en) Catalytic reactor