HYDROGEN PURIFICATION MEMBRANES, COMPONENTS AND FUEL PROCESSING SYSTEMS CONTAINING THE SAME

• US 20110116985A1
• Filed: 10/21/2010
• Published: 05/19/2011
• Est. Priority Date: 10/30/1996
• Status: Active Grant

• Current Assignee: DCNS SA (Government of France)
• Original Assignee: IdaTech LLC (IdaTech Ltd.)
• Inventors: Pledger, William A., Studebaker, R. Todd, Edlund, David J.
• Granted Patent: US 8,057,575 B2
• Time in Patent Office: Days
• US Class Current: 422/187
• CPC Class Codes: B01D 2313/20 Specific housing
• CPC Class Codes: B01D 2313/22 Cooling or heating elements
• CPC Class Codes: B01D 2313/221 Heat exchangers
• CPC Class Codes: B01D 2313/42 Catalysts within the flow path
• CPC Class Codes: B01D 2325/22 Thermal or heat-resistance properties
• CPC Class Codes: B01D 53/22 by diffusion manufacturing semi-permeable membranes B01D67/00; form, structure or properties of semi-permeable membranes B01D69/00; material for semi-permeable membranes B01D71/00
• CPC Class Codes: B01D 53/229 Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
• CPC Class Codes: B01D 63/06 Tubular membrane modules
• CPC Class Codes: B01D 63/08 Flat membrane modules
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01J 19/2475 Membrane reactors
• CPC Class Codes: B01J 2208/00061 of the reactants
• CPC Class Codes: B01J 2208/00088 Flow rate measurement
• CPC Class Codes: B01J 2208/00106 by indirect heat exchange
• CPC Class Codes: B01J 2208/00132 Tubes
• CPC Class Codes: B01J 2208/00141 Coils
• CPC Class Codes: B01J 2208/00256 in a heat exchanger for the heat exchange medium separate from the reactor
• CPC Class Codes: B01J 2208/00309 with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
• CPC Class Codes: B01J 2208/00371 gaseous
• CPC Class Codes: B01J 2208/00415 electric resistance heaters
• CPC Class Codes: B01J 2208/00495 : using insulating materials or refractories
• CPC Class Codes: B01J 2208/00504 : by means of a burner
• CPC Class Codes: B01J 2208/0053 : Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
• CPC Class Codes: B01J 2208/00539 : Pressure
• CPC Class Codes: B01J 2208/00548 : Flow
• CPC Class Codes: B01J 8/006 : by filtration
• CPC Class Codes: B01J 8/009 : Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
• CPC Class Codes: B01J 8/0257 : in a cylindrical annular shaped bed
• CPC Class Codes: B01J 8/0285 : Heating or cooling the reactor for tubular reactors in furnaces B01J8/062
• CPC Class Codes: B01J 8/04 : the fluid passing successively through two or more beds
• CPC Class Codes: B01J 8/0465 : the beds being concentric
• CPC Class Codes: B01J 8/0469 : the beds being superimposed one above the other
• CPC Class Codes: B01J 8/0496 : Heating or cooling the reactor
• CPC Class Codes: B01J 8/062 : being installed in a furnace
• CPC Class Codes: B01J 8/067 : Heating or cooling the reactor B01J8/062 takes precedence
• CPC Class Codes: C01B 2203/0227 : containing a catalytic reforming step
• CPC Class Codes: C01B 2203/0233 : the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0244 : the reforming step being an autothermal reforming step, e.g. secondary reforming processes
• CPC Class Codes: C01B 2203/0261 : containing a catalytic partial oxidation step [CPO]
• CPC Class Codes: C01B 2203/0283 : containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/0405 : Purification by membrane separation
• CPC Class Codes: C01B 2203/041 : In-situ membrane purification during hydrogen production
• CPC Class Codes: C01B 2203/044 : Selective oxidation of carbon monoxide
• CPC Class Codes: C01B 2203/0445 : Selective methanation
• CPC Class Codes: C01B 2203/047 : the impurity being carbon monoxide
• CPC Class Codes: C01B 2203/0475 : the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/066 : with fuel cells
• CPC Class Codes: C01B 2203/0811 : by combustion of fuel
• CPC Class Codes: C01B 2203/0816 : Heating by flames
• CPC Class Codes: C01B 2203/0822 : the fuel containing hydrogen
• CPC Class Codes: C01B 2203/0827 : at least part of the fuel being a recycle stream
• CPC Class Codes: C01B 2203/0844 : the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
• CPC Class Codes: C01B 2203/085 : by electric heating
• CPC Class Codes: C01B 2203/0866 : by combination of different heating methods
• CPC Class Codes: C01B 2203/0877 : by direct injection of fluid
• CPC Class Codes: C01B 2203/0883 : by indirect heat exchange
• CPC Class Codes: C01B 2203/0888 : by evaporation of a fluid
• CPC Class Codes: C01B 2203/1011 : Packed bed of catalytic structures, e.g. particles, packing elements
• CPC Class Codes: C01B 2203/1041 : Composition of the catalyst
• CPC Class Codes: C01B 2203/1058 : Nickel catalysts
• CPC Class Codes: C01B 2203/1076 : Copper or zinc-based catalysts
• CPC Class Codes: C01B 2203/1217 : Alcohols
• CPC Class Codes: C01B 2203/1223 : Methanol
• CPC Class Codes: C01B 2203/1235 : Hydrocarbons
• CPC Class Codes: C01B 2203/1241 : Natural gas or methane
• CPC Class Codes: C01B 2203/1247 : Higher hydrocarbons
• CPC Class Codes: C01B 2203/1258 : Pre-treatment of the feed
• CPC Class Codes: C01B 2203/1276 : Mixing of different feed components
• CPC Class Codes: C01B 2203/1288 : Evaporation of one or more of the different feed components
• CPC Class Codes: C01B 2203/142 : At least two reforming, decomposition or partial oxidation steps in series
• CPC Class Codes: C01B 2203/146 : At least two purification steps in series
• CPC Class Codes: C01B 2203/1604 : Starting up the process
• CPC Class Codes: C01B 2203/1628 : Controlling the pressure
• CPC Class Codes: C01B 2203/1633 : Measuring the pressure
• CPC Class Codes: C01B 2203/1657 : the product being hydrogen
• CPC Class Codes: C01B 2203/1676 : Measuring the composition of the product
• CPC Class Codes: C01B 2203/169 : Controlling the feed
• CPC Class Codes: C01B 2203/1695 : Adjusting the feed of the combustion
• CPC Class Codes: C01B 2203/82 : Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
• CPC Class Codes: C01B 3/32 : by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
• CPC Class Codes: C01B 3/323 : Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
• CPC Class Codes: C01B 3/38 : using catalysts
• CPC Class Codes: C01B 3/382 : Multi-step processes
• CPC Class Codes: C01B 3/384 : the catalyst being continuously externally heated
• CPC Class Codes: C01B 3/503 : characterised by the membrane
• CPC Class Codes: C01B 3/505 : Membranes containing palladium
• CPC Class Codes: C01B 3/586 : the reaction being a methanation reaction
• CPC Class Codes: H01M 8/0612 : from carbon-containing material
• CPC Class Codes: H01M 8/0618 : Reforming processes, e.g. autothermal, partial oxidation or steam reforming
• CPC Class Codes: H01M 8/0631 : Reactor construction specially adapted for combination reactor/fuel cell hydrogen C01B3/00; reactors for physicochemical processes B01J19/00
• CPC Class Codes: H01M 8/0687 : Reactant purification by the use of membranes or filters
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 20/10 : Process efficiency
• CPC Class Codes: Y02P 20/129 : Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
• CPC Class Codes: Y10S 48/05 : Diffusion membrane for gas reaction or separation

Abstract

Hydrogen-producing fuel processing systems, hydrogen purification membranes, hydrogen purification devices, fuel processing and fuel cell systems that include hydrogen purification devices, and methods for operating the same. In some embodiments, operation of the fuel processing system is initiated by heating at least the reforming region of the fuel processing system to at least a selected hydrogen-producing operating temperature. In some embodiments, an electric heater is utilized to perform this initial heating. In some embodiments, use of the electric heater is discontinued after startup, and a burner or other combustion-based heating assembly combusts a fuel to heat at least the hydrogen producing region, such as due to the reforming region utilizing an endothermic catalytic reaction to produce hydrogen gas.

Claims

1. (canceled)

2. A hydrogen-producing fuel processing system, comprising:

a steam reforming chamber containing a steam reforming catalyst, wherein the steam reforming chamber is configured to receive a feed stream including methanol and water and produce a reformate stream therefrom, wherein the reformate stream contains hydrogen gas as a majority component and further includes other gases;

a membrane module configured to receive the reformate stream and divide the reformate stream into a byproduct stream and a hydrogen-rich stream, the membrane module comprising;

a plurality of hydrogen-selective membranes, each being generally planar and having a reformate side and a permeate side, wherein the plurality of hydrogen-selective membranes are spaced-apart from each other and oriented with their permeate sides generally facing each other to define a harvesting conduit extending therebetween, wherein the hydrogen-rich stream is formed from a portion of the reformate stream that passes through the plurality of hydrogen-selective membranes to the harvesting conduit, with a remaining portion of the reformate stream which remains on the reformate side of the plurality of hydrogen-selective membranes forming the byproduct stream, and further wherein the hydrogen-rich stream has a greater concentration of hydrogen gas than the byproduct stream;

a support within the harvesting conduit and configured to support the membranes, wherein the support includes a pair of generally opposed surfaces which are configured to provide support to a respective one of the permeate sides of the plurality of hydrogen-selective membranes; and

a product outlet port in fluid communication with the harvesting conduit and through which the hydrogen-rich stream is withdrawn from the membrane module; and

a polishing region configured to reduce a concentration of any carbon monoxide present in the hydrogen-rich stream and to produce a product hydrogen stream therefrom.

3. The hydrogen-producing fuel processing system of claim 2, wherein the polishing region includes a methanation catalyst bed.

4. The hydrogen-producing fuel processing system of claim 2, wherein the hydrogen-producing fuel processing system further includes a feedstock delivery system configured to supply the feed stream to the steam reforming chamber.

5. The hydrogen-producing fuel processing system of claim 2, wherein at least a portion of the plurality of hydrogen-selective membranes is formed from a palladium-copper alloy.

6. The hydrogen-producing fuel processing system of claim 2, wherein the membrane module includes at least one gasket configured to form a gas-tight seal between the support and at least one of the plurality of hydrogen-selective membranes.

7. The hydrogen-producing fuel processing system of claim 6, wherein the at least one gasket forms the gas-tight seal around at least one of the plurality of hydrogen-selective membranes.

8. The hydrogen-producing fuel processing system of claim 6, wherein the at least one gasket includes a graphite gasket.

9. The hydrogen-producing fuel processing system of claim 2, wherein the membrane module includes at least two end plates, wherein the at least two end plates are secured together to form an enclosure that contains the plurality of hydrogen-selective membranes, wherein the at least two end plates are secured together by a retention structure, and further wherein the retention structure includes at least one of a weld and a bolt.

10. The hydrogen-producing fuel processing system of claim 2, wherein the support includes a plurality of components.

11. The hydrogen-producing fuel processing system of claim 2, wherein the support includes a metallic support.

12. The hydrogen-producing fuel processing system of claim 11, wherein the support includes at least one of voids and slots configured to provide a flow path for the hydrogen-rich stream as it flows through the harvesting conduit.

13. The hydrogen-producing fuel processing system of claim 2, wherein the hydrogen-producing fuel processing system further includes an electric resistance heater in thermal communication with at least the steam reforming catalyst and configured to heat the steam reforming catalyst to a suitable operating temperature of 200 to 500°

C.

14. The hydrogen-producing fuel processing system of claim 2, wherein the hydrogen-producing fuel processing system further includes a control system.

15. A method for starting operation of the hydrogen-producing fuel processing system of claim 2, the method comprising:

electrically heating, during a startup period, the steam reforming catalyst to a selected hydrogen-producing operating temperature of at least 200°

C.;

wherein, when heated to the selected hydrogen-producing operating temperature, the steam reforming catalyst is configured to catalyze, via a steam reforming reaction, formation of the reformate stream from the feed stream;

ceasing the electrically heating;

delivering the feed stream to the steam reforming chamber;

producing the reformate stream from the feed stream;

separating the reformate stream into the hydrogen-rich stream;

reducing the concentration of carbon monoxide in the hydrogen-rich stream with the polishing region to produce the product hydrogen stream;

combusting at least a portion of the byproduct stream to produce a heated exhaust stream; and

heating at least the steam reforming catalyst with the heated exhaust stream to maintain the steam reforming catalyst at a hydrogen-producing temperature.

16. A method for starting operation of a hydrogen-producing fuel processing system, the method comprising:

electrically heating, during a startup period, a steam reforming region containing a steam reforming catalyst to a selected hydrogen-producing operating temperature of at least 200°

C.;

wherein when heated to the selected hydrogen-producing operating temperature, the steam reforming catalyst is configured to catalyze, via a steam reforming reaction, the formation of a mixed gas stream containing hydrogen gas as a majority component and other gases from a feed stream containing methanol and water that is delivered thereto;

ceasing the electrically heating;

delivering the feed stream to the steam reforming region;

producing the mixed gas stream from the feed stream;

separating the mixed gas stream into a hydrogen-rich stream, which contains hydrogen gas of greater purity than the mixed gas stream, and a byproduct stream, which contains at least a substantial portion of the other gases, utilizing at least one hydrogen-selective membrane, wherein the hydrogen-rich stream is formed from a portion of the mixed gas stream that passes through the at least one hydrogen-selective membrane and the byproduct stream is formed from a portion of the mixed gas stream that does not pass through the at least one hydrogen-selective membrane;

purifying the hydrogen-rich stream in a polishing region configured to reduce a concentration of at least one of the other gasses in the hydrogen-rich stream and produce a product hydrogen stream;

combusting at least a portion of the byproduct stream to produce a heated exhaust stream; and

heating the steam reforming region with the heated exhaust stream.

17. The method of claim 16, wherein the polishing region includes a methanation catalyst bed, and further wherein the purifying includes purifying with the methanation catalyst bed.

18. The method of claim 16, wherein the hydrogen-producing fuel processing system further includes a feedstock delivery system configured to supply the feed stream to the steam reforming region, and further wherein the delivering the feed stream includes delivering the feed stream with the feedstock delivery system.

19. The method of claim 16, wherein the method further includes controlling the operation of the hydrogen-producing fuel processing system.

20. The method of claim 16, wherein the electrically heating includes utilizing an electric resistance heater to heat the steam reforming region.

21. The method of claim 16, wherein the method further includes detecting that the steam reforming catalyst has been heated to the selected hydrogen-producing operating temperature, and further wherein the ceasing the electrically heating includes ceasing the electrically heating responsive to the detecting that the steam reforming catalyst has been heated to the selected hydrogen-producing operating temperature.

22. The method of claim 16, wherein the ceasing the electrical heating includes ceasing the electrical heating before the steam reforming region begins to produce the mixed gas stream.

23. The method of claim 16, wherein the ceasing the electrical heating includes ceasing the electrical heating after the steam reforming region begins to produce the mixed gas stream.