Steam reformer with internal hydrogen purification

• US 5,861,137 A
• Filed: 10/30/1996
• Issued: 01/19/1999
• Est. Priority Date: 10/30/1996
• Status: Expired due to Term

• Current Assignee: DCNS SA (Government of France)
• Original Assignee: Northwest Power Systems LLC (IdaTech Ltd.)
• Inventors: Edlund, David J.
• Primary Examiner(s): BHAT, NINA NMN
• Application Number:
  US08/741,057
• Time in Patent Office: 811 Days
• Field of Search: 48/76, 48/127.7, 48/127.9, 48/63, 422/217, 422/218, 423/652, 423/653, 423/654, 423/655
• US Class Current: 423/652
• CPC Class Codes: B01J 19/2475 Membrane reactors
• CPC Class Codes: B01J 2208/00053 of the heat exchange medium
• CPC Class Codes: B01J 2208/00061 of the reactants
• CPC Class Codes: B01J 2208/00106 by indirect heat exchange
• CPC Class Codes: B01J 2208/00141 Coils
• 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 2208/00415 electric resistance heaters
• CPC Class Codes: B01J 2208/00495 using insulating materials or refractories
• 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 8/009 Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
• 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 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/041 : In-situ membrane purification during hydrogen production
• 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 2203/0822 : the fuel containing hydrogen
• CPC Class Codes: C01B 2203/0827 : at least part of the fuel being a recycle stream
• CPC Class Codes: C01B 2203/085 : by electric heating
• CPC Class Codes: C01B 2203/0866 : by combination of different heating methods
• 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 2203/1241 : Natural gas or methane
• CPC Class Codes: C01B 2203/1247 : Higher hydrocarbons
• 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 2203/82 : Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
• CPC Class Codes: C01B 3/323 : Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
• CPC Class Codes: C01B 3/382 : Multi-step processes
• CPC Class Codes: C01B 3/501 : by diffusion
• 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: C12F 5/00 : Preparation of denatured alcohol
• CPC Class Codes: Y02P 20/10 : Process efficiency

Abstract

A steam reformer with internal hydrogen purification includes internal bulk hydrogen purification, internal hydrogen polishing to remove trace levels of carbon monoxide and carbon dioxide, an integrated combustion method utilizing waste gas to heat the reformer, efficient integration of heat transfer, and a compact design. The steam reformer shown includes a concentric cylindric architecture nesting an annular combustion region, an annular reforming region, an annular hydrogen transport region, and a cylindrical polishing region.

Claims

1. A process for the production of hydrogen containing concentrations of carbon monoxide and carbon dioxide below a given level, comprising:

reacting steam and at least one of an alcohol vapor and a hydrocarbon vapor at a temperature approximately in the range of 200 degrees C. to 600 degrees C. and a total pressure of at least two atmospheres to produce product hydrogen, carbon monoxide, and carbon dioxide;

conducting said reacting step in the vicinity of a hydrogen-permeable and hydrogen-selective membrane whereby said product hydrogen permeates said membrane and concentrations of said carbon monoxide and said carbon dioxide above said given level permeate said membrane;

placing a methanation catalyst bed containing a methanation catalyst at the permeate side of said membrane;

providing means to heat the methanation catalyst to a temperature approximately in the range of 200 degrees C. to 600 degrees C. whereby said carbon monoxide and carbon dioxide permeating through said membrane convert to methane and yield a product hydrogen stream with concentrations of carbon monoxide and carbon dioxide below said given level; and

withdrawing said product hydrogen stream from said methanation catalyst bed.

2. A process according to claim 1 wherein said alcohol vapor is a methanol vapor and said reacting step occurs at a temperature approximately in the range of 200 degrees celsius to 400 degrees celsius.

3. A process according to claim 1 wherein between 50 percent and 80 percent of a theoretically available amount of hydrogen is recovered as said product hydrogen and the remaining amount of said theoretically available amount of hydrogen is withdrawin along with reforming byproduct gasses as a byproduct stream.

4. A process according to claim 3 wherein wherein said remaining amount of hydrogen in said by product stream is mixed with air and combusted to provide heat supporting said reforming step.

5. A steam reformer comprising:

a tubular hydrogen-permeable and hydrogen-selective membrane;

a first bed comprising a reforming catalyst and surrounding at least part of said membrane;

an inlet to said first bed receiving a mixture of steam and at least one of an alcohol vapor and a hydrocarbon vapor;

an outlet from said first bed releasing reforming byproduct gasses;

a heating element heating said first bed to an operating temperature approximately between 200 degrees C. and 600 degrees C.;

a second bed comprising a methanation catalyst placed at the permeate side of said membrane; and

a reformer outlet withdrawing hydrogen gas from said second bed.

6. A reformer according to claim 5 wherein said membrane comprises one of porous metal, porous ceramic, and porous carbon.

7. A reformer according to claim 5 wherein said membrane comprises non-porous hydrogen-permeable metal.

8. A reformer according to claim 7 wherein said membrane comprises at least one of palladium and palladium alloys.

9. A reformer according to claim 8 wherein said membrane comprises at least one of an alloy of palladium with 30-50 wt % copper, an alloy of palladium with 5-30 wt % silver, an alloy of palladium with 1-10% yttrium, and an alloy of palladium with 1-10% cerium.

10. A reformer according to claim 5 wherein said heating element comprises at least one radiant, electric resistive heating element.

11. A reformer according to claim 5 wherein said heating element comprises a third bed containing an oxidation catalyst arranged around at least a portion of said first bed such that said reforming byproduct gasses pass into said third bed, mix with an air source, catalytically ignite to generate heat, and discharge from said reformer.

12. A reformer according to claim 11 wherein said air source is heated prior to injection into said third bed.

13. A reformer according to claim 12 wherein said air source is heated by at least one of heat exchange with said hydrogen being withdrawn and said third bed.

14. A reformer according to claim 11 wherein a liquid methanol and liquid water feed is vaporized and preheated prior to injection into said first bed by heat exchange with at least one of said discharged purified hydrogen product stream or said combustion-gas discharge stream.

15. A reformer according to claim 11 wherein sufficient hydrogen remains in said reforming byproduct gasses passing into said first bed to provide when catalytically ignited sufficient heat to maintain said operating temperature.

16. A reformer according to claim 11 wherein said third bed operates at a total pressure less than a total pressure within said first bed.

17. A reformer according to claim 16 wherein said third bed operates at near ambient pressure.

18. A reformer according to claim 17 wherein a restricted orifices through which said reforming byproduct gasses flow from said first bed and into said third bed, causes a pressure differential between said third bed and said first bed.

19. A reformer according to claim 5 wherein at least one electric resistance heating element heats said first bed to said operating temperature.

20. A reformer according to claim 19 wherein said at least one heating element inserts into a bore of said tubular hydrogen-permeable and hydrogen-selective membrane.

21. A reformer according to claim 19 wherein said at least one heating element at least one of inserts into said first bed and surrounds the circumference of said first bed.