Compact fuel processor for producing a hydrogen rich gas

• US 20020094310A1
• Filed: 12/05/2001
• Published: 07/18/2002
• Est. Priority Date: 12/05/2000
• Status: Active Grant

• Current Assignee: Texaco Incorporated (Chevron Corp.)
• Original Assignee: Texaco Incorporated (Chevron Corp.)
• Inventors: Krause, Curtis L., Wolfenbarger, James K., Martin, Paul F.
• Granted Patent: US 7,455,817 B2
• Time in Patent Office: Days
• US Class Current: 422/617
• CPC Class Codes: B01J 19/0013 Controlling the temperature of the process
• CPC Class Codes: B01J 19/2475 Membrane reactors
• CPC Class Codes: B01J 19/2485 Monolithic reactors
• CPC Class Codes: B01J 2208/00141 Coils
• CPC Class Codes: B01J 2208/00176 outside the reactor
• CPC Class Codes: B01J 2208/00194 Tubes
• CPC Class Codes: B01J 2208/00203 Coils
• CPC Class Codes: B01J 2208/00407 outside the reactor bed
• CPC Class Codes: B01J 2208/00415 electric resistance heaters
• CPC Class Codes: B01J 2208/00716 Means for reactor start-up
• CPC Class Codes: B01J 2208/00814 the particulate material being provides in prefilled containers
• CPC Class Codes: B01J 2208/025 Two or more types of catalyst
• CPC Class Codes: B01J 2219/0002 Plants assembled from modules joined together
• CPC Class Codes: B01J 2219/00083 Coils
• CPC Class Codes: B01J 2219/00135 Electric resistance heaters
• CPC Class Codes: B01J 2219/182 horizontal
• CPC Class Codes: B01J 2219/185 vertical
• CPC Class Codes: B01J 2219/1944 spiral
• 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 8/0278 Feeding reactive fluids for solid material B01J8/0015
• CPC Class Codes: B01J 8/0285 : Heating or cooling the reactor for tubular reactors in furnaces B01J8/062
• CPC Class Codes: B01J 8/0423 : through two or more otherwise shaped beds
• CPC Class Codes: B01J 8/0453 : the beds being superimposed one above the other
• CPC Class Codes: B01J 8/048 : the beds being superimposed one above the other
• CPC Class Codes: B01J 8/0488 : the beds being placed in separate reactors
• CPC Class Codes: B01J 8/0492 : Feeding reactive fluids for solid material, see B01J8/0015
• CPC Class Codes: B01J 8/0496 : Heating or cooling the reactor
• CPC Class Codes: B01J 8/067 : Heating or cooling the reactor B01J8/062 takes precedence
• CPC Class Codes: C01B 2203/0244 : the reforming step being an autothermal reforming step, e.g. secondary reforming processes
• CPC Class Codes: C01B 2203/0283 : containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/0288 : containing two CO-shift steps
• CPC Class Codes: C01B 2203/044 : Selective oxidation of carbon monoxide
• CPC Class Codes: C01B 2203/0455 : Purification by non-catalytic desulfurisation
• CPC Class Codes: C01B 2203/0465 : Composition of the impurity
• CPC Class Codes: C01B 2203/047 : the impurity being carbon monoxide
• CPC Class Codes: C01B 2203/0485 : the impurity being a sulfur compound
• CPC Class Codes: C01B 2203/0495 : the impurity being water
• CPC Class Codes: C01B 2203/066 : with fuel cells
• CPC Class Codes: C01B 2203/0805 : Methods of heating the process for making hydrogen or synthesis gas
• 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 2203/0894 : Generation of steam
• CPC Class Codes: C01B 2203/1011 : Packed bed of catalytic structures, e.g. particles, packing elements
• CPC Class Codes: C01B 2203/1017 : characterised by the form of the structure
• CPC Class Codes: C01B 2203/1023 : Catalysts in the form of a monolith or honeycomb
• CPC Class Codes: C01B 2203/1035 : Catalyst coated on equipment surfaces, e.g. reactor walls
• CPC Class Codes: C01B 2203/1041 : Composition of the catalyst
• CPC Class Codes: C01B 2203/1082 : Composition of support materials
• CPC Class Codes: C01B 2203/1205 : Composition of the feed
• CPC Class Codes: C01B 2203/1235 : Hydrocarbons
• CPC Class Codes: C01B 2203/1276 : Mixing of 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 2203/147 : Three or more purification steps in series
• CPC Class Codes: C01B 2203/1604 : Starting up the process
• CPC Class Codes: C01B 2203/80 : Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
• CPC Class Codes: C01B 2203/82 : Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
• CPC Class Codes: C01B 3/16 : using catalysts
• 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 3/386 : Catalytic partial combustion
• CPC Class Codes: C01B 3/48 : followed by reaction of water vapour with carbon monoxide
• CPC Class Codes: C01B 3/583 : the reaction being the selective oxidation of carbon monoxide
• CPC Class Codes: H01M 8/04022 : Heating by combustion
• CPC Class Codes: H01M 8/04037 : Electrical heating
• CPC Class Codes: H01M 8/04059 : Evaporative processes for the cooling of a fuel cell
• CPC Class Codes: H01M 8/0612 : from carbon-containing material
• 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 8/0668 : Removal of carbon monoxide or carbon dioxide
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

An apparatus for carrying out a multi-step process of converting hydrocarbon fuel to a substantially pure hydrogen gas feed includes a plurality of modules stacked end-to-end along a common axis. Each module includes a shell having an interior space defining a passageway for the flow of gas from a first end of the shell to a second end of the shell opposite the first end, and a processing core being contained within the interior space for effecting a chemical, thermal, or physical change to a gas stream passing axially through the module. the multi-step process includes: providing a fuel processor having a plurality of modules stacked end-to-end along a common axis; and feeding the hydrocarbon fuel successively through each of the modules in an axial direction through the tubular reactor to produce the hydrogen rich gas.

Claims

1. An apparatus for converting hydrocarbon fuel into a hydrogen rich gas, comprising a plurality of modules stacked end-to-end along a common axis, wherein each module of the plurality of modules includes:

a shell having an interior space defining a passageway for the flow of a gas stream from a first end of the shell to a second end of the shell opposite the first end, and a processing core being contained within the interior space for effecting a chemical, thermal, or physical change to the gas stream passing axially therethrough.

2. The apparatus as described in claim 1, wherein the plurality of modules are cylindrical in shape.

3. The apparatus as described in claim 1, wherein each module of the plurality of modules includes an annular lip at either the first end or the second end of the shell and an annular recessed portion at the opposite end of the shell, and wherein the annular lip of one module is receivable into the annular recess of the adjacent module.

4. The apparatus as described in claim 1, wherein at least one module of the plurality of modules includes an annular layer of thermally insulative material disposed between the shell and the respective processing core.

5. The apparatus as described in claim 1, wherein at least one module of the plurality of modules includes a porous support member mounted in proximity to the first end of the shell.

6. The apparatus as described in claim 1, wherein at least one module of the plurality of modules includes a porous support member mounted in proximity to the second end of the shell.

7. The apparatus as described in claim 6, wherein the porous support member is selected from the group consisting of a screen, mesh, perforated plate, and porous sintered plate.

8. The apparatus as described in claim 1, wherein the plurality of modules includes a first module, wherein the processing core of the first module includes a partial oxidation catalyst.

9. The apparatus as described in claim 8, wherein the first module also includes a steam reforming catalyst.

10. The apparatus as described in claim 8, wherein the partial oxidation catalyst includes a metal selected from the group consisting of platinum, palladium, rhodium, ruthenium, nickel, cobalt, and any combinations thereof.

11. The apparatus as described in claim 9, wherein the steam reforming catalyst includes a metal selected from the group consisting of platinum, palladium, rhodium, ruthenium, iridium, nickel, potassium, and combinations thereof.

12. The apparatus as described in claim 10, wherein the metal of the partial oxidation catalyst is supported on a material selected from the group consisting of magnesia, alumina, titania, zirconia, and silica.

13. The apparatus as described in claim 11, wherein the metal of the steam reforming catalyst is supported on a material selected from the group consisting of magnesia, alumina, silica, zirconia, and magnesium aluminate.

14. The apparatus as described in claim 1, wherein the plurality of modules includes a second module, wherein the processing core of the second module includes a first heat exchanger for cooling the gas stream.

15. The apparatus as described in claim 1, wherein the plurality of modules includes a third module, wherein the processing core of the third module includes a desulfurization agent.

16. The apparatus as described in claim 14, wherein the desulfurization agent includes zinc oxide.

17.he. The apparatus as described in claim 1, wherein the plurality of modules includes a fourth module, wherein the processing core of the fourth module includes an inert material for mixing components of the gas stream passing therethrough.

18. The apparatus as described in claim 17, wherein the inert material comprises ceramic beads.

19. The apparatus as described in claim 17, wherein the fourth module is designed to introduce water to the gas stream.

20. The apparatus as described in claim 1, wherein the plurality of modules includes a fifth module, wherein the processing core of the fifth module includes:

a water gas shift catalyst bed; and

a heat exchanger positioned within the water gas shift catalyst bed for maintaining a desired shift reaction temperature range.

21. The apparatus as described in claim 20, wherein the water gas shift catalyst is a low temperature water gas shift catalyst.

22. The apparatus as described in claim 21 wherein the low temperature water gas shift catalyst includes a material selected from the group consisting of copper, copper oxide, zinc, platinum, rhenium, palladium, rhodium, and gold.

23. The apparatus as described in claim 20, wherein the water gas shift catalyst is a high temperature water gas shift catalyst.

24. The apparatus as described in claim 23, wherein the high temperature water gas shift catalyst includes a material selected from the group consisting of ferric oxide, chromic oxide, copper, iron silicide, platinum, and palladium.

25. The apparatus as described in claim 1, wherein the plurality of modules includes a sixth module, wherein the processing core of the sixth module includes a second heat exchanger for cooling the gas stream.

26. The apparatus as described in claim 1, wherein the plurality of modules includes a seventh module, wherein the processing core of the seventh module includes:

a carbon monoxide oxidation catalyst bed; and

a heat exchanger positioned within the carbon monoxide oxidation catalyst bed for maintaining a desired oxidation reaction temperature range.

27. The apparatus as described in claim 26, wherein the seventh module is designed to introduce an oxygen-containing stream to the gas stream prior to contact with the carbon monoxide oxidation bed.

28. The apparatus as described in claim 26, wherein the carbon monoxide oxidation catalyst bed includes a material selected from the group consisting of platinum, palladium, iron, chromium, manganese, iron oxide, chromium oxide, manganese oxide, ruthenium, palladium, gold, and any combinations thereof.

29. An apparatus for converting hydrocarbon fuel into a hydrogen rich gas, comprising a

plurality of modules stacked end-to-end along a common axis;

wherein each module of the plurality of modules includes;

a shell having an interior space defining a passageway for the flow of a gas stream from a first end of the shell to a second end of the shell opposite the first end, and

a processing core being contained within the interior space for effecting a chemical, thermal, or physical change to the gas stream passing axially therethrough; and

wherein the plurality of modules includes;

a first module containing a partial oxidation catalyst bed,

a second module positioned adjacent to the first module containing a first heat exchanger for cooling the gas stream,

a third module positioned adjacent to the second module containing a desulfurization agent,

a fourth module positioned adjacent the third module containing an inert material for mixing components of the gas stream passing therethrough,

a fifth module positioned adjacent to the fourth module containing a water gas shift catalyst bed,

a sixth module positioned adjacent to the fifth module containing a second heat exchanger for cooling the gas stream, and

a seventh module positioned adjacent to the sixth module containing a carbon monoxide oxidation catalyst bed.

30. An apparatus for converting hydrocarbon fuel into a hydrogen rich gas, comprising a

plurality of modules stacked end-to-end along a common axis;

wherein each module of the plurality of modules includes;

a shell having an interior space defining a passageway for the flow of a gas stream from a first end of the shell to a second end of the shell opposite the first end, and

a processing core being contained within the interior space for effecting a chemical, thermal, or physical change to the gas stream passing axially therethrough; and

wherein the plurality of modules includes;

a first module containing a partial oxidation catalyst bed,

a second module positioned adjacent to the first module containing a first heat exchanger for cooling the gas stream,

a third module positioned adjacent to the second module containing a desulfurization agent,

a fourth module positioned adjacent to the third module containing a water gas shift catalyst bed,

a fifth module positioned adjacent to the fourth module containing a second heat exchanger for cooling the gas stream, and

a sixth module positioned adjacent to the fifth module containing a carbon monoxide oxidation catalyst bed.

31. A process for converting hydrocarbon fuel into a hydrogen rich gas comprising:

providing a fuel processor having a plurality of modules stacked end-to-end along a common axis; and

feeding the hydrocarbon fuel successively through each of the modules in an axial direction to produce the hydrogen rich gas.

32. The process as described in claim 31, wherein the plurality of modules includes:

a first module for the partial oxidation and steam reforming of the hydrocarbon fuel to produce a first module effluent;

a second module positioned adjacent to the first module for cooling the first module effluent to produce a second module effluent;

a third module positioned adjacent to the second module, wherein the third module desulfurizes the second module effluent to produce a third module effluent;

a fourth module positioned adjacent the third module, wherein the fourth module mixes water with the third module effluent to produce a fourth module effluent;

a fifth module positioned adjacent to the fourth module, wherein the fifth module reacts the water and the carbon monoxide contained in the fourth module effluent to produce a fifth module effluent having a reduced carbon monoxide concentration;

a sixth module positioned adjacent to the fifth module for cooling the fifth module effluent to produce a sixth module effluent;

a seventh module positioned adjacent to the sixth module for oxidizing at least some carbon monoxide to produce the hydrogen rich gas.

33. The process as described in claims 32, wherein the hydrocarbon fuel may be preheated by the second module, the fifth module, the sixth module, the seventh module, or any combination thereof.

34. The process as described in claims 32, wherein the first module operates at a temperature ranging from about 550°

C. to about 900°

C.

35. The process as described in claim 32, wherein the second module effluent is from about 200°

C. to about 600°

C.

36. The process as described in claim 32, wherein the fifth module operates at a temperature ranging from about 150°

C. to about 400°

C.

37. The process as described in claim 32, wherein the fifth module effluent is cooled to a temperature of from about 90°

C. to about 150°

C.

38. The process as described in claim 32, wherein the seventh module operates at a temperature of from about 90°

C. to about 150°

C.

The process as described in claim 32, wherein the hydrogen rich gas contains less than 50 ppm carbon monoxide.

39. The process as described in claim 31, wherein the plurality of modules includes:

a first module for the partial oxidation and steam reforming of the hydrocarbon fuel to produce a first module effluent;

a second module positioned adjacent to the first module for cooling the first module effluent to produce a second module effluent;

a third module positioned adjacent to the second module, wherein the third module desulfurizes the second module effluent to produce a third module effluent;

a fourth module positioned adjacent to the third module, wherein the fourth module reacts water and the carbon monoxide contained in the third module effluent to produce a fourth module effluent having a reduced carbon monoxide concentration;

a fifth module positioned adjacent to the fourth module for cooling the fourth module effluent to produce a fifth module effluent;

a sixth module positioned adjacent to the fifth module for oxidizing at least some carbon monoxide to produce the hydrogen rich gas.

40. The process as described in claims 39, wherein the hydrocarbon fuel may be preheated by the second module, the fourth module, the fifth module, the sixth module, or any combination thereof.

41. The process as described in claims 39, wherein the first module operates at a temperature ranging from about 550°

C. to about 900°

C.

42. The process as described in claim 39, wherein the second module effluent is from about 200°

C. to about 600°

C.

43. The process as described in claim 39, wherein the fourth module operates at a temperature ranging from about 150°

C. to about 400°

C.

44. The process as described in claim 39, wherein the fourth module effluent is cooled to a temperature of from about 90°

C. to about 150°

C.

45. The process as described in claim 39, wherein the sixth module operates at a temperature of from about 90°

C. to about 150°

C.

46. The process as described in claim 39, wherein the hydrogen rich gas contains less than 50 ppm carbon monoxide.