Integrated reformer and shift reactor

• US 7,066,973 B1
• Filed: 05/02/2000
• Issued: 06/27/2006
• Est. Priority Date: 08/26/1996
• Status: Expired due to Term

• Current Assignee: Nuvera Fuel Cells
• Original Assignee: Nuvera Fuel Cells
• Inventors: Clawson, Lawrence G., Mitchell, William L., Dorson, Matthew H., Bentley, Jeffrey M.
• Primary Examiner(s): NECKEL, ALEXA DOROSHENK
• Application Number:
  US09/562,787
• Time in Patent Office: 2,247 Days
• Field of Search: 48/61, 48/62.R, 48/75, 48/63, 48/64, 48/89, 48/94, 482/14.R, 481/20, 481/279, 481/28, 481/97.R, 481/981, 482/11, 481/983, 482/12, 481/986, 48/95, 481/987, 481/19, 482/15, 482/14.A, 422188-195, 422/198, 422/200, 422/201, 422/211, 422/648.1, 422650-656
• US Class Current: 48/197.00R
• CPC Class Codes: B01J 19/0046 Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays synthesis methods per se C40B50/00
• CPC Class Codes: B01J 2208/00203 Coils
• 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 2208/00849 outside the bed, e.g. baffles
• 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 8/048 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 8/0496 Heating or cooling the reactor
• CPC Class Codes: C01B 2203/0244 the reforming step being an autothermal reforming step, e.g. secondary reforming processes
• 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 2203/045 Purification by catalytic desulfurisation
• 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 2203/066 with fuel cells
• CPC Class Codes: C01B 2203/0894 Generation of steam
• CPC Class Codes: C01B 2203/1058 Nickel catalysts
• CPC Class Codes: C01B 2203/1229 Ethanol
• CPC Class Codes: C01B 2203/1235 Hydrocarbons
• CPC Class Codes: C01B 2203/127 : Catalytic desulfurisation
• CPC Class Codes: C01B 2203/1276 : Mixing of different feed components
• 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 2203/1614 : Controlling the temperature
• CPC Class Codes: C01B 2203/1685 : Control based on demand of downstream process
• CPC Class Codes: C01B 2203/169 : Controlling the feed
• CPC Class Codes: C01B 2203/82 : Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
• CPC Class Codes: C01B 3/382 : Multi-step processes
• CPC Class Codes: C01B 3/48 : followed by reaction of water vapour with carbon monoxide

Abstract

A hydrocarbon fuel reformer for producing diatomic hydrogen gas is disclosed. The reformer includes a first reaction vessel, a shift reactor vessel annularly disposed about the first reaction vessel, including a first shift reactor zone, and a first helical tube disposed within the first shift reactor zone having an inlet end communicating with a water supply source. The water supply source is preferably adapted to supply liquid-phase water to the first helical tube at flow conditions sufficient to ensure discharge of liquid-phase and steam-phase water from an outlet end of the first helical tube. The reformer may further include a first catalyst bed disposed in the first shift reactor zone, having a low-temperature shift catalyst in contact with the first helical tube. The catalyst bed includes a plurality of coil sections disposed in coaxial relation to other coil sections and to the central longitudinal axis of the reformer, each coil section extending between the first and second ends, and each coil section being in direct fluid communication with at least one other coil section.

Claims

1. A shift reactor for subjecting carbon monoxide and water to a water-gas shift reaction to produce carbon dioxide and diatomic hydrogen comprising:

a shift reactor vessel including a first shift reaction zone, the first shift reaction zone having a first shift catalyst bed, an input end for receiving reformate constituents including carbon monoxide and an outlet end for discharging shift-reacted constituents including carbon dioxide and hydrogen gas; and

,

a first helical tube disposed within the first shift reaction zone and in direct contact with the catalyst of the shift bed, the first helical tube having an inlet end communicating with an oxygen-containing gas supply source and an outlet end communicating with a fuel processing vessel.

2. The shift reactor of claim 1 wherein the shift reactor vessel has a central longitudinal axis, the first shift reaction zone has a first end and a second end, and the first helical tube includes a plurality of coiled sections, each coiled section being disposed in coaxial relation to the other coiled sections and to the central longitudinal axis, each coiled section also being disposed between the first and second ends of the first shift reaction zone, and in direct fluid communication with at least one other coiled section.

3. The shift reactor of claim 2 wherein the first helical tube is configured to permit the oxygen-containing gas to travel through each coiled section in a direction opposite to a direction traveled by the oxygen-containing gas through an adjacent coiled section.

4. The shift reactor of claim 1 wherein the first catalyst bed is a high temperature shift catalyst.

5. The shift reactor of claim 1 wherein the shift reactor vessel is annularly disposed about the fuel processing vessel.

6. The shift reactor of claim 1 wherein the fuel processing vessel has an inlet communicating with the outlet end of the first helical tube and configured to deliver the oxygen-containing gas tangentially into the fuel processing vessel.

7. The shift reactor of claim 1 wherein the fuel processing vessel includes a partial oxidation zone adapted to react a first reactant mixture including oxygen-containing gas from the first helical tube and hydrocarbon fuel.

8. The shift reactor of claim 7 wherein the fuel processing vessel further includes a steam reforming zone adapted to receive heat energy from the partial oxidation zone and to react a second reactant mixture including hydrocarbon fuel and water.

9. The shift reactor of claim 8 wherein the steam reforming zone is annularly disposed about the partial oxidation zone.

10. The shift reactor of claim 8 wherein the partial oxidation zone has a first end and a second end, an inlet proximate to the first end and communicating with the first helical tube, and an outlet proximate to the second end and communicating with the steam reforming zone, and wherein the steam reforming zone has an outlet communicating with the first shift reaction zone.

11. The shift reactor of claim 8 wherein the steam reforming zone includes a steam reforming catalyst suitable for catalyzing a steam reforming reaction.

12. The shift reactor of claim 11 wherein the steam reforming catalyst includes nickel.

13. The shift reactor of claim 7 wherein the steam reforming zone is adapted to receive reactants downstream from the partial oxidation zone.

14. The shift reactor of claim 1 further comprising a second helical tube disposed within the first shift reaction zone and having an inlet end communicating with a hydrocarbon fuel supply.

15. The shift reactor of claim 14 wherein:

the shift reactor vessel has a central longitudinal axis coincident with a first axis of symmetry of the first helical tube and coincident with a second axis of symmetry of the second helical tube;

the first shift reaction zone has a first end and a second end;

the first helical tube has a plurality of first coils and the second helical tube has a plurality of second coils;

each first coil is disposed in coaxial relation to the other first coils, is disposed between the first and second ends, and is in direct fluid communication with at least one other first coil;

the first helical tube is configured to permit the oxygen-containing gas flowing there through to travel through each first coil in a direction opposite to a direction traveled by the oxygen-containing gas through adjacent first coils;

each second coil is disposed in coaxial relation to the other second coils, is disposed between the first and second ends, and is in direct fluid communication with at least one other second coil; and

,

the second helical tube is configured to permit the fuel flowing there through to travel through each second coil in a direction opposite to a direction traveled by the fuel through adjacent second coils.

16. The shift reactor of claim 14 further comprising:

a second shift reaction zone disposed in the shift reactor vessel downstream of the first shift reaction zone; and

,

a third helical tube disposed within the second shift reaction zone and having an inlet end communicating with a water supply source.

17. The shift reactor of claim 16 wherein the second shift reaction zone includes a low-temperature shift catalyst.

18. The shift reactor of claim 16 further comprising an adiabatic shift reaction zone interposed between the first and second shift reaction zones.

19. The shift reactor of claim 16 further comprising:

a fuel processing vessel about which the shift reactor vessel is annularly disposed, the

fuel processing having a fuel processor inlet adapted to permit tangential delivery of reactants into the fuel processing; and

,

an inlet conduit interconnecting the fuel processor inlet with an outlet of the first helical tube and an outlet of the second helical tube.

20. The shift reactor of claim 19 wherein:

the inlet end of the second helical tube is adapted to receive a mixture of fuel and water;

the fuel processing vessel includes a steam reforming zone annularly disposed about a partial oxidation zone;

the partial oxidation zone is operably interposed between the inlet conduit and an inlet of the steam reforming zone; and

,

the steam reforming zone communicates with the input side.

21. The shift reactor of claim 20 further comprising a circuit adapted to route steam generated in the third helical tube to the inlet end of the second helical tube.

22. The shift reactor of claim 20 further comprising a plenum interconnecting the steam reforming zone with the input side.

23. The shift reactor of claim 22 further comprising a steam inlet communicating with the plenum.

24. The shift reactor of claim 23 further comprising a circuit adapted to direct steam generated in the third helical tube to the inlet end of the second helical tube and to the steam inlet.

25. A shift reactor for subjecting carbon monoxide and water to a water-gas shift reaction to produce carbon dioxide and diatomic hydrogen comprising:

a shift reactor vessel having a first shift catalyst bed, an input zone for receiving reformate constituents including carbon monoxide and an outlet zone for discharging shift-reacted constituents including carbon dioxide and hydrogen gas; and

,

a tube disposed within the shift reactor vessel and having an inlet end communicating with a source of unreformed hydrocarbon fuel, the tube situated within the shift reactor vessel to directly contact the catalyst of the first shift catalyst bed and permit transfer of heat energy from the shift-reacted constituents and catalyst to the unreformed hydrocarbon fuel.

26. The shift reactor of claim 25 further comprising an inlet conduit interconnecting the inlet end and the fuel supply source, and a water supply source communicating with the inlet conduit to permit water to mix with the fuel in the inlet conduit and flow with the fuel into the tube.

27. The shift reactor of claim 25 wherein the first catalyst bed disposed in the shift reactor vessel includes a high-temperature shift catalyst in contact with the tube.

28. The shift reactor of claim 25 wherein the tube is helical.

29. The shift reactor of claim 28 wherein:

the shift reactor vessel has a central longitudinal axis, a first end, and a second end;

the tube includes a plurality of coil sections;

each coil section is disposed in coaxial relation to the other coil sections and to the central longitudinal axis, each coil section extends between the first and second ends, and each coil section is in direct fluid communication with at least one other coil section; and

,

the tube is configured to permit the unreformed hydrocarbon fuel to travel through each coil section in a direction opposite to a direction traveled by the fuel through adjacent coil sections.

30. A hydrocarbon fuel reformer for producing diatomic hydrogen gas comprising:

a first reforming reaction vessel containing a reforming catalyst bed;

a shift reactor vessel annularly disposed about the first reaction vessel and including a first shift reactor zone, the first shift reactor zone having a first shift catalyst bed, an input side for receiving reformats constituents including carbon monoxide and an outlet side for discharging shift-reacted constituents including carbon dioxide and hydrogen gas; and

,

a first helical tube disposed within the first shift reactor zone contacting the catalyst of the shift catalyst bed and having an inlet end communicating with a water supply source.

31. The reformer of claim 30 wherein the water supply source is adapted to supply liquid-phase water to the first helical tube at flow conditions sufficient to ensure discharge of liquid-phase and steam-phase water from an outlet end of the first helical tube.

32. The reformer of claim 30 wherein the first catalyst bed disposed in the first shift reactor zone includes a low-temperature shift catalyst in contact with the first helical tube.

33. The reformer of claim 30 wherein:

the shift reactor vessel has a central longitudinal axis;

the first shift reactor zone has a first end and a second end;

the first helical tube includes a plurality of coil sections; and

,

each coil section is disposed in coaxial relation to the other coil sections and to the central longitudinal axis, each coil section extends between the first and second ends, and each coil section is in direct fluid communication with at least one other coil section.

34. A fuel processor for producing diatomic hydrogen gas comprising:

a vessel having a first end, a second end, and an outer wall;

a partial oxidation zone disposed in the vessel, extending between the first and second ends, and bounded by a first inner wall; and

a steam reforming zone interposed between the first inner wall and the outer wall, the first inner wall having a port disposed near the first end to define a first transition between a first flow path of reactants through the partial oxidation zone and a second flow path of reactants through the steam reforming zone in a direction substantially opposite the first flow path.

35. The fuel processor of claim 34 wherein the steam reforming zone is bounded between the first inner wall and a second inner wall, the fuel processor further comprising a shift reaction zone interposed between the second inner wall and the outer wall and operably communicating with the steam reforming zone.

36. The fuel processor of claim 35 wherein the steam reforming zone has a port disposed near the second end to define a second transition between the second flow path and a third flow path of reactants through the shift reaction zone in a direction substantially opposite the second flow.

37. The fuel processor of claim 35 wherein the second inner wall is permeable to permit a third flow of reactants through the shift reaction zone in directions substantially orthogonal to the first and second flows.

38. A reactor for producing hydrogen from hydrocarbons comprising:

a reforming reaction vessel containing a reforming catalyst;

a first shift reaction zone annularly disposed about the reforming reaction vessel, the shift reaction zone containing a first shift catalyst; and

,

a boiler tube in the first shift reaction zone for carrying a heat transfer medium, the tube being located so as to permit heat transfer between a first portion of the tube and reaction constituents in the first shift reaction zone.

39. The reactor of claim 38, further comprising:

a second shift reaction zone containing a second shift catalyst; and

,

the boiler tube being located so as to permit heat transfer between a second portion of the tube and reaction constituents in the second shift reaction zone.

40. The reactor of claim 39, wherein the second portion of the boiler tube being in contact with the second catalyst.

41. The reactor of claim 38, wherein the first portion of the boiler tube being in contact with the first catalyst.

42. The reactor of claim 41, wherein the second portion of the boiler tube being in contact with the second catalyst.

43. The reactor of claim 38, wherein the heat transfer medium is water and further comprising:

a water separator located outside the reaction vessel for separating water from steam generated in the boiler tube; and

,

the boiler tube being operatively connected to the water separator.

44. The reactor of claim 38, further including a means to adjust a pressure in the tube so as to control the temperature of the heat transfer medium in the tube and thereby affect the temperature in the first shift reaction zone.

45. The reactor of claim 43, including a valve on the water separator to adjust a pressure in the boiler tube so as to control the temperature of the water, steam, or water/steam in the tube and thereby affect the temperature in the first shift reaction zone.

46. The reactor of claim 38, further comprising:

a fuel conduit for delivering a fuel stream to a portion of the reaction vessel for reaction;

a means for introducing steam from the boiler tube into the fuel stream from the fuel conduit so as to effect mixing of the steam with the fuel.

47. The reactor of claim 38, further comprising:

a fuel conduit for delivering a fuel stream to a portion of the reaction vessel for reaction;

a water separator located outside the reaction vessel for separating water from steam generated in the boiler tube, the boiler tube being operatively connected to the water separator;

a steam conduit directing steam from the water separator to a means for introducing steam from the water separator into the fuel stream so as to effect mixing of the steam with the fuel; and

,

a chamber having an inner wall with an arcuate portion, the chamber being adapted to permit partial oxidation of hydrocarbons in the fuel and steam mixture, the chamber having an inlet which directs the fuel/steam mixture at a tangent to the arcuate portion of the inner wall of the chamber.

48. A reactor as in claim 38, including a mixing manifold for delivering fuel to the reaction vessel.