Ceramic oxygen transport membrane array reactor and reforming method

• US 9,452,401 B2
• Filed: 10/07/2014
• Issued: 09/27/2016
• Est. Priority Date: 10/07/2013
• Status: Active Grant

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Kelly, Sean M., Christie, Gervase Maxwell, Rosen, Lee J., Robinson, Charles, Wilson, Jamie R., Gonzalez, Javier E., Doraswami, Uttam R.
• Primary Examiner(s): Akram, Imran
• Application Number:
  US14/508,297
• Publication Number:
  US 20150098872A1
• Time in Patent Office: 721 Days
• US Class Current: 1/1
• CPC Class Codes: B01J 12/007 in the presence of catalytically active bodies, e.g. porous plates
• CPC Class Codes: B01J 19/242 in series
• CPC Class Codes: B01J 19/2425 in parallel
• CPC Class Codes: B01J 19/243 spirally, concentrically or zigzag wound
• CPC Class Codes: B01J 19/2475 Membrane reactors
• 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 2208/00938 Flow distribution elements
• CPC Class Codes: B01J 2219/00006 Large-scale industrial plants
• CPC Class Codes: B01J 2219/0004 Processes in series
• CPC Class Codes: B01J 2219/0006 of the heat exchange medium
• CPC Class Codes: B01J 2219/00117 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 8/009 Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
• CPC Class Codes: B01J 8/065 Feeding reactive fluids
• CPC Class Codes: B01J 8/067 Heating or cooling the reactor B01J8/062 takes precedence
• CPC Class Codes: C01B 13/0255 characterised by the type of membrane
• 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 2203/0894 Generation of steam
• CPC Class Codes: C01B 2203/127 Catalytic desulfurisation
• CPC Class Codes: C01B 3/382 Multi-step processes
• CPC Class Codes: C01B 3/384 : the catalyst being continuously externally heated
• CPC Class Codes: F22B 1/003 : using combustion of hydrogen with oxygen power plants using steam created by combustion of hydrogen with oxygen F01K25/005
• CPC Class Codes: F22B 1/16 : the heat carrier being hot liquid or hot vapour, e.g. waste liquid, waste vapour
• CPC Class Codes: Y02P 20/129 : Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

A commercially viable modular ceramic oxygen transport membrane reforming reactor for producing a synthesis gas that improves the thermal coupling of reactively-driven oxygen transport membrane tubes and catalyst reforming tubes required to efficiently and effectively produce synthesis gas.

Claims

1. An oxygen transport membrane panel for transferring radiant heat to a plurality of catalytic reforming reactors, the oxygen transport membrane panel comprising:

a panel frame; and

a plurality of oxygen transport membrane repeating units arranged in a tightly packed linear or co-planar orientation;

wherein each oxygen transport membrane repeating unit comprises two or more oxygen transport membrane tubes coupled together and configured to be in fluid communication with either a feed manifold or an exhaust manifold; and

wherein each oxygen transport membrane tube having a permeate side located on an interior surface of the tube and a retentate side located on an exterior surface of the tube;

wherein the plurality of oxygen transport membrane repeating units are supported by said panel frame and are configured to separate oxygen from an oxygen containing stream contacting the retentate side of the tubes in cross-flow arrangement and react the permeated oxygen with a gas stream containing hydrogen and carbon containing species introduced into the permeate side of the tubes thereby producing radiant heat and a steam containing reaction product stream;

wherein the catalytic reforming reactors are configured to produce synthesis gas in the presence of the radiant heat and a hydrocarbon containing reactant stream optionally containing the reaction product stream from the oxygen transport membrane panels; and

wherein the catalytic reforming reactors are arranged in a plane substantially parallel to the oxygen transport membrane panels.

2. The oxygen transport membrane tube assembly of claim 1 wherein the plurality of oxygen transport membrane tubes are arranged in a juxtaposed orientation.

3. The oxygen transport membrane tube assembly of claim 2 wherein at least some of the plurality of oxygen transport membrane tubes are arranged in a serpentine orientation.

4. The oxygen transport membrane tube assembly of claim 1 wherein the plurality of oxygen transport membrane tubes are arranged in a generally parallel orientation.

5. The oxygen transport membrane tube assembly of claim 1 wherein the plurality of ceramic to ceramic coupling elements further comprise one or more ceramic linear connectors configured for fluidically coupling two adjacent oxygen transport membrane tubes in a linear orientation.

6. The oxygen transport membrane tube assembly of claim 1 wherein the plurality of ceramic to ceramic coupling elements further comprise one or more ceramic U-shaped connectors configured for fluidically coupling two adjacent oxygen transport membrane tubes.

7. The oxygen transport membrane tube assembly of claim 1 wherein the plurality of ceramic to ceramic coupling elements further comprise one or more ceramic M-shaped connectors configured for coupling three or more oxygen transport membrane tubes.

8. The oxygen transport membrane tube assembly of claim 1 further comprising one or more isolation valve assemblies disposed between the first ceramic to metal coupling element and the feed manifold and/or between the second ceramic to metal coupling element and the exhaust manifold.

9. The oxygen transport membrane panel of claim 1 wherein the oxygen transport membrane repeating units comprises a plurality of oxygen transport membrane tubes, said oxygen transport membrane tubes comprising a dense layer, a porous support and an intermediate porous layer located between the dense layer and the porous support, wherein said dense layer and the intermediate porous layer comprise a mixture of an ionic conductive material and an electrically conductive material, wherein said dense layer and said intermediate porous layer are effective in conducting oxygen ions and electrons.

10. The oxygen transport membrane panel of claim 9 wherein the oxygen transport membrane tubes additionally comprise a porous surface exchange layer in contact with the dense layer opposite to the intermediate porous layer.

11. The oxygen transport membrane panel of claim 10 wherein the porous surface exchange layer of the oxygen transport membrane tubes has a thickness of from about 10 microns to about 40 microns, a porosity of from about 30 percent to about 60 percent and a pore diameter of from about 1 micron to about 4 microns.

13. The oxygen transport membrane panel of claim 9 wherein the porous surface exchange layer of the oxygen transport membrane tubes forms the retentate side of the oxygen transport membrane tubes.

14. The oxygen transport membrane panel of claim 9 wherein said ionic conductive material of the oxygen transport membrane tubes comprises fluorite.

15. The oxygen transport membrane panel of claim 9 wherein said intermediate porous layer has a thickness of from about 10 microns and about 40 microns, a porosity of from about 25 percent and about 40 percent and an average pore diameter of from about 0.5 microns and about 3 microns.

16. The oxygen transport membrane panel of claim 9 wherein said dense layer of the oxygen transport membrane tubes has a thickness of from about 10 microns and about 50 microns.

17. The oxygen transport membrane panel of claim 9 which additionally comprises a catalyst.

18. The oxygen transport membrane panel of claim 17 wherein said catalyst is loaded inside the oxygen transport membrane tubes, integrated in the intermediate porous layer of the oxygen transport membrane tubes, integrated in the porous support layer adjacent to the intermediate porous layer of the oxygen transport membrane tubes and/or the interior surface of the oxygen transport membrane tubes is coated or activated with said catalyst.

19. The oxygen transport membrane panel of claim 18 wherein the catalyst particles promote oxidation of the hydrogen containing stream.

20. The oxygen transport membrane panel of claim 19 wherein said catalyst promoted the reforming of a hydrogen containing stream.

21. The oxygen transport membrane panel of claim 19 wherein said catalyst comprises gadolinium doped ceria.

22. The oxygen transport membrane panel of claim 9 wherein the outside diameter of each oxygen transport membrane tube is the same or different and is in the range of about 8 mm to 20 mm and the length/diameter ratio in the range of 50 to 150.

23. The oxygen transport membrane panel of claim 9 wherein catalytic reforming reactor is integrated within the oxygen transport membrane panel, and/or within a separate catalyst reforming panel.

24. The oxygen transport membrane panel of claim 9 wherein said oxygen transport membrane tubes are arranged in an M-pin arrangement.

25. The oxygen transport membrane panel of claim 24 wherein said M-pin arrangement comprises at least four (4) oxygen transport membrane tubes connected in series with ceramic to ceramic seals and ceramic coupling adapters, and two (2) ceramic to metal adapters configured to be sealably connect the ends of the M-pin arrangement to the feed and outlet manifolds of an oxygen transport membrane panel.

26. The oxygen transport membrane panel of claim 25 wherein said M-pin arrangement additionally comprises one or more of ceramic U-shaped connectors configured for fluidically coupling adjacent tubes.

27. The oxygen transport membrane panel of claim 24 which comprising a plurality of M-pin arrangements.

12. The oxygen transport membrane panel of 10 wherein the support layer of the oxygen transport membrane tubes has a thickness of from about 0.5 mm to about 10.0 mm and a pore size 50 microns or less.

28. An oxygen transport membrane array module comprising;

a frame or support structure

one or more oxygen transport membrane panels supported by the frame, each panel comprising a plurality of oxygen transport membrane repeating units arranged in a tightly packed linear and co-planar orientation wherein each oxygen transport membrane repeating unit contains two or more oxygen transport membrane tubes coupled together at one end to form a multi-pass arrangement and the other end of the tubes configured to be in fluid communication with a first feed manifold or a first exhaust manifold; and

one or more catalytic reforming panels attached to the frame in a juxtaposed orientation with respect to the one or more the oxygen transport membrane panels, each catalytic reforming panel comprising a plurality of reforming repeating units arranged in a tightly packed linear or co-planar orientation wherein each reforming repeating unit comprises at least one multi-pass reforming tube in fluid communication with a second feed manifold or a second exhaust manifold; and

wherein the catalytic reforming panels are arranged in a plane parallel to the oxygen transport membrane panels.

29. The oxygen transport membrane array module of claim 28 wherein the catalyst reformer panel comprises multi-pass catalytic reforming tubes for producing synthesis gas from a hydrocarbon containing reactant feed stream in the presence of heat, wherein said multi-pass reforming tubes are in fluid communication with a feed manifold or an exhaust manifold;

wherein said multi-pass reforming tubes contains at least one steam reforming catalyst configured to produce the synthesis gas from the hydrocarbon containing reactant feed stream.

30. The oxygen transport membrane array module of claim 28 wherein each multi-pass reforming tube contains steam reforming catalysts configured to produce a synthesis gas from a hydrocarbon containing reactant feed stream in the presence of the radiant heat and steam produced by the oxygen transport membrane tubes.

31. The oxygen transport membrane array module of claim 29 wherein the surface area ratio between the catalytic reforming panels and the oxygen transport membrane panels radiating heat to the catalytic reforming reactors is from about 0.4 to about 1.0.

32. The oxygen transport membrane array module of claim 29 wherein the view factor between the oxygen transport membrane panels radiating heat to the catalytic reforming panels is greater than or equal to about 0.4.

33. The oxygen transport membrane array module of claim 32 wherein said synthesis gas is produced from a hydrocarbon containing reactant feed stream in the presence of radiant heat and steam, wherein at least a part of said heat and steam is received from a plurality of reactively driven oxygen transport membrane tubes.

34. The oxygen transport membrane array module of claim 31 wherein the multi-pass catalytic reforming tubes are constructed of Incoloy 800HT.

35. The oxygen transport membrane array module of claim 29 wherein the catalytic reforming tubes are filled with a metal or ceramic catalyst support material.

36. The oxygen transport membrane array module of claim 35 wherein said catalyst support material is a folded metal foil, metal mesh, metal foam, extruded metal/ceramic pellets or a combination thereof, wherein said catalyst support material is impregnated or wash-coated on exposed surfaces with at least one steam reforming catalyst.

37. The oxygen transport membrane array module of claim 35 wherein the interior surface of the reforming tubes is coated or activated with at least one steam reforming catalyst.

38. An oxygen transport membrane based reforming reactor pack assembly comprising two or more oxygen transport membrane array modules in accordance with claim 28.

39. The oxygen transport membrane based reforming reactor pack assembly of claim 38 wherein said membrane array modules are stacked within a refractory-lined steel container or housing and manifolded together to form an oxygen transport membrane based reforming reactor pack assembly.

40. The oxygen transport membrane based reforming reactor pack assembly of claim 39 wherein membrane array modules are manifolded together to form a pack assembly, wherein said modules are manifolded together in one or more dedicated zones in the pack assembly.

41. The oxygen transport membrane based reforming reactor pack assembly of claim 40 wherein said at least one of said dedicated zones includes an inlet circuit configured to provide a mixed-preheated-feed to the feed manifolds associated with the catalyst reformer panels and optionally to the oxygen transport membrane panels and an outlet circuit configured or adapted to receive and withdraw the synthesis gas produced in the catalyst containing reformer panels.

42. The oxygen transport membrane based reforming reactor pack assembly of claim 41 wherein said at least one of said dedicated zones includes a recycle circuit adapted to provide a portion of the synthesis gas from the exit manifolds of the catalytic reformer panels to the feed manifold associated with the oxygen transport membrane panels.

43. The oxygen transport membrane based reforming reactor pack assembly of claim 42 wherein a portion of the synthesis gas is drawn through to the feed manifold of the oxygen transport membrane panels as a recycle flow.

44. The oxygen transport membrane based reforming reactor pack assembly of claim 43 wherein said oxygen transport membrane based reforming reactor pack assembly comprises one or more gas recycle ejectors to facilitate the recycle of a portion of the synthesis gas product stream from the exit manifold associated with the reformer panel to the oxygen transport membrane panel feed manifold.

45. The oxygen transport membrane based reforming reactor pack assembly of claim 43 which comprises an air inlet and distribution system to provide supplemental cooling air to the pack assembly.

46. The oxygen transport membrane based reforming reactor pack assembly of claim 43 which comprises a force or pressure actuated valve, door or moveable panel to provide pressure relief for the pack assembly.

47. An oxygen transport membrane based syngas furnace train comprising multiple oxygen transport membrane based reforming reactor pack assemblies in accordance with claim 38.

48. The oxygen transport membrane based syngas furnace train of claim 47 which comprises two or more oxygen transport membrane based reforming reactor pack assemblies in series airflow through said furnace train.

49. The oxygen transport membrane based furnace train of claim 48 which comprises an air inlet and distribution system to provide supplemental cooling air to the furnace train.

50. The oxygen transport membrane based furnace train of claim 49 comprising a force or pressure actuated valve, door, or movable panel provides furnace pressure relief to the furnace train.

51. An oxygen transport membrane based syngas plant comprising a plurality of oxygen transport membrane based furnace train units in accordance with claim 47, wherein preheated air is supplied to each train unit, said airflow conveyed in series through the train units, and wherein oxygen depleted air is collected from the outlet of each train unit.