Ceramic oxygen transport membrane array reactor and reforming method

• US 9,486,765 B2
• Filed: 10/07/2014
• Issued: 11/08/2016
• 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, Robinson, Charles, Wilson, Jamie R., Gonzalez, Javier E., Doraswami, Uttam R.
• Primary Examiner(s): Akram, Imran
• Application Number:
  US14/508,344
• Publication Number:
  US 20150098868A1
• Time in Patent Office: 763 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

The invention relates to a commercially viable modular ceramic oxygen transport membrane reforming reactor configured using repeating assemblies of oxygen transport membrane tubes and catalytic reforming reactors.

Claims

1. An oxygen transport membrane tube assembly comprising:

a plurality of ceramic oxygen transport membrane tubes coupled together in series such that the tube assembly has a first end configured to be in fluid communication with a feed manifold and a second end configured to be in fluid communication with an exhaust manifold;

a plurality of ceramic to ceramic coupling elements coupling respective ends of adjacent ceramic oxygen transport membrane tubes;

a first ceramic to metal coupling element connected to the first end of the oxygen transport membrane tube assembly and configured to connect to a feed manifold such that the plurality of ceramic oxygen transport membrane tubes are in fluid communication with the feed manifold;

a second ceramic to metal coupling element connected to the second end of the oxygen transport membrane tube assembly and configured to connect to an exhaust manifold such that the plurality of ceramic oxygen transport membrane tubes are in fluid communication with the exhaust manifold

wherein the plurality of coupled oxygen transport membrane tubes comprise a tubular porous support comprising an oxide material, a dual phase intermediate porous layer comprising a mixture of an electrically conducting perovskite structured material and an ionically conducting fluorite structure material, the intermediate porous layer disposed on the porous support; and

a dual phase dense layer comprising a mixture of an electrically conducting perovskite structured material and an ionically conducting fluorite structure material, wherein the interior surface of the porous support defines a reactive side of the oxygen transport membrane tube and the outermost surface of the oxygen transport membrane tube defines a retentate side;

wherein the plurality of coupled oxygen transport membrane tubes are configured to separate oxygen from an oxygen containing stream contacting the outer surface of the oxygen transport membrane tubes through oxygen ion transport through the dense layer and intermediate porous layer to the reactive side of the oxygen transport membrane tubes at elevated temperatures and a difference in partial pressure of oxygen between the retentate side and the reactive side of the oxygen transport membrane tubes;

wherein the oxygen transport membrane tubes are configured to receive a hydrogen containing stream at the reactive side from the feed manifold and oxidize the hydrogen with the oxygen transported through the layers of the oxygen transport membrane tubes to produce heat and the difference in partial pressure of oxygen across the oxygen transport membrane tubes.

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 tube assembly of claim 8 wherein the isolation valve assembly further comprises:

a housing fluidly coupled to the first end of the tube assembly, the housing having an inlet end and an opposing discharge end, the housing further defining an a flow path between the inlet end and the discharge end wherein a portion of the housing proximate to one of the ends is configured as a chamfered seat;

a restraining pin or structure disposed in the housing apart from the chamfered seat and projecting into the flow path;

a ceramic ball disposed in the flow path of the housing between the chamfered seat and the restraining pin or structure and configured to rest against the restraining pin and allow gas flow through the flow path during normal operation of the tube assembly and to seat against the chamfered seat and cut-off gas flow in the flow path upon a failure of any of the oxygen transport membrane tubes within the tube assembly.

10. The oxygen transport membrane tube assembly of claim 9 wherein the chamfered seat is disposed proximate the outlet end of the housing and configured to cut off the hydrogen containing feed stream to the tube assembly.

11. The oxygen transport membrane tube assembly of claim 9 wherein the chamfered seat is disposed proximate the inlet end of the housing and configured to cut off an exit path from the tube assembly and prevent backflow into the tube assembly from the exhaust manifold.

12. The oxygen transport membrane tube assembly of claim 1 wherein each of the plurality of the oxygen transport membrane tubes has an outside diameter of between about 8 mm to about 20 mm and a length to diameter ratio in the range of between about 50 to about 150.

13. The oxygen transport membrane tube assembly of claim 1 wherein the plurality of oxygen transport membrane tubes are configured to operate at a maximum allowable working pressure of about 500 psia.

14. The oxygen transport membrane tube assembly of claim 1 further comprising a strain relief mechanism 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.

15. The oxygen transport membrane tube assembly of claim 1 wherein the plurality of oxygen transport membrane tubes each optionally have an active region and an inactive region, the inactive region disposed proximate the ceramic to ceramic seal or the ceramic to metal coupling elements and comprising the porous support without one or more of the porous intermediate layer, dense layer, and surface exchange layer.

16. The oxygen transport membrane tube assembly of claim 15 further wherein the plurality of oxygen transport membrane tubes each have an active region and an inactive region, the inactive region disposed proximate the ceramic to metal coupling elements and comprising the porous support without one or more of the porous intermediate layer, dense layer, and surface exchange layer.

17. The oxygen transport membrane tube assembly of claim 1 further comprising a catalyst disposed within the plurality of oxygen transport membrane tubes.

18. The oxygen transport membrane tube assembly of claim 17 wherein the catalyst promotes reforming of the hydrogen containing stream.

20. The oxygen transport membrane tube assembly of claim 1 which additionally comprises an oxygen transport membrane isolation valve assembly, wherein said assembly comprises:

a housing fluidly coupled to an end of an oxygen transport membrane tube, the housing having an inlet end and an opposing discharge end, the housing further defining an a flow path between the inlet end and the discharge end wherein a portion of the housing proximate to one of the ends is configured as a chamfered seat;

a restraining pin or structure disposed in the housing apart from the chamfered seat and projecting into the flow path;

a ceramic ball disposed in the flow path of the housing between the chamfered seat and the restraining pin or structure and configured to rest against the restraining pin and allow gas flow through the flow path during normal operation of the oxygen transport membrane tube and to seat against the chamfered seat and cut-off gas flow in the flow path upon a failure of the oxygen transport membrane.

21. The oxygen transport membrane tube assembly of claim 20 wherein the chamfered seat of said valve assembly is disposed proximate the outlet end of the housing and configured to cut off a feed stream to the oxygen transport membrane.

22. The oxygen transport membrane tube of claim 20 wherein the chamfered seat of said valve assembly is disposed proximate the inlet end of the housing and configured to cut off an exit path from the oxygen transport membrane and prevent backflow into the oxygen transport membrane from the exit manifold.

19. An oxygen transport membrane tube assembly comprising:

a plurality of ceramic oxygen transport membrane tubes coupled together in series such that the tube assembly has a first end configured to be in fluid communication with a feed manifold and a second end configured to be in fluid communication with an exhaust manifold;

a plurality of ceramic to ceramic coupling elements coupling respective ends of adjacent ceramic oxygen transport membrane tubes;

a first ceramic to metal coupling element connected to the first end of the oxygen transport membrane tube assembly and configured to connect to a feed manifold such that the plurality of ceramic oxygen transport membrane tubes are in fluid communication with the feed manifold;

a second ceramic to metal coupling element connected to the second end of the oxygen transport membrane tube assembly and configured to connect to an exhaust manifold such that the plurality of ceramic oxygen transport membrane tubes are in fluid communication with the exhaust manifold;

wherein the plurality of coupled oxygen transport membrane tubes further comprise an active region and one or more inactive regions, the active regions comprising a tubular porous support comprising an oxide material, a dual phase intermediate porous layer comprising a mixture of an electrically conducting perovskite structured material and an ionically conducting fluorite structure material, the intermediate porous layer disposed on the porous support; and

a dual phase dense layer comprising a mixture of an electrically conducting perovskite structured material and an ionically conducting fluorite structure material, wherein the interior surface of the porous support defines a reactive side of the oxygen transport membrane tube and the outermost surface of the oxygen transport membrane tube defines a retentate side;

wherein the active regions of the oxygen transport membrane tubes are configured to separate oxygen from an oxygen containing stream contacting the outermost surface of the oxygen transport membrane tubes through oxygen ion transport through the dense layer and intermediate porous layer to the reactive side of the oxygen transport membrane tubes at elevated temperatures and a difference in partial pressure of oxygen across the oxygen transport membrane tubes;

wherein the oxygen transport membrane tubes are configured to receive a hydrogen containing stream at the reactive side from the feed manifold and oxidize the hydrogen with the oxygen transported through the layers of the oxygen transport membrane tubes to produce heat and the difference in partial pressure of oxygen across the oxygen transport membrane tubes; and

wherein the one or more inactive regions comprise the porous support without one or more of the layers and the one or more inactive regions are proximate one or more of the coupling elements.