Ceramic oxygen transport membrane array reactor and reforming method

• US 9,776,153 B2
• Filed: 10/07/2014
• Issued: 10/03/2017
• 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:
  US14/508,326
• Publication Number:
  US 20150096506A1
• Time in Patent Office: 1,092 Days
• 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 system for utilizing heat generated in reactively-driven oxygen transport membrane tubes to generate steam, heat process fluid and/or provide energy to carry out endothermic chemical reactions. The system provides for improved thermal coupling of oxygen transport membrane tubes to steam generation tubes or process heater tubes or reactor tubes for efficient and effective radiant heat transfer.

Claims

1. An oxygen transport membrane panel for transferring radiant heat to a plurality of steam generators, the oxygen transport membrane panel comprising:

a panel frame; and

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

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 oxygen transport membrane tube;

wherein the plurality of oxygen transport membrane panels are configured to separate oxygen from an oxygen containing stream contacting the retentate side of the oxygen transport membrane tubes in cross-flow arrangement and react the permeated oxygen with a gas stream containing hydrogen fuel or hydrocarbon fuel introduced into the permeate side of the oxygen transport membrane tubes thereby producing radiant heat and a reaction product stream;

wherein the plurality of steam generators are configured to produce steam from a source of feed water in the presence of the radiant heat from the oxygen transport membrane panels; and

wherein the plurality of steam generators comprise a feed water, or feed steam manifold, a steam exhaust manifold, and a plurality of steam tubes disposed in a juxtaposed orientation with respect to the one or more the oxygen transport membrane tubes and the plurality of steam tubes in fluid communication with the feed water manifold and the steam collection manifold.

2. The oxygen transport membrane panel of claim 1 wherein said plurality of oxygen transport membrane repeating units are orientated within and supported by said panel frame.

3. The oxygen transport membrane panel of claim 2 wherein said plurality of oxygen transport membrane repeating units hang from said panel frame.

4. The oxygen transport membrane panel of claim 2 wherein the plurality of oxygen transport membrane tubes are arranged in a juxtaposed orientation.

5. The oxygen transport membrane panel of claim 4 wherein the plurality of oxygen transport membrane tubes are arranged in a serpentine orientation.

6. The oxygen transport membrane panel of claim 1 wherein the plurality of oxygen transport membrane tubes are arranged in a generally parallel orientation.

7. The oxygen transport membrane panel 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.

8. The oxygen transport membrane panel 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.

9. The oxygen transport membrane panel 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.

10. The oxygen transport membrane panel 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.

11. The oxygen transport membrane panel of claim 1 wherein said steam generators are configured to produce steam and/or supercritical steam from a source of feed water in the presence of the radiant heat from the oxygen transport membrane panels.

12. The oxygen transport membrane panel of claim 1 wherein each oxygen transport membrane tube is a composite material 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 effective in conducting oxygen ions and electrons.

13. An oxygen transport membrane array module comprising;

a frame assembly

one or more oxygen transport membrane panels according to claim 1 supported by said frame assembly, each panel comprising 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 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 fuel feed manifold and an exhaust manifold; and

one or more steam generators, disposed in a juxtaposed orientation with respect to the one or more the oxygen transport membrane panels, wherein each steam generator comprises a plurality of steam tubes in fluid communication with a feed water manifold and a steam collection manifold.

14. The oxygen transport membrane array module of claim 13 wherein said plurality of steam tubes are arranged in an array separate and juxtaposed from the oxygen transport membrane panels.

15. An oxygen transport membrane based steam generating reactor for producing steam, said reactor comprising one or more oxygen transport membrane array modules in accordance with claim 13.

16. The oxygen transport membrane based reactor of claim 15 wherein said one or more oxygen transport membrane array modules are housed in an insulated hot-air duct adjacent to a common feed water or feed steam drum arranged in a cooler zone and a common steam manifold or drum arranged in a separate zone apart from said cooler zone.

17. An oxygen transport membrane panel for transferring radiant heat to a process gas heater, the oxygen transport membrane panel comprising:

a panel frame; and

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 comprises 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 either a feed manifold or an exhaust manifold;

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 oxygen transport membrane tube;

wherein the plurality of oxygen transport membrane panels are configured to separate oxygen from an oxygen containing stream contacting the retentate side of the oxygen transport membrane tubes in cross-flow

arrangement and react the permeated oxygen with a gas stream containing hydrogen fuel or hydrocarbon fuel introduced into the permeate side of the oxygen transport membrane tubes thereby producing radiant heat and a reaction product stream;

wherein said plurality of process gas heaters are configured receive radiant heat from the oxygen transport membrane panels; and

wherein the plurality of process gas heaters comprise a feed manifold, an exhaust manifold, and a plurality of process gas tubes disposed in a juxtaposed orientation with respect to the one or more the oxygen transport membrane tubes and the plurality of gas tubes in fluid communication with the feed manifold and the gas exhaust manifold.

18. An oxygen transport membrane array module comprising;

a frame assembly

one or more oxygen transport membrane panels according to claim 17 oriented within said frame assembly, each panel comprising 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 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 fuel feed manifold and an exhaust manifold; and

the one or more process gas heaters, disposed in a juxtaposed orientation with respect to the one or more the oxygen transport membrane panels, wherein each process gas heater comprises a plurality of process gas tubes in fluid communication with a feed manifold and a gas collection manifold.

19. The oxygen transport membrane array module of claim 18 wherein said plurality of gas tubes are orientated within a separate panel.