Method of thermally-stabilizing an oxygen transport membrane-based reforming system

• US 10,118,823 B2
• Filed: 12/15/2015
• Issued: 11/06/2018
• Est. Priority Date: 12/15/2015
• Status: Active Grant

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Kelly, Sean M., Swami, Sadashiv M., Peck, John D.
• Primary Examiner(s): Call, Douglas B
• Application Number:
  US14/969,486
• Publication Number:
  US 20170166445A1
• Time in Patent Office: 1,057 Days
• CPC Class Codes: C01B 13/0251 by making use of membranes
• 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 2203/0844 the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
• CPC Class Codes: C01B 2203/142 At least two reforming, decomposition or partial oxidation steps in series
• CPC Class Codes: C01B 3/382 Multi-step processes

Abstract

A method of operating an oxygen transport membrane based reforming system employing one or more packs of thermally coupled panels of reformer tubes and oxygen transport membrane (“OTM”) reactors close to thermo-neutral point is provided. The method produces syngas by converting a hydrocarbon-containing feed, such as natural gas in the reformer tubes of a pack by endothermic steam reforming reactions. The heat required for endothermic reforming reactions is provided by exothermic oxidizing reactions occurring inside the OTM reactors of the pack. At a thermo-neutral point the heat released by exothermic reactions matches the heat required to support endothermic reactions and heat losses in the pack. The method modulates the flow rate of hydrocarbon-containing feed and/or steam-to-carbon ratio of the combined feed to the pack to maintain the surface temperature of oxygen transport membrane reactors below a target maximum temperature. The syngas product oxygen-to-carbon ratio is maintained within a desired target range such that the OTM based reforming system is operated close to thermo-neutral point.

Claims

1. A method for thermally-stabilizing an oxygen transport membrane-based reforming system for the production of syngas, said system comprises at least one reforming reactor pack assembly, said assembly comprising two or more panel array modules, wherein each panel array module comprises a reforming panel comprising an array of reforming catalyst containing reforming reactors and an oxygen transport membrane panel comprising an array of catalyst-containing oxygen transport membrane reactors, said method comprising:

partially reforming a combined feed stream comprising a hydrocarbon-containing feed stream and steam in the presence of heat in said reforming catalyst containing reforming reactors to produce a partially-reformed synthesis gas stream comprising hydrogen, carbon monoxide, carbon dioxide, steam and unreformed hydrocarbon gas;

feeding the partially-reformed synthesis gas stream to a reactant side of a reactively-driven and catalyst-containing oxygen transport membrane reactor, wherein the oxygen transport membrane reactor is configured to separate oxygen from an oxygen-containing stream to produce an oxygen permeate and an oxygen-depleted retentate stream;

reacting a portion of the partially-reformed synthesis gas stream with oxygen permeated through the at least one oxygen transport membrane reactor to produce a difference in oxygen partial pressure across the oxygen transport membrane reactor and generate a steam-containing heated reaction product stream and heat;

transferring the heat generated as a result of the reaction via convection to the oxygen-depleted retentate stream and via radiation and convection to at least one catalyst-containing reforming reactor configured to produce a synthesis gas product stream; and

reforming the unreformed hydrocarbon gas in the partially-reformed synthesis gas stream in the presence of one or more catalysts contained in the oxygen transport membrane reactor;

wherein said method comprises modulating the flow rate of the combined feed stream to the reforming reactors by adjusting the flow rate of hydrocarbon-containing feed, or the flow rate of steam, or the flow rate of both the hydrocarbon-containing feed and the flow rate of steam while maintaining a steam-to-carbon ratio effective to thermally stabilize the temperature of said oxygen transport membrane-based reforming system in a target temperature range from about 750°

C. to about 1000°

C.

2. The method of claim 1 wherein the steam-to-carbon ratio of the combined feed stream is from about 0.5 to about 3.

3. The method of claim 2 wherein the steam-to-carbon ratio of the combined feed stream is from about 1.0 to about 2.5.

4. The method of claim 3 wherein the steam-to-carbon ratio of the combined feed stream is from about 1.0 to about 2.0.

5. The method of claim 1 wherein the combined feed stream is fed to the reforming reactor at a flow rate and steam-to-carbon ratio effective to stabilize the temperature of said the oxygen transport membrane reactor in a range from about 900 to 1000°

C.

6. The method of claim 1 wherein the surface temperature of the oxygen transport membrane reactor is measured with at least one temperature measuring device selected from a thermocouple device, a pyrometer device, an optical camera-type device or combinations thereof.

7. The method of claim 6 wherein said temperature measuring device is a thermocouple device.

8. The method of claim 1 wherein the flow rate of the combined feed stream is decreased when the temperature of the oxygen transport membrane reactor falls below a predetermined target temperature within the target temperature range, and the flow rate of the combined feed stream is increased when the temperature of the oxygen transport membrane reactor increases above a predetermined target temperature within the target temperature range.

9. The method of claim 8 wherein the combined feed stream steam-to-carbon ratio is maintained constant while the flow rate of the combined feed stream is decreased or increased.

10. The method of claim 8 wherein the flow rate of the combined feed stream is decreased in an amount effective to allow the reactor temperature to increase at a rate of from about 0.5°

C. per minute to about 10°

C. per minute.

11. The method of claim 10 wherein the flow rate of the combined feed stream is decreased in an amount effective to allow the reactor temperature to increase at a rate of from about 1°

C. per minute to about 5°

C. per minute.

12. The method of claim 8 wherein the flow rate of the combined feed stream is increased in an amount effective to allow the reactor temperature to decrease at a rate of from about 0.5°

C. per minute to about 10°

C. per minute.

13. The method of claim 12 wherein the flow rate of the combined feed stream is increased in an amount effective to allow the reactor temperature to decrease at a rate of from about 1°

C. per minute to about 5°

C. per minute.

14. The method of claim 1 wherein the flow and temperature of the oxygen-containing stream to the reactor pack assembly is controlled such that the oxygen-to-carbon ratio of the produced syngas is maintained in a range of from about 0.45 to about 0.75.

15. The method of claim 1 wherein the wherein the combined feed stream is fed to the reforming reactor at a flow rate and a steam-to-carbon ratio effective to maintain the oxygen transport membrane reactor at a target temperature in a range of from about 950°

C. to about 1000°

C., and the flow and temperature of the oxygen-containing stream to the oxygen transport membrane reactor is controlled such that the oxygen-to-carbon ratio of the produced syngas is in a range of from about 0.45 to about 0.75.

16. A method for thermally-stabilizing an oxygen transport membrane-based reforming system during operation, wherein said system comprises at least one reforming reactor pack assembly, said assembly comprising two or more panel array modules, wherein each panel array module comprises a reforming panel comprising an array of reforming catalyst containing reforming reactors and an oxygen transport membrane panel comprising an array of catalyst-containing oxygen transport membrane reactors, the method comprising the steps of:

partially-reforming a combined feed stream comprising a hydrocarbon-containing feed stream and steam in the presence of heat in said reforming catalyst containing reforming reactor to produce a partially-reformed synthesis gas stream comprising hydrogen, carbon monoxide, carbon dioxide, steam and unreformed hydrocarbon gas;

feeding the partially-reformed synthesis gas stream to a reactant side of a reactively-driven and catalyst-containing oxygen transport membrane reactor, wherein the oxygen transport membrane reactor is configured to separate oxygen from an oxygen-containing stream, to produce an oxygen permeate and an oxygen-depleted retentate stream;

reacting a portion of the partially-reformed synthesis gas stream with oxygen permeated through the at least one oxygen transport membrane reactor to produce the difference in oxygen partial pressure across the at least one oxygen transport membrane reactor and generate a steam-containing heated reaction product stream and heat;

transferring the heat generated as a result of the reaction via convection to the oxygen-depleted retentate stream and via radiation and convection to at least one catalyst-containing reforming reactor configured to produce a synthesis gas stream; and

reforming the unreformed hydrocarbon gas in the partially-reformed synthesis gas stream in the presence of one or more catalysts contained in the oxygen transport membrane reactor and the heat to produce a synthesis gas product stream;

wherein the flow and temperature of the oxygen-containing stream to said oxygen transport membrane reactor is controlled such that the oxygen-to-carbon ratio of the produced syngas is in a target range of from about 0.45 to about 0.75 .

17. The method of claim 16 wherein the flow and temperature of the inlet air flow stream to said reactor pack assembly is controlled such that the oxygen-to-carbon ratio of the produced syngas is in a target range of from about 0.55 to about 0.60.

18. The method of claim 16 wherein the temperature of the oxygen-containing stream is decreased when the oxygen-to-carbon ratio of the produced syngas falls below a predetermined target value within the target range.

19. The method of claim 16 wherein the temperature of the oxygen-containing stream is increased when the oxygen-to-carbon ratio of the produced syngas rises above a predetermined target value within the target range.

20. A method for thermally-stabilizing an oxygen transport membrane-based reforming system during operation, wherein said system comprises at least one reforming reactor pack assembly, said assembly comprising two or more panel array modules, wherein each panel array module comprises a reforming panel comprising an array of reforming catalyst containing reforming reactors and an oxygen transport membrane panel comprising an array of catalyst-containing oxygen transport membrane reactors, the method comprising the steps of:

partially-reforming a combined feed stream comprising a hydrocarbon-containing feed stream and steam in the presence of heat in said reforming catalyst containing reforming reactor to produce a partially-reformed synthesis gas stream comprising hydrogen, carbon monoxide, carbon dioxide, steam and unreformed hydrocarbon gas;

feeding the partially-reformed synthesis gas stream to a reactant side of a reactively-driven and catalyst-containing oxygen transport membrane reactor, wherein the oxygen transport membrane reactor is configured to separate oxygen from an oxygen-containing stream, to produce an oxygen permeate and an oxygen-depleted retentate stream;

reacting a portion of the partially-reformed synthesis gas stream with oxygen permeated through the at least one oxygen transport membrane reactor to produce the difference in oxygen partial pressure across the at least one oxygen transport membrane reactor and generate a steam-containing heated reaction product stream and heat;

transferring the heat generated as a result of the reaction via convection to the oxygen-depleted retentate stream and via radiation and convection to at least one catalyst-containing reforming reactor configured to produce a synthesis gas stream;

reforming the unreformed hydrocarbon gas in the partially-reformed synthesis gas stream in the presence of one or more catalysts contained in the oxygen transport membrane reactor and the heat to produce a synthesis gas product stream;

determining an oxygen-to-carbon ratio of the synthesis gas product stream from composition measurements of the hydrocarbon-containing feed stream and the synthesis gas product stream;

wherein said method comprises feeding the combined feed stream to the reforming reactor at a flow rate and a steam-to-carbon ratio effective to maintain the oxygen-to-carbon ratio of the synthesis gas product stream in a target range of from about 0.45 to about 0.75.