CA2414657A1 - Electric power generation with heat exchanged membrane reactor - Google Patents

Electric power generation with heat exchanged membrane reactor Download PDF

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Publication number
CA2414657A1
CA2414657A1 CA002414657A CA2414657A CA2414657A1 CA 2414657 A1 CA2414657 A1 CA 2414657A1 CA 002414657 A CA002414657 A CA 002414657A CA 2414657 A CA2414657 A CA 2414657A CA 2414657 A1 CA2414657 A1 CA 2414657A1
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Prior art keywords
reactor
membrane
reforming
hydrogen
combustion
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CA002414657A
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French (fr)
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CA2414657C (en
Inventor
Harry William Deckman
John William Fulton Jr.
Jeffrey Michael Grenda
Frank Hershkowitz
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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Priority claimed from US09/606,887 external-priority patent/US6830596B1/en
Priority to JP2002507722A priority Critical patent/JP2004502623A/en
Priority to EP01946649A priority patent/EP1294637A2/en
Priority to PCT/US2001/019917 priority patent/WO2002002460A2/en
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Priority to CA2414657A priority patent/CA2414657C/en
Publication of CA2414657A1 publication Critical patent/CA2414657A1/en
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Publication of CA2414657C publication Critical patent/CA2414657C/en
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
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    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
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    • B01J19/2475—Membrane reactors
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    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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    • B01J2208/00309—Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
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Abstract

This invention is directed to a head exchanged membrane reactor for electric power generation. More specifically, the invention comprises a membrane reactor system that employs catalytic or thermal steam reforming and a water gas shift reaction on one side of the membrane (3), and hydrogen combustion on the other side of the membrane (5).
Heat of combustion is exchanged through the membrane (4) to heat the hydrocarbon fuel and provide heat for the reforming reaction. In one embodiment, the hydrogen is combusted with compressed air to produce lectricity. A carbon dioxide product stream is produced in inherently separated form and at pressure to facilitate injection of the C02 into a well for the purpose of sequestering carbon from the earth's atmosphere.

Claims (34)

1. A hydrogen membrane reactor comprising:
a reforming zone wherein. a feed containing at least water and carbon-containing species undergoes a reforming reaction to produce hydrogen, a combustion zone wherein hydrogen produced in the reaction zone is combusted to produce heat and energy, a membrane separating said reforming zone and said combustion zone, said membrane functions to permit permeance of hydrogen and transmissions of heat through the membrane, where said reactor is configured to utilize at least a portion of the heat of the hydrogen combustion in the reforming reaction and at least a portion of the energy to produce electricity.
2. The reactor of claim 1 where the reforming reaction is a steam reforming reaction and said feed is steam and hydrocarbons.
3. The reactor of claim 2 where the reaction occurs proximate to the membrane.
4. The reactor of claim 3 where a catalyst is used to catalyze the steam reforming reaction said catalyst being selected from the group comprising:

a. Noble metals and noble metal oxides b. Transition metals and transition metal oxides c. Group VIA metals d. Ag, Ce, Cu, La, Mo, Sn, Ti, Y, Vin, and combinations thereof.
5. The reactor of claim 4 wherein said catalyst is select from the group comprising Ni, NiO, Rh, Pt, and combinations thereof.
6. The reactor of claim 1 wherein said reforming reaction is conducted at a temperature ranging from about 400° to about 1400°C.
7. The reactor of claim. 6 wherein said reforming reaction is conducted at a temperature ranging from about 700°C to about 1300°C.
8. The reactor of claim 1 wherein said feed is provided at a pressure ranging from about one (1) bar to about three hundred (300) bars.
9. The reactor of claim 7 wherein said pressure ranges from about five (5) bars to about fifty (50) bars.
10. The reactor of claim 1 wherein said membrane has a hydrogen permeance ranging from about one (1) to about one million (10 6 moles/(m2-day-atm H2).
11. The reactor of claim 1 wherein the pressure of the reforming zone is from about 0 to 100 bar higher than the pressure of the combustion zone.
12. The reactor of claim 11 wherein the pressure of the combustion zone is from about 0 to 50 bar higher than the pressure of the reforming zone.
13. The reactor of claim 1 wherein said membrane is fabricated from materials selected from the group comprising alumina, zirconia, silicon carbide, silicon nitride, MgO, TiO2, La2O3, SiO2, perovskite, hexaaluminate, high nickel content alloys, Hastelloys, cermets, and combinations thereof.
14. The reactor of claim 1 wherein said membrane reactor is comprised of one or more modules, each module having: (a) a reforming zone, a combustion zone, and a membrane separating said reaction and combustion zones, (b) a distribution and collection means for said reforming and combustion zones, (c) one or more membranes, {d) flow channels between said membrane elements; and (e) sealing means between combustion and reforming zones.
15. The reactor of claim 1 wherein said membrane is an asymmetric membrane, comprising a porous support having thickness of 0.1 to millimeters and pores of 0.05 to 30 microns, and on one side a selective diffusion layer having thickness of about 100 angstroms to 500 microns.
16. The reactor of claim 15 wherein said asymmetric membrane is a catalytic membrane wherein a catalyst is incorporated on either membrane surface or within or on pore structures of the membrane.
17. The reactor of claim 14 wherein catalyst is incorporated into said channels of the modules.
18. The reactor of claim 1 wherein a catalyst is used to catalyze the combustion of hydrogen, where said catalyst is selected from the group comprising:

a. Hexaaluminates, perovskites, and mixed metal oxides, b. Metals and metal oxides of elements in groups 6b, 7b, and 8, c. Metals and oxides of Fe, Rh, Pd, and Pt, or combinations thereof.
19. The reactor of claim 1 where the effluent of the reforming zone is a concentrated carbon dioxide stream that is cooled, compressed, and injected into a reservoir for sequestration of carbon.
20, The reactor of claim 19 where said concentrated carbon dioxide stream is injected into geological formations to facilitate sequestration of carbon.
21. The reactor of claim 19 where said concentrated carbon dioxide is injected into deep water to facilitate sequestration of carbon.
22. A method for generating power using a heat exchanged hydrogen membrane reactor, comprising the steps of:

a. supplying a carbon containing feed and water and/or steam to a reformer side of the membrane reactor, said reactor having reforming and combustion zones separated by a membrane;

b. reacting the feed with the water to form hydrogen and at least carbon monoxide, said reacting being accomplished within the reforming zone and proximate to the membrane;

c. permeating a substantial portion of the hydrogen through the membrane to the combustion zone of the reactor;

d. combusting at least a portion of the permeated hydrogen, said combusting occurring at or proximate to the membrane whereby a portion of the heat from said combusting is transmitted through the membrane to the reforming zone of the reactor for use in further reacting the feed and water to further produce hydrogen.
23. The method of claim 23 wherein compressed air is supplied to the combustion zone of the reactor whereupon the air is heated by the combustion and the heated air and effluent is used to power a turbine.
24. The method of claim 22 wherein said carbon monoxide is reacted to form carbon dioxide.
25. The method of claim 24 wherein a portion of the carbon dioxide is recycled to the reforming zone to suppress carbon deposition.
26. The method of claim 22 wherein. said reacting of the carbon containing feed and water is catalyzed.
27. The method of claim 26 wherein said catalyst comprises:
nobel metals nobel metal oxides transition metal oxides Group VIII metals
28 Group VIII metal oxides Cz, Ce, Cu, La, Mo, Mg, Sn, Ti, Y, Zr, or combination thereof 28. The method of claim 27 wherein said catalyst comprises Ni, NiO, Rh, Pt or combination thereof.
29. The method of claim 27 wherein said catalyst is on or in said membrane.
30. The method of claim 22 wherein said feed and water and/or steam is supplied at a pressure ranging from about one bar to about 300 bars.
31. The method of claim 30 wherein said pressure range from about 5 bars to about 40 bars.
32. The method of claim 23 where said heated air and effluent is at a temperature ranging from about 700°C to about 1400°C.
33. The method of claim 24 wherein said carbon dioxide is sequestered.
34. The method of claim 24 wherein said carbon dioxide is used, at least in part, as an enhanced recovery mechanism in oil wells.
CA2414657A 2000-06-29 2002-12-18 Electric power generation with heat exchanged membrane reactor Expired - Fee Related CA2414657C (en)

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WO2002002460A2 (en) 2002-01-10

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