Fuel cell anode exhaust fuel recovery by adsorption

• US 20070017369A1
• Filed: 07/25/2005
• Published: 01/25/2007
• Est. Priority Date: 07/25/2005
• Status: Active Grant

• Current Assignee: Bloom Energy Corporation
• Original Assignee: Bloom Energy Corporation
• Inventors: Finn, John, McElroy, James, LeVan, M.
• Granted Patent: US 7,591,880 B2
• Time in Patent Office: Days
• US Class Current: 95/96
• CPC Class Codes: B01D 2253/102 Carbon
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2257/80 Water
• CPC Class Codes: B01D 2258/0208 from fuel cells
• CPC Class Codes: B01D 2259/40003 Methods relating to valve switching
• CPC Class Codes: B01D 2259/40056 Gases other than recycled product or process gas
• CPC Class Codes: B01D 2259/4006 Less than four
• CPC Class Codes: B01D 2259/40062 Four
• CPC Class Codes: B01D 2259/40081 Counter-current
• CPC Class Codes: B01D 2259/40086 by using a purge gas B01D2259/4009 takes precedence
• CPC Class Codes: B01D 2259/402 using two beds
• CPC Class Codes: B01D 2259/4566 for use in transportation means
• CPC Class Codes: B01D 53/0462 Temperature swing adsorption
• CPC Class Codes: B01D 53/047 Pressure swing adsorption
• CPC Class Codes: B01D 53/261 by adsorption
• CPC Class Codes: H01M 2008/147 Fuel cells with molten carbonates
• CPC Class Codes: H01M 8/04014 Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
• CPC Class Codes: H01M 8/04089 of gaseous reactants
• CPC Class Codes: H01M 8/04097 with recycling of the reactants H01M8/04119, H01M8/04104 take precedence
• CPC Class Codes: H01M 8/04141 : by water containing exhaust gases
• CPC Class Codes: H01M 8/04164 : by condensers, gas-liquid separators or filters
• CPC Class Codes: H01M 8/0618 : Reforming processes, e.g. autothermal, partial oxidation or steam reforming
• CPC Class Codes: H01M 8/0625 : in a modular combined reactor/fuel cell structure
• CPC Class Codes: H01M 8/0662 : Treatment of gaseous reactants or gaseous residues, e.g. cleaning
• CPC Class Codes: H01M 8/0668 : Removal of carbon monoxide or carbon dioxide
• CPC Class Codes: H01M 8/1246 : the electrolyte consisting of oxides
• CPC Class Codes: Y02C 20/40 : of CO2
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product

Abstract

A method of operating a fuel cell system includes providing a fuel inlet stream into a fuel cell stack, operating the fuel cell stack to generate electricity and a hydrogen containing fuel exhaust stream, separating at least a portion of hydrogen contained in the fuel exhaust stream using partial pressure swing adsorption, and providing the hydrogen separated from the fuel exhaust stream into the fuel inlet stream.

Claims

1. A method of operating a fuel cell system, comprising:

providing a fuel inlet stream into a fuel cell stack;

operating the fuel cell stack to generate electricity and a hydrogen containing fuel exhaust stream;

separating at least a portion of hydrogen contained in the fuel exhaust stream using partial pressure swing adsorption; and

providing the hydrogen separated from the fuel exhaust stream into the fuel inlet stream.

2. The method of claim 1, wherein:

the fuel inlet stream comprises a hydrocarbon fuel inlet stream;

the fuel cell stack comprises a solid oxide fuel cell stack;

the fuel exhaust stream comprises hydrogen, carbon monoxide, water vapor and carbon dioxide;

the step of separating comprises adsorbing at least a majority of the carbon dioxide and a portion of the water vapor in the fuel exhaust stream in at least one adsorbent bed while allowing at least a majority of the hydrogen and carbon monoxide in the fuel exhaust stream to be passed through the at least one adsorbent bed; and

the step of providing hydrogen comprises providing the hydrogen and carbon monoxide separated from the fuel exhaust stream into the hydrocarbon fuel inlet stream.

3. The method of claim 2, the step of separating comprises:

providing unpressurized fuel exhaust stream into a first adsorbent bed to adsorb at least a majority of the carbon dioxide and a portion of the water vapor in the fuel exhaust stream in the first adsorbent bed until the first adsorbent bed is saturated while regenerating a second adsorbent bed by providing air having a relative humidity of 50% or less through the second adsorbent bed to desorb adsorbed carbon dioxide and water vapor; and

providing unpressurized fuel exhaust stream into the second adsorbent bed to adsorb at least a majority of the carbon dioxide and a portion of the water vapor in the fuel exhaust stream in the second adsorbent bed until the second adsorbent bed is saturated while regenerating the first adsorbent bed by providing air having a relative humidity of 50% or less through the first adsorbent bed to desorb adsorbed carbon dioxide and water vapor.

4. The method of claim 1, further comprising:

humidifying the fuel inlet stream using water vapor contained in the fuel exhaust stream;

after the step of humidifying, condensing and removing at least a part of the water vapor in the fuel exhaust stream; and

performing the step of separating after the step of condensing and removing.

5. The method of claim 1, further comprising:

separating the fuel exhaust stream into at least two streams;

recycling a first fuel exhaust stream into the fuel inlet stream; and

separating at least a portion of hydrogen and carbon monoxide contained in a second fuel exhaust stream using the partial pressure swing adsorption, and providing the hydrogen and carbon monoxide separated from the second fuel exhaust stream into the fuel inlet stream.

6. The method of claim 5, further comprising:

cooling the fuel exhaust stream to 200 degrees Celsius or less prior to the step of separating the fuel exhaust stream into at least two streams;

using a first blower or compressor to controllably recycle a desired amount of the first fuel exhaust stream into the fuel inlet stream; and

using a second blower or compressor to controllably provide a desired amount of hydrogen and carbon monoxide separated from the second fuel exhaust stream into the fuel inlet stream.

7. The method of claim 1, further comprising:

cooling the fuel exhaust stream to 200 degrees Celsius or less; and

using a blower or compressor to controllably provide a desired amount of hydrogen and carbon monoxide separated from the cooled fuel exhaust stream into the fuel inlet stream.

8. The method of claim 1, wherein the step of separating comprises:

(a) a first feed/purge step comprising;

providing a feed gas inlet stream comprising at least a portion of the fuel exhaust stream into a first adsorbent bed;

collecting a feed gas outlet stream comprising at least one separated component of the feed gas at a first output;

providing a purge gas inlet stream into a second adsorbent bed; and

collecting a purge gas outlet stream at a second output;

(b) a first flush step, conducted after the first feed/purge step, the first flush step comprising;

providing the purge gas inlet stream into the first adsorbent bed;

collecting the purge gas outlet stream, which comprises at least one component of the feed gas that was trapped in a void volume of the first adsorbent bed, at the first output;

providing the feed gas inlet stream into the second adsorbent bed; and

collecting the feed gas outlet stream, which comprises a portion of the purge gas that was trapped in a void volume of the second bed, at the second output;

(c) a second feed/purge step, conducted after the first flush step, the second feed/purge step comprising;

providing the feed gas inlet stream into the second adsorbent bed;

collecting the feed gas outlet stream comprising at least one separated component of the feed gas at the first output;

providing the purge gas inlet stream into the first adsorbent bed; and

collecting the purge gas outlet stream at the second output; and

(d) a second flush step, conducted after the second feed/purge step, the second flush step comprising;

providing the purge gas inlet stream into the second adsorbent bed;

collecting the purge gas outlet stream, which comprises at least one component of the feed gas that was trapped in a void volume of the second adsorbent bed, at the first output;

providing the feed gas inlet stream into the first adsorbent bed; and

collecting a feed gas outlet stream, which comprises a portion of the purge gas that was trapped in a void volume of the first bed, at the second output.

9. The method of claim 8, wherein:

the first output comprises a gas stream containing the hydrogen separated from the fuel exhaust stream which is provided into the fuel inlet stream;

the second output comprises a gas stream containing carbon dioxide which is provided to a burner; and

a duration of the first and the second feed/purge steps is at least five times as long as a duration of the first and the second flush steps.

10. The method of claim 9, wherein:

the feed gas inlet stream is provided in each of the first and the second adsorbent beds in a first direction in steps (a), (b), (c) and (d);

in the first and the second feed/purge steps, the purge gas inlet stream is provided into each of the first and the second adsorbent beds in a different direction from the first direction; and

in the first and the second flush steps, the purge gas inlet stream is provided into each of the first and the second adsorbent beds in the first direction.

11. The method of claim 9, wherein:

the feed gas inlet stream comprises hydrogen, carbon monoxide, water vapor and carbon dioxide;

the purge gas inlet stream comprises air having a 50% or less relative humidity;

the at least one separated component which is collected at the first output comprises hydrogen and carbon monoxide;

at least a majority of the carbon dioxide and a portion of the water vapor in the feed gas inlet stream are adsorbed by the first and the second adsorbent beds during the first and the second feed/purge steps, respectively;

the adsorbed carbon dioxide and water vapor are removed from the first and the second adsorbent beds by the purge gas inlet stream, during the second and the first feed/purge steps, respectively;

the removed carbon dioxide and water vapor are collected with the purge gas outlet stream at the second output during the second and the first feed/purge steps; and

the adsorbent material of the first and the second adsorbent beds comprises activated carbon.

12. A fuel cell system, comprising:

a fuel cell stack;

a partial pressure swing adsorption unit comprising a plurality of adsorbent beds;

a first conduit which operatively connects a fuel exhaust outlet of the fuel cell stack to a first inlet of the partial pressure swing adsorption unit;

a second conduit which operatively connects a purge gas source to a second inlet of the partial pressure swing adsorption unit; and

a third conduit which operatively connects an outlet of the partial pressure swing adsorption unit to a fuel inlet of the fuel cell stack.

13. The system of claim 12, wherein:

the fuel cell stack comprises a solid oxide fuel cell stack;

the plurality of adsorbent beds comprise a material which preferentially adsorbs carbon dioxide to hydrogen and carbon monoxide; and

the system lacks a compressor which in operation compresses the fuel cell stack fuel exhaust stream to be provided into the partial pressure swing adsorption unit.

14. The system of claim 12, further comprising a blower or compressor having an inlet which is operatively connected to the partial pressure swing adsorption unit and an outlet which is operatively connected to a fuel inlet of the fuel cell stack, wherein in operation, the blower or compressor controllably provides a desired amount of hydrogen and carbon monoxide separated from a fuel cell stack fuel exhaust stream into the fuel cell stack fuel inlet stream.

15. The system of claim 12, further comprising a condenser and water separator having an inlet which is operatively connected to the fuel cell stack fuel exhaust outlet and an outlet which is operatively connected to an inlet of the partial pressure swing adsorption unit.

16. The system of claim 15, further comprising a fuel humidifier having a first inlet operatively connected to a hydrocarbon fuel inlet conduit, a second inlet operatively connected to the fuel cell stack fuel exhaust outlet, a first outlet operatively connected to the fuel cell stack fuel inlet, and a second outlet operatively connected to the condenser and water separator, wherein in operation, the fuel humidifier humidifies a fuel inlet stream using water vapor contained in a fuel cell stack fuel exhaust stream.

17. The system of claim 12, further comprising a fuel splitter having an inlet operatively connected to the fuel cell stack fuel exhaust outlet, a first outlet operatively connected to the condenser and water separator, and a second outlet operatively connected to the fuel cell stack fuel inlet.

18. The system of claim 17, wherein:

the fuel splitter comprises a multi-way valve;

the first outlet of the multi-way valve is operatively connected to an inlet of a blower or compressor;

an outlet of the blower or compressor is connected to a fuel cell stack hydrocarbon fuel inlet conduit; and

in operation the blower or compressor controllably provides a desired amount of the fuel cell stack fuel exhaust stream into the fuel cell stack fuel inlet stream.

19. The system of claim 12, wherein:

the plurality of adsorbent beds comprises a first adsorbent bed and a second adsorbent bed;

in operation, the first adsorbent bed performs the following functions;

(a) receives the feed gas inlet stream comprising at least a portion of the fuel cell stack fuel exhaust stream from the first conduit and provides at least one separated component of the feed gas to the third conduit in a first feed/purge step;

(b) receives the purge gas inlet stream from the second conduit and provides a purge gas outlet stream, which comprises at least one component of the feed gas that was trapped in a void volume of the first bed to the third conduit in a first flush step, conducted after the first feed/purge step;

(c) receives a purge gas inlet stream from the second conduit and provides a purge gas outlet stream to an output different from the third conduit in a second feed/purge step, conducted after the first flush step; and

(d) receives the feed gas inlet stream from the first conduit and provides a feed gas outlet stream, which comprises a portion of the purge gas that was trapped in a void volume of the first bed, to at an output different from the third conduit in a second flush step, conducted after the second feed/purge step; and

in operation, the second bed performs the following functions;

(a) receives a purge gas inlet stream from the second conduit and provides a purge gas outlet stream to at an output different from the third conduit in a first feed/purge step;

(b) receives the feed gas inlet stream from the first conduit and provides the feed gas outlet stream, which comprises a portion of the purge gas that was trapped in a void volume of the second bed, to an output different from the third conduit in a first flush step, conducted after the first feed/purge step;

(c) receives the feed gas inlet stream from the first conduit and provides the feed gas outlet stream comprising at least one separated component of the feed gas to the third conduit in a second feed/purge step, conducted after the first flush step; and

(d) receives the purge gas inlet stream from the second conduit and provides the purge gas outlet stream, which comprises at least one component of the feed gas that was trapped in a void volume of the second bed to the first conduit in a second flush step, conducted after the second feed/purge step.

20. A fuel cell system, comprising:

a fuel cell stack; and

a separation means for separating at least a portion of hydrogen contained in a fuel cell stack fuel exhaust stream using partial pressure swing adsorption and for providing the hydrogen separated from the fuel exhaust stream into a fuel cell stack fuel inlet stream.

21. The system of claim 20, wherein:

the fuel inlet stream comprises a hydrocarbon fuel inlet stream;

the fuel cell stack comprises a solid oxide fuel cell stack;

the fuel exhaust stream comprises hydrogen, carbon monoxide, water vapor and carbon dioxide;

the separation means is a means for adsorbing at least a majority of the carbon dioxide and a portion of the water vapor in the fuel exhaust stream while allowing at least a majority of the hydrogen and carbon monoxide in the fuel exhaust stream to be passed through into the hydrocarbon fuel inlet stream.

22. The system of claim 20, further comprising:

a first means for providing a feed gas inlet stream comprising at least a portion of the fuel cell stack fuel exhaust stream;

a second means for providing a purge gas inlet stream;

a third means for collecting at least one separated component of the feed gas;

a fourth means for;

(a) receiving the feed gas inlet stream from the first means and for providing at least one separated component of the feed gas to the third means in a first feed/purge step;

(b) receiving the purge gas inlet stream from the second means and for providing a purge gas outlet stream, which comprises at least one component of the feed gas that was trapped in a void volume of the fourth means to the third means in a first flush step, conducted after the first feed/purge step;

(c) receiving a purge gas inlet stream from the second means and for providing a purge gas outlet stream to an output different from the third means in a second feed/purge step, conducted after the first flush step; and

(d) receiving the feed gas inlet stream from the first means and for providing a feed gas outlet stream, which comprises a portion of the purge gas that was trapped in a void volume of the fourth means, to at an output different from the third means, in a second flush step, conducted after the second feed/purge step; and

a fifth means for;

(a) receiving a purge gas inlet stream from the second means and for providing a purge gas outlet stream to at an output different from the third means in a first feed/purge step;

(b) receiving the feed gas inlet stream from the first means and for providing the feed gas outlet stream, which comprises a portion of the purge gas that was trapped in a void volume of the fifth means, to an output different from the third means in a first flush step, conducted after the first feed/purge step;

(c) receiving the feed gas inlet stream from the first means and for providing the feed gas outlet stream comprising at least one separated component of the feed gas to the third means in a second feed/purge step, conducted after the first flush step; and

(d) receiving the purge gas inlet stream from the second means and for providing the purge gas outlet stream, which comprises at least one component of the feed gas that was trapped in a void volume of the fifth means to the first means in a second flush step, conducted after the second feed/purge step.

23. A method of operating a fuel cell system, comprising:

providing a fuel inlet stream into a fuel cell stack;

operating the fuel cell stack to generate electricity and a hydrogen containing fuel exhaust stream;

separating at least a portion of hydrogen contained in the fuel exhaust stream using temperature swing adsorption; and

providing the hydrogen separated from the fuel exhaust stream into the fuel inlet stream.