Partial pressure swing adsorption system for providing hydrogen to a vehicle fuel cell

• US 7,520,916 B2
• Filed: 07/25/2005
• Issued: 04/21/2009
• Est. Priority Date: 07/25/2005
• Status: Expired due to Fees

• Current Assignee: Bloom Energy Corporation
• Original Assignee: Bloom Energy Corporation
• Inventors: Venkataraman, Swaminathan, McElroy, James F., LeVan, M. Douglas, Mitlitsky, Fred, Finn, John E.
• Primary Examiner(s): Smith; Duane
• Assistant Examiner(s): Hawkins; Karla
• Application Number:
  US11/188,123
• Publication Number:
  US 20070017367A1
• Time in Patent Office: 1,366 Days
• Field of Search: 95/96, 951/19, 951/39, 961/21, 961/26, 429/12, 429/13, 429/19
• US Class Current: 95/96
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2257/108 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 2259/402 using two beds
• CPC Class Codes: B01D 2259/4566 for use in transportation means
• CPC Class Codes: B01D 53/047 Pressure swing adsorption
• CPC Class Codes: B01D 53/053 with storage or buffer vessel
• CPC Class Codes: B01D 53/261 by adsorption
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/043 Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/066 with fuel cells
• CPC Class Codes: C01B 2203/067 the reforming process taking place in the fuel cell
• CPC Class Codes: C01B 2203/0805 Methods of heating the process for making hydrogen or synthesis gas
• CPC Class Codes: C01B 2203/0811 by combustion of fuel
• CPC Class Codes: C01B 2203/0822 the fuel containing hydrogen
• CPC Class Codes: C01B 2203/0827 at least part of the fuel being a recycle stream
• CPC Class Codes: C01B 2203/1241 : Natural gas or methane
• CPC Class Codes: C01B 2203/148 : involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
• CPC Class Codes: C01B 3/384 : the catalyst being continuously externally heated
• CPC Class Codes: C01B 3/48 : followed by reaction of water vapour with carbon monoxide
• CPC Class Codes: C01B 3/56 : by contacting with solids; Regeneration of used solids C01B3/508 takes precedence
• CPC Class Codes: H01M 2008/1095 : Fuel cells with polymeric electrolytes
• CPC Class Codes: H01M 8/04097 : with recycling of the reactants H01M8/04119, H01M8/04104 take precedence
• CPC Class Codes: H01M 8/04171 : using adsorbents, wicks or hydrophilic material
• CPC Class Codes: H01M 8/04313 : characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
• CPC Class Codes: H01M 8/04447 : of anode reactants at the inlet or inside the fuel cell
• CPC Class Codes: H01M 8/04753 : of fuel cell reactants
• CPC Class Codes: H01M 8/0668 : Removal of carbon monoxide or carbon dioxide
• CPC Class Codes: Y02C 20/40 : of CO2
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 20/10 : Process efficiency
• CPC Class Codes: Y02P 20/151 : Reduction of greenhouse gas [GHG] emissions, e.g. CO2
• CPC Class Codes: Y02P 30/00 : Technologies relating to oil refining and petrochemical industry

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 to a hydrogen storage vessel or to a hydrogen using device.

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 to a hydrogen storage vessel or to a hydrogen using device;

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.

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; and

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.

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 2, wherein the step of providing the hydrogen comprises providing the hydrogen separated from the fuel exhaust stream to the hydrogen storage vessel.

5. The method of claim 2, wherein the step of providing the hydrogen comprises providing the hydrogen separated from the fuel exhaust stream to the hydrogen using device.

6. The method of claim 2, wherein:

the hydrogen using device comprises a PEM fuel cell system located in a vehicle; and

the step of providing the hydrogen comprises providing the hydrogen to the hydrogen storage vessel and then providing the hydrogen from the hydrogen storage vessel to the PEM fuel cell system, or providing the hydrogen to the PEM fuel cell system without providing the hydrogen to the hydrogen storage vessel.

7. The method of claim 6, further comprising scrubbing carbon monoxide from a hydrogen containing stream before the step of providing hydrogen to the PEM fuel cell system and after the step of separating the hydrogen from the fuel exhaust stream by partial pressure swing adsorption.

8. The method of claim 7, wherein the step of scrubbing carbon monoxide comprises scrubbing carbon monoxide using pressure swing adsorption or a Sabatier reaction.

9. The method of claim 2, further comprising:

dividing the hydrogen separated from the fuel exhaust stream into a first stream and a second stream;

providing the first stream into the hydrocarbon fuel inlet stream; and

providing the second stream to the hydrogen storage vessel or the hydrogen using device.

10. The method of claim 9, further comprising alternating between providing the hydrogen separated from the fuel exhaust stream into the hydrocarbon fuel inlet stream and providing the hydrogen separated from the fuel exhaust to the hydrogen storage vessel.

11. The method of claim 1, further comprising:

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

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

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

providing all hydrogen separated from the fuel exhaust stream to a hydrogen storage vessel or to a hydrogen using device without recycling hydrogen separated from the fuel exhaust stream into the fuel inlet stream and without recycling a portion of the fuel exhaust stream into the fuel inlet stream.

12. 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;

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

providing a first portion of the separated hydrogen to the hydrogen using device or to the hydrogen storage vessel; and

providing a second portion of the separated hydrogen to the fuel inlet stream.

13. 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 hydrogen using device or to a hydrogen storage vessel;

the plurality of adsorbent beds comprise 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.

14. The system of claim 13, 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 and water vapor 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.

15. The system of claim 13, wherein the third conduit operatively connects an outlet of the partial pressure swing adsorption unit to the hydrogen storage vessel.

16. The system of claim 13, wherein the third conduit operatively connects an outlet of the partial pressure swing adsorption unit to the hydrogen using device.

17. The system of claim 13, further comprising a selector valve having an inlet operatively connected to an outlet of the partial pressure swing adsorption unit, a first outlet operatively connected to the hydrogen storage vessel or to the hydrogen using device, and a second outlet operatively connected to a fuel inlet of the fuel cell stack.

18. The system of claim 17, further comprising a carbon monoxide scrubbing device having an inlet operatively connected to an outlet of the partial pressure swing adsorption unit and an outlet operatively connected to a PEM fuel cell system located in a vehicle, wherein in operation, the carbon monoxide scrubbing device scrubs carbon monoxide being provided with the hydrogen from the partial pressure swing adsorption unit and provides the hydrogen either directly or indirectly to the PEM fuel cell system.

19. The system of claim 18, wherein the carbon monoxide scrubbing device comprises a pressure swing adsorption unit or a Sabatier reactor.

20. The system of claim 13, 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; and

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.

21. The system of claim 13, 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; and

a multi-way valve 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 conduit.

22. 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 to a hydrogen storage vessel or to a hydrogen using device;

wherein the separation means comprises;

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;

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; and

a sixth means for dividing the hydrogen separated from the fuel exhaust stream into a first stream and a second stream, for providing the first stream into the hydrocarbon fuel inlet stream, and for providing the second stream to the hydrogen storage vessel or the hydrogen using device.

23. The system of claim 22, wherein the separation means is a means for separating at least the portion of hydrogen contained in the fuel cell stack fuel exhaust stream using partial pressure swing adsorption and for providing the hydrogen separated from the fuel exhaust stream to a PEM fuel cell system located in a vehicle either by providing the hydrogen to the hydrogen storage vessel, which then provides the hydrogen to the PEM fuel cell system, or by providing the hydrogen to the PEM fuel cell system without providing the hydrogen to the hydrogen storage vessel.

24. The system of claim 22, further comprising a scrubbing means for scrubbing carbon monoxide from a gas stream provided from the separation means to the hydrogen storage vessel or to the hydrogen using device.

25. The system of claim 22, 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; and

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.