Hydrogen storage method and system

• US 10,017,324 B2
• Filed: 01/12/2016
• Issued: 07/10/2018
• Est. Priority Date: 06/10/2010
• Status: Active Grant

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Drnevich, Raymond Francis
• Primary Examiner(s): Oquendo, Carib A
• Application Number:
  US14/993,768
• Publication Number:
  US 20160122128A1
• Time in Patent Office: 910 Days
• CPC Class Codes: B01D 53/261 by adsorption
• CPC Class Codes: B01D 53/263 by absorption
• CPC Class Codes: B65G 5/00 Storing fluids in natural or artificial cavities or chambers in the earth
• 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 2203/0288 containing two CO-shift steps
• CPC Class Codes: C01B 2203/0294 containing three or more CO-shift steps
• 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 3/00 Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it separation of gases by physical means B01D; Purification of hydrogen production of water gas or synthesis gas from solid carbonaceous material C10J; purifying or modifying the chemical compositions of combustible technical gases containing carbon monoxide C10K
• CPC Class Codes: C01B 3/34 by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: C01B 3/48 followed by reaction of water vapour with carbon monoxide
• CPC Class Codes: F17C 1/007 Underground or underwater storage
• CPC Class Codes: F17C 2221/012 Hydrogen
• CPC Class Codes: F17C 2221/013 Carbone dioxide
• CPC Class Codes: F17C 2223/0123 gaseous, e.g. CNG, GNC
• CPC Class Codes: F17C 2223/036 Very high pressure (>80 bar)
• CPC Class Codes: F17C 2265/068 Distribution pipeline networks
• CPC Class Codes: F17C 2270/0152 Salt caverns
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y02E 60/32 Hydrogen storage

Abstract

A method and system for storing and supplying hydrogen to a hydrogen pipeline in which a compressed hydrogen feed stream is introduced into a salt cavern for storage and a stored hydrogen stream is retrieved from the salt cavern and reintroduced into the hydrogen pipeline. A minimum quantity of stored hydrogen is maintained in the salt cavern to produce a stagnant layer having a carbon dioxide content along the cavern wall and the top of a residual brine layer located within the salt cavern. The compressed hydrogen feed stream is introduced into the salt cavern and the stored hydrogen stream is withdrawn without disturbing the stagnant layer to prevent carbon dioxide contamination from being drawn into the stored hydrogen stream being reintroduced into the hydrogen pipeline. This allows the stored hydrogen stream to be reintroduced into the hydrogen pipeline without carbon dioxide removal.

Claims

1. A system for storing and supplying hydrogen to a hydrogen pipeline at a combined carbon monoxide and carbon dioxide content of less than 10 parts per million, comprising:

a compressor for compressing a feed stream of the hydrogen to produce a compressed hydrogen feed stream;

a salt cavern having a residual brine layer located at a bottom region of a salt cavern and side regions extending upwardly from the bottom region of the salt cavern;

at least one conduit in communication with the salt cavern for injecting the compressed hydrogen feed stream into a salt cavern to produce stored hydrogen within the salt cavern and for withdrawing a stored hydrogen stream composed of stored hydrogen from the salt cavern and without carbon dioxide purification, the at least one conduit having at least one lower end located in an interior region of the salt cavern and spaced above the brine layer and from the side regions of the salt cavern;

a flow network configured to selectively connect the compressor to the at least one conduit such that the compressed hydrogen feed stream is injected into the salt cavern is injected at an injection ratio equal to an injection flow rate of the compressed hydrogen feed stream to an actual cavern volume of no greater than 7.5 scfd/cf and at an injection velocity of the compressed hydrogen feed stream of no greater than 100 feet per second and the stored hydrogen stream is withdrawn at a withdrawal ratio equal to the withdrawal flow rate of the stored hydrogen stream to the actual cavern volume of no greater than 10.0 scfd/cf and at a withdrawal velocity of the stored hydrogen stream of no greater than 150 feet per second to produce the stored hydrogen within the salt cavern and to selectively connect the at least one conduit to the hydrogen pipeline such that the stored hydrogen stream is injected into the pipeline; and

that salt cavern having at least a minimum quantity of the stored hydrogen within the salt cavern before, during, and between times at which the compressed hydrogen feed stream is injected and at which the stored hydrogen stream.

2. The system of claim 1, wherein the at least one lower end of the at least one conduit is spaced below a top region of the salt cavern, located opposite to the bottom region of the salt cavern.

3. The system of claim 1, wherein the flow network has a drying unit positioned within the flow network to remove water from the stored hydrogen stream prior to injection into the pipeline.

4. The system of claim 1, wherein the compressor compresses the hydrogen feed stream such that the compressed hydrogen feed stream is injected into the salt cavern at a cavern pressure that is above the pipeline pressure;

and

the flow network is configured to reduce the cavern pressure of the stored hydrogen stream to the pipeline pressure prior to injecting the stored hydrogen stream into the pipeline.

5. The system of claim 4, wherein the at least one conduit is an injection conduit from which the compressed hydrogen feed stream is injected into the salt cavern and a withdrawal conduit from which the stored hydrogen stream is withdrawn from the salt cavern through a withdrawal conduit.

6. The system of claim 1, wherein the at least one conduit comprises an injection conduit having a flow diffuser from which at least the compressed hydrogen feed stream is injected into the salt cavern.

7. The system of claim 1, wherein the minimum volume of the hydrogen stored within the salt cavern is maintained at a volume ratio equal to a stored volume of the hydrogen to the actual cavern volume of no less than 29.0 scf/cf;

the at least one lower end of the at least one conduit is open;

the at least one lower end of the at least one conduit is spaced from the residual brine layer at a lower vertical distance of no less than 250 feet;

the at least one lower end of the at least one conduit is spaced from the side regions of the salt cavern at a lateral distance of no less than 40 feet from a vertical line extending between 10 and 250 feet below the at least one lower end of the at least one conduit; and

the flow rates and velocities are limited such that, as measured at the at least one lower end of the at least one conduit, the compressed hydrogen feed stream.

8. A method of storing and supplying hydrogen to a hydrogen pipeline comprising:

compressing a feed stream of the hydrogen to produce a compressed hydrogen feed stream;

injecting the compressed hydrogen feed stream into a salt cavern to produce stored hydrogen within the salt cavern and withdrawing a stored hydrogen stream, composed of the stored hydrogen, from the salt cavern, the salt cavern having a residual brine layer located at a bottom region of the salt cavern and side regions extending upwardly from the bottom region of the salt cavern;

introducing the stored hydrogen stream after having been withdrawn from the salt cavern into the pipeline;

maintaining at least a minimum quantity of the stored hydrogen within the salt cavern before, during, and between times at which the compressed hydrogen feed stream is injected and at which the stored hydrogen stream is withdrawn; and

limiting flow rates and velocities at which the compressed hydrogen feed stream is injected into the salt cavern such that, the compressed hydrogen feed stream is injected at an injection ratio equal to an injection flow rate of the compressed hydrogen feed stream to an actual cavern volume of no greater than 7.5 scfd/cf and at an injection velocity of the compressed hydrogen feed stream of no greater than 100 feet per second and the stored hydrogen stream is withdrawn at a withdrawal ratio equal to an withdrawal flow rate of the stored hydrogen stream to the actual cavern volume of no greater than 10.0 scfd/cf and at a withdrawal velocity of the stored hydrogen stream of no greater than 150 feet per second such that the stored hydrogen stream is withdrawn from the salt cavern.

9. The method of claim 8, further comprising:

removing water from the stored hydrogen stream prior to injection into the pipeline.

10. The method of claim 8, wherein a combined carbon monoxide and carbon dioxide content of the hydrogen stored and supplied to the hydrogen pipeline is less than 10 parts per million.

11. The method of claim 8, further comprising:

compressing the hydrogen feed stream to a pressure above a pipeline pressure within the pipeline;

storing the hydrogen at a cavern pressure that is above the pipeline pressure;

removing the stored hydrogen stream from the salt cavern as a consequence of the cavern pressure; and

reducing the pressure of the stored hydrogen stream to the pipeline pressure prior to injecting the stored hydrogen stream into the pipeline.

12. The method of claim 8, wherein the compressed hydrogen feed stream is injected into the salt cavern through an injection conduit and the stored hydrogen stream is withdrawn from the salt cavern through a withdrawal conduit.

13. The method of claim 12, wherein the injection conduit includes a flow diffuser from which at least the compressed hydrogen feed stream is injected into the salt cavern.

14. The method of claim 12, wherein the minimum volume of the hydrogen stored within the salt cavern is maintained at a volume ratio equal to a stored volume of the hydrogen to the actual cavern volume of no less than 29.0 scf/cf;

the at least one lower end of the injection conduit is open;

the at least one lower end of the injection conduit is spaced from the residual brine layer at a lower vertical distance of no less than 250 feet;

the at least one lower end of the injection conduit is spaced from the side regions of the salt cavern at a lateral distance of no less than 12 feet from a vertical line extending between 10 and 250 feet below the at least one lower end of the injection conduit.

15. The method of claim 14, wherein the at least one lower end of the injection conduit is spaced below a top region of the salt cavern, located opposite to the bottom region of the salt cavern;

and

the at least one lower end of the injection conduit is spaced from the top region of the salt cavern at an upper vertical distance of no less than 50 feet.

16. The method of claim 14 or claim 15, wherein the hydrogen feed stream contains less than 1.0 ppmv carbon dioxide and less than 8 ppmv carbon monoxide and a sum of a carbon dioxide content and carbon monoxide content in the stored hydrogen stream is less than 10 ppmv.

17. The method of claim 14 or claim 15, wherein hydrogen feed stream contains less than 0.1 ppmv carbon dioxide and less than 0.6 ppmv carbon monoxide and a sum of a carbon dioxide content and carbon monoxide content in the stored hydrogen stream is less than 1.0 ppmv.