Methods for storing hydrogen in a salt cavern with a permeation barrier

• US 9,284,120 B2
• Filed: 02/18/2014
• Issued: 03/15/2016
• Est. Priority Date: 05/25/2012
• Status: Active Grant

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Oates, Rommel M.
• Primary Examiner(s): LAGMAN, FREDERICK LYNDON
• Application Number:
  US14/182,582
• Publication Number:
  US 20140161533A1
• Time in Patent Office: 756 Days
• Field of Search: 405/53, 405/54
• US Class Current: 1/1
• CPC Class Codes: B65G 5/00 Storing fluids in natural or artificial cavities or chambers in the earth
• CPC Class Codes: B65G 5/005 in porous layers
• CPC Class Codes: F17C 1/007 Underground or underwater storage
• CPC Class Codes: F17C 2203/0604 Liners
• CPC Class Codes: F17C 2221/012 Hydrogen
• 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 2227/0157 Compressors
• CPC Class Codes: F17C 2260/036 Avoiding leaks
• CPC Class Codes: F17C 2270/0152 Salt caverns
• CPC Class Codes: Y02E 60/32 Hydrogen storage

Abstract

A novel method and system for storing high purity hydrogen into a salt cavern is provided. Particularly, the storage process involves storing high purity hydrogen into a salt cavern without seepage or leakage of the stored hydrogen through the salt cavern walls, by creating a substantially impermeable permeation barrier along the salt cavern walls. The cavern pressure is monitored and controlled to ensure formation and maintenance of the substantially impermeable permeation barrier. Optional temperature treatments may also be incorporated as desired.

Claims

1. A method for storing high purity hydrogen product in a salt cavern, comprising:

removing the high purity hydrogen product from a high purity hydrogen pipeline;

compressing the high purity hydrogen product to produce a compressed high purity hydrogen product;

introducing the compressed high purity hydrogen product comprising a purity of about 99% or greater into the salt cavern to produce stored high purity hydrogen within the salt cavern;

thereby

pressurizing at least a portion of the walls of the salt cavern walls characterized by a halite structure having a minimum purity of at least about 75% of sodium chloride, to substantially confine the stored high purity hydrogen within the salt cavern at a pressure, and measuring and adjusting the pressure to maintain the pressure between a predetermined lower limit and a predetermined upper limit.

2. The method of claim 1, further comprising the steps of:

detecting the pressure to exceed the predetermined upper limit; and

withdrawing at least a portion of the stored hydrogen from the salt cavern to the high purity hydrogen pipeline to reduce the pressure below the predetermined upper limit.

3. The method of claim 2, further comprising lowering the pressure to a pressure insufficient to fracture the walls of the salt cavern.

4. The method of claim 1, further comprising the steps of:

detecting the pressure to drop below the predetermined lower limit; and

introducing a portion of the high purity hydrogen product from the high purity hydrogen pipeline into the salt cavern to increase the pressure above the predetermined lower limit.

5. The method of claim 4, further comprising increasing the pressure to a pressure above the lower limit that is sufficient to counteract creep closure of the walls of the cavern.

6. The method of claim 1, further comprising:

detecting the pressure to approach an upper limit; and

withdrawing at least a portion of the stored hydrogen from the salt cavern to the hydrogen pipeline to reduce the pressure.

7. The method of claim 1, further comprising:

detecting the pressure to approach the predetermined lower limit; and

introducing a portion of the high purity hydrogen product from the high purity hydrogen pipeline into the salt cavern to increase the pressure.

8. The method of claim 1, wherein the predetermined lower limit is greater than about 0.2 psi per linear foot of depth of the cavern and the upper limit is less than about 1 psi per linear foot of depth of the cavern.

9. The method of claim 1, further comprising increasing a temperature of least a portion of the walls of the salt cavern by about 0.1°

F. per foot of cavern depth.

10. The method of claim 1, further comprising introducing the compressed high purity hydrogen product into the salt cavern when the pressure is at or below the predetermined lower limit, and withdrawing at least a portion of the stored hydrogen from the salt cavern when the pressure is at or above the predetermined upper limit.

11. The method of claim 1, wherein the compressed high purity hydrogen product comprises a purity of about 99.9% or greater.

12. The method of claim 1, wherein the compressed high purity hydrogen product comprises a purity of about 99.99% or greater.

13. The method of claim 1, wherein the compressed high purity hydrogen product comprises a purity of about 99.999% or greater.

14. The method of claim 1, further comprising transferring heat from the compressed high purity hydrogen product to a well casing so as to increase the temperature of the well casing.

15. The method of claim 1, wherein the predetermined lower limit is greater than about 0.85 psi per linear foot of depth of the cavern and the upper limit is less than about 1 psi per linear foot of depth of the cavern.

16. The method of claim 1, further comprising performing a mechanical integrity test of the salt cavern that is occupied with the stored high purity hydrogen.

17. The method of claim 1, transferring at least another portion of the heat of compression from the compressed hydrogen gas to the walls of the salt cavern.

18. The method of claim 1, further comprising regulating the temperature of the compressed high purity hydrogen product between about 200°

F. and 400°

F.

19. The method of claim 1, further comprising increasing a temperature of least a portion of the walls of the salt cavern by about 0.1°

F. per foot of cavern depth.

20. A method for confining stored high purity hydrogen gas in a salt cavern that is operated in a hydrogen depleted state, comprising:

withdrawing a portion of the stored high purity hydrogen gas from the salt cavern to a level at which a pressure of the remaining portion of the stored high purity hydrogen gas is reduced below a predetermined lower limit;

introducing a sufficient amount of compressed fluid into the salt cavern to reduce an effective volume of the salt cavern and thereby pressurize the remaining portion of the stored high purity hydrogen gas to increase the pressure in the cavern to at least the predetermined lower limit; and

confining the stored high purity hydrogen gas at the pressure at or above the predetermined lower limit along at least a portion of the walls of the salt cavern.

21. The method of claim 20, wherein each of the compressed fluid and the stored gas is selected from the group consisting of brine, hydrogen product, inert gases, and any combination thereof.

22. The method of claim 20, wherein the stored gas comprises high purity stored hydrogen comprising a purity of 99% or greater.

23. The method of claim 20, wherein the stored gas is high purity hydrogen product comprising a purity of 99% or greater, and further wherein said method comprises:

removing the high purity hydrogen product from a hydrogen pipeline;

compressing the high purity hydrogen product to produce a compressed hydrogen high purity product;

introducing the compressed hydrogen high purity product into the salt cavern; and

displacing at least a portion of the compressed fluid from out of the salt cavern, thereby maintaining substantial confinement of the stored high purity hydrogen gas at the pressure above the predetermined lower limit.

24. The method of claim 20, comprising the steps of:

retaining the compressed fluid within the salt cavern such that the pressure in the salt cavern remains above the predetermined lower limit during operation of the salt cavern; and

maintaining the pressure of the remaining portion of the stored gas to remain below a predetermined upper limit.

25. A method for operating a salt cavern containing a high purity hydrogen product, the salt cavern connected to a high purity hydrogen product pipeline, said method for operating comprising:

establishing a predetermined lower pressure limit and a predetermined upper pressure limit within the salt cavern comprising a high purity hydrogen product to establish pressure conditions within the salt cavern that substantially confines the high purity hydrogen product therewithin;

monitoring at least the cavern pressure to provide a real-time pressure reading;

comparing the pressure reading to the predetermined lower pressure limit and the upper pressure limit,

adjusting the volume of the high purity hydrogen product in the salt cavern such that when the real-time pressure reading indicates that the pressure exceeds the predetermined upper pressure limit, at least a portion of the high purity hydrogen product is withdrawn to the high purity hydrogen product pipeline, and when the real-time pressure reading indicates that the pressure is below the predetermined lower pressure limit, at least a portion of high purity hydrogen product from the high purity hydrogen pipeline is introduced into the salt cavern from the hydrogen product pipeline; and

wherein the stored high purity hydrogen product is substantially confined within the salt cavern between the predetermined lower pressure limit and the predetermined upper pressure limit during the operation of the salt cavern.

26. A method for operating a salt cavern containing one of more fluids including at least a high purity hydrogen product and salt brine, the salt cavern connected to a high purity hydrogen product pipeline and a brine pond containing salt brine, comprising:

establishing a predetermined lower pressure limit and predetermined upper pressure limit within the salt cavern comprising a stored high purity hydrogen product observed to establish pressure conditions within the salt cavern that substantially confines the high purity hydrogen product therewithin;

monitoring at least the cavern pressure to provide a real-time pressure reading;

comparing the pressure reading to the predetermined lower pressure limit and the upper pressure limit,

adjusting the pressure reading of the salt cavern such that when the real-time pressure reading indicates that the pressure is trending upwards and approaching the predetermined upper pressure limit, at least one of the fluids is withdrawn and when the real-time pressure reading indicates that the pressure is trending downwards and approaching the predetermined lower pressure limit, at least one of the fluids is introduced into the salt cavern; and

wherein the stored high purity hydrogen product is substantially confined within the salt cavern at a pressure that is maintained between the predetermined lower pressure limit and the predetermined upper pressure limit during the operation of the salt cavern.