Hydrogen supply method and system

• US 9,651,199 B1
• Filed: 01/16/2017
• Issued: 05/16/2017
• Est. Priority Date: 02/16/2012
• Status: Active Grant

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Oates, Rommel M., Dadebo, Solomon
• Primary Examiner(s): REID, MICHAEL ROBERT
• Application Number:
  US15/407,035
• Publication Number:
  US 20170130902A1
• Time in Patent Office: 120 Days
• Field of Search: 137 3, 137 4, 137 88, 137 93, 1372361, 405 53, 405 59
• CPC Class Codes: B65G 5/00 Storing fluids in natural or artificial cavities or chambers in the earth
• CPC Class Codes: F17C 1/007 Underground or underwater storage
• CPC Class Codes: F17C 13/02 Special adaptations of indicating, measuring, or monitoring equipment measuring in general G01
• CPC Class Codes: F17C 2221/012 Hydrogen
• CPC Class Codes: F17C 2223/0123 gaseous, e.g. CNG, GNC
• CPC Class Codes: F17C 2227/00 Transfer of fluids, i.e. method or means for transferring the fluid; Heat exchange with the fluid
• CPC Class Codes: F17D 1/00 Pipe-line systems conveying articles or materials through a pipe- line by means of a fluid carrier B65G51/00, B65G53/00; liquids B67D; special devices for transferring liquids from bulk storage containers into vehicles or boats or vice versa, e.g. loading or unloading vehicles or portable containers B67D7/00; conveying material which has been excavated by a dredger or soil shifter through a pipe-line E02F7/10; sewer pipe-line systems E03F3/00; thermal insulation of pipe-lines F16L59/00; central heating systems F24D
• CPC Class Codes: F17D 1/02 for gases or vapours
• CPC Class Codes: F17D 1/04 for distribution of gas
• CPC Class Codes: F17D 1/17 by mixing with another liquid , i.e. diluting
• CPC Class Codes: F17D 3/00 Arrangements for supervising or controlling working operations
• CPC Class Codes: F17D 3/16 for eliminating particles in suspension from liquids by sedimentation B01D21/00; separation by filtration or otherwise B01D24/00 - B01D51/00; centrifugal apparatus B04
• CPC Class Codes: Y02E 60/32 Hydrogen storage
• CPC Class Codes: Y02E 60/34 Hydrogen distribution
• CPC Class Codes: Y02P 90/45 Hydrogen technologies in production processes
• CPC Class Codes: Y10T 137/0318 Processes
• CPC Class Codes: Y10T 137/0329 Mixing of plural fluids of diverse characteristics or conditions
• CPC Class Codes: Y10T 137/2509 By optical or chemical property
• CPC Class Codes: Y10T 137/402 Distribution systems involving geographic features
• CPC Class Codes: Y10T 137/7025 Pipe line transport
• CPC Class Codes: Y10T 137/87676 : With flow control

Abstract

A method and system for supplying additional hydrogen from a reservoir of stored hydrogen in a salt cavern to a hydrogen pipeline to assist in meeting customer demand for hydrogen is provided. Contaminants introduced while the stored hydrogen stream is in the salt cavern may cause the crude hydrogen stream to not have the required product purity specification. The stored hydrogen is removed from the salt cavern as a crude hydrogen stream and thereafter diluted with higher purity hydrogen formed from the pipeline to form a hydrogen product stream at or below the product purity specification. The hydrogen product can be formed without removal of any of the contaminants in the crude stream, thereby creating a more cost effective and simplified supply process compared to conventional processes employing a salt cavern for hydrogen supply.

Claims

1. A method for supplying hydrogen from a salt cavern to assist in meeting end-user demand for hydrogen at a purity of greater than 99% that is supplied by a pipeline, the method comprising:

removing a crude hydrogen stream from the salt cavern having a first flow rate and containing at least one contaminant imparted by the salt cavern such that the at least one contaminant in the crude hydrogen stream does not meet a pre-established pipeline product purity specification;

mixing the crude hydrogen stream with a hydrogen dilution stream having a second flow rate to form a hydrogen product stream, the hydrogen dilution stream formed from hydrogen in the pipeline and containing each of the at least one contaminants lower than the pre-established pipeline product purity specification;

controlling the first flow rate of the crude hydrogen stream or the second flow rate of the hydrogen dilution stream such that the hydrogen product stream contains hydrogen at the purity of greater than 99% with the at least one contaminant found in the crude hydrogen stream at or below the pre-established pipeline product purity specification; and

supplying the hydrogen product stream to the end-user.

2. The method of claim 1, wherein the hydrogen in the hydrogen product stream has a purity greater than 99.9%.

3. The method of claim 1, wherein the second flow rate of the hydrogen dilution stream is controlled by:

sampling concentration levels of the at least one contaminants in the crude hydrogen stream to generate a first measurement of the concentration levels;

sampling concentration levels of the at least one contaminants in the hydrogen dilution stream to generate a second measurement of the concentration levels;

utilizing the first measurement of the concentration levels and the second measurement of the concentration levels along with the first flow rate of the crude hydrogen stream to determine a calculated value of concentration levels of the at least one contaminants in the hydrogen product stream by performing material balances for each of the at least one contaminants in the crude hydrogen stream such that the calculated level of the contaminants in the hydrogen product stream will be at or below the pre-established product purity specification.

4. The method of claim 3, wherein integrity checks are performed to assess reliability of the first measurement of the concentration levels and the second measurement of the concentration levels.

5. The method of claim 3, further comprising:

sampling concentration levels of the contaminants in the hydrogen product stream to generate a third measurement of the concentration levels;

correcting the third measurement with a trailing bias value to generate a reconciled value;

determining deviations between the reconciled value and the calculated value of concentration levels of contaminants in the hydrogen product stream to generate model errors;

updating the trailing bias with the model errors for subsequent use of the trailing bias; and

exporting the hydrogen product stream when the model errors are less than acceptable limits.

6. The method of claim 1, wherein stored hydrogen in the cavern is at a pressure that is above the pipeline pressure, such that at least a portion of the stored hydrogen is removed from the salt cavern as the crude hydrogen stream under impetus of the cavern pressure being higher than that of the pipeline pressure.

7. The method of claim 1, wherein none of the contaminants contained in the crude hydrogen stream are removed prior to mixing by the hydrogen dilution stream.

8. The method of claim 1, wherein the at least one contaminant contained in the crude hydrogen stream is partially removed prior to mixing by the hydrogen dilution stream.

9. The method of claim 8, wherein the at least one contaminant comprises water vapor.

10. A method for supplying additional hydrogen to a hydrogen pipeline from a salt cavern to assist in meeting end-use demand, the method comprising:

removing stored hydrogen from the salt cavern at a first flow rate as a crude hydrogen stream containing at least one contaminant comprising carbon dioxide or water vapor contaminants at a level higher than that allowed by a product purity specification for the hydrogen in the hydrogen pipeline; and

mixing the crude hydrogen stream at the first flow rate with a higher purity hydrogen from the hydrogen pipeline having a second flow rate under flow rate conditions to form a hydrogen product stream comprising hydrogen at a purity of greater than 99% with at least the carbon dioxide or the water vapor contaminants at concentrations at or below the product purity specification.

11. The method of claim 10, wherein a flow network is positioned between the hydrogen pipeline and the salt cavern to remove the higher purity hydrogen from the hydrogen pipeline to store in the salt cavern as the stored hydrogen, and to supply at least a portion of the stored hydrogen from the salt cavern to the hydrogen pipeline.

12. The method of claim 10, wherein at least part of the hydrogen product stream is supplied to an end-user.

13. The method of claim 10, wherein the first flow rate of the crude hydrogen stream is regulated to a target flow rate set by a control system.

14. The method of claim 13, wherein the control system sets the target flow rate on the basis of impurity concentration measurements taken within the crude hydrogen stream.

15. The method of claim 14, wherein the impurity concentration measurements are taken with an analyzer bank containing sensing elements.

16. The method of claim 15, wherein for each contaminant having an impurity level that exceeds the product purity specification, the control system performs overall material balance and contaminant material balances to calculate the second flow rate of the higher purity hydrogen required for reducing at least the carbon dioxide or the water vapor contaminants at or below the product purity specification.

17. The method of claim 10, wherein the product purity specification requires a balance of the contaminants to comprise at least light hydrocarbons, carbon monoxide or hydrogen sulfide at or below the product purity specification.

18. The method of claim 10, further comprising using a control system that controls the first flow rate of the crude hydrogen stream or controls the second flow rate of the higher purity hydrogen.

19. The method of claim 18, further comprising using the control system to regulate the second flow rate of the higher purity hydrogen to a target flow rate.

20. The method of claim 10, wherein none of the contaminants contained in the crude hydrogen stream are removed prior to mixing by the higher purity hydrogen.

21. The method of claim 10, wherein at least a portion of the water vapor contaminant contained in the crude hydrogen stream is removed prior to mixing with the higher purity hydrogen.

22. The method of claim 10, wherein the at least one contaminant in the crude hydrogen stream comprises water vapor and carbon dioxide.

23. The method of claim 10, wherein the higher purity hydrogen comprises hydrogen at a purity of greater than 99.9% and further comprises at least the carbon dioxide and the water vapor contaminants at a concentration that is no greater than 80% of the carbon dioxide and water vapor contaminant levels in the product purity specification.