Treatment of hydrogen/hydrocarbon mixtures on adsorbents regenerated at high pressure

• US 7,381,242 B2
• Filed: 02/05/2003
• Issued: 06/03/2008
• Est. Priority Date: 02/15/2002
• Status: Expired due to Term

• Current Assignee: L'Air Liquide SA
• Original Assignee: L'Air Liquide SA
• Inventors: De Souza, Guillaume, Tromeur, Pascal
• Primary Examiner(s): Lawrence; Frank M
• Application Number:
  US10/504,454
• Publication Number:
  US 20050172803A1
• Time in Patent Office: 1,945 Days
• Field of Search: 95 95-106, 951/43, 951/44, 951/47, 951/48, 959/00, 959/01, 959/02, 961/32, 423/248, 423/648.1
• US Class Current: 95/95
• CPC Class Codes: B01D 2253/102 Carbon
• CPC Class Codes: B01D 2253/104 Alumina
• CPC Class Codes: B01D 2253/106 Silica or silicates
• CPC Class Codes: B01D 2253/306 Surface area, e.g. BET-specific surface
• CPC Class Codes: B01D 2253/311 Porosity, e.g. pore volume
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2257/102 Nitrogen
• CPC Class Codes: B01D 2257/50 Carbon oxides
• CPC Class Codes: B01D 2257/702 Hydrocarbons
• CPC Class Codes: B01D 2257/80 Water
• CPC Class Codes: B01D 2259/40062 Four
• 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 2259/4146 Contiguous multilayered adsorbents
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01D 53/047 Pressure swing adsorption
• CPC Class Codes: B01D 53/261 by adsorption
• CPC Class Codes: C01B 2203/042 Purification by adsorption on solids
• CPC Class Codes: C01B 2203/048 the impurity being an organic compound
• CPC Class Codes: C01B 3/56 by contacting with solids; Regeneration of used solids C01B3/508 takes precedence
• CPC Class Codes: C07C 7/12 : by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers

Abstract

A method of PSA gas separation for a gas mixture containing hydrogen and hydrocarbon impurities. The gas mixture is put in contact with silica gel and activated carbon so as to adsorb the impurities in the gas mixture. Hydrogen rich and waste gas flows are produced. The waste gas flow may be sent to the combustible network of a petrochemical site, without having to make a pressure adjustment to the waste gas.

Claims

1. A method which may be used for a PSA separation of a gas mixture, wherein said gas mixture comprises hydrogen and impurities which comprise at least one hydrocarbon (C_nH_m), comprising:

a) contacting said gas mixture with a first adsorbent, wherein said first adsorbent comprises a silica gel, and a second adsorbent, wherein said second comprises an activated charcoal;

b) adsorbing at least a portion of the impurities of said gas mixture with said first and said second adsorbents;

c) producing hydrogen at a production pressure (P′

);

d) desorbing at least a portion of said impurities from said adsorbents; and

e) producing a waste gas stream, wherein said waste gas stream has a regeneration pressure (P″

) between about 2 bar absolute and about 10 bar absolute and wherein said waste gas stream further comprises said impurities, wherein said regeneration pressure (P″

) is greater than or equal to a pressure of a fuel network of a petrochemical facility on which the PSA unit is installed.

2. The method of claim 1, wherein said regeneration pressure (P″

) is greater than 3 bar absolute.

3. The method of claim 1, wherein said regeneration pressure (P″

) is greater than 4 bar absolute.

5. The method of claim 1, wherein said gas mixture comprises an adsorption pressure (P) between about 20 bar absolute and about 50 bar absolute.

6. The method of claim 1, further comprising contacting said gas mixture with an activated alumina adsorbent prior to contact with said first and said second adsorbents.

7. The method of claim 6, wherein said activated alumina comprises:

a) a surface area per unit mass greater than about 200 m²/g; and

b) a pore volume greater than about 0.25 cm³/g.

8. The method of claim 7, wherein said surface area is greater than about 270 m²/g.

9. The method of claim 1, wherein said silica gel comprises:

a) a surface area per unit mass greater than about 400 m²/g; and

b) a pore volume greater than about 0.25 cm³/g.

10. The method of claim 9, wherein said surface area is greater than about 600 m²/g.

11. The method of claim 1, wherein said activated charcoal comprises:

a) a surface area per unit mass greater than about 600 m²/g; and

b) a pore volume greater than about 0.25 cm³/g.

12. The method of claim 11, wherein said surface area is greater than about 850 m²/g.

13. The method of claim 11, wherein said production pressure (P′

) is between about 20 bar absolute and 50 bar absolute.

14. The method of claim 1, wherein said hydrogen produced comprises a purity greater than about 98.5 vol %.

15. The method of claim 13, wherein said hydrogen produced comprises a purity greater than about 98.5 vol %.

16. The method of claim 1, further comprising sending said waste gas stream to the fuel network of the petrochemical facility.

17. The method of claim 16, wherein said petrochemical facility comprises a refinery.

18. The method of claim 1, further comprising sending said produced waste gas stream to a pipeline network, wherein said network comprises a gas flowing at a pressure between about 3 bar absolute and about 8 bar absolute.

19. The method of claim 1, wherein said gas mixture further comprises at least one member selected from the group consisting of:

a) carbon dioxide;

b) water;

c) nitrogen; and

d) carbon monoxide.

20. The method of claim 1, wherein said gas mixture comprises hydrocarbons with at least 3 carbon atoms in the hydrocarbon chain.

21. The method of claim 20, wherein said hydrocarbons comprise at least one member selected from the group consisting of:

a) propane;

b) propene;

c) butane;

d) butene;

e) pentane;

f) hexane;

g) benzene;

h) toluene;

i) xylene; and

j) isomers thereof.

22. The method of claim 1, wherein said gas mixture is contacted with said first adsorbent before being contacted with said second adsorbent.

23. The method of claim 1, wherein said gas mixture is produced with a catalytic reforming means.

4. A method which may be used for a PSA separation of a gas mixture, wherein said gas mixture comprises hydrogen and impurities which comprise at least one hydrocarbon (C_nH_m), comprising:

a) contacting said gas mixture with a first adsorbent, wherein said first adsorbent comprises a silica gel, and a second adsorbent, wherein said second comprises an activated charcoal;

b) adsorbing at least a portion of the impurities of said gas mixture with said first and said second adsorbents;

c) producing hydrogen at a production pressure (P′

);

d) desorbing at least a portion of said impurities from said adsorbents; and

e) producing a waste gas stream, wherein said waste gas stream has a regeneration pressure (P″

) between about 2 bar absolute and about 10 bar absolute and wherein said waste gas stream further comprises said impurities, further comprising producing said waste gas stream at said regeneration pressure (P″

) in the absence of a compression means, wherein said genreation regeneration pressure (P″

) is greater than or equal to a pressure of a fuel network of a petrochemical facility on which the PSA unit is installed.

24. A method which may be used for a PSA separation of a gas mixture, wherein said gas mixture comprises hydrogen and impurities which comprise at least one hydrocarbon (C_nH_m), comprising:

a) contacting said gas mixture with a first adsorbent, wherein said first adsorbent comprises an adsorbent which adsorbs at least one hydrocarbon (C_nH_m), and a second adsorbent, wherein said second comprises an activated charcoal;

b) adsorbing at least a portion of the impurities of said gas mixture with said first and said second adsorbents;

c) producing hydrogen at a production pressure (P′

);

d) desorbing at least a portion of said impurities from said adsorbents; and

e) producing a waste gas stream, wherein said waste gas stream has a regeneration pressure (P″

) between about 2 bar absolute and about 10 bar absolute and wherein said waste gas stream further comprises said impurities, wherein said regeneration pressure (P″

) is greater than or equal to a pressure of a fuel network of a petrochemical facility on which the PSA unit is installed.

25. A method which may be used for a PSA separation of a gas mixture, wherein said gas mixture comprises hydrogen and impurities which comprise at least one hydrocarbon (CnHm), comprising:

a) contacting said gas mixture with an activated alumina adsorbent;

b) contacting said gas mixture with a first adsorbent, wherein said first adsorbent comprises a silica gel, and a second adsorbent, wherein said second comprises an activated charcoal;

c) adsorbing at least a portion of the impurities of said gas mixture with said first and said second adsorbents;

d) producing hydrogen at a production pressure (P′

);

e) desorbing at least a portion of said impurities from said adsorbents;

f) producing a waste gas stream, wherein said waste gas stream has a regeneration pressure (P″

) above about 3 bar absolute and wherein said waste gas stream further comprises said impurities; and

g) sending said waste gas stream to the pipeline network of a fuel network of a petrochemical facility, wherein said pipeline network comprises a gas flowing at a pressure above about 3 bar absolute, wherein said regeneration pressure (P″

) is greater than or equal to the pressure of the pipeline network.