Selective removal of nitrogen from natural gas by pressure swing adsorption

• US 6,444,012 B1
• Filed: 10/30/2000
• Issued: 09/03/2002
• Est. Priority Date: 10/30/2000
• Status: Expired due to Term

• Current Assignee: Engelhard Corporation (BASF SE)
• Original Assignee: Engelhard Corporation (BASF SE)
• Inventors: Dolan, William B., Butwell, Kenneth F.
• Primary Examiner(s): Spitzer, Robert H.
• Application Number:
  US09/699,664
• Time in Patent Office: 673 Days
• Field of Search: 95/96--06, 951/14, 951/15, 951/30, 951/43--48, 959/01, 959/02
• US Class Current: 95/99
• CPC Class Codes: B01D 2253/106 Silica or silicates
• CPC Class Codes: B01D 2253/108 Zeolites
• CPC Class Codes: B01D 2253/1085 characterized by a silicon-aluminium ratio
• CPC Class Codes: B01D 2253/25 Coated, impregnated or composite adsorbents
• CPC Class Codes: B01D 2253/308 Pore size
• CPC Class Codes: B01D 2257/102 Nitrogen
• CPC Class Codes: B01D 2257/702 Hydrocarbons
• CPC Class Codes: B01D 2257/7025 Methane
• CPC Class Codes: B01D 2259/40001 Methods relating to additional, e.g. intermediate, treatment of process gas
• CPC Class Codes: B01D 2259/40052 Recycled product or process gas
• CPC Class Codes: B01D 2259/40056 Gases other than recycled product or process gas
• CPC Class Codes: B01D 2259/40081 Counter-current
• CPC Class Codes: B01D 2259/4009 using hot gas
• CPC Class Codes: B01D 2259/403 using three beds
• 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: C07C 7/13 by molecular-sieve technique
• CPC Class Codes: C07C 9/04 Methane production by treatment of sewage C02F11/04; natural gas, synthetic natural gas C10L3/06
• CPC Class Codes: C10L 3/10 Working-up natural gas or synthetic natural gas
• CPC Class Codes: Y02C 20/20 of methane
• CPC Class Codes: Y02P 20/156 : Methane [CH4]
• CPC Class Codes: Y10S 95/901 : Activated carbon
• CPC Class Codes: Y10S 95/902 : Molecular sieve

Abstract

A pressure swing adsorption process for the separation of nitrogen from natural gas utilizes two separate pressure swing adsorption stages, the first containing a hydrocarbon-selective adsorbent and the second containing a nitrogen-selective adsorbent. In the process, the product stream from the first pressure swing adsorption unit contains a natural gas stream having a reduced hydrocarbon content and the product stream from the second pressure swing adsorption unit is a natural gas stream having a reduced nitrogen concentration. The product from the second pressure swing adsorption unit is used to desorb the hydrocarbons from the first pressure swing adsorption unit so as to add the hydrocarbons, which have heat value to the product natural gas stream. Periodically, heating the nitrogen-selective adsorbent with heated product stream from the second pressure swing adsorption unit has been found to improve the capacity of the nitrogen-selective adsorbent to adsorb nitrogen.

Claims

1. A pressure swing absorption (PSA) process for the separation of nitrogen from a mixture of the same with methane which comprises:

(a) passing a feed stream comprising said mixture in contact with a nitrogen-selective sorbent in a PSA unit so as to preferentially adsorb nitrogen and produce a methane-rich product stream containing at least 70 mol. % methane and a low pressure purge stream having a higher molar concentration of nitrogen than said mixture; and

(b) subsequent to step (a), periodically heating said nitrogen-selective sorbent with the methane-rich product stream to drive off accumulated methane from such sorbent.

2. The process of claim 1, wherein subsequent to step (b), cooling said nitrogen-selective sorbent.

3. The process of claim 2, wherein said nitrogen-selective sorbent is cooled by contact with a gas stream which contains at least 30 mole % nitrogen.

4. The process of claim 3, wherein said nitrogen-selective sorbent is cooled with a gas stream containing at least 90 mole % nitrogen.

5. The process of claim 4, wherein said stream to cool said nitrogen-selective sorbent comprises at least 90% nitrogen with the balance methane.

6. The process of claim 2, wherein said cooling is provided by contacting said nitrogen-selective sorbent with a gas stream fed countercurrent to the direction of said feed stream.

7. The process of claim 6, wherein said feed stream does not contain water or carbon dioxide.

8. The process of claim 2, wherein said cooling is provided by contacting said nitrogen-selective sorbent with a gas stream fed co-current to the direction of said feed stream.

9. The process of claim 8, wherein said feed stream contains water and/or carbon dioxide.

10. The process of claim 1, wherein said nitrogen-selective sorbent is a CTS-1 crystalline titanium silicate having a pore size of 3 to less than 4 Å

.

11. The process of claim 1, wherein said nitrogen-selective sorbent is a barium exchanged ETS-4 crystalline titanium silicate wherein barium comprises at least 30% of the exchangeable cations of said titanium silicate.

12. The process of claim 1 comprising co-currently depressurizing said PSA unit to form a recycle stream rich in methane, said recycle stream having a pressure less than said methane-rich product stream, but greater than said purge stream, recycling said recycle stream to said feed stream.

13. The process of claim 1, wherein said feed stream comprises natural gas.

14. A process for the separation of nitrogen and hydrocarbons from a natural gas stream, which comprises:

passing said natural gas stream to a first pressure swing adsorption unit containing a hydrocarbon-selective sorbent so as to preferentially adsorb at least C4+ hydrocarbons to produce a first product stream comprising methane, nitrogen and a reduced level of said hydrocarbons relative to said natural gas stream; and

passing said first product stream to a second pressure swing absorption unit containing a nitrogen-selective sorbent so as to preferentially adsorb nitrogen and produce a second product stream enriched with methane and a low pressure purge stream having a higher molar concentration of nitrogen than said first product stream.

15. The process of claim 14 comprising;

passing said second product stream in contact with said hydrocarbon-selective sorbent subsequent to formation of said first product stream so as to adsorb said C4+ hydrocarbons into said second product stream.

16. The process of claim 14, wherein said hydrocarbon-selective sorbent preferentially adsorbs C3+ hydrocarbons.

17. The process of claim 14 comprising co-currently pressurizing said first pressure swing adsorption unit to form a lower pressure product stream, combining said first product stream and said lower pressure product stream to form a combined stream and contacting said combined stream with said nitrogen-selective sorbent.

18. The process of claim 17, wherein the pressure of said first product stream is reduced to the pressure of said lower pressure product stream prior to said combining.

19. The process of claim 14 comprising co-currently depressurizing said second pressure swing adsorption unit to form a low pressure recycle stream having a pressure lower than said second product stream and higher than said purge stream, combining said low pressure recycle stream with said first product stream to form a first combined recycle stream and passing said first combined recycle stream in contact with said nitrogen selective sorbent.

20. The process of claim 19 comprising co-currently depressurizing said first PSA unit to form a lower pressure product stream, combining said first product stream, said lower pressure product stream and said low pressure recycle stream to form a second combined recycle stream and contacting said second combined recycle stream with said nitrogen-selective sorbent.

21. The process of claim 20, wherein the pressure of said first product stream is lowered to the pressure of said lower pressure product stream and the pressure of said low pressure recycle stream is raised to the pressure of said lower pressure product stream prior to combining.

22. The process of claim 19, wherein the pressure of said low pressure recycle stream is raised and the pressure of said first product stream is lowered so that said low pressure recycle stream and said first product stream are at the same pressure prior to combining.

23. The process of claim 19, comprising equalizing the pressure of said second PSA subsequent to forming said low pressure recycle stream and prior to forming said purge stream.

24. The process of claim 14, wherein said hydrocarbon-selective sorbent is silica.

25. The process of claim 24, wherein said nitrogen-selective sorbent is CTS-1 titanium silicate having a pore size of about 3 to less than 4 Å

.

26. The process of claim 14, wherein said nitrogen-selective sorbent is CTS-1 titanium silicate having a pore size of about 3 to less than 4 Å

.

27. The process of claim 14 comprising periodically heating said nitrogen-selective sorbent subsequent to formation of said second product stream and said purge stream to drive off accumulated methane from said nitrogen-selective sorbent.

28. The process of claim 27, comprising heating said second product stream to form a heated second product stream and passing said heated second product stream in contact with said nitrogen-selective sorbent so as to heat said nitrogen-selective sorbent.

29. The process of claim 28, wherein said second product stream is heated to a temperature of at least about 200°

F.

30. The process of claim 28 comprising passing said second product stream subsequent to heating said nitrogen-selective sorbent into contact with said hydrocarbon-selective sorbent.

31. The process of claim 14, wherein said nitrogen-selective sorbent is barium exchanged ETS-4 titanium silicate wherein barium represents at least 30% of the exchangeable cations on said titanium silicate.

32. The process of claim 14, wherein said natural gas stream contains over 4 mole % nitrogen.

33. The process of claim 14 , wherein said first product stream is essentially devoid of C4+ hydrocarbon.

34. The process of claim 33, wherein said first product stream has reduced levels of propane relative to said natural gas stream.

35. A pressure swing absorption (PSA) process for the separation of nitrogen from a mixture of the same with methane which comprises:

(a) passing a feed stream comprising said mixture in contact with a nitrogen-selective sorbent in a PSA unit so as to preferentially adsorb nitrogen and produce a methane-rich product stream containing at least 70 mol. % methane and a low pressure purge stream having a higher molar concentration of nitrogen than said mixture; and

(b) co-currently depressurizing said PSA unit to form a recycle stream rich in methane, said recycle stream having a pressure less than said methane-rich product stream, but greater than said purge stream, recycling said recycle stream to said feed stream.

36. The process of claim 35, wherein said feed stream comprises natural gas.

37. The process of claim 35, wherein said nitrogen-selective sorbent is a CTS-1 crystalline titanium silicate having a pore size of 3 to less than 4 Å

.

38. The process of claim 35, wherein said nitrogen-selective sorbent is a barium exchanged ETS-4 crystalline titanium silicate wherein barium comprises at least 30% of the exchangeable cautions of said titanium silicate.