Process for removing sulphur compounds including hydrogen sulphide and mercaptans from gas streams

• US 7,425,314 B2
• Filed: 11/28/2003
• Issued: 09/16/2008
• Est. Priority Date: 11/28/2002
• Status: Active Grant

• Current Assignee: Shell USA Incorporated (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Van De Graaf, Jolinde Machteld
• Primary Examiner(s): Vanoy; Timothy C
• Application Number:
  US10/536,532
• Publication Number:
  US 20060110305A1
• Time in Patent Office: 1,754 Days
• Field of Search: 423/220, 423/228, 423/229, 423/230, 423/242.1, 423/242.7, 423/243.01, 423/244.01, 481/273, 481/275
• US Class Current: 423/220
• CPC Class Codes: B01D 2253/108 Zeolites
• CPC Class Codes: B01D 2253/308 Pore size
• CPC Class Codes: B01D 2257/30 Sulfur compounds
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/306 Organic sulfur compounds, e.g. mercaptans
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2259/40086 by using a purge gas B01D2259/4009 takes precedence
• CPC Class Codes: B01D 53/04 with stationary adsorbents B01D53/025 takes precedence
• CPC Class Codes: B01D 53/1456 Removing acid components
• CPC Class Codes: B01D 53/1487 Removing organic compounds
• CPC Class Codes: B01D 53/1493 Selection of liquid materials for use as absorbents
• CPC Class Codes: C10L 3/10 Working-up natural gas or synthetic natural gas
• CPC Class Codes: C10L 3/102 of acid contaminants
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

A process for the removal of hydrogen sulfide and mercaptans from a gas stream containing a high ratio of mercaptans to hydrogen sulfide, wherein the first step removes hydrogen sulfide by washing the gas stream with an aqueous washing solution comprising water, a physical solvent and a chemical solvent. The first removal step is followed by a second removal step by which mercaptans are removed from the washed gas stream by means of molecular sieves.

Claims

1. A process for the removal of hydrogen sulphide and mercaptans from a gas stream having a high ratio of mercaptans to hydrogen sulphide and comprising hydrogen sulphide and mercaptans, wherein the process comprises:

washing the gas stream with an aqueous washing solution comprising 10 to 45 wt % (based on total solution) of water, 10 to 40 wt % (based on total solution) of a physical solvent, and 20 to 60 wt % (based on total solution) of an amine, to yield a washed gas stream;

followed by removing mercaptans from the washed gas stream by means of molecular sieves, in which process the amount of mercaptans removed by the aqueous washing solution from the gas stream is between 60 and 96% (of total removed mercaptans in steps one and two), and the amount of mercaptans removed by the molecular sieves is between 4 and 40% (of total removed mercaptans in step one and two).

2. A process according to claim 1, in which the gas stream comprises 0.05 to 20 vol % hydrogen sulphide, 10 to 1500 ppmv mercaptans and 0 to 40 vol % carbon dioxide.

3. A process according to claim 2, in which the gas stream comprises hydrogen sulphide in an amount between 0.15 and 0.6 vol %.

4. A process according to claim 3, in which the ratio of the amount of mercaptans (expressed as ppmv) to the amount of hydrogen sulphide (expressed as vol %) in the gas stream is at least 50.

5. A process according to claim 4, in which the gas stream is natural or associated gas.

6. A process according to claim 5, in which the physical solvent is sulfolane.

7. A process according to claim 6, in which the amine is a secondary or tertiary amine.

8. A process according to claim 7, in which the aqueous washing solution comprises 20 to 35 wt % based on total solution of water, 20 to 35 wt % of a physical solvent and 40 to 55 wt % of an amine.

9. A process according to claim 8, in which the washed gas stream obtained in the washing step is cooled to a temperature between 5 and 45°

C., where after any condensate is separated from the washed gas stream.

10. A process according to claim 9, in which the washing step is carried out at a temperature of at least 20°

C. and at a pressure between 15 and 90 bara.

11. A process according to claim 10, wherein the removing step uses a crystalline molecular sieve of the type selected from the group of zeolite type A and zeolite type X.

12. A process according to claim 11, wherein the removing step is carried out at a pressure between 15 and 90 bara.

13. A process according to claim 12, in which the regeneration gas of the second step containing mercaptans is remixed with the starting gas stream or is treated in a dedicated absorber.

14. A process for the removal of hydrogen sulfide and mercaptans from a gas stream that comprises hydrogen sulfide and a mercaptan and having a high ratio of mercaptans to hydrogen sulfide, wherein said process comprises:

washing said gas stream with an aqueous washing solution, comprising from 10 wt % to 45 wt % water, from 10 wt % to 40 wt % physical solvent, and from 20 wt % to 60 wt % amine, wherein said wt % is based on the total weight of said aqueous washing solution, to remove from said gas stream between 60% to 96% of the total mercaptans removed from said gas stream by said process to thereby yield a washed gas stream; and

using a molecular sieve to remove from said washed gas stream a portion of the mercaptans contained in said washed gas stream amounting to between 4% to 40% of the total mercaptans removed from said gas stream by said process to thereby yield a treated gas stream having an amount of mercaptans that is less than that of said gas stream and in the range of from 5 ppmv to 60 ppmv.

15. A process as recited in claim 14, wherein said gas stream comprises from 0.05 to 20 vol % hydrogen sulfide, from 10 to 1500 ppmv mercaptan, and from 0 to 40 vol % carbon dioxide.

16. A process as recited in claim 15, further comprising:

cooling said washed gas stream and separating condensate therefrom prior to said using step of said process.

17. A process as recited in claim 16, wherein said using step of said process includes the use of at least two mol sieve reactor vessels each of which contains a bed of said molecular sieve wherein at least one of said mol sieve reactor vessels is operating in an adsorbing mode and at least one of said mol sieve reactor vessels is operating in a desorption mode.

18. A process as recited in claim 17, further comprising:

utilizing a portion of said treated gas stream as a regeneration gas for regenating said bed of molecular sieve of said at least one of said mol sieve reactor vessels operating in said desorption mode to yield a regenerating gas containing mercaptans.

19. A process as recited in claim 18, further comprising:

mixing said regenerating gas containing mercaptans with said gas stream that undergoes said washing step.

20. A process as recited in claim 19, wherein said physical solvent is sulfolane.