Integrated heavy hydrocarbon removal, amine treating and dehydration

• US 20070006729A1
• Filed: 07/06/2005
• Published: 01/11/2007
• Est. Priority Date: 07/06/2005
• Status: Active Grant

• Current Assignee: BASF Catalysts LLC (BASF SE)
• Original Assignee: BASF Catalysts LLC (BASF SE)
• Inventors: Mitariten, Michael
• Granted Patent: US 7,442,233 B2
• Time in Patent Office: Days
• US Class Current: 95/92
• 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 2253/108 Zeolites
• CPC Class Codes: B01D 2253/116 Molecular sieves other than zeolites
• CPC Class Codes: B01D 2256/245 Methane
• CPC Class Codes: B01D 2257/702 Hydrocarbons
• CPC Class Codes: B01D 2257/80 Water
• CPC Class Codes: B01D 2259/40001 Methods relating to additional, e.g. intermediate, treatment of process gas
• CPC Class Codes: B01D 2259/40022 with two sub-steps
• CPC Class Codes: B01D 2259/40056 Gases other than recycled product or process gas
• CPC Class Codes: B01D 2259/40062 Four
• CPC Class Codes: B01D 2259/4009 using hot gas
• CPC Class Codes: B01D 2259/404 using four beds
• CPC Class Codes: B01D 53/0462 Temperature swing adsorption
• CPC Class Codes: B01D 53/1462 Removing mixtures of hydrogen sulfide and carbon dioxide
• CPC Class Codes: B01D 53/229 Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
• CPC Class Codes: B01D 53/261 by adsorption
• CPC Class Codes: C07C 7/11 by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
• 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
• 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: C10L 3/102 : of acid contaminants
• CPC Class Codes: Y02C 20/40 : of CO2
• CPC Class Codes: Y02P 20/10 : Process efficiency
• CPC Class Codes: Y02P 20/151 : Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The present invention is directed to an improved integrated process for the removal of heavy hydrocarbons, carbon dioxide, hydrogen sulfide, and water from a raw natural gas feed stream. More specifically, the integrated process of the present invention comprises a three step process involving the adsorption of heavy hydrocarbons and water on an adsorbent bed selective for the same, a subsequent aqueous lean amine treatment for the absorptive removal of acid gases, such as carbon dioxide and hydrogen sulfide, and an adsorptive removal of water. The process of the present invention results in a highly purified natural gas product stream.

Claims

1. A process for the purification of a raw natural gas feed stream, wherein said process comprising the steps of:

(1) passing said raw natural gas feed stream through an adsorbent unit containing an adsorbent, said adsorbent selective for removal of heavy hydrocarbons and water from said natural gas feed stream, and thereby forming a first effluent stream;

(2) passing said first effluent stream in contact with an aqueous amine absorbent, wherein said aqueous amine absorbent removes acid gases from said first effluent stream thereby forming a natural gas product effluent having an acid gas content less than said first effluent stream;

(3) recirculating said natural gas product effluent through said adsorbent unit containing an adsorbent selective for removal of water; and

(4) collecting a natural gas product stream having an amount of water and heavy hydrocarbons less than said raw natural gas stream.

2. The process of claim 1, wherein said adsorbent selective for removal of heavy hydrocarbons and water is selected from the group consisting of silica gels, molecular sieves, activated aluminas, and activated carbons, or a combination thereof.

3. The process of claim 2, wherein said adsorbent is one or more silica gels.

4. The process of claim 1, wherein said adsorbent in said adsorbent unit is regenerated by the release of the adsorbed heavy hydrocarbons and water using a heated purge stream.

5. The process of claim 4, wherein said adsorbent in said adsorbent unit is regenerated using a heated raw natural gas feed stream, wherein said regeneration results in a waste stream comprising heavy hydrocarbons.

6. The process of claim 5, wherein said waste stream is re-circulated to said raw natural gas product stream.

7. The process of claim 5, wherein said waste gas stream is cooled to partially condense the water and heavy hydrocarbons resulting in a vapor stream substantially reduced in water and heavy hydrocarbons.

8. The process of claim 7 wherein said vapor stream is re-circulated to said raw natural gas feed stream.

9. The process of claim 7, wherein said vapor stream is re-circulated to said first effluent stream.

10. The process of claim 1, wherein a bulk acid gas membrane used for the bulk removal of acid gases is placed between said adsorbent unit and said aqueous amine absorbent.

13. The natural gas purification system of claim 11, wherein said first adsorbent and said second adsorbent comprise the same adsorbent.

14. The natural gas purification system of claim 13, wherein said adsorbent is one or more silica gels.

21. The process of claim 1, wherein said adsorption unit comprises four columns, each of said columns containing an adsorbent selective for the adsorption of water and heavy hydrocarbons.

11. A natural gas purification system to dehydrate and remove heavy hydrocarbons from a raw natural gas stream comprising:

(1) a first adsorption unit comprising a first adsorbent, wherein said first adsorbent is selective for the adsorption of heavy hydrocarbons and water;

(2) an amine treatment absorber for the absorption of acid gases to produce an acid gas-reduced effluent having an acid gas content less than said raw natural gas stream;

(3) means to direct effluent from said first adsorption unit to said amine treatment absorber; and

(4) means to direct said acid gas-reduced effluent to said first adsorption unit comprising second adsorbent selective for removal of water.

12. A natural gas purification system of claim 11, wherein said adsorbent is selected from the group consisting of silica gels, molecular sieves, activated aluminas, and activated carbons, or a combination thereof.

15. The natural gas purification system of claim 11, wherein said system provides a heating means for regeneration of said first and said second adsorbents, wherein said heating means comprises means to heat raw natural gas feed stream and means to direct said heated raw natural gas stream through said first and second adsorbents, said regeneration resulting in a waste stream comprising heavy hydrocarbons and water.

16. The natural gas purification system of claim 15, wherein said system provides a means for re-circulating said waste stream to said raw natural gas feed.

17. The natural gas purification system of claim 15, wherein said system provides a means for cooling and condensing water and heavy hydrocarbons from said waste stream resulting in a vapor stream substantially devoid of water and heavy hydrocarbons and re-circulating said vapor stream to said raw natural gas stream.

18. The natural gas purification system of claim 11, wherein a bulk acid gas membrane used for the bulk removal of acid gases is placed between said adsorbent unit and said aqueous amine absorbent.

19. The natural gas purification system of claim 11, wherein said adsorption unit comprises at least four columns, each of said columns containing an adsorbent selective for the adsorption of water and heavy hydrocarbons, wherein said adsorbent is selected from the group consisting of silica gels, molecular sieves, activated aluminas, and activated carbons, or a combination thereof.

20. The natural gas purification system of claim 18, wherein said columns are identical columns each containing the same adsorbent, which is selective for the adsorption of heavy hydrocarbons and water.

22. The process of claim 20, wherein said adsorption unit operates as a multiple timed cycle wherein each of said first, second, third, and fourth columns cycle through each of four sequential steps, comprising of:

(1) the pre-amine treatment adsorption of heavy hydrocarbons and water;

(2) the post-amine treatment adsorption of water;

(3) the heat regeneration using a heated gas stream; and

(4) the cooling using a non-heated gas stream; and

wherein each column is simultaneously in a different one of said sequential steps.

23. A process for the purification of a raw natural gas feed stream, wherein said process comprising the steps of:

(1) passing said raw natural gas feed stream in contact with an aqueous amine absorbent, wherein said aqueous amine absorbent removes acid gases from said raw natural gas feed stream thereby forming a natural gas product effluent having an acid gas content less than said raw natural gas feed stream;

(2) recirculating said natural gas product effluent through an adsorbent unit containing an adsorbent, said adsorbent selective for removal of heavy hydrocarbons and water from said natural gas product effluent; and

(3) collecting a natural gas product stream having an amount of water and heavy hydrocarbons less than said raw natural gas stream.