Propane recovery methods

• US 6,116,050 A
• Filed: 12/04/1998
• Issued: 09/12/2000
• Est. Priority Date: 12/04/1998
• Status: Expired due to Term

• Current Assignee: IPSI, LLC (Bechtel Group Incorporated)
• Original Assignee: IPSI, LLC (Bechtel Group Incorporated)
• Inventors: Yao, Jame, Elliot, Douglas G., Lee, Rong-Jwyn, Chen, Jong Juh
• Primary Examiner(s): DOERRLER, WILLIAM CHARLES
• Application Number:
  US09/209,931
• Time in Patent Office: 648 Days
• Field of Search: 62/630, 62/631, 62/620
• US Class Current: 62/630
• CPC Class Codes: F25J 2200/04 in a dual pressure main column system
• CPC Class Codes: F25J 2200/50 using multiple (re-)boiler-condensers at different heights of the column
• CPC Class Codes: F25J 2200/74 Refluxing the column with at least a part of the partially condensed overhead gas
• CPC Class Codes: F25J 2200/76 Refluxing the column with condensed overhead gas being cycled in a quasi-closed loop refrigeration cycle
• CPC Class Codes: F25J 2200/78 Refluxing the column with a liquid stream originating from an upstream or downstream fractionator column
• CPC Class Codes: F25J 2205/04 in the feed line, i.e. upstream of the fractionation step
• CPC Class Codes: F25J 2210/06 Splitting of the feed stream, e.g. for treating or cooling in different ways
• CPC Class Codes: F25J 2210/12 Refinery or petrochemical off-gas
• CPC Class Codes: F25J 2230/60 the fluid being hydrocarbons or a mixture of hydrocarbons
• CPC Class Codes: F25J 2235/60 the fluid being (a mixture of) hydrocarbons
• CPC Class Codes: F25J 2240/02 Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
• CPC Class Codes: F25J 2270/02 Internal refrigeration with liquid vaporising loop
• CPC Class Codes: F25J 2270/12 External refrigeration with liquid vaporising loop
• CPC Class Codes: F25J 2270/60 Closed external refrigeration cycle with single component refrigerant [SCR], e.g. C1-, C2- or C3-hydrocarbons
• CPC Class Codes: F25J 2270/88 Quasi-closed internal refrigeration or heat pump cycle, if not otherwise provided
• CPC Class Codes: F25J 2280/02 Control in general, load changes, different modes ("runs"), measurements
• CPC Class Codes: F25J 2280/40 Control of freezing of components
• CPC Class Codes: F25J 3/0209 Natural gas or substitute natural gas
• CPC Class Codes: F25J 3/0219 Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
• CPC Class Codes: F25J 3/0233 separation of CnHm with 1 carbon atom or more
• CPC Class Codes: F25J 3/0242 : separation of CnHm with 3 carbon atoms or more

Abstract

The present invention is directed to methods for separating and recovering propane, propylene and heavier hydrocarbons, i.e., the C₃ + hydrocarbons, from a gas feed, e.g., raw natural gas or a refinery or petroleum plant gas stream. These methods employ sequentially configured first and second distillation columns, e.g., a de-methanizer tower followed by a de-ethanizer tower. A cooled gas feed condensate is separated in the first column into methane and a liquid phase comprising ethane and heavier hydrocarbons. The liquid phase is separated in the second column into a gas phase primarily comprising ethane and a second liquid phase primarily comprising the desired C₃₊ hydrocarbons. At least a portion of the second gas phase is introduced into the first distillation column as an overhead reflux to improve the separation of C₃₊ hydrocarbons. The methods of the present invention permit separation and recovery of more than about 99% of the C₃₊ hydrocarbons in the gas feed at higher operating pressures. Further, by cooling the second gas phase with a liquid condensed in a lower tray of the first column, significant capital and operating costs may be saved. By using the self refrigeration system, the need for external refrigeration is eliminated and the separation efficiency is improved in the first column. Accordingly, the processes of the present invention result in achieving higher liquid recovery levels with lower capital requirements and significant savings in operation.

Claims

1. A process for the separation of C₃₊ hydrocarbons from a hydrocarbon-containing gas feed under pressure, comprising:

introducing a cooled gas/condensate feed into a de-methanizer column at one or more feed trays;

providing heat to a portion of said de-methanizer column below said feed trays to substantially strip off methane and ethane from said gas/condensate feed;

separating said gas/condensate feed in said de-methanizer column into a first gas phase primarily comprising methane and ethane and into a first liquid phase primarily comprising C₂₊ hydrocarbons;

introducing said first liquid phase into a de-ethanizer column at one or more feed trays;

separating said first liquid phase in said de-ethanizer column into a second gas phase primarily comprising ethane and a second liquid phase primarily comprising C₃₊ hydrocarbons;

cooling said second gas phase by countercurrent heat exchange with a mixture comprising condensed liquid withdrawn from said de-methanizer column at a tray located below said feed trays and a portion of liquid separated from said gas/condensate feed before its introduction into said de-methanizer column;

separating said cooled second gas phase into a first gaseous fraction primarily comprising ethane and a second liquid fraction;

cooling and condensing said first gaseous fraction primarily comprising ethane;

introducing into said de-methanizer column as an overhead reflux said cooled and condensed first gaseous fraction primarily comprising ethane;

introducing into said de-ethanizer column said second liquid fraction; and

recovering from the bottom of said de-ethanizer column said second liquid phase primarily comprising C₃₊ hydrocarbons.

2. The process of claim 1 wherein at least about 94% by weight of the C₃₊ hydrocarbons in said gas feed are recovered in said second liquid phase.

3. The process of claim 1 wherein ethane and carbon dioxide comprise at least about 85 percent-by-volume of said first gaseous fraction of said second gas phase.

4. The process of claim 1 wherein said first gas phase is heated by countercurrent heat exchange with at least one of said first gaseous fraction and said gas feed and thereafter compressed to produce a residue gas.

5. The process of claim 1 wherein said overhead reflux further comprises a portion of said residue gas.

6. The process of claim 5 wherein up to about 5 percent-by-volume of said residue gas is included in said overhead reflux.

7. The process of claim 6 wherein the pressure of said included residue gas is substantially equal to the pressure of said first gaseous fraction.

8. The process of claim 5 further comprising including in said overhead reflux a sufficient volume of residue gas to prevent the formation of solids comprising ice, hydrates and mixtures thereof in said overhead reflux.

9. The process of claim 8 wherein up to about 10 percent-by-volume of said residue gas is included in said overhead reflux to prevent the formation of solids comprising ice, hydrates and mixtures thereof.

10. The process of claim 1 wherein said gas feed is cooled by countercurrent heat exchange with a refrigerant stream comprising a portion of said first liquid phase and resulting in partial vaporization of said refrigerant stream;

and

separating said partially vaporized refrigerant stream into a third liquid phase which is introduced into said de-ethanizer column and a third gas phase which is introduced into said de-methanizer column as a stripping gas.

11. The process of claim 10 wherein said refrigerant stream is drawn from one or more trays located below the first feed tray of said de-methanizer.

12. The process of claim 10 wherein said refrigerant stream is further cooled prior to supplying refrigeration for said feed gas.

13. The process of claim 10 wherein said third gas phase is partially condensed by compressing and cooling.

14. The process of claim 13 wherein said mixture used to cool said second gas phase is introduced back into said de-methanizer a location below the tray from which said condensed liquid was withdrawn.

15. A process for the separation of C₃₊ hydrocarbons from a hydrocarbon-containing gas feed under pressure, comprising:

introducing a cooled gas/condensate feed into a first distillation column at one or more feed trays;

providing heat to a portion of said first distillation column below said feed trays to substantially strip off methane and ethane from said gas feed;

separating said gas/condensate feed in said first column into a first gas phase primarily comprising methane and ethane and into a first liquid phase primarily comprising C₂₊ hydrocarbons;

introducing said first liquid phase into a second distillation column at one or more feed trays;

separating said first liquid phase in said second distillation column into a second gas phase primarily comprising ethane and a second liquid phase primarily comprising C₃₊ hydrocarbons;

cooling and condensing said second gas phase primarily comprising ethane;

introducing into said first distillation column as an overhead reflux at least a portion of said cooled and condensed second gas phase primarily comprising ethane; and

recovering from the bottom of said second distillation column said second liquid phase primarily comprising C₃₊ hydrocarbons.

16. The process of claim 15 wherein at least about 94 percent-by-weight of the C₃₊ hydrocarbons in said gas feed are recovered in said second liquid phase.

17. The process of claim 15 wherein ethane and carbon dioxide comprise at least about 85 percent-by-volume of said second gas phase.

18. The process of claim 15 wherein said overhead reflux further comprises a portion of a residue gas recovered from said first gas phase.

19. The process of claim 18 wherein up to about 5 percent-by-volume of said residue gas is included in said overhead reflux.

20. The process of claim 19 wherein the pressure of said 5 percent-by-volume of residue gas is substantially equal to the pressure of said second gas phase.

21. The process of claim 18 further comprising including in said overhead reflux a sufficient volume of residue gas to prevent the formation of solids comprising ice, hydrates and mixtures thereof in said overhead reflux.

22. The process of claim 21 wherein up to about 10 percent-by-volume of said residue gas is included in said overhead reflux to prevent the formation of solids comprising ice, hydrates and mixtures thereof.

23. The process of claim 15 wherein said gas feed is cooled by countercurrent heat exchange with a refrigerant stream comprising a portion of said first liquid phase and resulting in partial vaporization of said refrigerant stream;

and

separating said partially vaporized refrigerant stream into a third liquid phase which is introduced into said second distillation column and a third gas phase which is introduced into said first distillation column as a stripping gas.

24. The process of claim 23 wherein said refrigerant stream is drawn from one or more trays below the first feed tray of said first column.

25. The process of claim 23 wherein said refrigerant stream is cooled prior to supplying refrigeration for said gas feed.

26. The process of claim 24 wherein said third gas phase is partially condensed by compressing and cooling.

27. The process of claim 15 wherein the said second gas phase after cooling is separated into a first fraction primarily comprising ethane for introduction into said first distillation column as the overhead reflux and a second fraction for re-introduction into said second distillation column.

28. A process for the separation of C₃₊ hydrocarbons from a hydrocarbon-containing gas feed under pressure, comprising:

introducing a cold gas/condensate feed into a first distillation column at one or more feed trays;

separating said gas/condensate feed in said first distillation column into a first gas phase primarily comprising methane and ethane and into a first liquid phase primarily comprising C₂₊ hydrocarbons;

heating and compressing said first gas phase to produce a residue gas for delivery to a pipeline;

introducing said first liquid phase into a second distillation column at one or more feed trays;

separating said first liquid phase in said second distillation column into a second gas phase primarily comprising ethane and a second liquid phase primarily comprising C₃₊ hydrocarbons;

cooling said second gas phase by countercurrent heat exchange with a condensed liquid withdrawn from said first distillation column at a tray located below said feed trays;

separating said cooled second gas phase into a first fraction primarily comprising ethane and a second fraction primarily comprising C₃₊ hydrocarbons;

introducing into said first distillation column an overhead reflux comprising said first fraction and up to about five percent-by-weight of said residue gas;

introducing into said second distillation column said second fraction; and

recovering from the bottom of said second distillation column substantially pure C₃₊ hydrocarbons comprising at least about 94 percent-by-weight of the C₃₊ hydrocarbons in said gas/condensate feed.

29. The process of claim 28 wherein said gas/condensate feed is cooled by countercurrent heat exchange with a refrigerant stream comprising a portion of said first liquid phase and resulting in partial vaporization of said refrigerant stream.

30. The process of claim 29 further comprising separating said partially vaporized refrigerant stream into a third liquid phase which is introduced into said second distillation column and a third gas phase which is introduced into said first distillation column as a stripping gas.

31. A process for the separation of C₃₊ hydrocarbons from a hydrocarbon-containing gas feed under pressure, comprising:

introducing a cooled gas/condensate feed into a de-methanizer column at one or more feed trays;

separating said gas/condensate feed in said de-methanizer column into a first gas phase primarily comprising methane and ethane and into a first liquid phase primarily comprising C₂₊ hydrocarbons;

introducing said first liquid phase into a de-ethanizer column at one or more feed trays;

separating said first liquid phase in said de-ethanizer column into a second gas phase primarily comprising ethane and a second liquid phase primarily comprising C₃₊ hydrocarbons;

cooling said second gas phase by countercurrent heat exchange with a mixture comprising condensed liquid withdrawn from said de-methanizer column at a tray located below said feed trays and a portion of liquid separated from said gas/condensate feed before its introduction into said de-methanizer column;

separating said cooled second gas phase into a first gaseous fraction primarily comprising ethane and a second liquid fraction;

heating said first gas phase by countercurrent heat exchange with at least one of said first gaseous fraction and said gas feed and thereafter compressing said heated gas phase to produce a residue gas;

cooling and condensing said first gaseous fraction primarily comprising ethane;

introducing into said de-methanizer column as an overhead reflux said cooled and condensed first gaseous fraction primarily comprising ethane;

introducing into said de-ethanizer column said second liquid fraction; and

recovering from the bottom of said de-ethanizer column said second liquid phase primarily comprising C₃₊ hydrocarbons.

32. The process of claim 31 wherein up to about 5 percent-by-volume of said residue gas is included in said overhead reflux.

33. The process of claim 32 wherein the pressure of said 5 percent-by-volume of residue gas is substantially equal to the pressure of said first gaseous fraction.

34. The process of claim 31 further comprising including in said overhead reflux a sufficient volume of residue gas to prevent the formation of solids comprising ice, hydrates and mixtures thereof in said overhead reflux.

35. The process of claim 34 wherein up to about 10 percent-by-volume of said residue gas is included in said overhead reflux to prevent the formation of solids comprising ice, hydrates and mixtures thereof.

36. A process for the separation of C₃₊ hydrocarbons from a hydrocarbon-containing gas feed under pressure, comprising:

introducing a cooled gas/condensate feed into a de-methanizer column at one or more feed trays;

separating said gas/condensate feed in said de-methanizer column into a first gas phase primarily comprising methane and ethane and into a first liquid phase primarily comprising C₂ + hydrocarbons;

using a portion of said first liquid phase as a refrigerant stream to cool said gas feed resulting in partial vaporization of said refrigerant stream;

introducing another portion of said first liquid phase into a de-ethanizer column at one or more feed trays;

separating said first liquid phase in said de-ethanizer column into a second gas phase primarily comprising ethane and a second liquid phase primarily comprising C₃₊ hydrocarbons;

cooling said second gas phase by countercurrent heat exchange with a mixture comprising condensed liquid withdrawn from said de-methanizer column at a tray located below said feed trays and a portion of liquid separated from said gas/condensate feed before its introduction into said de-methanizer column;

separating said cooled second gas phase into a first gaseous fraction primarily comprising ethane and a second liquid fraction;

separating said partially vaporized refrigerant stream into a third liquid phase which is introduced into said de-ethanizer column and a third gas phase which is introduced into said de-methanizer column as a stripping gas;

cooling and condensing said first gaseous fraction primarily comprising ethane;

introducing into said de-methanizer column as an overhead reflux said cooled and condensed first gaseous fraction primarily comprising ethane;

introducing into said de-ethanizer column said second liquid fraction; and

recovering from the bottom of said de-ethanizer column said second liquid phase primarily comprising C₃₊ hydrocarbons.

37. The process of claim 36 wherein said refrigerant stream is drawn from one or more trays located below the first feed tray of said de-methanizer.

38. The process of claim 36 wherein said refrigerant stream is further cooled prior to supplying refrigeration for said feed gas.

39. The process of claim 36 wherein said third gas phase is partially condensed by compressing and cooling.

40. A process for the separation of C₃₊ hydrocarbons from a hydrocarbon-containing gas feed under pressure, comprising:

introducing a cooled gas/condensate feed into a de-methanizer column at one or more feed trays;

separating said gas/condensate feed in said de-methanizer column into a first gas phase primarily comprising methane and ethane and into a first liquid phase primarily comprising C₂ + hydrocarbons;

introducing said first liquid phase into a de-ethanizer column at one or more feed trays;

separating said first liquid phase in said de-ethanizer column into a second gas phase primarily comprising ethane and a second liquid phase primarily comprising C₃ + hydrocarbons;

cooling said second gas phase by countercurrent heat exchange with a mixture comprising condensed liquid withdrawn from said de-methanizer column at a tray located below said feed trays and a portion of liquid separated from said gas/condensate feed before its introduction into said de-methanizer column;

introducing said heated mixture back into said de-methanizer column at a location below the tray from which said condensed liquid was withdrawn;

separating said cooled second gas phase into a first gaseous fraction primarily comprising ethane and a second liquid fraction;

cooling and condensing said first gaseous fraction primarily comprising ethane;

introducing into said de-methanizer column as an overhead reflux said cooled and condensed first gaseous fraction primarily comprising ethane;

introducing into said de-ethanizer column said second liquid fraction; and

recovering from the bottom of said de-ethanizer column said second liquid phase primarily comprising C₃₊ hydrocarbons.

41. A process for the separation of C₃₊ hydrocarbons from a hydrocarbon-containing gas feed under pressure, comprising:

introducing a cooled gas/condensate feed into a first distillation column at one or more feed trays;

separating said gas/condensate feed in said first column into a first gas phase primarily comprising methane and ethane and into a first liquid phase primarily comprising C₂ + hydrocarbons;

introducing said first liquid phase into a second distillation column at one or more feed trays;

separating said first liquid phase in said second distillation column into a second gas phase primarily comprising ethane and a second liquid phase primarily comprising C₃ + hydrocarbons;

cooling and condensing said second gas phase primarily comprising ethane;

introducing into said first distillation column as an overhead reflux at least a portion of said cooled and condensed second gas phase primarily comprising ethane and up to about 5 percent-by-volume of a residue gas recovered from said first gas phase; and

recovering from the bottom of said second distillation column said second liquid phase primarily comprising C₃₊ hydrocarbons.

42. The process of claim 41 wherein the pressure of said 5 percent-by-volume of residue gas is substantially equal to the pressure of said second gas phase.

43. A process for the separation of C₃₊ hydrocarbons from a hydrocarbon-containing gas feed under pressure, comprising:

introducing a cooled gas/condensate feed into a first distillation column at one or more feed trays;

separating said gas/condensate feed in said first column into a first gas phase primarily comprising methane and ethane and into a first liquid phase primarily comprising C₂ + hydrocarbons;

introducing said first liquid phase into a second distillation column at one or more feed trays;

separating said first liquid phase in said second distillation column into a second gas phase primarily comprising ethane and a second liquid phase primarily comprising C₃ + hydrocarbons;

cooling and condensing said second gas phase primarily comprising ethane;

introducing into said first distillation column as an overhead reflux at least a portion of said cooled and condensed second gas phase primarily comprising ethane and up to about 10 percent-by-volume of a residue gas recovered from said first gas phase to prevent the formation in said overhead reflux of solids comprising ice, hydrates and mixtures thereof; and

recovering from the bottom of said second distillation column said second liquid phase primarily comprising C₃₊ hydrocarbons.

44. A process for the separation of C₃₊ hydrocarbons from a hydrocarbon-containing gas feed under pressure, comprising:

introducing a cooled gas/condensate feed into a first distillation column at one or more feed trays;

separating said gas/condensate feed in said first column into a first gas phase primarily comprising methane and ethane and into a first liquid phase primarily comprising C₂ + hydrocarbons;

using a portion of said first liquid phase as a refrigerant stream to cool said gas feed resulting in partial vaporization of said refrigerant stream;

introducing another portion of said first liquid phase into a second distillation column at one or more feed trays;

separating said first liquid phase in said second distillation column into a second gas phase primarily comprising ethane and a second liquid phase primarily comprising C₃ + hydrocarbons;

separating said partially vaporized refrigerant stream into a third liquid phase which is introduced into said second distillation column and a third gas phase which is introduced into said first distillation column as a stripping gas;

cooling and condensing said second gas phase primarily comprising ethane;

introducing into said first distillation column as an overhead reflux at least a portion of said cooled and condensed second gas phase primarily comprising ethane; and

recovering from the bottom of said second distillation column said second liquid phase primarily comprising C₃₊ hydrocarbons.

45. The process of claim 44 wherein said refrigerant stream is drawn from one or more trays below the first feed tray of said first column.

46. The process of claim 44 wherein said refrigerant stream is cooled prior to supplying refrigeration for said gas feed.

47. The process of claim 44 wherein said third gas phase is partially condensed by compressing and cooling.