Integrated processing of natural gas into liquid products

• US 20030136146A1
• Filed: 01/18/2002
• Published: 07/24/2003
• Est. Priority Date: 01/18/2002
• Status: Active Grant

• Current Assignee: BP Corporation North America Incorporated (BP PLC)
• Original Assignee: BP Corporation North America Incorporated (BP PLC)
• Inventors: Fischer-Calderon, Ernesto, Sawchuk, Jeffrey H., Briscoe, Michael D., Gradassi, Michael J.
• Granted Patent: US 6,743,829 B2
• Time in Patent Office: Days
• US Class Current: 62/613
• CPC Class Codes: C01B 2203/0205 containing a reforming step
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/062 Hydrocarbon production, e.g. Fischer-Tropsch process
• CPC Class Codes: C01B 3/34 by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: C01B 3/506 at low temperatures
• CPC Class Codes: F25J 1/0022 Hydrocarbons, e.g. natural gas
• CPC Class Codes: F25J 1/0035 by gas expansion with extraction of work
• CPC Class Codes: F25J 1/004 by flash gas recovery F25J1/0267 takes precedence
• CPC Class Codes: F25J 1/0042 by liquid expansion with extraction of work
• CPC Class Codes: F25J 1/0208 in combination with an internal quasi-closed refrigeration loop, e.g. with deep flash recycle loop F25J1/021 takes precedence
• CPC Class Codes: F25J 1/021 using a deep flash recycle loop
• CPC Class Codes: F25J 1/0229 Integration with a unit for using hydrocarbons, e.g. consuming hydrocarbons as feed stock
• CPC Class Codes: F25J 2200/04 in a dual pressure main column system
• CPC Class Codes: F25J 2200/08 in a triple pressure main column system
• CPC Class Codes: F25J 2200/70 Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
• CPC Class Codes: F25J 2200/74 Refluxing the column with at least a part of the partially condensed overhead gas
• CPC Class Codes: F25J 2205/02 using simple phase separation in a vessel or drum
• CPC Class Codes: F25J 2210/04 Mixing or blending of fluids with the feed stream
• CPC Class Codes: F25J 2215/04 Recovery of liquid products
• CPC Class Codes: F25J 2220/62 Separating low boiling components, e.g. He, H2, N2, Air
• CPC Class Codes: F25J 2230/60 : the fluid being hydrocarbons or 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 2240/30 : Dynamic liquid or hydraulic expansion with extraction of work, e.g. single phase or two-phase turbine
• CPC Class Codes: F25J 2240/40 : Expansion without extracting work, i.e. isenthalpic throttling, e.g. JT valve, regulating valve or venturi, or isentropic nozzle, e.g. Laval
• CPC Class Codes: F25J 2245/02 : Recycle of a stream in general, e.g. a by-pass stream
• 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 2270/90 : External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
• CPC Class Codes: F25J 2280/02 : Control in general, load changes, different modes ("runs"), measurements
• CPC Class Codes: F25J 3/0209 : Natural gas or substitute natural gas
• CPC Class Codes: F25J 3/0233 : separation of CnHm with 1 carbon atom or more
• CPC Class Codes: F25J 3/0257 : separation of nitrogen from air F25J3/04, production of nitrogen in general C01B21/00
• CPC Class Codes: F25J 3/029 : of helium
• CPC Class Codes: F25J 3/061 : Natural gas or substitute natural gas
• CPC Class Codes: F25J 3/0635 : separation of CnHm with 1 carbon atom or more
• CPC Class Codes: F25J 3/066 : separation of nitrogen from air F25J3/04, production of nitrogen in general C01B21/00
• CPC Class Codes: F25J 3/069 : of helium
• CPC Class Codes: F25J 3/0695 : Start-up or control of the process; Details of the apparatus used
• CPC Class Codes: Y02P 20/10 : Process efficiency

Abstract

An integrated process for producing LNG and GTL products is provided comprising cooling natural gas in at least one cooling step so as to provide a cooled natural gas stream; processing the cooled natural gas stream in at least two expansion/separation cycles, each expansion/separation cycle comprising the Substeps of (a) isentropically or isenthalpically expanding at least a portion of the cooled natural gas steam for producing a natural gas vapor component and a LNG component, (b) separating at least a portion of the natural gas vapor component from the LNG component, and (c) repeating substeps (a) through (b) wherein at least a portion of the LNG component from the previous expansion/separation cycle is directed to each successive Substep (a) and wherein the final LNG product is the LNG component after the final separating step and is substantially liquid at substantially atmospheric pressure; and converting at least a portion of one or more of the expansion/separation cycle natural gas vapor components into a GTL product.

Claims

1. An integrated process for producing LNG and GTL products comprising the steps of:

cooling natural gas in at least one cooling step so as to provide a cooled natural gas stream;

processing said cooled natural gas stream in at least two expansion/seperation cycles, each expansion/separation cycle comprising the Substeps of;

a. isentropically or isenthalpically expanding at least a portion of said cooled natural gas steam and producing a natural gas vapor component and a LNG component;

b. separating at least a portion of said natural gas vapor component from said LNG component; and

c. repeating Substeps a. through b.,

wherein at least a portion of said LNG component from said previous expansion/separation cycle is directed to each successive Substep a.,

wherein said final LNG product is said LNG component after said final separating step and is substantially liquid at substantially atmospheric pressure; and

converting at least a portion of one or more of said expansion/separation cycle natural gas vapor components into a GTL product.

2. The integrated process of claim 1 wherein each of said expansion/separation cycles comprise an isenthalpic expansion of said cooled natural gas streams and said LNG components across a Joule Thompson valve wherein the pressure of said cooled natural gas stream and each successive LNG component are each reduced by at least 15 psig.

3. The integrated process of claim 1 wherein said first expansion/separation cycle comprises reducing the pressure of said cooled natural gas stream by at least 30 psig and reducing the temperature of such cooled natural gas stream by at least 10°

F.

4. The integrated process of claim 1 wherein the expanded pressure of said natural gas vapor component and said LNG component from said first expansion/separation cycle step is not less than 75 psia and wherein at least a portion of said natural gas vapor component from said first expansion/separation cycle is directed to said converting step.

5. The integrated process of claim 1 wherein said converting step further comprises:

a pre-reforming step for reducing the molar concentration of ethane and higher boiling point hydrocarbon in said natural gas vapor components and producing a pre-reformed natural gas vapor;

a reforming step for converting at least a portion of said pre-reformed natural gas vapor to synthesis gas;

a downstream GTL product conversion step for converting said synthesis gas into at least one GTL product and a stream of unconverted synthesis gas; and

a recycling step wherein at least a portion of said stream of unconverted synthesis gas is recycled to either said pre-reforming step or said reforming step;

wherein at least a portion of one or more of said natural gas vapor components is directed to at least one step selected from the group consisting of said pre-reforming step, said reforming step, and said recycling step.

6. The integrated process of claim 5 wherein said recycling step comprises a compression step for recycling said stream of unconverted synthesis gas and said one or more of said natural gas vapor components is added upstream of said compression step.

7. The integrated process of claim 1 wherein at least a portion of said GTL product is at least one member selected from the group consisting of products of a Fischer Tropsch reaction, methanol, and dimethyl ether.

8. The integrated process of claim 1 wherein said at least two expansion/separation cycles are conducted without a processing step for separation and removal of NGL'"'"'s.

9. An integrated process for producing LNG and GTL products comprising:

cooling natural gas in at least one cooling step so as to provide a cooled natural gas stream;

isentropically or isenthalpically expanding at least a portion of said cooled natural gas steam in a first expansion step and producing a first natural gas vapor component and a first LNG component;

separating at least a portion of said first natural gas vapor component from said first LNG component;

isentropically or isenthalpically expanding at least a portion of said first LNG component in a second expansion step and producing a second natural gas vapor component and a second LNG component;

separating at least a portion of said second natural gas vapor component from said second LNG component; and

converting at least a portion of one or more of said first and second natural gas vapor components into a GTL product.

10. The integrated process of claim 9 wherein said first and second expansion steps each comprise an isenthalpic expansion of said cooled natural gas stream and said first LNG component across a Joule Thompson valve wherein the pressure of said cooled natural gas stream and said first LNG component are each reduced by at least 15 psig.

11. The integrated process of claim 9 wherein said first expansion step comprises reducing the pressure of such cooled natural gas stream by at least 30 psig and reducing the temperature of such cooled natural gas stream by at least 10°

F.

12. The integrated process of claim 9 wherein said first natural gas component comprises a higher mole percent of nitrogen and a lower mole percent of ethane and all higher boiling point hydrocarbon than said cooled natural gas stream.

13. The integrated process of claim 9 wherein said second LNG product is substantially liquid at substantially atmospheric pressure.

14. The integrated process of claim 9 wherein the expanded pressure of said first expansion step is not less than 75 psia and wherein at least a portion of said first natural gas vapor component is directed to said converting step.

15. The integrated process of claim 9 wherein said converting step further comprises:

a pre-reforming step for reducing the molar concentration of ethane and higher boiling point hydrocarbon in said first or second natural gas vapor components and producing a pre-reformed natural gas vapor;

a reforming step for converting at least a portion of said pre-reformed natural gas vapor to synthesis gas;

a downstream GTL product conversion step for converting said synthesis gas into at least one GTL product and a stream of unconverted synthesis gas; and

a recycling step wherein at least a portion of said stream of unconverted synthesis gas is recycled to either said pre-reforming step or said reforming step;

wherein at least a portion of said first or second natural gas vapor components is directed to at least one step selected from the group consisting of said pre-reforming step, said reforming step, and said recycling step.

16. The integrated process of claim 15 wherein said recycling step comprises a compression step for recycling said stream of unconverted synthesis gas and at least a portion of said first or second natural gas vapor component is added upstream of said compression step.

17. The integrated process of claim 15 wherein at least a portion of said first natural gas vapor component becomes a fuel source for at least one member selected from the group consisting of a LNG refrigeration compressor and said reforming step.

18. The integrated process of claim 9 wherein at least a portion of said GTL product is at least one member selected from the group consisting of products of a Fischer Tropsch reaction, methanol, and dimethyl ether.

19. The integrated process of claim 9 wherein said first and second expansion steps and any processing steps conducted therebetween are conducted without a processing step for separation and removal of NGL'"'"'s.

20. An integrated process for producing LNG and GTL products comprising:

cooling natural gas in at least one cooling step so as to provide a cooled natural gas stream;

isentropically or isenthalpically expanding at least a portion of said cooled natural gas steam in a first autorefrigeration step and producing a first natural gas vapor component and a first LNG component;

separating at least a portion of said first natural gas vapor component from said first LNG component;

isentropically or isenthalpically expanding at least a portion of said first LNG component in a second autorefrigeration step and producing a second natural gas vapor component and a second LNG component;

separating at least a portion of said second natural gas vapor component from said second LNG component;

compressing at least a portion of one or more of said first and second natural gas vapor components and producing a compressed natural gas feedstock having a higher temperature than either of said first and second natural gas vapor components; and

converting at least a portion of said compressed natural gas feedstock to a GTL product.

21. The integrated process of claim 20 wherein the expanded pressure of said first expansion step is not less than 75 psia and wherein at least a portion of said first natural gas vapor component is directed to said converting step.

22. The integrated process of claim 20 wherein:

the temperature of said cooled natural gas stream is not more than −

20°

F.;

the temperature of said cooled natural gas stream is reduced by at least 3°

F. in said first autorefrigeration step; and

the temperature of said second natural gas vapor component is at least 3°

F. below that of said first LNG component.

23. The integrated process of claim 20 wherein said first and second autorefrigeration steps each comprise an isenthalpic expansion of said cooled natural gas stream and said first LNG component across a Joule Thompson valve wherein the pressure of said cooled natural gas stream and said first LNG component are each reduced by at least 15 psig.

24. The integrated process of claim 20 wherein said first autorefrigeration step comprises reducing the pressure of such cooled natural gas stream by at least 30 psig and reducing the temperature of such cooled natural gas stream by at least 10°

F.

25. The integrated process of claim 20 wherein said converting step further comprises:

a pre-reforming step for reducing the molar concentration of ethane and higher boiling point hydrocarbon of said compressed natural gas feedstock and producing a pre-reformed natural gas feedstock;

a reforming step for converting at least a portion of said pre-reformed natural gas feedstock to synthesis gas;

a downstream conversion step comprising at least one reaction step selected from the group consisting of conversion of synthesis gas to hydrogen, conversion of synthesis gas to methanol, conversion of synthesis gas to dimethyl ether, and conversion of synthesis gas to a product of a Fischer Tropsch reaction, said downstream conversion step converting said synthesis gas into said GTL product and a stream of unconverted synthesis gas; and

a recycling step wherein at least a portion of said stream of unconverted synthesis gas is recycled to either said pre-reforming step or said reforming step;

wherein at least a portion of said compressed natural gas feedstock is directed to at least one step selected from the group consisting of said pre-reforming step, said reforming step, and said recycling step.

26. The integrated process of claim 20 wherein said first and second autorefrigeration steps and any processing steps conducted therebetween are conducted without a processing step for separation and removal of NGL'"'"'s.

27. An integrated process for producing LNG and GTL products comprising:

cooling natural gas in at least one cooling step so as to provide a cooled natural gas stream;

isentropically or isenthalpically expanding at least a portion of said cooled natural gas steam in a first autorefrigeration step and producing a first natural gas vapor component and a first LNG component;

separating at least a portion of said first natural gas vapor component from said first LNG component;

isentropically or isenthalpically expanding at least a portion of said first LNG component in a second autorefrigeration step and producing a second natural gas vapor component and a second LNG component;

separating at least a portion of said second natural gas vapor component from said second LNG component;

isentropically or isenthalpically expanding at least a portion of said second LNG component in a third autorefrigeration step and producing a third natural gas vapor component and a LNG product;

separating at least a portion of said third natural gas vapor component from said LNG product; and

converting at least a portion of one or more of said first, second and third natural gas vapor components into a GTL product.

28. The integrated process of claim 27 wherein said LNG product is substantially liquid at substantially atmospheric pressure.

29. The integrated process of claim 27 wherein said portion of one or more of said first, second and third natural gas vapor components is compressed producing a compressed GTL feedstock having a higher temperature than any of said first, second and third natural gas vapor components exiting said first, second and third autorefrigeration steps.

30. The integrated process of claim 27 wherein at least a portion of either or both of said first or second natural gas vapor components is converted into GTL product and at least a portion of said third natural gas vapor is compressed, refrigerated and directed to any one or more of said cooled natural gas stream, said first LNG component, said second LNG component, or said LNG product.

31. The integrated process of claim 27 wherein said first and third autorefrigeration steps and any processing steps conducted therebetween are conducted without a processing step for separation and removal of NGL'"'"'s.

32. A LNG product produced by a process comprising the steps of:

cooling natural gas in at least one cooling step so as to provide a cooled natural gas stream;

processing said cooled natural gas stream in at least two expansion/seperation cycles, each expansion/separation cycle comprising the Substeps of;

a. isentropically or isenthalpically expanding at least a portion of said cooled natural gas steam and producing a natural gas vapor component and a LNG component;

b. separating at least a portion of said natural gas vapor component from said LNG component; and

d. repeating Substeps a. through b.,

wherein at least a portion of said LNG component from said previous expansion/separation cycle is directed to each successive Substep a., and

wherein said final LNG product is said LNG component after said final separating step and is substantially liquid at substantially atmospheric pressure; and

converting at least a portion of one or more of said expansion/separation cycle natural gas vapor components into a GTL product.

33. The LNG product of claim 32 wherein said LNG product comprises:

not more than 2.0 mole percent of nitrogen;

not more than 1.0 mole percent of helium; and

not more than 18 mole percent of the total of ethane and all hydrocarbons having a boiling point greater than ethane.

34. The LNG product of claim 32 wherein the heating value of said LNG product is at least 1000 Btu/scf and not more than 1200 Btu/scf.

35. The LNG product of claim 32 wherein said LNG product comprises:

not more than 0.3 mole percent of nitrogen;

not more than 0.2 mole percent of the total of helium; and

not less than 18 mole percent of the total of ethane and all hydrocarbons having a boiling point greater than ethane.

36. The LNG product of claim 35 wherein the heating value of said LNG product is not less than 1200 and not more than 1600.

37. The LNG product of claim 35:

wherein said converting step comprises converting at least a portion of said natural gas vapor component into Fischer Tropsch reaction products;

wherein at least a portion of said Fischer Tropsch reaction products directly or after subsequent processing of said Fischer Tropsch reaction products, comprises at least one heavier hydrocarbon selected from the group consisting of ethane, propane, and butane; and

wherein said LNG product comprises at least a portion of said at least one heavier hydrocarbon produced from said converting step.