Process and apparatus for the production of heavier hydrocarbons from gaseous light hydrocarbons

• US 4,833,170 A
• Filed: 02/05/1988
• Issued: 05/23/1989
• Est. Priority Date: 02/05/1988
• Status: Expired due to Term

• Current Assignee: REG Synthetic Fuels, LLC (Chevron Corp.)
• Original Assignee: G.T.G., Inc.
• Inventors: Agee, Kenneth L.
• Primary Examiner(s): MARS, HOWARD
• Application Number:
  US07/152,878
• Time in Patent Office: 473 Days
• Field of Search: 518/703, 518/704
• US Class Current: 518/703
• CPC Class Codes: C07C 1/0485 Set-up of reactors or accessories; Multi-step processes
• CPC Class Codes: C07C 2521/04 Alumina
• CPC Class Codes: C07C 2521/08 Silica
• CPC Class Codes: C07C 2521/12 Silica and alumina
• CPC Class Codes: C07C 2523/75 Cobalt

Abstract

A process and apparatus for the production of heavier hydrocarbons from one or more gaseous light hydrocarbons is provided. The process comprises reacting the gaseous light hydrocarbons by autothermal reforming with air in the presence of recycled carbon dioxide and steam to produce a synthesis gas stream containing hydrogen and carbon monoxide. The synthesis gas stream is reacted in the presence of a hydrocarbon synthesis catalyst containing cobalt to form heavier hydrocarbons and water from the hydrogen and carbon monoxide. The heavier hydrocarbons and water are separated, and the resulting residue gas stream is subjected to catalytic combustion with additional air to form a product stream comprising carbon dioxide and nitrogen. The carbon dioxide is separated from the nitrogen to produce a nitrogen product stream, and at least a portion of the separated carbon dioxide is recycled to the autothermal reforming step.

Claims

1. A process for the production of heavier hydrocarbons from one or more gaseous light hydrocarbons comprising the steps of:

(a) reacting said gaseous light hydrocarbons with air to partially oxidize a portion thereof and produce a gas stream comprising unreacted light hydrocarbons, hydrogen, carbon monoxide and nitrogen;

(b) reacting the gas stream from step (a) with steam and carbon dioxide in the presence of a steam reforming catalyst to convert a substantial portion of the unreacted light hydrocarbons therein to additional hydrogen and carbon monoxide and to produce a synthesis gas stream containing hydrogen and carbon monoxide in desired proportion;

(c) reacting the synthesis gas stream from step (b) in the presence of a hydrocarbon synthesis catalyst containing cobalt to form heavier hydrocarbons and water from hydrogen and carbon monoxide in said stream;

(d) separating heavier hydrocarbons and water from the product stream of step (c) leaving a residue gas stream comprised of unreacted hydrogen and carbon monoxide, light hydrocarbons, carbon dioxide and nitrogen;

(e) subjecting the residue gas stream from step (d) to catalytic combustion with additional air to form a product stream comprising carbon dioxide, water vapor and nitrogen;

(f) separating carbon dioxide from the product stream of step (e); and

(g) utilizing at least a portion of the carbon dioxide separated in step (f) for carrying out step (b).

2. The process of claim 1 wherein steps (a) and (b) are each carried out at a pressure in the range of from about atmospheric to about 100 psig and a temperature in the range of from about 1500°

F. to about 3500°

F.

3. The process of claim 2 wherein step (c) is carried out at substantially the same pressure as steps (a) and (b) and at a temperature in the range of from about 350°

F. to about 550°

F.

4. The process of claim 1 wherein said hydrocarbon synthesis catalyst comprises from about 5 to about 50 parts by weight cobalt per 100 parts by weight of silica, alumina or silica-alumina support.

5. The process of claim 4 wherein said catalyst is further characterized to include from about 0.1 to about 5 parts by weight of potassium per 100 parts by weight of said support.

6. The process of claim 1 wherein the rates of steam and carbon dioxide utilized in carrying out step (b) are varied to control the molar ratio of hydrogen to carbon monoxide in the synthesis gas stream produced at substantially 2:

1.

7. The process of claim 1 wherein the catalytic combustion of step (e) is carried out at a pressure in the range of from about atmospheric to about 100 psig and a temperature in the range of from about 400°

F. to about 1000°

F.

8. The process of claim 1 wherein step (d) comprises:

cooling said product stream of step (c) whereby said heavier hydrocarbons and water are condensed; and

withdrawing said condensed heavier hydrocarbons and water from the resulting residue gas stream.

9. The process of claim 8 which is further characterized to include the steps of:

separating said heavier hydrocarbons from said water; and

utilizing at least a portion of said separated water to form steam used in step (b).

10. The process of claim 9 which is further characterized to include the steps of:

subjecting said separated hydrocarbons to fractionation to produce a product stream containing selected hydrocarbon components and a residue hydrocarbon stream; and

recycling said residue hydrocarbon stream to step (a).

11. A process for the production of heavier hydrocarbons from one or more gaseous light hydrocarbons comprising the steps of:

(a) reacting said gaseous light hydrocarbons with air to partially oxidize a portion thereof and produce a gas stream comprising unreacted light hydrocarbons, hydrogen, carbon monoxide and nitrogen;

(b) reacting the gas stream from step (a) with steam and carbon dioxide in the presence of a steam reforming catalyst containing nickle to convert a substantial portion of the unreacted light hydrocarbons therein to additional hydrogen and carbon monoxide to produce a synthesis gas stream containing hydrogen and carbon monoxide in a molar ratio of about 2;

1;

(c) reacting the synthesis gas stream from step (b) in the presence of a hydrocarbon synthesis catalyst containing cobalt to form heavier hydrocarbons and water from hydrogen and carbon monoxide in said stream;

(d) cooling the product stream of step (c) whereby said heavier hydrocarbons and water are condensed;

(e) withdrawing said condensed heavier hydrocarbons and water from the resulting residue gas stream;

(f) separating said condensed heavier hydrocarbons from said condensed water;

(g) utilizing at least a portion of said separated water to form steam used in step (b);

(h) subjecting the residue gas stream from step (e) to catalytic combustion with additional air to form a product stream comprising carbon dioxide, water vapor and nitrogen;

(i) separating carhon dioxide from the product stream of step (h);

(j) utilizing at least a portion of the carbon dioxide separated in step (i) in carrying out step (b); and

(k) varying the rates of water utilized in accordance with step (g) and carbon dioxide utilized in accordance with step (j) for carrying out step (b) to thereby control the molar ratio of hydrogen to carbon monoxide in the synthesis gas stream produced in step (b) at about 2;

1.

12. The process of claim 11 wherein steps (a) and (b) are each carried out at a pressure in the range of from about atmospheric to about 100 psig and a temperature in the range of from about 1500°

F. to about 3500°

F.

13. The process of claim 12 wherein step (c) is carried out at substantially the same pressure as steps (a) and (b) and at a temperature in the range of from about 350°

F. to about 550°

F.

14. The process of claim 11 wherein said hydrocarbon synthesis catalyst comprises from about 5 to about 50 parts by weight cobalt per 100 parts by wweight of silica, alumina or silica-alumina support.

15. The process of claim 14 wherein said catalyst is further characterized to include from about 0.1 to about 5 parts by weight of potassium per 100 parts by weight of said support.

16. The process of claim 11 wherein the catalytic combustion of step (e) is carried out at a pressure in the range of from about atmospheric to about 100 psig and a temperature in the range of from about 400°

F. to about 1000°

F.

17. The process of claim 11 which is further characterized to include the steps of:

subjecting said separated condensed heavier hydrocarbons from step (f) to fractionation to produce a hydrocarbon product stream containing selected hydrocarbon components and a residue hydrocarbon stream; and

recycling said residue hydrocarbon stream to step (a).

18. The process of claim 11 which is further characterized to include the step of exchanging heat between said gaseous light hydrocarbons prior to carrying out step (a) with the synthesis gas stream produced in step (b).

19. The process of claim 18 wherein steps (a) and (b) are carried out in a single synthesis gas generation vessel.

20. The process of claim 11 which is further characterized to include the steps of:

prior to carrying out step (h), reacting the residue gas stream produced in step (e) a second time in the presence of a hydrocarbon synthesis catalyst containing cobalt to form additional heavier hydrocarbons and water from unreacted hydrogen and carbon monoxide contained in said residue gas stream;

cooling the resulting product stream whereby said additional heavier hydrocarbons and water are condensed; and

withdrawing said condensed heavier hydrocarbons and water from the resulting residue gas stream.