Removal of sulfur from naphtha

• US 10,443,001 B2
• Filed: 08/11/2017
• Issued: 10/15/2019
• Est. Priority Date: 10/28/2016
• Status: Active Grant

• Current Assignee: UOP Llc (Honeywell International Inc.)
• Original Assignee: UOP Llc (Honeywell International Inc.)
• Inventors: Jani, Priyesh Jayendrakumar, Bisht, Deepak, Khan, Tuhin Suvra, Rokkam, Ram Ganesh, Roy, Pijus Kanti, Zink, Steven F., Kumar, Avnish
• Primary Examiner(s): Boyer, Randy
• Assistant Examiner(s): Valencia, Juan C
• Application Number:
  US15/675,025
• Publication Number:
  US 20180119032A1
• Time in Patent Office: 795 Days
• CPC Class Codes: B01D 3/14 Fractional distillation or use of a fractionation or rectification column
• CPC Class Codes: B01D 3/143 by two or more of a fractionation, separation or rectification step
• CPC Class Codes: B01D 53/1468 Removing hydrogen sulfide
• CPC Class Codes: B01D 53/52 Hydrogen sulfide
• CPC Class Codes: B01J 23/85 Chromium, molybdenum or tungsten
• CPC Class Codes: C07C 15/20 Polycyclic condensed hydrocarbons
• CPC Class Codes: C07C 5/02 by hydrogenation simultaneous hydrogenation and dehydrogenation C07C5/52
• CPC Class Codes: C07C 7/148 by treatment giving rise to a chemical modification of at least one compound
• CPC Class Codes: C07C 9/22 with more than fifteen carbon atoms
• CPC Class Codes: C07D 335/08 Naphthothiopyrans; Hydrogenated naphthothiopyrans
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 35/04 Catalytic reforming
• CPC Class Codes: C10G 45/02 to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
• CPC Class Codes: C10G 45/44 Hydrogenation of the aromatic hydrocarbons

Abstract

A process and apparatus for reducing the sulfur content of naphtha. The process includes introducing at least a portion of a naphtha feed stream to a selective hydrodesulfurization zone under selective hydrodesulfurization conditions in the presence of a selective hydrodesulfurization catalyst to form a low sulfur stream which contains mercaptan and thiophene compounds. At least a portion of the low sulfur stream is separated into at least two streams, a mercaptan rich stream containing mercaptan and thiophene compounds and an overhead stream containing hydrogen sulfide and liquid petroleum gas. The mercaptan rich stream is treated in an adsorbent zone to remove at least a portion of the mercaptan and thiophene compounds to form a mercaptan lean stream.

Claims

1. A process for reducing the sulfur content of full range naphtha comprising:

introducing at least a portion of a naphtha feed stream to a selective hydrodesulfurization zone under selective hydrodesulfurization conditions in the presence of a selective hydrodesulfurization catalyst to form a low sulfur stream, the low sulfur stream containing mercaptan compounds and thiophene compounds;

separating at least a portion of the low sulfur stream into at least two streams, a mercaptan rich stream containing mercaptan compounds and thiophene compounds, and an overhead stream containing hydrogen sulfide and liquid petroleum gas, and a thiophene rich stream; and

treating the mercaptan rich stream in an adsorbent zone to remove at least a portion of the mercaptan compounds and the thiophene compounds to form a mercaptan lean stream.

2. The process of claim 1 wherein the mercaptan rich stream has a T5 boiling point of about 20°

C. to about 40°

C., a T95 boiling point of about 95°

C. to about 105°

C., and a final boiling point of about 110°

C. to about 130°

C., and the second mercaptan lean stream has a T5 boiling point of about 100°

C. to about 110°

C., a T95 boiling point of about 210°

C. to about 240°

C., and a final boiling point of about 250°

C. to about 280°

C.

3. The process of claim 1 wherein the second mercaptan lean stream has a T5 boiling point of about 20°

C. to about 40°

C., a T95 boiling point of about 55°

C. to about 65°

C., and a final boiling point of about 70°

C. to about 75°

C., and the mercaptan rich stream has a T5 boiling point of about 60°

C. to about 70°

C., a T95 boiling point of about 210°

C. to about 240°

C., and a final boiling point of about 250°

C. to about 280°

C.

4. The process of claim 1 wherein the mercaptan rich stream has a T5 boiling point of about 20°

C. to about 40°

C., a T95 boiling point of about 210°

C. to about 240°

C., and a final boiling point of about 250°

C. to about 280°

C.

5. The process of claim 1, wherein the mercaptan rich stream has a T5 boiling point of about 20°

C. to about 40°

C., a T95 boiling point of about 95°

C. to about 105°

C., and a final boiling point of about 110°

C. to about 130°

C., and the thiophene rich stream has a T5 boiling point of about 100°

C. to about 110°

C., a T95 boiling point of about 210°

C. to about 240°

C., and a final boiling point of about 250°

C. to about 280°

C.

6. The process of claim 1 wherein the adsorbent zone contains an adsorbent comprising at least one of a molecular sieve, metal loaded alumina, reactive metal adsorbent, and an alumina-zeolite composite adsorbent.

7. The process of claim 1 wherein the adsorbent zone comprises at least two adsorbent beds.

8. The process of claim 1 wherein the mercaptan rich stream alternately flows to the at least two adsorbent beds.

9. The process of claim 1 further comprising:

treating the naphtha feed stream in a caustic extraction zone to form a reduced sulfur stream;

separating the reduced sulfur stream into an overhead stream having a T5 boiling point of about 0°

C. to about 10°

C., a T95 boiling point of about 55°

C. to about 65°

C., and a final boiling point of about 65°

C. to about 70°

C., and a bottoms stream having a T5 boiling point of about 60°

C. to about 70°

C., a T95 boiling point of about 210°

C. to about 240°

C., and a final boiling point of about 250°

C. to about 280°

C., and wherein the bottoms stream comprises the at least the portion of the naphtha feed stream being introduced to the selective hydrodesulfurization zone.

10. The process of claim 1 further comprising:

treating the naphtha feed stream in a selective hydrogenation reaction zone under selective hydrogenation conditions in the presence of a selective hydrogenation catalyst to form a hydrogenated naphtha feed stream; and

wherein introducing the at least the portion of the naphtha feed stream to the selective hydrodesulfurization zone comprises introducing at least a portion of the hydrogenated naphtha feed stream to the selective hydrodesulfurization zone.

11. The process of claim 10 further comprising:

separating the low sulfur stream into a gas stream and a liquid low sulfur stream; and

wherein separating the at least the portion of the low sulfur stream into the at least two streams comprises separating the liquid low sulfur stream into the at least two streams.

12. A process for reducing the sulfur content of full range naphtha comprising:

introducing at least a portion of a naphtha feed stream to a selective hydrodesulfurization zone under selective hydrodesulfurization conditions in the presence of a selective hydrodesulfurization catalyst to form a low sulfur stream, the low sulfur stream containing mercaptan compounds and thiophene compounds;

separating at least a portion of the low sulfur stream into at least three streams, a mercaptan rich stream containing mercaptan compounds and thiophene compounds, an overhead stream containing hydrogen sulfide and liquid petroleum gas; and

a second mercaptan lean stream;

treating the mercaptan rich stream in an adsorbent zone to remove at least a portion of the mercaptan compounds and the thiophene compounds to form a first mercaptan lean stream.

17. The process of claim 12 wherein the mercaptan rich stream has a T5 boiling point of about 20°

C. to about 40°

C., a T95 boiling point of about 95°

C. to about 105°

C., and a final boiling point of about 110°

C. to about 130°

C., and the second mercaptan lean stream has a T5 boiling point of about 100°

C. to about 110°

C., a T95 boiling point of about 210°

C. to about 240°

C., and a final boiling point of about 250°

C. to about 280°

C.

18. The process of claim 12 wherein the second mercaptan lean stream has a T5 boiling point of about 20°

C. to about 40°

C., a T95 boiling point of about 55°

C. to about 65°

C., and a final boiling point of about 70°

C. to about 75°

C., and the mercaptan rich stream has a T5 boiling point of about 60°

C. to about 70°

C., a T95 boiling point of about 210°

C. to about 240°

C., and a final boiling point of about 250°

C. to about 280°

C.

13. An apparatus for reducing the sulfur content of naphtha comprising:

a selective hydrodesulfurization zone having an inlet and an outlet;

a stripper column having an inlet, an overhead vapor outlet, and a liquid outlet, the outlet of the selective hydrodesulfurization zone being in fluid communication with the inlet of the stripper column;

an adsorbent zone having an inlet and an outlet, the liquid outlet of the stripper column being in fluid communication with the inlet of the adsorbent zone;

a caustic extraction zone having an inlet and an outlet; and

a splitter column having an inlet, an overhead outlet, and a liquid outlet, the outlet of the caustic extraction zone being in fluid communication with the inlet of the splitter column, and the liquid outlet of the splitter column being in fluid communication with the inlet of the selective hydrodesulfurization zone.

14. The apparatus of claim 13 wherein the stripper column has a second liquid outlet, and further comprising:

a second adsorbent zone having an inlet and an outlet, the second liquid outlet of the stripper column being in fluid communication with the inlet of the second adsorbent zone.

15. The apparatus of claim 13 further comprising:

a selective hydrogenation reaction zone having an inlet and an outlet, the outlet of the selective hydrogenation reaction zone being in fluid communication with the inlet of the selective hydrodesulfurization zone.

16. The apparatus of claim 15 further comprising:

a separator having an inlet, and vapor outlet, and a liquid outlet, the inlet of the separator being in fluid communication with the outlet of the selective hydrodesulfurization zone, the liquid outlet of the separator being in fluid communication with the inlet of the stripper column.