Mixed decyl mercaptans compositions and methods of making same

Patent metadata

Field	Value
Publication number	US-9738601-B2
Application number	US-201615296837-A
Country	US
Kind code	B2
Filing date	Oct 18, 2016
Priority date	Dec 28, 2015
Publication date	Aug 22, 2017
Grant date	Aug 22, 2017

Abstract

Compositions comprising branched C 10 mercaptans selected from the group consisting of 5-methyl-1-mercapto-nonane, 3-propyl-1-mercapto-heptane, 4-ethyl-1-mercapto-octane, 2-butyl-1-mercapto-hexane, 5-methyl-2-mercapto-nonane, 3-propyl-2-mercapto-heptane, 4-ethyl-2-mercapto-octane, 5-methyl-5-mercapto-nonane, and combinations thereof.

First claim

What is claimed is:

1. A process comprising:
reacting hydrogen sulfide (H 2 S) and a feedstock comprising one or more branched C 10 monoolefins in the presence of an initiating agent to produce a crude composition, wherein the one or more branched C 10 monoolefins comprise 5-methyl-1-nonene, 3-propyl-1-heptene, 4-ethyl-1-octene, 2-butyl-1-hexene, or combinations thereof; and
recovering a reaction product from the crude compositions, wherein the reaction product comprises mercaptans, wherein at least 50 wt. % of the mercaptans are 1) branched C 10 mercaptans selected from the group consisting of 5-methyl-1-mercapto-nonane, 3-propyl-1-mercapto-heptane, 4-ethyl-1-mercapto-octane, 2-butyl-1-mercapto-hexane, 5-methyl-2-mercapto-nonane, 3-propyl-2-mercapto-heptane, 4-ethyl-2-mercapto-octane, and combinations thereof; and 2) 5-methyl-5-mercapto-nonane.

2. The process of claim 1 , wherein the reaction product comprises at least about 25 wt. % branched C 10 mercaptans.

3. A process comprising:
reacting hydrogen sulfide (H 2 S) and a feedstock comprising one or more branched C 10 monoolefins in the presence of an initiating agent to produce a crude composition, wherein the one or more branched C 10 monoolefins comprise 5-methyl-1-nonene, 3-propyl-1-heptene, 4-ethyl-1-octene, 2-butyl-1-hexene, or combinations thereof; and
recovering a reaction product from the crude composition, wherein the reaction product comprises at least about 5 wt. % branched C 20 sulfides represented by structure R 1 —S—R 2 , wherein R 1 and R 2 are each independently a branched C 10 alkyl group derived from the one or more branched C 10 monoolefins, and wherein the branched C 10 alkyl group is selected from the group consisting of

wherein * designates the attachment point to the S atom of the branched C 20 sulfide.

4. The process of claim 1 , wherein the reaction product comprises (i) at least about 50 wt. % mercaptans; and (ii) at least about 10 wt. % sulfides, wherein at least about 50 wt. % of the sulfides are branched C 20 sulfides represented by the structure R 1 —S—R 2 , wherein R 1 and R 2 are each independently a functional group derived from the one or more branched C 10 monoolefins.

5. The process of claim 1 , wherein the initiating agent comprises ultraviolet radiation.

6. The process of claim 5 , wherein the initiating agent further comprises a phosphite promoter, a photoinitiator, or both.

7. The process of claim 1 , wherein the initiating agent comprises an acid catalyst.

8. The process of claim 1 , wherein the initiating agent comprises a hydrodesulfurization catalyst.

9. The process of claim 5 , wherein the crude composition comprises C 10 mercaptans comprising from about 70 wt. % to about 95 wt. % C 10 primary mercaptans, from about 10 wt. % to about 20 wt. % C 10 secondary mercaptans, and from about 0 wt. % to about 5 wt. % C 10 tertiary mercaptans.

10. The process of claim 7 , wherein the crude composition comprises C 10 mercaptans comprising from about 0 wt. % to about 5 wt. % C 10 primary mercaptans, from about 80 wt. % to about 95 wt. % C 10 secondary mercaptans, and from about 5 wt. % to about 20 wt. % C 10 tertiary mercaptans.

11. The process of claim 8 , wherein the crude composition comprises C 10 mercaptans comprising from about 5 wt. % to about 30 wt. % C 10 primary mercaptans, from about 60 wt. % to about 75 wt. % C 10 secondary mercaptans, and from about 5 wt. % to about 15 wt. % C 10 tertiary mercaptans.

12. The process of claim 1 , further comprising, prior to the reacting, separating the feedstock comprising the one or more branched C 10 monoolefins from an effluent stream obtained from a 1-hexene production process.

13. The process of claim 1 , wherein the reacting occurs at a temperature of from about 0° C. to about 300° C. and at a H 2 S to olefin molar ratio of from about 1:1 to about 15:1.

14. The process of claim 6 , wherein the initiating agent further comprises the phosphite promoter, wherein the phosphite promoter is used in an amount of from about 0.01 wt. % to about 5 wt. % based on a weight of olefins.

15. The process of claim 14 , wherein the phosphite promoter is characterized by formula P(OR 5 ) 3 , wherein each R 5 can independently be a C 1 -C 18 hydrocarbyl group.

16. The process of claim 15 , which each R 5 can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group; a phenyl group, a tolyl group, a xylyl group, or a naphthyl group.

17. The process of claim 6 , wherein the initiating agent further comprises the photoinitiator, wherein the photoinitiator is used in an amount of from about 0.05 wt. % to about 5 wt. % based on the weight of olefins present in the feed mixture.

18. The process of claim 17 , wherein the photoinitiator comprises 1-hydroxy-cyclohexyl-phenyl-ketone, benzophenone, Bis-(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methy-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-1-propanone, or combinations thereof.

19. The process of claim 7 , wherein the acid catalyst comprises an acid washed clay; an acid washed bentonite; a tetrafluoroethylene polymer resin modified with perfluorovinyl ether groups terminated with sulfonate groups; a macroreticular, sulfonated, crosslinked copolymer of styrene and divinyl benzene; or combinations thereof.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Matson Michael S
• Byers Jim D
• Kreider Jason L

Classifications

• C07C319/04 Primary

  by addition of hydrogen sulfide or its salts to unsaturated compounds · CPC title

• C07C321/04 Primary

  of an acyclic saturated carbon skeleton · CPC title

• C07C319/16

  by addition of hydrogen sulfide or its salts to unsaturated compounds · CPC title

• C07C321/14

  of an acyclic saturated carbon skeleton · CPC title

• B01J2219/1203

  Incoherent waves · CPC title