Mixed decyl mercaptans compositions and methods of making same

Patent metadata

Field	Value
Publication number	US-10011564-B2
Application number	US-201715669097-A
Country	US
Kind code	B2
Filing date	Aug 4, 2017
Priority date	Dec 28, 2015
Publication date	Jul 3, 2018
Grant date	Jul 3, 2018

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. Compositions comprising C 11+ mercaptans, wherein the C 11+ mercaptans are characterized by structure R 6 —SH, wherein R 6 is an alkyl group derived from one or more C 11+ monoolefins, and wherein the one or more C 11+ monoolefins comprise C 11 internal monoolefins, C 12 internal monoolefins, C 13 internal monoolefins, C 14 internal monoolefins, 1-tetradecene, 1-hexadecene, or 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 C 11+ monoolefins in the presence of an initiating agent to produce a C 11+ mercaptans crude composition, wherein the feedstock comprises at least about 70 wt. % of one or more C 11+ monoolefins, based on the total weight of the feedstock, and wherein the C 11+ monoolefins comprise C 11 and C 12 internal monoolefins; C 13 and C 14 internal monoolefins; C 14 and C 16 linear alpha monoolefins; or combinations thereof; wherein the C 11+ mercaptans crude composition comprises less than about 10 wt. % C 22+ sulfides, based on the total weight of the crude composition, wherein the C 22+ sulfides are characterized by structure R 7 —S—R 8 , and wherein both R 7 and R 8 are each independently a functional group derived from the one or more C 11+ monoolefins.

2. The process of claim 1 , wherein the feedstock comprises (A) at least about 30 wt. % C 11 internal monoolefins, and (B) at least about 40 wt. % C 12 internal monoolefins; based on the total weight of the feedstock.

3. The process of claim 1 , wherein the feedstock comprises (A) at least about 35 wt. % C 13 internal monoolefins, and (B) at least about 35 wt. % C 14 internal monoolefins; based on the total weight of the feedstock.

4. The process of claim 1 , wherein the feedstock comprises (A) at least about 50 wt. % 1-tetradecene, and (B) at least about 20 wt. % 1-hexadecene; based on the total weight of the feedstock.

5. The process of claim 1 further comprising recovering a reaction product from the C 11+ mercaptans crude composition, wherein the reaction product comprises at least about 50 wt. % C 11+ mercaptans, based on the total weight of the reaction product, wherein the C 11+ mercaptans are characterized by structure R 6 —SH, wherein R 6 is an alkyl group derived from the one or more C 11+ monoolefins, and wherein the C 11+ monoolefins comprise C 11 internal monoolefins, C 12 internal monoolefins, C 13 internal monoolefins, C 14 internal monoolefins, 1-tetradecene, 1-hexadecene, or combinations thereof.

6. The process of claim 5 , wherein the reaction product further comprises less than about 20 wt. %, C 22+ sulfides, based on the total weight of the reaction product, wherein the C 22+ sulfides are characterized by structure R 7 —S—R 8 , wherein both R 7 and R 8 are each independently an alkyl group derived from the one or more C 11+ monoolefins, and wherein the C 11+ monoolefins comprise C 11 internal monoolefins, C 12 internal monoolefins, C 13 internal monoolefins, C 14 internal monoolefins, 1-tetradecene, 1-hexadecene, or combinations thereof.

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

8. The process of claim 7 , wherein the initiating agent further comprises a phosphite promoter, a photoinitiator, a sulfur scavenger, an antioxidant, or combinations thereof.

9. The process of claim 8 , 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 total weight of olefins in the feedstock.

10. The process of claim 9 , 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.

11. The process of claim 10 , wherein each R 5 can be a methyl group, anethyl 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.

12. The process of claim 8 , 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 a total weight of olefins in the feedstock.

13. The process of claim 12 , 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.

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

15. The process of claim 14 , 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.

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

17. 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 C 11+ monoolefins molar ratio of from about 1:1 to about 15:1.

18. A process comprising:
reacting hydrogen sulfide (H 2 S) and a feedstock comprising one or more C 11+ monoolefins in the presence of an initiating agent to produce a C 11+ mercaptans crude composition, wherein the feedstock comprises at least about 70 wt. % of one or more C 11+ monoolefins, based on the total weight of the feedstock, and wherein the C 11+ monoolefins comprise C 11 internal monoolefins, C 12 internal monoolefins, C 13 internal monoolefins, C 14 internal monoolefins, 1-tetradecene, 1-hexadecene, or combinations thereof; and
recovering a reaction product from the C 11+ mercaptans crude composition, wherein the reaction product comprises (A) at least about 50 wt. % C 11+ mercaptans, based on the total weight of the reaction product, wherein the C 11+ mercaptans are characterized by structure R 6 —SH, wherein R 6 is an alkyl group derived from the one or more C 11+ monoolefins; and (B) less than about 15 wt. % C 22+ sulfides, based on the total weight of the reaction product, wherein the C 22+ sulfides are characterized by structure R 7 —S—R 8 , wherein both R 7 and R 8 are each independently an alkyl group derived from the one or more C 11+ monoolefins.

19. The process of claim 18 further comprising recovering a C 22+ sulfides composition from the C 11+ mercaptans crude composition, wherein the C 22+ sulfides composition comprises at least about 50 wt. %, C 22+ sulfides, based on the total weight of the C 22+ sulfides composition, wherein the C 22+ sulfides are characterized by structure R 7 —S—R 8 , wherein both R 7 and R 8 are each independently an alkyl group derived from the one or more C 11+ monoolefins.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

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

Classifications

• C07C319/16

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

• C07C319/04 Primary

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

• B01J2219/1203

  Incoherent waves · CPC title

• B01J19/123

  Ultraviolet light · CPC title

• B01J2219/0877

  Liquid · CPC title