Method for oxidation of sulfur-containing compounds

Patent metadata

Field	Value
Publication number	US-12134593-B2
Application number	US-201917268311-A
Country	US
Kind code	B2
Filing date	Aug 20, 2019
Priority date	Aug 20, 2018
Publication date	Nov 5, 2024
Grant date	Nov 5, 2024

Abstract

Various embodiments disclosed relate to a method of oxidizing sulfur-containing compounds. The method involves contacting a sulfur-containing compound with a helmet phthalocyaninato-type catalyst in the presence of an oxidant. The present invention also provides a method of removing undesired sulfur-containing compounds from a fluid, such as natural gas, crude oil or an aqueous waste stream.

First claim

What is claimed is:

1. A method of oxidizing a sulfur-containing compound, comprising:
contacting the sulfur-containing compound with a catalyst in the presence of an oxidant, the catalyst having the structure:

wherein
M is a metal,
axial ligand L is a solvent molecule or absent,
at each occurrence, R A and R B are independently chosen from —H, halide, an organic group, and a hydrophilic group, or R A and R B together form a fused aromatic ring with the ring upon which R A and R B are substituted, R A and R B together having the structure:

 and
at each occurrence, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently chosen from —H, halide, an organic group, a hydrophilic group, a salt thereof, a substituted or unsubstituted (C 1 -C 50 )hydrocarbyl ester thereof, and a combination thereof, and

wherein the sulfur-containing compound is a thioether or has the structure

wherein each of X and Y is independently C 1 -C 20 alkyl, C 6 -C 10 aryl or C 2 -C 10 heteroaryl, each of which may be optionally substituted, wherein X and Y are optionally linked so as to form a ring.

2. The method of claim 1 , wherein the only oxidant present in stoichiometric or greater quantities is molecular oxygen of ambient air.

3. The method of claim 1 , wherein the catalyst has the structure:

wherein
M is a metal,
L is a solvent molecule or absent, and
at each occurrence, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently chosen from —H, halide, an organic group, and a hydrophilic group.

4. The method of claim 1 , wherein at each occurrence, the hydrophilic group is independently chosen from —C(O)OH, —O—C(O)OH, —P(O)(OH) 2 , —OP(O)(OH) 2 , —S(O)(O)OH, —OS(O)(O)OH, a salt thereof, a substituted or unsubstituted (C 1 -C 50 )hydrocarbyl ester thereof, and a combination thereof.

5. The method of claim 1 , wherein the catalyst has the structure:

wherein axial ligand L is H 2 O.

6. The method of claim 1 , wherein the catalyst has the structure:

in salt form, or

7. The method of claim 1 , wherein the contacting is performed at room temperature.

8. The method of claim 1 , wherein the sulfur-containing compound is in solution.

9. The method of claim 1 , wherein the sulfur-containing compound is in the vapor phase.

10. The method of claim 1 , wherein the sulfur-containing compound is in a crude oil, a refined oil, a natural gas, an aqueous waste stream, an exhaust gas waste stream, a combustion gas waste stream, or a mixture thereof.

11. The method of claim 1 , wherein the solvent comprises water, C 1 -C 10 alcohol, non-polar organic solvent, or a combination thereof.

12. The method of claim 1 , wherein the sulfur-containing compound is a thioether.

13. The method of claim 1 , wherein the sulfur-containing compound is

14. A method of removing sulfur-containing compounds from a fluid, comprising:
contacting the fluid and sulfur-containing compounds with a catalyst in the presence of an oxidant to produce an oxidized sulfur-containing compound; and then
separating the oxidized sulfur-containing compound from the fluid, wherein
the catalyst has the structure

wherein
M is a metal,
axial ligand L is a solvent molecule or absent,
at each occurrence, R A and R B are independently chosen from —H, halide, an organic group, and a hydrophilic group, or R A and R B together form a fused aromatic ring with the ring upon which R A and R B are substituted, R A and R B together having the structure:

 and
at each occurrence, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently chosen from —H, halide, an organic group, a hydrophilic group, a salt thereof, a substituted or unsubstituted (C 1 -C 50 )hydrocarbyl ester thereof, and a combination thereof; and

wherein contacting the fluid and the sulfur-containing compounds to produce the oxidized sulfur-containing compound comprises producing the oxidized sulfur-containing compound from a compound that is a thioether or that has the structure

wherein each of X and Y is independently C 1 -C 20 alkyl, C 6 -C 10 aryl or C 2 -C 10 heteroaryl, each of which may be optionally substituted, wherein X and Y are optionally linked so as to form a ring.

15. The method of claim 14 , wherein the fluid is a crude oil, a refined oil, a hydrocarbon mixture, a fossil fuel, a natural gas, petroleum, coal, an aqueous waste stream, an exhaust gas waste stream, a combustion gas waste stream, a combusted crude oil, a combusted refined oil, a combusted hydrocarbon mixture, a combusted fossil fuel, a combusted natural gas, combusted petroleum, combusted coal, or a mixture thereof.

16. The method of claim 14 , wherein the fluid is a liquid, a gas, or a mixture thereof.

17. The method of claim 14 , wherein the contacting step is performed at room temperature.

18. The method of claim 14 , wherein the oxidant is molecular oxygen in ambient air and no other oxidant is present in stoichiometric or greater quantities.

19. The method of claim 1 , wherein contacting the sulfur-containing compound with the catalyst comprises contacting a composition comprising the sulfur-containing compound with the catalyst, wherein the composition further comprises an aromatic thiol, a non-aromatic thiol, a substituted or unsubstituted alkylthiol,

or a combination thereof, wherein X is C 1 -C 20 alkyl, C 6 -C 10 aryl, or C 2 -C 10 heteroaryl, n is 0-10, and m is 0-10.

Assignees

• Wisys Tech Foundation Inc

Inventors

• Mcgaff Robert William

Classifications

• C07F15/025

  without a metal-carbon linkage · CPC title

• C07D333/76

  Dibenzothiophenes · CPC title

• C07C319/24

  by reactions involving the formation of sulfur-to-sulfur bonds · CPC title

• B01J2531/842

  Iron · CPC title

• B01J2231/70

  Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues · CPC title