Cold process for removal of sulfur in straight run diesel by ozone and tert-butyl hydroperoxide

Patent metadata

Field	Value
Publication number	US-9365780-B2
Application number	US-201414183821-A
Country	US
Kind code	B2
Filing date	Feb 19, 2014
Priority date	Feb 19, 2014
Publication date	Jun 14, 2016
Grant date	Jun 14, 2016

Abstract

A method and process to remove sulfur compounds from a real fuel product of straight-run diesel (SRD) by the action of ozone bubbling and tert-butyl hydroperoxide (t-BUOOH) under normal laboratory conditions is disclosed. Slight desulfurization is taken place after ozone bubbling process which may be assigned to a removal of sulfur compounds in a gaseous form (SO x ). Most of the organically bound sulfur and/or elemental sulfur and hydrogen sulfide still exist in the ozonized samples. Sulfur removal from SRD samples was achieved by combining ozone bubbling with extraction by using different solvents to remove the oxidized sulfur compound (polar) from ozonized samples. This method provides a considerable level of total sulfur reduction where the reduction of sulfur reaches 93%.

First claim

What is claimed is:

1. A process for desulfurization of straight-run diesel (SRD), comprising: bubbling ozone into SRD, the SRD having a sulfur content of 1.41 mass % before desulfurization; and measuring levels of total sulfur and kinematic viscosity for the ozone bubbled SRD, wherein the bubbling of the ozone is performed at a rate of 36,000 μg/min.

2. The process of claim 1 , wherein ozone is bubbled into the SRD at room temperature and atmospheric pressure.

3. The process of claim 1 , wherein a time of the bubbling is one of 0, 15, 30, 60, and 90 minutes.

4. The process of claim 3 , further comprising decreasing a total sulfur content in the SRD by the ozone bubbling at 30 minutes.

5. The process of claim 3 , further comprising decreasing a total sulfur content in the SRD by the ozone bubbling at 60 minutes.

6. The process of claim 3 , further comprising decreasing a total sulfur content in the SRD by the ozone bubbling at 90 minutes.

7. The process of claim 1 , wherein total sulfur content % is measured by fuel spectrometer and kinematic viscosity is measured at 40° C. by a viscosity analyzer.

8. The process of claim 1 , further comprising forming SO x gases in the SRD after exposure to the ozone.

9. A process for desulfurization of straight-run diesel (SRD), comprising:
bubbling ozone into SRD;
extracting the bubbled SRD using two different solvents in two different operations, and the SRD having a sulfur content of 1.41 mass %; and
then measuring levels of total sulfur and kinematic viscosity for the extracted SRD, wherein a first solvent used for the extracting consists of acetonitrile (ACN) and a second solvent used for the extracting consists of dimethyl formamide (DMF).

10. The method of claim 9 , wherein the bubbling of the ozone is performed at a rate of 36,000 μg/min.

11. The process of claim 9 , wherein ozone is bubbled into the straight-run diesel at room temperature and atmospheric pressure.

12. The process of claim 9 , wherein a first time of bubbling is one of 0, 15, 30, 60, and 90 minutes.

13. The process of claim 9 , wherein the extracting includes use of acetonitrile as 1:2 v/v (volume of SRD/volume of ACN) for extraction in one operation.

14. The process of claim 9 , wherein the extracting includes use of DMF as 1:2 v/v (volume of SRD/volume of DMF) for extraction in one operation.

15. The process of claim 9 , wherein the extracting includes use of ACN as 1:2 v/v (volume of SRD/volume of ACN) by extraction in two operations comprising 50 ml of ozonized SRD extracted by 50 ml of the ACN, and then the extracted SRD is extracted again by 50 ml of the ACN.

16. The process of claim 9 , wherein the extracting includes use of DMF as 1:2 v/v (volume of SRD/volume of DMF) by extraction in two operations, comprising 50 ml of ozonized SRD extracted by 50 ml of the DMF, and then the extracted SRD is extracted again by 50 ml of the DMF.

17. The process of claim 16 , wherein the extracted SRD is analyzed for total sulfur content % by a fuel spectrometer and for kinematic viscosity at 40° C. by a viscosity analyzer.

18. A process, comprising:
desulfurization of straight-run diesel (SRD) by alternating ozone bubbling and extraction process, each extraction using dimethyl formamide (DMF); and
measuring levels of total sulfur after each extraction process.

19. The method of claim 18 , wherein each bubbling of the ozone is performed at a rate of 36,000 μg/min.

20. The process of claim 19 , wherein the ozone bubbling process is under room temperature and atmospheric pressure.

21. The process of claim 18 , wherein a first operation of ozone bubbling is for a period of 60 minutes.

22. The process of claim 21 , wherein the process of extraction after the first time of ozone bubbling includes uses the DMF as 1:2 v/v (volume of SRD/volume of DMF) by extraction in one operation, comprising 50 ml of ozonized SRD extracted by 100 ml of the DMF.

23. The process of claim 22 , wherein the extracted SRD is analyzed for total sulfur content %.

24. The process of claim 21 , wherein a second operation of ozone bubbling is for a period of 60 minutes.

25. The process of claim 24 , wherein:
the process of extraction after a first operation of ozone bubbling includes using the DMF as 1:2 v/v (volume of SRD/volume of DMF) by extraction in one operation, comprising 50 ml of ozonized SRD extracted by 100 ml of the DMF; and
a second operation of ozone bubbling is performed on the extracted SRD for a period of 60 minutes.

26. The process of claim 24 , wherein the ozonized SRD is extracted by the DMF.

27. The process of claim 26 , wherein the process of extraction includes DMF as 1:2 v/v (volume of SRD/volume of DMF) in one operation, comprising 50 ml of ozonized SRD extracted by 100 ml of DMF.

28. The process of claim 27 , wherein the extracted SRD is analyzed for total sulfur content.

29. A process for desulfurizing of straight-run diesel (SRD) by t-BuOH comprising:
adding t-BuOOH to SRD under vigorous stirring, the SRD having a sulfur content of ≅1.41 mass % before desulfurization;
extracting oxidized sulfur compounds;
bubbling ozone into the SRD; and
measuring levels of total sulfur of the desulfurized SRD.

30. The process of claim 29 , wherein the t-BuOOH used for oxidizing sulfur compounds is a 70% aqueous solution by volume.

31. The process of claim 29 , wherein the t-BUOOH is introduced into the SRD at room temperature and atmospheric pressure.

32. The process of claim 29 , wherein the t-BUOOH used for oxidation processes is introduced at one of 6.25, 12, and 25 ml into 120 ml of the SRD.

33. The process of claim 29 , further comprising forming oxidized products in the SRD after reacting with the t-BUOOH.

34. The process of claim 29 , wherein a solvent used for extraction process is acetonitrile (ACN).

35. The process of claim 29 , wherein the process of extraction in one operation includes use of ACN as 1:2 v/v (volume of SRD/volume of ACN), comprising 50 ml of oxidized SRD by the t-BUOOH extracted by 100 ml of ACN.

36. The process of claim 29 , wherein the process of extraction in two, three and four operations includes the use of ACN as 1:1 v/v (volume of SRD/volume of ACN), comprising 50 ml of oxidized SRD by the t-BUOOH extracted by 50 ml of ACN in each of two, three, and four operations.

37. The processes of claim 36 , wherein the extracted SRD is analyzed for detecting sulfur removal content % and kinematic viscosity at 40° C.

38. A process for desulfurizing of straight-run diesel (SRD) by t-BuOH comprising:
adding t-BuOH to SRD to oxidize compounds of the SRD;
extracting the oxidized compounds with acetonitrile (ACN) and dimethyl formamide (DMF);
bubbling ozone into the SRD; and
measuring of total sulfur content % of the desulfurized SRD.

39. The process of claim 38 , wherein the t-BuOOH used for oxidizing sulfur compounds is a 70% aqueous solution by volume.

40. The process of claim 38 , wherein the t-BUOOH is introduced into the SRD samples at room temperature and atmospheric pressure.

41. The process of claim 38 , wherein the t-BUOOH used for oxidation processes is introduced at 2

Assignees

• King Abdulaziz City Sci & Tech

Inventors

• Basfar Ahmed Ali
• Soliman Yasser S

Classifications

• C10G2300/202

  Heteroatoms content, i.e. S, N, O, P · CPC title

• C10G27/04

  with oxygen or compounds generating oxygen · CPC title

• C10G53/14

  including at least one oxidation step · CPC title

• C10G27/14 Primary

  with ozone-containing gases · CPC title