Dipyrromethenes and azadipyrromethenes as markers for petroleum products

• US 9,222,043 B2
• Filed: 09/20/2010
• Issued: 12/29/2015
• Est. Priority Date: 09/22/2009
• Status: Active Grant

• Current Assignee: Authentix, Inc.
• Original Assignee: Authentix, Inc.
• Inventors: Forshee, Philip B., Hundt, Greg R., Conroy, Jeffrey L.
• Primary Examiner(s): Geisel, Kara E
• Application Number:
  US12/885,741
• Publication Number:
  US 20110069307A1
• Time in Patent Office: 1,926 Days
• Field of Search: 356/300, 436/56
• US Class Current: 1/1
• CPC Class Codes: C10L 1/003 Marking, e.g. coloration by addition of pigments
• CPC Class Codes: C10L 1/1824 mono-hydroxy
• CPC Class Codes: C10L 1/1852 Ethers; Acetals; Ketals; Orthoesters
• CPC Class Codes: C10L 1/232 containing nitrogen in a heterocyclic ring C10L1/221 takes precedence
• CPC Class Codes: C10L 1/303 boron compounds
• CPC Class Codes: G01N 33/28 Oils , i.e. hydrocarbon liquidsgaseous fuels G01N33/225; edible oils or edible fats G01N33/03

Abstract

Marking a petroleum product includes adding a covert dye selected from the group consisting of azadipyrromethene dyes, dipyrromethene dyes, and any combination thereof to the petroleum product and distributing the dye in the petroleum product. A petroleum product selected for analysis may be spectroscopically analyzed for the presence of an azadipyrromethene dye, a dipyrromethene dye, or a combination thereof. A concentration of at least one azadipyrromethene or dipyrromethene dye present in the portion of the petroleum product may be determined to identify the petroleum product as counterfeit, adulterated, or authentic based on the determined concentration of the azadipyrromethene or dipyrromethene dye.

Claims

1. A marked petroleum fuel comprising a fuel additive, a mixture of a fluid petroleum fuel and a marker, wherein the marker consists of a single dye, and wherein the dye is selected from the group consisting of halogenated-boron dipyrromethene dyes characterized by the following structure:

2. The marked petroleum fuel of claim 1, wherein the petroleum fuel is selected from the group consisting of gasoline diesel fuel, biodiesel fuel, kerosene, liquefied petroleum gas, ethanol, and any combination thereof.

3. The marked petroleum fuel of claim 1, wherein the fuel additive is an oxygenate.

20. The method of claim 1 wherein the dye is present in an amount of from about 500 ppb to about 10,000 ppb.

24. The method of claim 1 wherein the dye is present in an amount of from about 0.1 ppb to about 1,000 ppb.

26. The method of claim 1 wherein the dye has an emission wavelength ranging from about 570 nm to about 815 nm.

4. A method of detecting a couterfeit or adulterated petroleum product, the method comprising:

spectroscopically analyzing a portion of the petroleum product for the presence of a marker, wherein the marker consists of a single dye, and wherein the single dye is a halogenated-boron dipyrromethene dyes characterized by the following structure;

5. The method of claim 4, wherein the petroleum product comprises an oxygenate.

6. The method of claim 5, wherein the oxygenate is selected from the group consisting of methanol, ethanol, gasoline grade t-butanol, methyl t-butyl ether, and any combination thereof.

7. The method of claim 4, wherein the identifying step further comprises comparing the determined concentration with a target concentration of the marker.

17. The method of claim 4 wherein spectroscopically analyzing a portion of the petroleum product comprises a direct-read measurement.

21. The method of claim 4 wherein the dye is present in an amount of from about 500 ppb to about 10,000 ppb.

25. The method of claim 4 wherein the dye is present in an amount of from about 0.1 ppb to about 1,000 ppb.

8. A method of detecting an adulterated petroleum product comprising spectroscopically analyzing a portion of the petroleum product for a presence of a marker, wherein the marker consists of a single dye, and wherein the single dye is a a halogenated-boron dipyrromethene dyes characterized by the following structure:

9. The method of claim 8, further comprising, previous to the spectroscopically analyzing the portion of the petroleum product, mixing the halogenated-boron dipyrromethene dye with the petroleum product.

10. The method of claim 8, wherein the fuel additive comprises an oxygenate.

11. The method of claim 10, wherein the oxygenate is selected from the group consisting of methanol, ethanol, gasoline grade t-butanol, methyl t-butyl ether, and any combination thereof, and wherein the marker is characterized by a resistance to solvatochromatic-based shifting of its fluorescent response when mixed with the petroleum fuel comprising the oxygenate.

18. The method of claim 8 wherein spectroscopically analyzing a portion of the petroleum product comprises a direct-read measurement.

22. The method of claim 8. wherein the dye is present in an amount of from about 500 ppb to about 10,000 ppb.

12. A method comprising adding a covert dye to a petroleum fuel comprising an oxygenate, wherein the covert dye consists of a single dye, and wherein the single dye is a halogenated-boron dipyrromethene dye characterized by the following structure:

13. The method of claim 12 further comprising identifying the petroleum fuel by spectroscopically analyzing a portion of the petroleum fuel for the presence of the covert dye.

14. The method of claim 12 wherein the oxygenate is selected from the group consisting of methanol, ethanol, gasoline grade t-butanol, methyl t-butyl ether, and any combination thereof.

15. The method of claim 12 further comprising:

determining a concentration of the covert dye present in a portion of the petroleum fuel; and

identifying the petroleum fuel as counterfeit, adulterated or authentic based on the determined concentration of the covert dye.

16. The method of claim 15 wherein the determining the concentration of the covert dye present in the portion of the petroleum fuel spectroscopically analyzes the portion of the petroleum fuel for the presence of the covert dye.

19. The method of claim 12 further comprising spectroscopically analyzing a portion of the petroleum fuel utilizing a direct-read measurement.

23. The method of claim 12 wherein the dye is present in an amount of from about 500 ppb to about 10,000 ppb.