Liquid compositions for marking liquid hydrocarbon motor fuels and other fuels, motor fuels and other fuels containing them and process for detecting the markers

Patent metadata

Field	Value
Publication number	US-10167435-B2
Application number	US-201213983728-A
Country	US
Kind code	B2
Filing date	Feb 7, 2012
Priority date	Feb 8, 2011
Publication date	Jan 1, 2019
Grant date	Jan 1, 2019

Abstract

The present disclosure includes liquid compositions that can be used for marking liquid hydrocarbon-based fuels and combustibles; these compositions include at least one marker, one or more solvents and, optionally, one or more functional additives other than the markers. The disclosure also includes a process for qualitative and quantitative detection of these markers present in a liquid hydrocarbon-based composition.

First claim

The invention claimed is:

1. A process for the qualitative detection of at least one marker in a motor fuel or other liquid hydrocarbon fuel comprising:
(a) the at least one marker, chosen from the following aliphatic or cycloaliphatic compounds:
tricyclodecenyl isobutyrate (3a,4,5,6,7,7a-hexahydro-4,7-methano-1 h-inden-5 (or 6) -yl) (CAS 67634-20-2);
tricyclodecenyl propionate (CAS 17511-60-3);
cis-3- hexenyl acetate (CAS 3681-71-8);
ethyl linalool (CAS 10339-55-6);
prenyl acetate (CAS 1191-16-8);
ethyl myristate (CAS 124-06-1);
para-tert-butylcyclohexyl acetate (CAS 32210-23-4);
tricyclodecenyl acetate (4,7-methano-1h-inden-6-ol, 3a,4,5,6,7,7a-hexahydro-) (CAS 5413-60-5);
ethyl caprate(CAS 110-38-3),
the at least one marker having a concentration of from 1 ppm to 20 ppm with regard to the motor fuel or other liquid hydrocarbon fuel;

(b) a solvent or a mixture of solvents; and
(c) one or more functional additives for motor fuels and/or other liquid hydrocarbon fuels, chosen from the detergents, dispersants, combustion improvers, anti-foaming agents, conductivity improvers, anti-corrosion additives, lubricity additives, anti-wear agents and/or friction modifiers, chelating agents and/or sequestrating agents of metals, demulsifiers, low temperature behaviour additives, metal passivators, acidity neutralizers, markers different from the markers; the process comprising the following steps:
analyzing a sample of the motor fuel or other liquid fuel containing the at least one marker by an analytic method; and
then detecting the at least one marker.

2. The process for the qualitative and quantitative detection according to claim 1 comprising a subsequent step of measuring the concentration of each of the markers detected within the motor fuel or other liquid hydrocarbon fuel.

3. A process of quantitative detection of at least one marker in a motor fuel or other liquid hydrocarbon fuel comprising:
(a) the at least one marker, chosen from the following aliphatic or cycloaliphatic compounds:
tricyclodecenyl isobutyrate (3a,4,5,6,7,7a-hexahydro-4,7-methano-1 h-inden-5 (or 6) -yl) (CAS 67634-20-2);
tricyclodecenyl propionate (CAS 17511-60-3);
cis-3- hexenyl acetate (CAS 3681-71-8);
ethyl linalool (CAS 10339-55-6);
prenyl acetate (CAS 1191-16-8);
ethyl myristate (CAS 124-06-1);
para-tert-butylcyclohexyl acetate (CAS 32210-23-4);
tricyclodecenyl acetate (4,7-methano-1h-inden-6-ol, 3a,4,5,6,7,7a-hexahydro-) (CAS 5413-60-5);
ethyl caprate(CAS 110-38-3),
the at least one marker having a concentration of from 1 ppm to 20 ppm with regard to the motor fuel or other liquid hydrocarbon fuel;

(b) a solvent or a mixture of solvents; and
(c) one or more functional additives for motor fuels and/or other liquid hydrocarbon fuels, chosen from the detergents, dispersants, combustion improvers, anti-foaming agents, conductivity improvers, anti-corrosion additives, lubricity additives, anti-wear agents and/or friction modifiers, chelating agents and/or sequestrating agents of metals, demulsifiers, low temperature behaviour additives, metal passivators, acidity neutralizers, markers different from the markers; the process comprising the following steps:
analysing a sample of motor fuel or other liquid fuel containing the at least one marker by an analytic method
detecting the marker or markers; and
measuring the concentration of each of the markers detected within the motor fuel or other liquid hydrocarbon fuel.

4. The process for detection of at least one marker according to claim 2 by multidimensional chromatography coupled with a mass spectrometer comprising the following steps:
(a) injection into a 1st chromatography column, of a liquid mixture comprising a liquid hydrocarbon composition containing one or more markers;
(b) separation of the marker or markers and any other compounds contained in the mixture;
(c) injection of the fraction into a 2nd chromatography column to ensure the complete separation of all the compounds, including the markers; and
(d) then passage through a mass spectrometer allowing each compound, to be specifically identified and optionally quantified.

5. The process for the qualitative detection according to claim 1 , wherein the analytic method is gas chromatography.

6. The process for the qualitative detection according to claim 5 , wherein the analytic method is multidimensional gas chromatography.

7. The process for the qualitative detection according to claim 1 , wherein the detection is performed by mass spectrometry.

8. The process for the qualitative and quantitative detection according to claim 2 , wherein the step of measuring the concentration is performed by mass spectrometry coupled with gas chromatography.

9. The process of quantitative detection according to claim 3 , wherein the analytic method is gas chromatography.

10. The process of quantitative detection according to claim 9 , wherein the analytic method is multidimensional gas chromatography.

11. The process of quantitative detection according to claim 3 , wherein the measurement of the concentration of each of the markers detected is performed by mass spectrometry coupled with gas chromatography.

12. The process for the qualitative and quantitative detection according to claim 1 , wherein the motor fuel or other liquid hydrocarbon fuel comprises from 2 to 3 ppm by mass of the markers a).

13. The process according to claim 1 , wherein the analysing and the detecting are performed after the motor fuel or other liquid hydrocarbon fuel has been stored at ambient temperature for 3 months.

14. The process according to claim 3 , wherein the analysing, the detecting, and the measuring are performed after the motor fuel or other liquid hydrocarbon fuel has been stored at ambient temperature for 3 months.

15. The process according to claim 1 , wherein the at least one marker is chosen from the following compounds:
tricyclodecenyl isobutyrate (3a,4,5,6,7,7a-hexahydro-4,7-methano-1 h-inden-5 (or 6) -yl) (CAS 67634-20-2);
tricyclodecenyl propionate (CAS 17511-60-3);
cis-3- hexenyl acetate (CAS 3681-71-8);
ethyl linalool (CAS 10339-55-6);
prenyl acetate (CAS 1191-16-8);
ethyl myristate (CAS 124-06-1); and
para-tert-butylcyclohexyl acetate (CAS 32210-23-4).

16. The process according to claim 3 , wherein the at least one marker is chosen from the following compounds:
tricyclodecenyl isobutyrate (3a,4,5,6,7,7a-hexahydro-4,7-methano-1 h-inden-5 (or 6) -yl) (CAS 67634-20-2);
tricyclodecenyl propionate (CAS 17511-60-3);
cis-3- hexenyl acetate (CAS 3681-71-8);
ethyl linalool (CAS 10339-55-6);
prenyl acetate (CAS 1191-16-8);
ethyl myristate (CAS 124-06-1); and
para-tert-butylcyclohexyl acetate (CAS 32210-23-4).

Assignees

• Amblard Benedicte
• Fadel Denis
• Mercier Jean Paul
• Tort Frederic
• Tremoliere Christian
• Total Marketing Services

Inventors

• Amblard Bénédicte
• Fadel Denis
• Mercier Jean-Paul
• Tort Frédéric
• Tremoliere Christian

Classifications

• G01N30/7206

  interfaced to gas chromatograph (interfaces in general for introducing or extracting samples to be analysed with specially adapted mass spectrometer, see H01J49/04) · CPC title

• C10L1/19

  Esters {ester radical containing compounds; ester ethers; carbonic acid esters (C10L1/1802, C10L1/1805, C10L1/1808, C10L1/1811, C10L1/1814, C10L1/1817 take precedence)} · CPC title

• G01N30/02

  Column chromatography · CPC title

• C10L1/003 Primary

  Marking, e.g. coloration by addition of pigments · CPC title

• C10L1/188 Primary

  Carboxylic acids; {metal} salts thereof {(C10L1/1802, C10L1/1805, C10L1/1808, C10L1/1811, C10L1/1814, C10L1/1817 take precedence)} · CPC title