Fluorescent labeling of hydrocarbons for source identification

• US 5,279,967 A
• Filed: 01/24/1992
• Issued: 01/18/1994
• Est. Priority Date: 01/24/1992
• Status: Expired due to Fees

• Current Assignee: Nalco Chemical Company (Ecolab, Inc.)
• Original Assignee: Nalco Chemical Company (Ecolab, Inc.)
• Inventors: Bode, Heinrich E.
• Primary Examiner(s): ALEXANDER, LYLE
• Application Number:
  US07/825,220
• Time in Patent Office: 725 Days
• Field of Search: 436/56, 44/419
• US Class Current: 436/56
• CPC Class Codes: G01N 2030/027 Liquid chromatography
• CPC Class Codes: G01N 21/643 non-biological material
• CPC Class Codes: G01N 30/90 Plate chromatography, e.g. thin layer or paper chromatography
• CPC Class Codes: G01N 33/2882 Markers
• CPC Class Codes: Y10T 436/13 Tracers or tags

Abstract

A hydrocarbon liquid identification and tracing system based on fluorescence, high pressure liquid chromatography or thin layer chromatography and N-substituted or N,N'"'"'-dialkyl-4-amino-1,8-naphthalimides as the fluorophores is described.

The liquid fuel tracing system based on the above naphthalimides is based on the 2ⁿ -1 binomial system and provides inexpensive and extremely accurate and sensitive monitoring and source identification.

Claims

1. An identification system for identification of a family of organic hydrocarbon fluids comprising the following method steps:

a) adding at least one of (n) fluorescent fluorophore labeling compounds to a hydrocarbon fluid to produce a mixture of the labeling compound with the hydrocarbon fluid representing the source point of the hydrocarbon fluid and labeling compound, the source point being at a different location from the destination point to which the mixture is transported, wherein the labeling compounds are N-substituted or n,N'"'"'-disubstituted 4-amino-1,8 naphthalimide homologs;

b) obtaining at a destination point a sample of a mixture of hydrocarbon fluid to which the (n) labeling compounds have been added according to step a;

c) passing the labeled hydrocarbon fluid through a predetermined separation device capable of separating the mixtures of hydrocarbon fluid from the labeling compounds based on the individual characteristics of the labeling compounds and detecting the presence or absence of the (n) number of fluorescent labeling compounds contained in the hydrocarbon fluid according to their separation and fluorescent characteristics; and

d) comparing the separation and fluorescence characteristics of the (n) number of fluorescent labeling compounds to known separation and fluorescent characteristics of the (n) fluorescent labeling compounds which facilitate the identification of the fluorescent labeling compounds in the hydrocarbon mixture, wherein a binary notation is employed such that the absence of detection of a specific fluorescent fluorophore labeling compound is represented by the value (0) and the presence of detection of a specific fluorescent fluorophore labeling compound is represented by (1), thus permitting the n number of labeling compounds to produce 2ⁿ -1 possible unique codes and wherein each unique code is correlated to the labeling of the organic hydrocarbon fluid that is representative of the organic hydrocarbon fluid which was labeled at its source, and thereby identifying the labeled organic hydrocarbon fluid.

2. The system according to claim 1 where the fluorescent emissions are detected by fluorescent detection and analysis resulting from the labeling compounds absorbing then emitting light at a different wavelength.

3. The system of claim 1 wherein the N,N'"'"' disubstituted-4-amino-1,8-naphthalimides are N,N'"'"' dialkyl substituted-4-amino-1,8-naphthalimides and the dialkyl substituents contain from 1 to about 20 carbon atoms and are linear, branched, or mixtures thereof.

4. The system of claim 1 wherein the fluorescent fluorophore labeling compounds include N,N'"'"'-di(alkoxyalkyl) substituted 4-amino-1,8-naphthalimide compounds where the alkoxyalkyl substituents [H₃ C-(CH₂)_n -O-(CH₂)_n - ] are selected from the group consisting of 3-methoxypropylamine, 3-ethoxypropylamine, 3-iso-propoxypropylamine, 3-n-butoxypropylamine and the equivalent branched groups thereof.

5. The system of claim 1 wherein the substituents are alkoxyalkyl substituents selected from the general formula H₃ C-(CH₂)₂ -[O-(CH₂)_n ]_m or wherein the substituents are alkyl substituents selected from the group consisting of C₁ -C₂₀ linear and branched alkyl groups, and further wherein the fluorophore adsorbent is selected from of the group consisting of silica gel, alumina, and aluminosilicates, and further wherein the polar organic solvent is selected from the group consisting of C₁ -C₆ alcohols, C₃ -C₆ ketones, C₂ -C₆ amides, dimethyl sulfoxide, dimethyl formamide, and C₁ -C₃ nitriles;

and further wherein the presence of said fluorophore compound and its homologs is determined by sampling a small volume of polar solvent-fluorophore and placing said sample on a thin-layer chromatographic plate containing a thin-layer of adsorbent selected from the group consisting of alumina, silica, and aluminosilicates, and eluting said thin layer plate with a developer solvent, drying, and exposing same to a light source emitting a wavelength, which excites a fluorescent emission which allows determination of a code and thereby providing the identity of said organic fluid.

6. The system of claim 1 wherein the labeling compound is n-N'"'"'-disubstituted 4-amino-1,8-naphthalamide and the homologs are selected from the group consisting of:

N-Methyl-4(aminomethyl)-1,8-naphthalimide,

N-Ethyl-4(aminoethyl)-1,8-naphthalimide,

N-n-Propyl-4(amino-n-propyl)-1,8-naphthalimide,

N-n-Butyl-4(amino-n-butyl)-1,8-naphthalimide,

N-n-Pentyl-4(amino-n-pentyl)-1,8-naphthalimide,

N-n-Hexyl-4(amino-n-hexyl)-1,8-naphthalimide,

N-n-Heptyl-4(amino-n-heptyl)-1,8-naphthalimide,

N-n-Octyl-4(amino-n-octyl)-1,8-naphthalimide,

N-n-Nonyl-4(amino-n-nonyl)-1,8-naphthalimide,

N-n-Decyl-4(amino-n-decyl)-1,8-naphthalimide,

N-iso-Butyl-4(amino-iso-butyl)-1,8-naphthalimide,

N-(3-Methoxypropyl)-4-amino-(3-methoxypropyl)-1,8-naphthalimide;

solvent;

methanol,

N-(3-Ethoxypropyl)-4-amino-(3-ethoxypropyl)-1,8-naphthalimide;

solvent;

ethanol,

N-(3-isopropoxypropyl)-4-amino-(3-isopropoxypropyl) 1,8-naphthalimide;

solvent;

isopropanol,

N-(3-n-Butoxypropyl)-4-amino-(3-n-butoxypropyl)-1,8-naphthalimide;

solvent;

n-butanol,

N-n-Butyl-4(aminoethyl)-1,8-naphthalimide and

N-n-Propyl-4(aminoethyl)-1,8-naphthalimide.

7. The system of claim 6 wherein the parent compound is 4-amino-1,8-naphththalimide and the homologs also include assymetric N,N'"'"'-dialkyl substituted 4-amino-1,8-naphthalamide compounds where the alkyl substituents are selected from the group consisting of methyl, ethyl, propyl, butyl pentyl, hexyl, heptyl, octyl, nonyl, decyl alkyl groups, and the equivalent branched groups thereof.

8. The system of claim 1 wherein the organic hydrocarbon fluid is a petroleum based fluid selected from the group consisting of gasoline, diesel fuel, and lubricating oils, the fluorophore labeling compounds comprise n,N'"'"'-disubstituted homologs of 4-amino-1, 8-naphthalimide, and the preselected analysis method is as follows:

1) obtain from the source of origin a sample of organic fluid of a known volume, said volume being of sufficient size to permit the detection of the fluorophore labeling compounds;

2) Add said sample to an amount of solid adsorbent, said adsorbent having the capacity to adsorb thereon the fluorophore labeling compounds;

3) Wash said solid adsorbent with a pure hydrocarbon liquid capable of removing all organic hydrocarbon fluid therefrom while leaving said fluorophore labeling compounds adsorbed thereon;

4) Then, washing said solid adsorbent with a polar solvent capable of removing and eluting said fluorophore labeling compounds from said adsorbent, the volume of said polar solvent relative to the volume of said organic fluid sample being in a ratio of from about 1;

1,000,0000 to about 1;

100, thereby providing a polar solvent-fluorophore labeling compound sample; and

5) Determining the presence or absence of said fluorophore compound and up to said n number of homologs thereof, thereby revealing said code and identifying said organic fluid.

9. The process of claim 8 wherein the fluorophore adsorbent is contained within a high pressure liquid chromatographic column and the presence of the fluorophore is detected by fluorescent technique and compared to standard curves for the same fluorophore compound and its homologs used to form the selected permutations of labeling compounds.

10. The system according to claim 1 where the labeling compounds are selected so that, during the analysis of the separation profile, the detected specific said fluorescent labels in the fluid are correlated to a known standard of discrete predetermined separation distances d1 through dn which indicates the presence or absence of said (1-n) fluorescent labels respectively.

11. The system according to claim 10 where the separation of the labeling compounds is done by thin layer chromatography (TLC) and the separated labeling compounds (1-n) are at distances d1 through dn which correlates to the known standards where the presence or absence of said (1-n) labeling compounds is indicated by the binary notation 1 or 0 respectively and thereby producing a binary number that is specific for the labeled hydrocarbon fluid.