WO1994012874A1 - Method of identifying liquid petroleum products - Google Patents
Method of identifying liquid petroleum products Download PDFInfo
- Publication number
- WO1994012874A1 WO1994012874A1 PCT/GB1993/002408 GB9302408W WO9412874A1 WO 1994012874 A1 WO1994012874 A1 WO 1994012874A1 GB 9302408 W GB9302408 W GB 9302408W WO 9412874 A1 WO9412874 A1 WO 9412874A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid petroleum
- petroleum product
- dye
- spectrum
- far red
- Prior art date
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000003209 petroleum derivative Substances 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000001228 spectrum Methods 0.000 claims abstract description 12
- 239000003502 gasoline Substances 0.000 claims description 13
- 239000000314 lubricant Substances 0.000 claims description 6
- -1 rare earth compound Chemical class 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000010913 used oil Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 claims 1
- 239000000975 dye Substances 0.000 description 19
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000004809 thin layer chromatography Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 239000003550 marker Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OYVFJKVYVDYPFV-UHFFFAOYSA-M 3-ethyl-2-[7-(3-ethyl-1,3-benzothiazol-3-ium-2-yl)hepta-2,4,6-trienylidene]-1,3-benzothiazole;iodide Chemical compound [I-].S1C2=CC=CC=C2[N+](CC)=C1/C=C/C=C/C=C/C=C1/N(CC)C2=CC=CC=C2S1 OYVFJKVYVDYPFV-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004146 Propane-1,2-diol Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- VYWYYJYRVSBHJQ-UHFFFAOYSA-N 3,5-dinitrobenzoic acid Chemical class OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 VYWYYJYRVSBHJQ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000490620 Vanellus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- BSIHWSXXPBAGTC-UHFFFAOYSA-N isoviolanthrone Chemical class C12=CC=CC=C2C(=O)C2=CC=C3C(C4=C56)=CC=C5C5=CC=CC=C5C(=O)C6=CC=C4C4=C3C2=C1C=C4 BSIHWSXXPBAGTC-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2835—Specific substances contained in the oils or fuels
- G01N33/2882—Markers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Definitions
- the present invention relates to a method of identifying liquid petroleum products through the application of far red or near infra red fluorescence spectroscopy.
- Petroleum refinery processes such as distillation are used to 5 break down crude oil into numerous useful products which may be marketed both for industrial and for domestic use. Such products are often blends which can contain up to six various components. It is therefore important to be able to accurately identify such blends and perhaps a specific component within the blend. 10
- the detection and identification of liquid hydrocarbons using chemical markers is well known.
- EP-A-512404 discloses a method of identifying liquid hydrocarbons by the addition of a derivative of 3, 5-dinitro-benzoic acid. Gas chromatographic separation followed by component detection using a suitable detector is used to identify 15 the chemical marker.
- US 4278444 discloses a method of detecting the presence of regular unleaded or super unleaded gasoline. A minor amount of an alkylated isodibenzanthrone is added to the gasoline and the presence of such is detected by running the sample on a 20 fluorescence spectrophotometer. The results are compared with predetermined standard results.
- the 25 present invention provides a quick, efficient and non-invasive method of identifying liquid petroleum products.
- a method of identifying a liquid petroleum product using a device comprising a laser source and a means for detecting a fluorescence signal said process comprising: a) a first step of adding to the liquid petroleum product, a material capable of fluorescing in the far red or near infra red region of the spectrum, b) a second step of exposing the liquid petroleum product obtained from said first step to the laser source at a wavelength in the far red or near infra red region of the spectrum suitable for exciting the material, c) determining the presence of the material in the .liquid petroleum product by detecting the fluorescence signal.
- the present invention provides a method of identifying liquid petroleum products by the addition of a fluorescence marker wherein the fluorescence signal is detected.
- the method of the present invention is carried out using a device which comprises a laser source, and means for detecting the fluorescence signal. It is preferred that the device is a hand-held portable unit, especially capable of operating from an internal power source.
- the method of the present invention is applicable to liquid petroleum products.
- liquid petroleum products is meant gasoline, aviation fuel, kerosine, paraffin, diesel fuels, lubricating oils, marine lubricants, fuel oils and used oils.
- the method is particularly applicable to the detection of lubricants and fuels.
- the liquid petroleum product containing the material is exposed to a laser source at a wavelength in the far red or near infra red region of the spectrum.
- far red and near infra red region is meant frequencies in the range of from 600 to 3000 nm.
- the method of the present invention requires the addition of a material which is capable of fluorescing in the far red or near infra red regions of the spectrum.
- Suitable materials include dyes and rare earth compounds which fluoresce at wavelengths in the range of from 600 to 1000 nm, preferably from 700 to 900 nm.
- Dyes suitable for use in the present invention include general commercial laser dyes, especially as defined in general formula I where X is C(dialkyl) or S, Y is C2 to C7 alkyl and n is 1 to 10.
- X is S
- Y is C2 alkyl
- n is 3.
- a dye according to general formula II may also be used in the present invention where X may be selected from C(dialkyl) or S, n may be from 1 to 10 and Y may be Et or (CH 2 ) S0 2 0"
- X is C(dimethyl)
- Y is (CH 2 ) S00 " and n is 3.
- Rare earth compounds also suitable for use in the present invention include those from the lanthanide and actinide series. Especially preferred is the use of rare earth metal salts of organic surfactant species, e.g. an alkyl or aryl sulphonate.
- organic surfactant species e.g. an alkyl or aryl sulphonate.
- the material may be added directly to the liquid petroleum product or may suitably be dissolved in an appropriate solvent to produce an intermediate dye concentrate.
- the material may be dissolved in acetone, dichloromethane, alcohols, toluene, glycols, base oils, alkyl benzene and esters.
- the preferred solvent is a glycol such as propane-1,2-diol.
- the liquid petroleum product may be added two materials to the liquid petroleum product in a predetermined weight ratio.
- the ratio of the fluorescence intensities observed for each dye is proportional to the predetermined weight ratio and may therefore be used to identify the liquid petroleum product.
- a particular advantage of the present invention is that very low concentrations of the materials are added to liquid petroleum product.
- the material may be present in a concentration from 0.001 to 1 ppm.
- the liquid petroleum product containing the material is exposed to a laser source at a wavelength in the far red or near infra red region of the spectrum.
- a suitable laser source may be a diode laser which has the advantages of low cost, small size, high reliability and direct current modulation of output which allows lock-in amplification to be used.
- the fluorescence signal emitted as a result of the laser excitation may be detected by any suitable means. It is preferred to use a silicon photodetector. The presence of the signal may suitably be identified by conversion to an electric signal. The signal may be measured by a visual display unit.
- the laser source, the silicon photodetector and the visual display component be provided in a portable unit.
- a particular advantage of the present invention is that the device provides a non-invasive method of detecting liquid petroleum products. Where the container accommodating the liquid petroleum has a light transmitting window or is made from a transparent material, extraction of the product is not required.
- a diode laser (1) emitting at a wavelength of 670 nm is used to illuminate a liquid petroleum product sample (2) incorporating a suitable material capable of fluorescing in the far red or near infra red region of the spectrum.
- the laser is recollimated by a glass lens (3) before entering the sample.
- Some of the fluorescence generated along with some of the reflected and scattered laser light is also recollimated by lens (3) , reflected by an aluminium coated mirror (4) positioned at 45° to the laser output and focused by means of lens (5) onto a silicon photodetector (6).
- a band pass filter (7) transmitting at the fluorescence wavelength is used to block the 670 nm reflected and scattered light.
- the photodetector output is amplified using a two-stage single chip amplifier.
- the output from the laser (11) after reflection by the sample (12) as the mirror (13) is passed through lens (14) and split by the beamsplitter (15) before passing to the photodetectors (16) and (17).
- a gasoline (BP Eurograde unleaded premium gasoline conforming to BS4040) containing a dye concentration of 100 ppb was prepared from a solution of 100 ppm of the following dye in propan-1,2-diol, hereinafter referred to as IR-125.
- IR-125 was purchased from Exiton (Laser Dyes) .
- the solution was subjected to laser excitation at 750 nm to provide a fluorescence maximum of 833 nm.
- Table 1 provides the data obtained from various gasoline products.
- Example 2 - IDENTIFICATION OF GASOLINE PRODUCTS
- This dye was purchased from Exciton (Laser Dyes) .
- the dye was dissolved in xylene rather than propane-1,2-diol. Again, samples were prepared with various concentrations of the dye. Results from the fluorescence measurements are given in Table 2.
- Non-laser excited fluorescence spectra (200 - 900 nm) were obtained for a sample of Vanellus C3 multigrade lubricant (ex BP) with and without 40 ppb of IR -125 dye. Both the fluorescence and absorption spectra (fluorescence maxima of 833 nm and absorption maxima of 795 nm) appear identical. Therefore the dye cannot readily be detected without use of laser excited fluorescence spectroscopy. Comparative Example 2 - THIN LAYER CHROMATOGRAPHY
- TLC Thin layer chromatography
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Pathology (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Food Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
A method of identifying a liquid petroleum product using a device comprising a laser source and a means for detecting a fluorescent signal comprising (a) a first step of adding to the liquid petroleum product a material capable of fluorescing in the far red or near infrared region of the spectrum; (b) a second step of exposing the liquid petroleum product obtained in the first step to the laser source at a wavelength in the far red or near infra region of the spectrum suitable for exciting the material; (c) determining the presence of the material in the liquid petroleum product by determining the fluorescence signal.
Description
METHOD OF IDENTIFYING LIQUID PETROLEUM PRODUCTS The present invention relates to a method of identifying liquid petroleum products through the application of far red or near infra red fluorescence spectroscopy.
Petroleum refinery processes such as distillation are used to 5 break down crude oil into numerous useful products which may be marketed both for industrial and for domestic use. Such products are often blends which can contain up to six various components. It is therefore important to be able to accurately identify such blends and perhaps a specific component within the blend. 10 The detection and identification of liquid hydrocarbons using chemical markers is well known. EP-A-512404 discloses a method of identifying liquid hydrocarbons by the addition of a derivative of 3, 5-dinitro-benzoic acid. Gas chromatographic separation followed by component detection using a suitable detector is used to identify 15 the chemical marker.
Furthermore, US 4278444 discloses a method of detecting the presence of regular unleaded or super unleaded gasoline. A minor amount of an alkylated isodibenzanthrone is added to the gasoline and the presence of such is detected by running the sample on a 20 fluorescence spectrophotometer. The results are compared with predetermined standard results.
We have now developed a method of identifying liquid petroleum products using a chemical marker which avoids both the preparation of standard data or the use of invasive analytical techniques. The 25 present invention provides a quick, efficient and non-invasive
method of identifying liquid petroleum products.
Thus, according to the present invention there is provided a method of identifying a liquid petroleum product using a device comprising a laser source and a means for detecting a fluorescence signal said process comprising: a) a first step of adding to the liquid petroleum product, a material capable of fluorescing in the far red or near infra red region of the spectrum, b) a second step of exposing the liquid petroleum product obtained from said first step to the laser source at a wavelength in the far red or near infra red region of the spectrum suitable for exciting the material, c) determining the presence of the material in the .liquid petroleum product by detecting the fluorescence signal. The present invention provides a method of identifying liquid petroleum products by the addition of a fluorescence marker wherein the fluorescence signal is detected.
The method of the present invention is carried out using a device which comprises a laser source, and means for detecting the fluorescence signal. It is preferred that the device is a hand-held portable unit, especially capable of operating from an internal power source.
The method of the present invention is applicable to liquid petroleum products. By liquid petroleum products is meant gasoline, aviation fuel, kerosine, paraffin, diesel fuels, lubricating oils, marine lubricants, fuel oils and used oils. The method is particularly applicable to the detection of lubricants and fuels. The liquid petroleum product containing the material is exposed to a laser source at a wavelength in the far red or near infra red region of the spectrum. By far red and near infra red region, is meant frequencies in the range of from 600 to 3000 nm.
The method of the present invention requires the addition of a material which is capable of fluorescing in the far red or near infra red regions of the spectrum. Suitable materials include dyes and rare earth compounds which fluoresce at wavelengths in the range
of from 600 to 1000 nm, preferably from 700 to 900 nm.
Dyes suitable for use in the present invention include general commercial laser dyes, especially as defined in general formula I where X is C(dialkyl) or S, Y is C2 to C7 alkyl and n is 1 to 10.
Preferably X is S, Y is C2 alkyl and n is 3. A dye according to general formula II may also be used in the present invention where X may be selected from C(dialkyl) or S, n may be from 1 to 10 and Y may be Et or (CH2) S020"
Preferbly X is C(dimethyl) , Y is (CH2) S00" and n is 3.
Rare earth compounds also suitable for use in the present invention include those from the lanthanide and actinide series. Especially preferred is the use of rare earth metal salts of organic surfactant species, e.g. an alkyl or aryl sulphonate.
The material may be added directly to the liquid petroleum product or may suitably be dissolved in an appropriate solvent to produce an intermediate dye concentrate. The material may be dissolved in acetone, dichloromethane, alcohols, toluene, glycols,
base oils, alkyl benzene and esters. The preferred solvent is a glycol such as propane-1,2-diol.
In some circumstances, it may be preferred to add two materials to the liquid petroleum product in a predetermined weight ratio. The ratio of the fluorescence intensities observed for each dye is proportional to the predetermined weight ratio and may therefore be used to identify the liquid petroleum product.
A particular advantage of the present invention is that very low concentrations of the materials are added to liquid petroleum product. Suitably, the material may be present in a concentration from 0.001 to 1 ppm.
The liquid petroleum product containing the material is exposed to a laser source at a wavelength in the far red or near infra red region of the spectrum. A suitable laser source may be a diode laser which has the advantages of low cost, small size, high reliability and direct current modulation of output which allows lock-in amplification to be used.
The fluorescence signal emitted as a result of the laser excitation may be detected by any suitable means. It is preferred to use a silicon photodetector. The presence of the signal may suitably be identified by conversion to an electric signal. The signal may be measured by a visual display unit.
It is preferred that the laser source, the silicon photodetector and the visual display component be provided in a portable unit.
A particular advantage of the present invention is that the device provides a non-invasive method of detecting liquid petroleum products. Where the container accommodating the liquid petroleum has a light transmitting window or is made from a transparent material, extraction of the product is not required.
The invention will now be described by way of example with reference to Figures 1 and 2 and the following examples.
A diode laser (1) emitting at a wavelength of 670 nm is used to illuminate a liquid petroleum product sample (2) incorporating a suitable material capable of fluorescing in the far red or near
infra red region of the spectrum. The laser is recollimated by a glass lens (3) before entering the sample. Some of the fluorescence generated along with some of the reflected and scattered laser light is also recollimated by lens (3) , reflected by an aluminium coated mirror (4) positioned at 45° to the laser output and focused by means of lens (5) onto a silicon photodetector (6). A band pass filter (7) transmitting at the fluorescence wavelength is used to block the 670 nm reflected and scattered light. The photodetector output is amplified using a two-stage single chip amplifier.
In Figure 2 the fluorescence spectra from a sample incorporating two dyes are recorded by using two detectors.
The output from the laser (11) after reflection by the sample (12) as the mirror (13) is passed through lens (14) and split by the beamsplitter (15) before passing to the photodetectors (16) and (17).
Example 1. IDENTIFICATION OF GASOLINE PRODUCTS
A gasoline (BP Eurograde unleaded premium gasoline conforming to BS4040) containing a dye concentration of 100 ppb was prepared from a solution of 100 ppm of the following dye in propan-1,2-diol, hereinafter referred to as IR-125. IR-125 was purchased from Exiton (Laser Dyes) .
100 ppm of the propan-1,2-diol solution was then diluted (1 part in 1000) with the gasoline to provide a final gasoline/dye
solution of 1000 ppb.
The solution was subjected to laser excitation at 750 nm to provide a fluorescence maximum of 833 nm.
Additional solutions containing 200 and 400 ppb dye were prepared in a similar manner.
Table 1 provides the data obtained from various gasoline products.
Example 2 - IDENTIFICATION OF GASOLINE PRODUCTS The procedure of Example 1 was repeated using a dye of the following structure. This dye was purchased from Exciton (Laser Dyes) .
The dye was dissolved in xylene rather than propane-1,2-diol. Again, samples were prepared with various concentrations of the dye. Results from the fluorescence measurements are given in Table 2.
Comparative Example 1 - NON-LASER EXCITED FLUORESCENCE
Non-laser excited fluorescence spectra (200 - 900 nm) were obtained for a sample of Vanellus C3 multigrade lubricant (ex BP) with and without 40 ppb of IR -125 dye. Both the fluorescence and absorption spectra (fluorescence maxima of 833 nm and absorption maxima of 795 nm) appear identical. Therefore the dye cannot readily be detected without use of laser excited fluorescence spectroscopy.
Comparative Example 2 - THIN LAYER CHROMATOGRAPHY
Thin layer chromatography (TLC) was carried out on a Vistra 7000 lubricant containing 40 ppb of IR - 125 dye. The analysis was repeated on the lubricant without the dye. The TLC traces were identical for both samples even when looking for weak fluorescence spots under various wavelength light sources (218, 280, 365, 510 and 700 nm) .
Table 1 - IDENTIFICATION OF GASOLINE PRODUCTS USING IR- 125 DYE
Table 2 - IDENTIFICATION OF GASOLINE PRODUCTS USING DTTCI
Claims
1. A method of identifying a liquid petroleum product using a device comprising a laser source and a means for detecting a fluorescence signal, said process comprising:
(a) a first step of adding to the liquid petroleum product a
5 material capable of fluorescing in the far red or near infra red region of the spectrum;
(b) a second step of exposing the liquid petroleum product obtained in said first step to the laser source at a wavelength in the far red or near infra red region of the spectrum suitable for
10 exciting the material;
(c) determining the presence of the material in the liquid petroleum product by detecting the fluorescence signal.
2. A method according to Claim 1 in which the device is a hand held portable unit.
15 3. A method according to Claim 1 or Claim 2 in which the liquid petroleum product is gasoline, aviation fuel, kerosine, paraffin, a diesel fuel, a lubricating oil, a marine lubricant, a fuel oil or a used oil.
4. A method according to any one of the preceding claims in 20 which the material capable of fluorescing in the far red or near infra red region of the spectrum is present at a concentration of from 0.001 to lppm.
5. A method according to any one of the preceding claims in which the material capable of fluorescing in the far red or near
25 infra red region of the spectrum is a dye or a rare earth 10
compound .
6. A method according to claim 5 in which the rare earth compound is a rare earth metal salt of an organic surfactant.
7. A method according to claim 5 in which the dye is according to general formula I where X is C(dialkyl) or S; Y is C2 to Cη alkyl and n is 1 to 10.
8. A method according to claim 7 in which X is S, Y is C alkyl and n is 3.
9. A method according to claim 5 in which the dye is according to general formula II where X is C(dialkyl) or S, Y is Et or
(CH2)4S020" and n is 1 to 10.
(ID
10. A method according to claim 9 in which X is C(dimethyl) , Y is (CH2)4S0 0" and n is 3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU55685/94A AU5568594A (en) | 1992-11-27 | 1993-11-23 | Method of identifying liquid petroleum products |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9224936.6 | 1992-11-27 | ||
GB929224936A GB9224936D0 (en) | 1992-11-27 | 1992-11-27 | Method of identifying liquid petroleum products |
GB9317930.7 | 1993-08-26 | ||
GB939317930A GB9317930D0 (en) | 1993-08-26 | 1993-08-26 | Method of identifying liquid petroleum products |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994012874A1 true WO1994012874A1 (en) | 1994-06-09 |
Family
ID=26302065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1993/002408 WO1994012874A1 (en) | 1992-11-27 | 1993-11-23 | Method of identifying liquid petroleum products |
Country Status (4)
Country | Link |
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CN (1) | CN1092864A (en) |
AP (1) | AP9300594A0 (en) |
AU (1) | AU5568594A (en) |
WO (1) | WO1994012874A1 (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5710046A (en) * | 1994-11-04 | 1998-01-20 | Amoco Corporation | Tagging hydrocarbons for subsequent identification |
US5723338A (en) * | 1994-11-04 | 1998-03-03 | Amoco Corporation | Tagging hydrocarbons for subsequent identification |
WO1999000666A1 (en) * | 1997-06-30 | 1999-01-07 | Boston Advanced Technologies, Inc. | Method and apparatus for marking and identifying liquids |
WO2003061918A2 (en) * | 2002-01-25 | 2003-07-31 | Heidel Gmbh & Co. Kg | Cutting tool |
DE19544516C3 (en) * | 1995-11-29 | 2003-12-11 | Siemens Ag | Control device for an automatic motor vehicle transmission |
DE10325537A1 (en) * | 2003-06-04 | 2005-01-05 | Fuchs Petrolub Ag | Apparatus and method for automatically detecting at least one fluorescent and / or light-absorbing indicator contained in a fuel |
KR101150106B1 (en) * | 2009-09-29 | 2012-06-14 | 미츠비시 쥬고교 가부시키가이샤 | Engine frame |
US9791407B2 (en) | 2012-10-23 | 2017-10-17 | Koc Universitesi | Method and an apparatus for the detection of a tagging material in fluids |
US9810632B2 (en) | 2014-07-17 | 2017-11-07 | Kuantag Nanoteknolojiler Gelistirme vs Uretim A.S. | Fluorescent substance detection system |
US10267740B2 (en) | 2012-03-30 | 2019-04-23 | Johnson Matthey Public Limited Company | Tracer and method of identifying tracer in product |
CN110907625A (en) * | 2019-12-06 | 2020-03-24 | 大连海事大学 | Method for distinguishing marine oil spill type based on multidimensional chemical fingerprint quantification model |
CN112525840A (en) * | 2020-11-25 | 2021-03-19 | 中海沥青股份有限公司 | Rapid identification method for petroleum asphalt source |
US11055726B2 (en) | 2015-06-18 | 2021-07-06 | Kuantag Nanoteknolojiler Gelistirme Ve Uretim A.S. | Integrated fuel tracking method of authentication in a fuel distribution network |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX9304188A (en) * | 1992-07-23 | 1994-03-31 | Basf Ag | USE OF ABSORBENT AND / OR FLUORESCENT COMPOUNDS IN THE INFRARED REGION AS MARKERS FOR LIQUIDS. |
JP5190362B2 (en) * | 2005-06-20 | 2013-04-24 | ビーピー オイル インターナショナル リミテッド | Improved disposable / sealable caps for spectroscopic probes |
CN102706975B (en) * | 2012-05-22 | 2013-08-14 | 山东出入境检验检疫局 | Method for identifying crude oil and fuel oil |
CN102706976B (en) * | 2012-05-23 | 2013-08-14 | 山东出入境检验检疫局 | Bayes method for distinguishing crude oil and fuel oil |
CN104034709A (en) * | 2014-06-06 | 2014-09-10 | 中国科学院长春光学精密机械与物理研究所 | Optical system of fluoroanalyzer |
Citations (2)
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US4755469A (en) * | 1982-09-27 | 1988-07-05 | Union Oil Company Of California | Oil tracing method |
US5093147A (en) * | 1990-09-12 | 1992-03-03 | Battelle Memorial Institute | Providing intelligible markings |
-
1993
- 1993-11-23 AU AU55685/94A patent/AU5568594A/en not_active Abandoned
- 1993-11-23 WO PCT/GB1993/002408 patent/WO1994012874A1/en active Application Filing
- 1993-11-25 AP APAP/P/1993/000594A patent/AP9300594A0/en unknown
- 1993-11-27 CN CN93121606A patent/CN1092864A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US4755469A (en) * | 1982-09-27 | 1988-07-05 | Union Oil Company Of California | Oil tracing method |
US5093147A (en) * | 1990-09-12 | 1992-03-03 | Battelle Memorial Institute | Providing intelligible markings |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5723338A (en) * | 1994-11-04 | 1998-03-03 | Amoco Corporation | Tagging hydrocarbons for subsequent identification |
US5928954A (en) * | 1994-11-04 | 1999-07-27 | Bp Amoco Corporation | Tagging hydrocarbons for subsequent identification |
US5710046A (en) * | 1994-11-04 | 1998-01-20 | Amoco Corporation | Tagging hydrocarbons for subsequent identification |
DE19544516C3 (en) * | 1995-11-29 | 2003-12-11 | Siemens Ag | Control device for an automatic motor vehicle transmission |
US6881381B1 (en) | 1997-06-30 | 2005-04-19 | On-Site Analysis, Inc. | Apparatus for marking and identifying liquids |
WO1999000666A1 (en) * | 1997-06-30 | 1999-01-07 | Boston Advanced Technologies, Inc. | Method and apparatus for marking and identifying liquids |
US5958780A (en) * | 1997-06-30 | 1999-09-28 | Boston Advanced Technologies, Inc. | Method for marking and identifying liquids |
WO2003061918A2 (en) * | 2002-01-25 | 2003-07-31 | Heidel Gmbh & Co. Kg | Cutting tool |
WO2003061918A3 (en) * | 2002-01-25 | 2004-04-01 | Heidel Gmbh & Co Kg | Cutting tool |
DE10325537B4 (en) * | 2003-06-04 | 2006-08-17 | Fuchs Petrolub Ag | Apparatus and method for automatically detecting at least one fluorescent and / or light-absorbing indicator contained in a liquid fuel during the filling process of the fuel into a machine |
DE10325537A1 (en) * | 2003-06-04 | 2005-01-05 | Fuchs Petrolub Ag | Apparatus and method for automatically detecting at least one fluorescent and / or light-absorbing indicator contained in a fuel |
US7466400B2 (en) | 2003-06-04 | 2008-12-16 | Fuchs Petrolub Ag | Device and method for automatically detecting at least one fluorescent and/or light absorbing indicator contained in a liquid service fluid during the process of filling the service fluid into a machine |
KR101150106B1 (en) * | 2009-09-29 | 2012-06-14 | 미츠비시 쥬고교 가부시키가이샤 | Engine frame |
US10267740B2 (en) | 2012-03-30 | 2019-04-23 | Johnson Matthey Public Limited Company | Tracer and method of identifying tracer in product |
US9791407B2 (en) | 2012-10-23 | 2017-10-17 | Koc Universitesi | Method and an apparatus for the detection of a tagging material in fluids |
US10054565B2 (en) | 2012-10-23 | 2018-08-21 | Koc Universitesi | Method and an apparatus for the detection of a tagging material in fluids |
US10203283B2 (en) | 2014-07-17 | 2019-02-12 | Kuantag Nanoteknolojiler Gelistirme Ve Uretim A.S. | Fluorescent substance detection system |
US9810632B2 (en) | 2014-07-17 | 2017-11-07 | Kuantag Nanoteknolojiler Gelistirme vs Uretim A.S. | Fluorescent substance detection system |
US11055726B2 (en) | 2015-06-18 | 2021-07-06 | Kuantag Nanoteknolojiler Gelistirme Ve Uretim A.S. | Integrated fuel tracking method of authentication in a fuel distribution network |
CN110907625A (en) * | 2019-12-06 | 2020-03-24 | 大连海事大学 | Method for distinguishing marine oil spill type based on multidimensional chemical fingerprint quantification model |
CN110907625B (en) * | 2019-12-06 | 2022-02-22 | 大连海事大学 | Method for distinguishing marine oil spill type based on multidimensional chemical fingerprint quantification model |
CN112525840A (en) * | 2020-11-25 | 2021-03-19 | 中海沥青股份有限公司 | Rapid identification method for petroleum asphalt source |
CN112525840B (en) * | 2020-11-25 | 2023-07-25 | 中海沥青股份有限公司 | Rapid identification method for petroleum asphalt source |
Also Published As
Publication number | Publication date |
---|---|
CN1092864A (en) | 1994-09-28 |
AP9300594A0 (en) | 1994-01-31 |
AU5568594A (en) | 1994-06-22 |
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