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WO2021058935A1 - Traceurs et procédé de marquage de liquides - Google Patents

Traceurs et procédé de marquage de liquides Download PDF

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Publication number
WO2021058935A1
WO2021058935A1 PCT/GB2020/051967 GB2020051967W WO2021058935A1 WO 2021058935 A1 WO2021058935 A1 WO 2021058935A1 GB 2020051967 W GB2020051967 W GB 2020051967W WO 2021058935 A1 WO2021058935 A1 WO 2021058935A1
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WIPO (PCT)
Prior art keywords
groups
fuel
substituted
hydrocarbon liquid
tracer compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB2020/051967
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English (en)
Inventor
Duncan MCCALLIEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johnson Matthey PLC
Original Assignee
Johnson Matthey PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Johnson Matthey PLC filed Critical Johnson Matthey PLC
Priority to US17/633,840 priority Critical patent/US20220298439A1/en
Priority to EP20764711.6A priority patent/EP4034614A1/fr
Priority to BR112022002497A priority patent/BR112022002497A2/pt
Publication of WO2021058935A1 publication Critical patent/WO2021058935A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/003—Marking, e.g. coloration by addition of pigments
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C10L1/1855—Cyclic ethers, e.g. epoxides, lactides, lactones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/16—Tracers which serve to track or identify the fuel component or fuel composition

Definitions

  • the present specification concerns marking liquids, especially hydrocarbon liquids, with tracer materials.
  • the present specification in particular concerns marking hydrocarbons which are taxable or liable to be subject to tampering or substitution, such as gasoline and diesel fuels for example.
  • tracers to hydrocarbon liquids.
  • a typical application is the tagging of hydrocarbon fuels in order to identify the fuel at a subsequent point in the supply chain. This may be done for operational reasons, e.g. to assist in distinguishing one grade of fuel from another, or for other reasons, in particular to ensure fuel quality, deter and detect adulteration and to provide a means to check that the correct tax has been paid.
  • other products such as vegetable oils may be marked to identify the product produced at a particular source, or certified to a particular standard.
  • One problem which is known to exist with the marking of fuel liquids in particular is the potential for the tracer to be removed, by evaporation from the fuel, by degradation of the tracer through ageing or exposure to environmental conditions such as heat, sunlight or air or alternatively by deliberate removal of the tracer for unlawful purposes such as for avoidance of tax.
  • Methods for deliberate removal of tracers include adsorption of the tracer onto common adsorbent materials such as charcoal or clays, exposure to radiation, such as ultraviolet light, oxidation etc.
  • a useful fuel tracer therefore needs to be resistant to removal by these common methods and also to more sophisticated treatments such as treatment with acids and/or bases. It is an aim of the invention to provide tracer compounds and methods of marking hydrocarbon liquids which are more resistant to removal of the tracer than other known tracers.
  • W02013/003573 discloses a method of marking a petroleum hydrocarbon or a liquid biologically derived fuel, the method comprising adding to said petroleum hydrocarbon or liquid biologically derived fuel at least one compound having the formula illustrated below:
  • R represents C 1 - C 18 alkyl, C 3 - C 18 alkenyl or C 3 - C 18 alkynyl.
  • a method of marking a hydrocarbon liquid comprising adding to said hydrocarbon liquid a tracer compound, the tracer compound being a substituted biphenol ether having a core structure of Formula I: wherein the two R groups are the same or different and selected from straight chain, branched or cyclic alkyl groups, phenyl or substituted phenyl groups, benzyl or substituted benzyl groups, or the two R groups form a single substituent linked intramolecularly to both oxygen atoms, and wherein one or both of the aromatic rings of the core structure is further substituted with at least one non-planar group.
  • the tracer compound being a substituted biphenol ether having a core structure of Formula I: wherein the two R groups are the same or different and selected from straight chain, branched or cyclic alkyl groups, phenyl or substituted phenyl groups, benzyl or substituted benzyl groups, or the two R groups form a single substituent linked intramolecularly to both oxygen atoms
  • substituted biphenol ether tracer compounds as defined above have several advantages over prior art tracers as discussed below.
  • the two aromatic rings in the biphenol ether of WO2013/003573 can rotate around the central bond to be co-planar.
  • the planar structure is susceptible to adsorption by active charcoal, which is a common laundering agent as mentioned in the background section.
  • the biphenol ether compounds have been modified such that one or both of the aromatic rings of the biphenol ether is additionally functionalized with a non-planar group (in addition to its ether functionalization).
  • a non-planar functionalization restricts rotation about the carbon-carbon bond connecting the two aromatic rings, particularly if it is ortho to the carbon-carbon bond between the rings.
  • non-planar substituents on the aromatic rings can also serve to improve the non-polar nature of the tracer molecule and protect the ether linkage from potential reaction.
  • the molecules are surprisingly quick-eluting by gas chromatography for their mass.
  • the combination of higher mass while remaining relatively quick-eluting is a very useful combination of properties as it means the tracer molecules elute at least with some of the components of the hydrocarbon liquid in which they are disposed but can still be resolved from those components by virtue of their mass.
  • the tracer molecules as described herein are heavier than most of the components of a typical fuel (gasoline or diesel fuel) but are still readily distinguishable from the fuel components which elute at a similar rate as the tracer molecules.
  • the tracer molecules of the present invention can consist of atoms selected only from the group carbon, hydrogen, and oxygen which is a specified requirement for certain fuel marking applications. Additionally, the tracer molecules do not contain reactive functional groups or fused-ring structures which would otherwise decrease their resistance to laundering.
  • the basic substituted biphenol ether structure enables a family of related tracer molecules to be derived. That is, forming a substituted biphenol ether confers the advantage that a suite of molecular tracers can be produced simply by varying the species that is reacted with the biphenol core.
  • the R groups of the biphenol ether while typically being C 1 to C 20 groups, can be intentionally varied to provide a suite of tracer compounds.
  • each biphenol ether will possess a different mass or affinity to the separation column, they can all be distinguishable from each other by gas chromatography mass spectrometry (GC-MS).
  • GC-MS gas chromatography mass spectrometry
  • Such a suite of tracer compounds is very useful for marking hydrocarbon liquids (e.g. fuels) from different sources and/or for marking a hydrocarbon liquid with a combination of different tracer molecules.
  • a method of marking a hydrocarbon liquid such as a gasoline or diesel fuel, a liquified petroleum gas fuel, or a biofuel, comprising adding a tracer compound as defined above to the hydrocarbon liquid.
  • hydrocarbon liquid such as a gasoline or diesel fuel, a liquified petroleum gas fuel, or a biofuel, comprising a tracer compound as defined above.
  • Figure 1 shows the structure of a substituted ortho-biphenol ether
  • Figure 2 shows a reaction scheme for the synthesis of a substituted ortho-biphenol from a substituted phenol
  • Figure 3 shows two possible reaction schemes for the synthesis of a substituted ortho-biphenol ether from a substituted ortho-biphenol
  • Figures 4(a) and 4(b) show examples of substituted ortho-biphenol ethers
  • Figure 5 shows a reaction scheme for the synthesis of 2,2'-dipropyloxy-3,3',5,5'-tetra-(tert)-butyl- biphenyl from 3,3',5,5'-tetra-(tert) butyl 2,2'-dihydroxy-biphenyl;
  • Figure 6 shows a section from the GC-MS results for the 2,2'-dipropyloxy-3,3',5,5'-tetra-(tert) butyl- biphenyl product
  • Figure 7 shows a reaction scheme for the synthesis of substituted para-biphenols
  • Figure 8 shows alkylation of a substituted phenol
  • Figure 9 shows the structure of substituted para-biphenol ethers
  • Figure 10 shows a reaction scheme for the synthesis of 3,5,3',5'-tetra-(tert)-butyl-4,4'- diphenoquinone
  • Figure 11 shows a reaction scheme for the synthesis of 3,5,3',5'-tetra-(tert)-butyl-4,4'- dihyhydroxybiphenyl
  • Figure 12 shows a section from the GC-MS results for the 3,5,3',5'-tetra-(tert)-butyl-4,4'- dihydroxy-biphenyl;
  • Figure 13 shows a reaction scheme for the synthesis of 4,4'-dipropyloxy-3,3',5,5'-tetra-(tert) butyl 4,4'-biphenyl;
  • Figure 14 shows a section of the GC-MS results for the 4,4'-dipropyloxy-3,3',5,5'-tetra-(tert) butyl 4,4'-biphenyl.
  • the present specification provides a tracer compound for marking a hydrocarbon liquid, the tracer compound being a substituted biphenol ether having a core structure of Formula I:
  • Formula I wherein the two R groups are the same or different and selected from straight chain, branched or cyclic alkyl groups, phenyl or substituted phenyl groups, benzyl or substituted benzyl groups, or the two R groups form a single substituent linked intramolecularly to both oxygen atoms, and wherein one or both of the aromatic rings of the core structure is further substituted with at least one non-planar group.
  • the or each non-planar group can consist of atoms selected from the group carbon, hydrogen, and oxygen.
  • the R groups can also consist of atoms selected from the group carbon, hydrogen, and oxygen.
  • the or each non-planar group can be a C 4 to C 20 non-planar group and can be a non-planar alkyl group such as a branched alkyl group, e.g. a tert-butyl group.
  • one or both of the aromatic rings of the core structure can be substituted with at least two of the non-planar groups.
  • the tracer compound has two non-planar substituents provided on each aromatic ring of the biphenol ether to inhibit rotation of the rings to a planar configuration, reduce planarity, and increase mass of the tracer.
  • the substituted biphenol ether can be an ortho-biphenol ether, a meta-biphenol ether, or a para- biphenol ether.
  • Ortho-biphenol ethers and para-biphenol ethers are preferred with ortho- biphenol ethers being particularly preferable as they can be manufactured at lower cost.
  • a method of marking a hydrocarbon liquid comprising adding a tracer compound as described herein to the hydrocarbon liquid.
  • the resultant product is a hydrocarbon liquid, such as a gasoline or diesel fuel, comprising the tracer compound.
  • the hydrocarbon liquid may be a pure compound such as hexane or octane or it may comprise a mixture of compounds such as a distillation fraction having a particular range of boiling points.
  • the hydrocarbon liquid may be intended for use as a chemical, a solvent or a fuel.
  • the tracer compounds as described herein are of particular use for marking liquid hydrocarbon fuels such as gasoline and diesel fuels or liquified petroleum gas.
  • a low-tax fuel such as an agricultural diesel may be marked in order to detect any subsequent sale and use for purposes such as road-vehicle fuel which would normally be taxed more highly.
  • unlawful dilution or substitution of a more highly taxed fuel with the low-taxed fuel may be detected by analysis of the highly taxed fuel to determine whether the tracer is present. Therefore, in these cases, it is highly beneficial to use a tracer compound in the low-taxed fuel which is not easily removed, or laundered, from the fuel to a level at which it can no longer be detected.
  • compounds as described herein are resistant to removal from hydrocarbon fuels by multiple known methods of fuel laundering.
  • the tracer compound is added to the hydrocarbon liquid in such an amount as to provide a concentration of the tracer compound which is detectable by readily available laboratory methods capable of identifying the tracer compound in the liquid at the concentrations used. Suitable methods include but are not limited to gas chromatography coupled with a suitable detector such as a mass spectrometer. Typical concentrations are within the range 1 mg/l to 10000 mg/l with the specific amount dependent on the detection method and limit of detection of the particular tracer compound used.
  • the tracer compound may be present at a higher concentration than 1000 ⁇ g/l although when the product to be marked is a high-volume commodity such as a motor-fuel, economic considerations usually favour lower levels of tracer compound.
  • the tracer compound may be supplied in the form of a concentrated dosing solution (or master-batch) of the tracer compound in a solvent.
  • the preferred solvent is a liquid which is similar to the liquid to be marked, although a different solvent, e.g. a single or mixed component aliphatic or aromatic solvent, may be used provided the presence of such a solvent can be tolerated in the hydrocarbon liquid to be marked.
  • a preferred solvent is naphtha.
  • the concentrated dosing solution can be added to the hydrocarbon liquid to be marked so as to produce the required final concentration of the tracer compound by dilution. More than one tracer compound may be added to the liquid.
  • R1 and R2 can be the same or different, straight chain, branched or cyclic alkyl groups, phenyl or substituted phenyl groups, benzyl or substituted benzyl groups.
  • R1 and R2 can also be the same substituent linked intramolecularly to both oxygen atoms.
  • Ortho-biphenols for example 3, 5, 3', 5'-tetra-(tert) -butyl2,2'-dihydroxy-biphenyl, can be generated from the reaction scheme in Figure 2.
  • a method as described in WO2017/175582 can be utilized.
  • An alternative method of coupling 2,4-di-tert-butylphenol has been reported using manganese dioxide in boiling heptane (paragraph 42 of US2012/0259126). Further methods have also been reported: using basic hydrogen peroxide (JP 2001/097908); or using potassium hydroxide, potassium hexacyanoferrate III and methanol (Adv. Synth and Catalysis 2004, 346(8), 993).
  • ortho-biphenols more specifically 5, 5' -alkyl-2, 2' -dihydroxy-biphenyls, can also be synthesized in good yield using copper II chloride, amine and air (see JP 2007/326798 and JP 2007/230975).
  • R could be a straight or branched alkyl group, a cyclic aliphatic group, a benzyl group, or a substituted benzyl group.
  • Figure 4(b) shows an alternative molecule in which a common substituent is provided to link the either groups.
  • the common linker can be a straight or branched alkyl, a cyclic aliphatic group, or a substituted or unsubstituted aromatic group.
  • Figure 5 shows a reaction scheme for the synthesis of 2,2'-dipropyloxy-3,3',5,5'-tetra-(tert) butyl- biphenyl from 3,3',5,5'-tetra-(tert)-butyl-2,2'-dihydroxy-biphenyl.
  • the synthesis procedure is summarized in the experimental section below.
  • the reaction was diluted in toluene, washed with water (2x), washed with brine (1x), dried over magnesium sulfate and evaporated down to give a yellow solid. Traces of dimethyl sulfoxide were removed from the mixture by adding methanol to the flask during evaporation. The product was analysed by GC-MS with a section from the results indicated in Figure 6. The di-alkylated product has mass 494.80. The solid can be recrystallized from acetone. Yield of the solid product was 0.663 g (73%).
  • this method can be successfully used to synthesise 2,2'-dipropyloxy- 3,3',5,5'-tetra-(tert)-butyl-biphenyl from 3,3',5,5'-tetra-(tert)-butyl-2,2'-dihydroxy-biphenyl.
  • the product was then subjected to a range of launder test as summarized the following section.
  • Samples of the tagged fuel were subjected to a series of launder tests where the fuel was subjected to commonly used laundering reagents.
  • the concentration of the taggant in laundered fuel was compared after a particular launder test with the concentration of the taggant in a sample of the same fuel which had not been subjected to a launder test.
  • a sample of tagged fuel that had not been subjected to laundering is referred to as tagged reference.
  • a typical GC sequence included tagged reference, untagged fuel, samples of laundered fuel, tagged reference. Reference samples were run at the beginning and end of any GC sequence to help eliminate instrument drift over the course of the sequence.
  • Hydrochloric acid wash Concentrated hydrochloric acid (36% cone., aq., 30 ml) was diluted with de-ionised water (70 ml). The diluted acid (25 ml) was mixed with tagged fuel (25 ml) and stirred for four hours at room temperature.
  • Sulfuric acid wash - Concentrated sulfuric acid (95% cone., aq., 10 ml) was diluted with de-ionised water (90 ml). The diluted acid (25ml) was mixed with tagged fuel (25 ml) and stirred for four hours at room temperature.
  • Nitric acid wash - Concentrated nitric acid (70% cone., aq., 15 ml) was diluted with de- ionised water (85 ml). The diluted acid (25ml) was mixed with tagged fuel (25 ml) and stirred for four hours at room temperature.
  • Sodium hydroxide wash - Sodium hydroxide pellets (40 g, 1 mole) were added to a beaker which was placed in a water bath. Deionised water (100 ml) was added to the beaker and the pellets were dissolved giving a 10M sodium hydroxide solution. Sodium hydroxide solution (25 ml, 10M) was mixed with tagged fuel (25 ml) and stirred for four hours at room temperature.
  • Potassium hydroxide wash Potassium hydroxide pellets (56 g, 1 mole) were added to a beaker which was placed in a water bath. Deionised water (100 ml) was added to the beaker and the pellets were dissolved giving a 10M potassium hydroxide solution. Potassium hydroxide solution (25 ml, 10M) was mixed with tagged fuel (25 ml) and stirred for four hours at room temperature.
  • Methanolic potassium hydroxide wash - Potassium hydroxide pellets (11.2 g, 0.2 moles) were added to a beaker.
  • Deionised water (10 ml) was added to the beaker giving a 20 M solution of potassium hydroxide.
  • Methanol 190 ml was added to the potassium hydroxide solution giving a 1 M methanolic potassium hydroxide solution.
  • Hydrogen peroxide wash - Hydrogen peroxide solution (35% cone., aq., 25 ml) was mixed with tagged fuel (25 ml) and stirred for four hours at room temperature.
  • Methanol wash - Methanol (25 ml) was mixed with tagged fuel (25 ml) and stirred for four hours at room temperature. When separating the phases the fuel was found to be the lower layer.
  • Acetonitrile wash - Acetonitrile (25 ml) was mixed with tagged fuel (25 ml) and stirred for four hours at room temperature. When separating the phases the fuel was found to be the lower layer.
  • Fuller's earth column A 10 cm glass column with 1 cm internal diameter was packed with Fuller's earth. Tagged fuel (50 ml) was passed through the column. Two repeat passes of the fuel through the column were undertaken using fresh adsorbant.
  • Alumina column - A 10 cm glass column with 1 cm internal diameter was packed with basic activated alumina (0.063 - 0.2 mm particle size). Tagged fuel (50 ml) was passed through the column. Two repeat passes of the fuel through the column were undertaken using fresh adsorbant.
  • Activated charcoal column A 10 cm glass column with 1 cm internal diameter was packed with activated charcoal (Norit RBAA-3 rod). Tagged fuel (50 ml) was passed through the column. Two repeat passes of the fuel through the column were undertaken using fresh adsorbant. Crushed charcoal was not used as minimal fuel will pass through even under reduced pressure over an hour.
  • Crushed sepiolite column A 10 cm column with 1 cm internal diameter was packed with sepiolite. Tagged fuel (50 ml) was passed through the column. Two repeat passes of the fuel through the column were undertaken using fresh adsorbant.
  • Activated charcoal stir- Activated charcoal powder (2.5 g, powder not pellets) was mixed with tagged fuel (50 ml) and stirred forfour hours at room temperature. The charcoal was filtered off using filter paper.
  • Heat - Fuel 50 ml was placed in a beaker and heated at 60°C for four hours.
  • Air sparging - Tagged fuel 50 ml was placed in a brown glass bottle and air was passed through at about 200 ml/min. The fuel was tested after 24 hours and 48 hours.
  • UV treatment Three scintillation vials were each filled with tagged fuel (25 ml). Two of the vials were placed under a bench top UV lamp (15W, 365nm). One vial was carefully laid on its side under the lamp whilst another was placed upright, without any lid, so that the lamp was directly over it. The distance of these vials from the light bulb was about 12 cm. The third vial was placed on a window sill. The fuel samples were tested after varying degrees of exposure.
  • results of the launder tests in diesel fuel are summarized in the table below indicating fuel type, launder test, and amount of tracer remaining after the test in terms of a percentage of the initial concentration of tracer in the fuel.
  • Para-biphenols can be generated from the reaction scheme in Figure 7.
  • the reaction scheme in Figure 7 uses manganese III acetylacetonate as the oxidant.
  • the synthesis of tetra-methyl biphenyl-diol and tetra-(tert)-butyl-biphenyl-diol using this method is described in MJS Dewar, T Nakaya, J. Am. Chem. Soc. 1968,90, 7134.
  • Examples of other commercially available starting materials include 2,6-di-iso-propyl phenol and 2,6-diphenyl phenol.
  • Figure 8 shows alkylation of 2,6-tert-butyl phenol as described in N. Kornblum, R. Selzer J. Am. Chem. Soc. 1961, 83, 3668.
  • Figure 8 shows alkylation of 2,6-tert-butyl phenol as described in N. Kornblum, R. Selzer J. Am. Chem. Soc. 1961, 83, 3668.
  • An alternative route to the type of molecule in Figure 9 is described in D. Mirk, B. Wibbeling, R. Froehlich, S. Waldvogel, Synlett 2004,11, 1970. It involves the oxidative coupling of ortho-alkyl substituted methoxy benzenes to form a bis-alkyl biphenol ether.
  • biphenol, phenylphenol and phenol-based marker chemicals are all detectable by GC-MS or GC-FID at concentrations from 1-10 ppm.
  • the molecules shown in Figure 9 are also detectable by GC-MS or GC-FID in fuels at similar concentrations.
  • the concentration of the ferricyanide was 0.53M and of the hydroxide 1.8M.
  • the alkaline ferricyanide solution (45 ml) was added quickly to a stirred solution of 2,6-di-tert-butylphenol.
  • the reaction mix immediately turned into a yellow solid, so xylene (25 ml) was added.
  • the reaction mix consisted of a yellow slurry suspended in a dark brown liquid. It was stirred for approximately three hours.
  • the reaction mix was then extracted with xylene and washed with water. The organic phases were combined and then dried over anhydrous magnesium sulfate.

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Abstract

L'invention concerne un procédé de marquage d'un liquide hydrocarboné comprenant l'ajout audit liquide hydrocarboné d'un composé traceur, le composé traceur étant un éther de biphénol substitué ayant une structure noyau de formule I : (I), Les deux groupes R étant identiques ou différents et choisis parmi des groupes alkyle ramifiés ou cycliques à chaîne droite, des groupes phényle ou phényle substitués, des groupes benzyle ou benzyle substitués, ou les deux groupes R forment un seul substituant lié de manière intramoléculaire aux deux atomes d'oxygène, et un ou les deux des cycles aromatiques de la structure noyau étant en outre substitués par au moins un groupe non planaire.
PCT/GB2020/051967 2019-09-23 2020-08-18 Traceurs et procédé de marquage de liquides Ceased WO2021058935A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US17/633,840 US20220298439A1 (en) 2019-09-23 2020-08-18 Tracers and method of marking liquids
EP20764711.6A EP4034614A1 (fr) 2019-09-23 2020-08-18 Traceurs et procédé de marquage de liquides
BR112022002497A BR112022002497A2 (pt) 2019-09-23 2020-08-18 Método de marcação de um líquido de hidrocarboneto, método de identificação de uma fonte de um líquido de hidrocarboneto, e, líquido de hidrocarboneto

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB201913663A GB201913663D0 (en) 2019-09-23 2019-09-23 Tracers and method of marking liquids
GB1913663.9 2019-09-23

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WO2021058935A1 true WO2021058935A1 (fr) 2021-04-01

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GB201913663D0 (en) 2019-11-06
GB2589681A (en) 2021-06-09
EP4034614A1 (fr) 2022-08-03
GB2589681B (en) 2022-10-05
BR112022002497A2 (pt) 2022-04-26
US20220298439A1 (en) 2022-09-22

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