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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
• • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
• • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/226—Organic compounds containing nitrogen containing at least one nitrogen-to-nitrogen bond, e.g. azo compounds, azides, hydrazines
• • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
• • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom

Definitions

• the present invention concerns marker compounds and compositions, in particular dye compounds and compositions.
• the invention further concerns the use of these compounds and compositions for marking hydrocarbon fuels.
• the invention is particularly advantageous, since the marker compounds and compositions are resistant to removal from hydrocarbons, and are also resistant to alteration or destruction to mask their marking effect.
• the present compounds are a significant improvement over conventional markers for identifying and marking rebated fuels or other hydrocarbons.
• Azo dyes were the earliest discovered solvent dyes. Because of their low cost and good solubility in many solvents, they are still being widely used for many applications. One of the most important applications is the colouring of petroleum products, so that different kinds or grades of products can be distinguished.
• tax regimes allow for different rates of taxation depending upon the use to which the fuel is to be put, and the individual or organisation using the fuel.
• fuels for agricultural use e.g. in agricultural vehicles, such as tractors, or in other machinery employed in farming
• the tax on fuel to be put to such uses is less than the equivalent tax levied for private use, such as in private cars or other vehicles.
• the tax rebate may be different for different fuels, or there may be several levels of tax on a single fuel, depending on its uses.
• a blue dye has similarly been applied to kerosene in the UK to distinguish kerosene rebated fuel from diesel rebated fuel.
• Dyes and markers are not only added to rebated fuels, but may be added for other purposes. For example, in many territories dyes are added to any potentially flammable substance as a warning, for safety reasons. In the UK, a violet dye is often added to methylated spirits for this purpose.
• a particular problem for rebated fuels is the requirement to ensure that the marker compound cannot be separated from the fuel, or rendered undetectable. If the dye or marker can be removed, or deactivated in some way, then a criminal organisation is able to buy the fuel at the rebated price and sell it on for a profit at a price below the full non-rebated price of the fuel. In many countries this has been an increasing problem as criminal gangs have found ever more sophisticated methods for processing rebated fuels to remove and/or mask dyes and markers.
• US 5,905,043 discloses diazo-type tags for organic fluids.
• the tags comprise two diazo-type units linked together by an amide bond.
• the tags are designed to be extracted from the fluid with an alkaline aqueous extractant, and then detected.
• US 5,827,332 discloses the use of specific azo dyes as pH dependent markers for hydrocarbons.
• the dyes are designed to be practically colourless in the hydrocarbon, but to exhibit strong colour when a protic acid developer is added in an alcoholic medium.
• the dyes employed are generally diazo compounds having a disubstituted amine-type substituent.
• US 4,514,226 discloses monoazo pyridine colorants. These compounds are indicated to be useful for dyeing and printing polyester materials, as well as being suitable as colourants for organic solvents.
• the dyes and markers disclosed in the prior art are still not entirely satisfactory. It is still possible to remove or deactivate them if sophisticated chemical processes are employed. Indeed, many of the dyes are designed to be removed before detection takes place, so that unscrupulous parties may easily remove the marker, provided that they are aware of its presence. In recent years a number of criminals have been apprehended after illegally removing or deactivating dyes and markers from rebated fuel in the UK and across Europe. Therefore, there is still a requirement to produce improved markers and/or dyes for use in rebated fuels.
• the present invention provides a compound for marking a hydrocarbon, the compound having one of the following structures, or a tautomeric form of one of the following structures: wherein R 1 is a substituent that does not comprise an aromatic unit; n is 0, or is an integer of from 1-5; D is the electron donor substituent; HP is the further hydrophobic substituent; p is an integer of from 1-4; q is an integer of from 1-4; wherein p+q does not exceed 5; at least one D is an OH group; and at least one HP is a straight chain alkyl group; and provided that the compound is not the following:
• this formula is intended to include and/or extend to all tautomeric forms of the above compounds.
• Tautomeric forms are two or more forms of a compound in equilibrium. One form is converted to another by migration of a hydrogen atom.
• a different tautomeric form may be the most common form, rather than the form corresponding to the above formula:
• the first form is termed the enol form whilst the second form is termed the keto form.
• the invention therefore extends also to the second possible tautomeric form (the keto form) as well as the first form (the enol form).
• the keto form has the general formula: where n is an integer of 1 or 2, and X is N, P, O or S.
• the marker compounds of the present invention are particularly advantageous, since they are suitable for adding to hydrocarbons to mark the hydrocarbons, but are difficult to remove. Without being bound by theory, it is believed that it is a combination of an electron donor group and a hydrophobic group on an aromatic group attached to a diazo unit that provides the compound with a resistance to removal from its lipophilic environment. The presence of a combination of at least one hydroxy group and at least one straight chain alkyl group ensures that the compounds are particularly effective. In addition, it further hinders removal of the markers if they are liquid at ambient temperature and pressure (the temperature and pressure at which the fuel is to be used, e.g. at atmospheric pressure from -30° to 50°C, preferably from 0° to 30°C). This is therefore also preferred.
• an electron donor substituent may be any substituent that is capable of donating electrons to a delocalised aromatic system.
• the electron donor may be capable of donating electrons by virtue of the direction of the dipole moment of the group, such as with groups that interact with the aromatic system only through ⁇ -bonds (e.g. alkyl groups).
• the electron donor may be capable of donating ⁇ -electrons into the aromatic system (e.g. halogen atoms, and groups attached through O and N atoms may donate lone pairs situated in orbitals having ⁇ character).
• the donor group attached to the aromatic system may in some cases be attached through an electronegative atom which withdraws electrons through the ⁇ -bond interaction, provided that the overall interaction is electron withdrawing when the ⁇ -interaction is taken into account.
• Cl, Br, I, O and N are all more electronegative than carbon and usually have an electron withdrawing effect through a ⁇ -bond interaction with carbon.
• these atoms are capable of donating lone pair electrons into an aromatic delocalised system, rendering many groups attached via these atoms electron donating overall, despite the ⁇ -bond effect.
• the groups employed in the present invention include hydroxy, alkoxy, amino and substituted (e.g. N-alkyl and N,N-dialkyl) amino groups.
• the present invention employs any of the above electron donating groups. A more detailed description of the preferred groups is given below.
• hydrophobic substituent in the context of the present invention is any substituent that renders the marker compound less soluble in water and/or more soluble in a hydrocarbon liquid, such as a hydrocarbon fuel.
• the substituents are generally lipophilic and are typically straight chain or branched alkyl groups, but are not limited to such groups. A more detailed description of the preferred groups is given below.
• the electron donor substituent and the further hydrophobic substituent may themselves be substituted if desired.
• the type of substitution of these substituents is not especially limited, provided that the function of the marker compound is not impaired.
• Preferred substituents are the same as for R 1 discussed below.
• At least one hydroxy group and at least one straight chain alkyl group must be present on one of the phenyl rings. It is preferred that the hydroxy group and the straight chain alkyl group are para to one another on the phenyl ring. It is also preferred that one of these groups (typically the hydroxy group) is ortho to the N 2 group on the ring.
• the electron donor substituent is not especially limited. Preferably it is selected from Cl, Br, I, a hydroxy group, an ether group, a primary secondary or tertiary amine group, a thiol group, and a thioether group. Most preferably it comprises a hydroxy group or an alkoxy (alkyl ether) group.
• the nature of the further hydrophobic substituent is also not especially limited.
• the further hydrophobic substituent is preferably selected from a primary secondary or tertiary alkyl group, an alicyclic group and a heterocyclic group. More preferably the further hydrophobic substituent is selected from a straight or branched chain higher hydrocarbon having from 6-40 carbon atoms. More preferably still, the further hydrophobic group comprises an alkyl group having from 6-20 carbon atoms, more preferably from 6-12 carbon atoms and most preferably from 6-9 carbon atoms.
• the further hydrophobic substituent thus may comprise straight chain alkyl groups selected from a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group, as well as the branched chain regioisomers of all of the above groups.
• the group R 1 may be any substituent, provided that the function of the marker compound is not impaired. However R 1 does not comprise an aromatic unit such as a phenyl unit. Thus, R 1 may comprise any organic group and/or one or more atoms from any of groups IIIA, IVA, VA, VIA or VIIA of the Periodic Table, such as a B, Si, N, P, O, or S atom or a halogen atom (e.g. F, Cl, Br or I).
• the organic group preferably comprises a hydrocarbon group.
• the hydrocarbon group may comprise a straight chain, a branched chain or a cyclic group. Independently, the hydrocarbon group may comprise an aliphatic group.
• the hydrocarbon group may comprise a saturated or unsaturated group.
• the hydrocarbon may comprise one or more alkene functionalities and/or one or more alkyne functionalities.
• the hydrocarbon comprises a straight or branched chain group, it may comprise one or more primary, secondary and/or tertiary alkyl groups.
• the hydrocarbon comprises a cyclic group it may comprise an aliphatic ring, a heterocyclic group, and/or fused ring derivatives of these groups.
• the number of carbon atoms in the hydrocarbon group is not especially limited, but preferably the hydrocarbon group comprises from 1-40 carbon (C) atoms.
• the hydrocarbon group may thus be a lower hydrocarbon (1-6 C atoms) or a higher hydrocarbon (7 C atoms or more, e.g. 7-40 C atoms).
• the number of atoms in the ring of the cyclic group is not especially limited, but preferably the ring of the cyclic group comprises from 3-10 atoms, such as 3, 4, 5, 6 or 7 atoms.
• the groups comprising heteroatoms described above in respect of R 1 may comprise one or more heteroatoms from any of groups IIIA, IVA, VA, VIA or VIIA of the Periodic Table, such as a B, Si, N, P, O, or S atom or a halogen atom (e.g. F, Cl, Br or I).
• groups IIIA, IVA, VA, VIA or VIIA of the Periodic Table such as a B, Si, N, P, O, or S atom or a halogen atom (e.g. F, Cl, Br or I).
• the substituent may comprise one or more of any of the common functional groups in organic chemistry, such as hydroxy groups, carboxylic acid groups, ester groups, ether groups, aldehyde groups, ketone groups, amine groups, amide groups, imine groups, thiol groups, thioether groups, sulphate groups, sulphonic acid groups, and phosphate groups etc.
• the substituent may also comprise derivatives of these groups, such as carboxylic acid anhydrides and carboxylic acid halides.
• any R 1 substituent may comprise a combination of two or more of the substituents and/or functional groups defined above.
• each R 1 comprises a hydroxy group, an amine group, a halogen, or an alkyl group having from 1-6 carbon atoms.
• the C 6 group not comprising the HP and D groups may be replaced by a C 5 N group if desired, as follows:
• tautomerism may occur, as discussed above.
• the hydrogen atom is typically attached to an N, P, O or S atom, such as in an NH 2 group, a PH 2 group, an OH group or an SH group.
• D preferably comprises or includes such a group.
• the C 6 group not comprising the HP and D groups may be replaced by a C 5 N group if desired, as follows:
• the C 6 group not comprising the OH and C 9 H 19 groups may be replaced by a C 5 N group if desired, as follows:
• the most preferred compound of the present invention is the following: or its tautomer:
• the compound comprising the C 6 group not comprising the OH and C 9 H 19 groups may be replaced by a C 5 N group if desired, as follows:
• the C 9 H 19 group specified in the above compounds may be replaced by a C 6 H 13 group, a C 7 H 15 group, a C 8 H 17 group or a C 10 H 21 group, a C 11 H 23 group or a C 12 H 25 group if desired.
• disperse dyes and solvent dyes have in common the property of being water insoluble. The difference between those dyes is mainly in their use. Disperse dyes are usually used in dispersed form in aqueous medium for synthetic fibres such as polyester and nylon.
• the solvent dyes are used to colour materials through their ability to dissolve in an organic solvent or other substance.
• the marker compounds of this invention are typically solvent dyes, but the invention is not limited to solvent dyes, and disperse dyes may be employed in some cases.
• the present invention further provides a composition for marking a hydrocarbon, the composition comprising a marker compound as defined above and one or more of:
• this composition is an additive composition adapted for addition to a hydrocarbon compound, such as a hydrocarbon fuel, to mark the compound.
• a hydrocarbon compound such as a hydrocarbon fuel
• the nature of the composition is not especially limited, provided that it is capable of marking the compound.
• Additives for inclusion in such compositions are well known in the art and are not especially limited.
• the composition may optionally comprise further markers, if necessary, such as those required by law (e.g. the Euromarker), anti-theft dyes, and/or colouring to render the fuel the same colour as existing fuels comprising current markers. This is preferred in order that the present colour scheme for rebated fuels is not altered.
• diesel may comprise a marker of the present invention, but in addition may comprise the dye used at present (Red 24) in order that users easily recognise the fuel according to its known colour.
• the composition may also comprise antioxidants, such as the quinizarin antioxidant employed in diesel in the UK at present.
• compositions include one or more of the following Approved Dyes in Table 1 and Approved anti-theft dyes in Table 2 below: Approved Dyes in various territories Territory Red Dyes Blue Dyes Yellow Dyes Green Dyes Austria Solvent Red equivalent (Dyeguard Red C®) Solvent Yellow 124 Belgium Solvent Red equivalent (Dyeguard Red C®) Solvent Yellow 124 Denmark Solvent Blue 79 Solvent Yellow 124 Rep.
• the anti-theft dyes of Table 2 are particularly preferable for use in the compositions of the present invention.
• the following Dye (Dye 6 in the Examples below) is particularly preferred for use in the present compositions:
• composition may further optionally comprise additives for aiding dissolution and/or miscibility of the composition with the hydrocarbon to be marked, or stabilising and/or fixing the resulting mixture.
• additives are well known in the art.
• a method for synthesising of a marker compound as defined above comprises coupling an R 1 n Ph-N 2 + moiety with an (D)p(HP)qPh moiety in a diazo coupling reaction, or coupling an (D) p (HP) q -N 2 + moiety with an R 1 n Ph moiety in a diazo coupling reaction, wherein R 1 , D, HP, n, p and q are as defined above.
• R 1 , D, HP, n, p and q are as defined above.
• the invention also provides a marked hydrocarbon fuel comprising a marker compound or composition as defined above.
• the hydrocarbon fuel is selected from a gasoline, a diesel, a paraffin and a kerosene fuel, although any type of fuel may be marked, if desired.
• the hydrocarbon comprises a straight chain or branched chain alkane, alkene, or fatty acid having from 3-30 carbon atoms, or a mixture of the above. More preferably still, the hydrocarbon comprises an alkane having from 5-20 carbon atoms.
• the hydrocarbon comprises pentane, hexane, heptane, octane, nonane, decane, undecane and/or dodecane.
• the marked hydrocarbon fuel can be formed by simply adding and/or mixing a marker compound or composition as defined above with a hydrocarbon fuel as defined above.
• the quantity of marker used in the fuel is not especially limited, and can be selected depending on the individual marker and fuel compound selected.
• the concentration of the marker compound employed is 0.05 mg/l or more, more preferably 0.5 mg/l or more, more preferably still 1 mg/l or more, 2 mg/l or more and most preferably from 0.1-100 mg/l.
• the invention further provides use of a marker in a hydrocarbon fuel for marking the fuel, wherein the marker comprises a compound or composition as defined above.
• Comparative Dye 1 was prepared by coupling 2-naphthol with diazotised aniline, according to the following protocol.
• Aniline (0.025 M, 2.33 g) and hydrochloric acid (35 %, 6 ml) were dissolved in water (10 ml) and cooled to ⁇ 5°C using ice/water bath.
• Sodium nitrite (0.025 M, 1.75 g) dissolved in water (10 ml) was then added to the cooled aniline solution over 5 minutes and the aniline/sodium nitrite mixture solution was stirred for a further 30 minutes in an ice bath.
• Starch-iodide paper was used to ensure excess nitrite ion and, at the end of diazotisation, 10w/w% sulphamic acid aqueous solution was added to remove the excess nitrite ion.
• This dye has maximum absorbance ( ⁇ max in diesel) at 470.2 nm; dyed diesel solution was prepared for testing using a dye concentration of 2 mg/l.
• Comparative Dye 2 was prepared by coupling 2-naphthol with diazotised o-anisidine (2-methoxyaniline, 0.025 M, 3.12 g). The synthesis procedure employed was the same as that for Dye 1 except o-anisidine was used instead of aniline. The reaction is depicted in Scheme 2:
• This dye has maximum absorbance ( ⁇ max in diesel) at 490.8 nm; dyed diesel solution was prepared for testing using a dye concentration of 3 mg/l.
• Comparative Dye 3 was prepared by coupling Naphthol AS (0.025 M, 6.6 g) with diazotised o-anisidine (2-methoxyaniline, 0.025 M, 3.12 g). The synthesis procedure was the same as that for Dye 2 except Naphthol AS was used instead of 2-naphthol. The reaction is depicted in Scheme 3:
• This dye has maximum absorbance ( ⁇ max in diesel) at 508.3 nm; dyed diesel solution was prepared for testing using a dye concentration of 5 mg/l.
• Comparative Dye 4 was prepared by coupling 5-amino-1-naphthol (0.025 M, 4.2 g) with diazotised aniline. The synthesis procedure was the same as that for Dye 1, except 5-amino-1-naphthol was used instead of 2-naphthol. The reaction is depicted in Scheme 4:
• This dye has maximum absorbance ( ⁇ max in diesel) at 495.1 nm; dyed diesel solution was prepared for testing using a dye concentration of 2.5 mg/l.
• Comparative Dye 5 was prepared by reaction of 1,4-diaminoanthraquinone with benzyl chloride.
• 1,4-diaminoanthraquinone (0.01 M, 2.65 g) and benzyl chloride (0.022 M, 2.87 g) were dissolved in DMF ( N , N -dimethylformamide, 100 ml) and the solution was refluxed for 12 hours.
• the product solution was then poured in to distilled water (300 ml) and the resulting dyes precipitated; filtration was improved by the addition of sodium chloride.
• the precipitated dye was filtered, washed with distilled water and dried at room temperature.
• the reaction is depicted in Scheme 5:
• This dye has maximum absorbance ( ⁇ max in diesel) at 568.9 nm; dyed diesel solution was prepared for testing using a dye concentration of 9 mg/l.
• Comparative Dye 6 is a commercially available dye from Hollidays (Yule Catto) in Huddersfield (UK).
• the commercial name of this dye is Sublaprint Blue 70038 (CI Solvent Blue 36). This dye has maximum absorbance ( ⁇ max in diesel) at 596.7 nm and 644.6 nm; dyed diesel solution was prepared for testing using a dye concentration of 2 mg/l.
• the structure of Dye 6 is depicted in Scheme 6:
• Dye 7 is a dye of the present invention, and was prepared by coupling nonylphenol (0.025 M, 5.75 g) with diazotised aniline. The synthesis procedure was the same as that for Dye 1, except nonylphenol was used instead of 2-naphthol. The resulting dye was of liquid form and separation was carried out using column separation method: there were clear two layers, dye and water/acetone mixture. The bottom part of the layers (water/acetone mixture) was drained. The resulting dye was dried over anhydrous Na 2 SO 4 at room temperature. The reaction is depicted in Scheme 7:
• This dye has maximum absorbance ( ⁇ max in diesel) at 402.0 nm; dyed diesel solution was prepared for testing using a dye concentration of 4 mg/l.
• Comparative Dye 8 was prepared by reaction of Rhodamine 6G (CI Basic Red 1) with sodium hydroxide. Rhodamine 6G (0.01 M, 4.8 g) and excess sodium hydroxide (0.08 M, 3.2 g) were dissolved in distilled water (100 ml) and this solution was heated up to 75°C. As the temperature was increased, the Rhodamine dye became insoluble in water and precipitated. After a further 30 minutes, the precipitated dye was filtered, washed with warm distilled water and dried in an oven (60°C) for 6 hours. The dried dye was then mixed with oleic acid (0.01 M, 3.1 g). The reaction is depicted in Scheme 8:
• This dye has maximum absorbance ( ⁇ max in diesel) at 531.6 nm; dyed diesel solution was prepared for testing using a dye concentration of 9 mg/l.
• Dyeguard Yellow 124 (CI Solvent Yellow 124), which will be added as the Euromarker throughout Europe. It is commercially available throughout Europe. This dye has maximum absorbance ( ⁇ max in diesel) at 406.8 nm; dyed diesel solution was prepared for testing using a dye concentration of 5 mg/l. Its structure is depicted in Scheme 9:
• Comparative Dye 10 is a mixture of CI Solvent Red 24 and quinizarin, which is the so-called 'Gas Oil Marker'. This dye is currently being used to mark rebated diesel in the UK. This dye has maximum absorbance ( ⁇ max in diesel) at 517.2 nm; dyed diesel solution was prepared for testing using the concentration of 1 part concentrate solution/1000 part oil.
• the structures of Red 24 and quinizarin are depicted in Scheme 10:
• Stability tests for each dye were carried out using 10 ml of dyed diesel.
• Each test was carried out by mixing the above chemicals with dyed diesel and shaking for a while and left overnight. Filtration using activated carbon was carried out twice for each case.
• the absorbance of the dye solution was measured before and after the laundering process at the wavelength of maximum absorption of the dyes using a Perkin-Elmer Lambda 15 UV-Visible light spectrophotometer.
• the percentage loss of each dye under the applied methods was determined using the following equation:
• Dye 9 which will be added throughout Europe as the 'Euromarker', showed relatively poor resistance (c.a. 77 % dye destroyed) against hydrochloric acid, although this dye solution increased to almost twice the absorbance following laundering with sodium hypochlorite. Filtration by activated carbon results resulted in more than half of Dye 9 being absorbed in the first filtration. After filtering twice, the original Dye 9 as well as some additives were totally removed.
• Dye 10 which is being used at present to mark rebated diesel in the UK, showed relatively poor resistance (c.a. 70 % dye destroyed) against hydrochloric acid. This dye had relatively good resistance (c.a. 30 % dye destroyed) against oxidative bleaching (NaOCl) when compared with the other dyes, although this dye was not as good as Dye 7. In particular, this dye was completely absorbed in the first filtration by activated carbon and clear diesel was obtained.
• Dye 7 (a marker compound of the present invention) shows very good resistance against all laundering processes employed. It is the only dye displaying an acceptable performance across the full range of decolourants employed. The colour strength of Dye 7 was even improved after treatment with hydrochloric acid and sodium hypochlorite (by 1.7 % and 12.8 %, respectively). Dye 7 had also relatively good resistance against sodium hydroxide as did Dyes 1, 2, 5 and 6. The most surprising and advantageous result was that this dye showed uniquely positive results against activated carbon filtration. Only half of this dye was absorbed after twice filtration whereas the other dyes were completely absorbed under the same condition, except Dyes 1 and 6 (c.a. 93 % and 89 % absorbed, respectively). It can therefore be concluded that Dye 7 would be suitable for use as a new oil marker having good resistance against acid, oxidative bleaching and filtering processes.
• Dye 7 has good resistance, especially against activated carbon filtration, and thus dye mixtures containing this dye will have acceptable resistance to laundering. Accordingly fuels could be produced using Dye 7 that have various colours.
• five different mixtures were prepared and tested, and the colour strength of each dye in the dye mixtures was quantified by measuring absorbance at ⁇ max of each dye. It should be noted that mixtures of dyes have been termed 'colours' for the purposes of this comparison. The five different colours tested were as follows:
• Dye 6 (at 644.4nm) also displayed some resistance to filtration, and Colours 11 and 15 had blue shade left after second filtration, although analysis showed that over 90% of dyes were absorbed and its performance was clearly inferior to Dye 7.
• Dye 10 (at 517.2nm) in Colours 12, 13 and 14 showed poor performances especially in the case of all filtering processes: no red shade was left after twice activated carbon filtration.
• Dye 7 with other Dyes, such as Dye 6, Dye 9 and Dye 10 can be used to mark oil having good resistance against known laundering processes such as activated carbon filtering, and the fuel hue can be varied by using different concentrations of the two dyes or adding other dyes for various colours.
• the marker compounds of the present invention show good resistance against HCl, NaOCl, NaOH, and activated carbon, i.e. across a wide range of agents commonly employed to destroy or remove markers.
• This dye showed superior results compared with all the other dyes against activated carbon filtration. Only half of this dye was absorbed after twice filtering with activated carbon whereas Dyes 2, 3, 4, 5, 8, 9 and 10 were completely absorbed under the same conditions; Dyes 1 and 6 also showed some resistance to activated carbon filtration, and may also be used in the compositions of the present invention in conjunction with the present markers, such as Dye 7.

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