HYDROCARBON PRODUCT MARKING

Abstract

The present invention relates to a method for marking a hydrocarbon product (HP) by using at least two markers, wherein the at least two markers have at least one same atom and / or functional group and the markers have different boiling points and / or different distillation profiles The markers are selected in such a way that the entire range of the distillation temperature T(BpL) and T(BpE) of the HP is covered. An atom portion originating from individual markers M1 and M2 in a marker mixture Mx is determined by performing a regression analysis for at least part of the distillation temperature range of the HP. Based on said analysis a marker mixture Mx is calculated and added to mark a HP. The invention also relates to a fuel marked by the method and methods for detecting adulteration in HP.

Description

1 / 35 HYDROCARBON PRODUCT MARKING FIELD OF THE INVENTION

[0001] The present invention relates to the technical field of hydrocarbon (HP) product marking and to a method for marking HPs with at least two markers containing at least one of the same atom and / or functional groups to ensure the qualitative as well as quantitative determination of adulteration of the marked HP. BACKGROUND OF THE INVENTION

[0002] Product marking is described as the process of adding a security marker or label, which may be a molecule, an atom, or a chemical compound, to a product that allows its origin to be traced or its adulteration to be prevented throughout the supply chain. Throughout the HP supply chain, various products such as crude oil, mineral oil, fuel oil, gasoline, diesel, etc., may be subject to marking to allow traceability of their origin or to prevent adulteration with lower quality products or products subject to lower or non-existent taxes. Many of these products may be subjected to a distillation process with the malicious intent of removing the markers from the marked hydrocarbon product and thus eliminating traceability.

[0003] For example, in many countries, diesel is subsidized for certain industrial sectors, such as agriculture or mining, while it is marketed with a high level of taxation for the automotive sector. The result is a very significant price difference due to the level Petition 870250081200, dated 10 / 09 / 2025, p. 14 / 63 2 / 35 different from taxation, which becomes an incentive for fraud, that is, the sale of agricultural fuel as automotive fuel. To detect this type of fraud, governments mark the agricultural fuel; if the marker is detected at service stations that sell automotive fuel, it can be proven that the fuel was being sold illegally. Criminals use distillation to remove the marker and then sell the unmarked product at the price of automotive fuel, with the consequent impact on tax revenue.

[0004] In another example, in some countries or regions, fuel is generally heavily subsidized, and in some local distribution centers, the selling price of HP is significantly lower than the international market price. Therefore, there is a clear incentive to buy subsidized fuel locally and illegally export it to later sell it at international prices for economic benefit, which affects the coffers of the producing country. In these cases, the local fuel is marked and controlled at the borders. Fraud or adulteration is detected if the exported cargo shows the presence of the marker. Smuggling networks once again use distillation as a method of laundering the product.Even when the marker is not completely removed and authorities manage to detect it in a suspicious shipment, the latency of the concentration due to the distillation process does not allow authorities to fairly quantify how much product was confiscated, and therefore it is impossible to apply current legislation that generally imposes penalties and fines depending on the damage caused to public coffers. Petition 870250081200, dated 10 / 09 / 2025, page 15 / 63 3 / 35

[0005] Since most products in the hydrocarbon distribution chain are complex mixtures of hydrocarbons, they all exhibit a distillation curve or profile over a wide temperature range, making homogeneous measurement by a single marker impossible. As a result, through a distillation process, the marker is distributed non-homogeneously in the different fractions, completely losing its original concentration and leaving many fractions completely marker-free. Or, in the worst case, the marker undergoes complete degradation, resulting in distillation products that are entirely marker-free. Thus, the qualitative and quantitative detection of the marker in the marked product is important as it helps prevent illicit activities aimed at obtaining monetary benefits.

[0006] Croud et al. (Fuel Processing Technology, 144, (2016), 341-347) discloses a method for marking diesel with a single marker that is resistant to distillation. Thus, fraudulent attempts to separate the diesel from the marker are doomed, as the marker can be detected by GC-MS in all distillation fractions of the marked diesel. However, this method has the disadvantage of not allowing quantification of adulteration unless a complex and time-consuming calibration process is required.

[0007] US patent 9688930 B2 discloses the use of multiple markers with different boiling points to cover the entire range of the labeled hydrocarbon product. Therefore, fraudulent distillation attempts are detected, as all distillation fractions will contain at least one of the markers. However, this method has the disadvantage of Petition 870250081200, dated 10 / 09 / 2025, page 16 / 63 4 / 35 that the quantification of adulteration can only be carried out through complex and time-consuming calibration and validation processes.

[0008] US patent 10808192 B2 discloses the use of two markers: one with a low boiling point (A) and another with a high boiling point (B). The sample is labeled with a specific A / B ratio. A distillation fractionation of the labeled hydrocarbon product is performed to determine the A / B ratio in each distillation fraction. When an unknown sample is analyzed, the concentration of A and B is measured, and the A / B ratio can be calculated and correlated with previously determined ratios. However, this method has the disadvantage that no correlation with previously determined ratios can be made if only one of the markers, A or B, is detected and measured in the adulterated product.

[0009] Therefore, there is a need to provide a suitable, convenient and robust method for marking a hydrocarbon product, which not only reveals fraudulent attempts at adulteration, mainly through distillation and / or dilution, but also allows for easy detection of the marker and its quantification. SUMMARY OF THE INVENTION

[0010] In a first aspect, the invention relates to a method of marking a hydrocarbon (HP) product comprising the steps of: A. Selection of a hydrocarbon (HP) to be labeled and recording of the HP distillation profile to determine the initial temperature T(BpL) and the final temperature T(BpE) at which distillation occurs; Petition 870250081200, dated 10 / 09 / 2025, page 17 / 63 5 / 35 B. Selection of at least two compatible and distillable markers (M1, M2) to label the HP, wherein said markers comprise at least one of the same atom and / or functional group to be analyzed by a suitable analytical technique, wherein M1 and M2 individually have different boiling points and / or different distillation profiles, wherein one of M1 or M2 has a boiling point temperature T(BpM1) being lower than T(BpL) or one of M1 or M2 has a boiling point temperature within the distillation temperature range of the HP [T(BpL) < T(BpM1) < T(BpE)], and being at most 20% higher than T(BpL), and wherein one of M1 or M2 has a boiling point temperature T(BpM2) higher than T(BpE) or the other M1 or M2 has a boiling point temperature that is within the distillation temperature range of the HP HP [T(BpL) < T(BpM2) < T(BpE)], and being at most 20% lower than T(BpE); C. selection of a Ct value for total atom concentration, where the Ct value is selected based on the analytical technique and on at least one of the same atoms and / or functional groups to be analyzed by said analytical technique, selected in step B); D. Preparation of individual solutions n1 and n2 of markers M1 and M2 in HP, respectively, preferably at the Ct value, and determination, before fractional distillation, of the initial concentration and initial total mass of at least one of the same atom and / or functional group in n1 and n2 using the analytical technique selected in step D. Petition 870250081200, dated 10 / 09 / 2025, page 18 / 63 6 / 35 B); E. Performing separate fractional distillation of solutions n1 and n2 to obtain fractions F; F. determination of the concentration and total mass of at least one of the same atom and / or functional group in each fraction F using the analytical technique selected in step B); G. Calculate the percentage of the atomic mass (%) relative to the initial total mass of at least one of the same atoms and / or functional groups determined in step D) in each fraction F and determine the cumulative percentage of the atomic mass for each fraction F; H. determination of an atom portion originating from individual markers M1 and M2 in a mixture of markers Mx by performing a regression analysis to determine a relationship between the cumulative percentage of the atom mass for each fraction F as determined in step G) for each of the solutions n1 and n2 and the HP distillation profile determined in step A) for at least part of the HP distillation temperature range; I. Calculation of a marker mixture composition Mx based on the atom portion determined in step H) for each marker M1 and M2, the weight fraction of each atom and / or functional group in each marker M1 and M2, and the purity of markers M1 and M2; J. Preparation of the marker mixture (Mx) by mixing the quantities of markers determined in step I) and adding it to the hydrocarbon product HP at around the Ct value.

[0011] In a second aspect, the invention relates to a Petition 870250081200, dated 10 / 09 / 2025, page 19 / 63 7 / 35 fuel marked by the method described in this document.

[0012] In another aspect, the invention relates to a method for detecting adulteration in a hydrocarbon (HP) product comprising the steps of: a) sampling of a labeled HP according to the method described in this document, said HP having a predetermined Ct value; b) detection and calculation of the Ct value in the HP sample using an appropriate analytical technique; c) assessment of potential HP adulteration by comparing the Ct value determined in step b) with the predetermined Ct value from step a).

[0013] In a final aspect, the invention relates to a method for detecting adulteration in a hydrocarbon (HP) product comprising the steps of: a) sampling of a first HP; b) detection and, if present, quantification of an atom and / or functional group by means of an appropriate analytical technique; c) determination of the quantity of a second labeled HP according to the method described in this document, based on the atom and / or functional group quantified in step b). BRIEF DESCRIPTION OF THE DRAWINGS / FIGURES

[0014] Figs. 1a and 1a illustrate the distillation curves of example E1, in particular the distillation profile of the pure hydrocarbon product HP1 (gasoline) (Fig. 1a), the distillation profiles of the three solutions of the three markers E1-M1, E1-M2 or E1-M3, each dissolved in HP1 (Fig. 1b) and the Petition 870250081200, dated 10 / 09 / 2025, page 20 / 63 8 / 35 distillation profiles of the pure hydrocarbon product HP1 and the distillation profile of a mixture of markers Mx including fractions of E1-M1, E1-M2 or E1-M3 in HP1 (Fig. 1c), as calculated by regression analysis.

[0015] Figs. 2a-c illustrate the distillation curves of example E2, in particular the distillation profile of the pure hydrocarbon product HP2 (diesel) (Fig. 2a), the distillation profiles of four solutions of the four markers E2-M1, E2-M2, E2-M3 or E2-M4, each dissolved in HP2 (Fig. 2b) and the distillation profiles of the pure hydrocarbon product HP2 and the distillation profile of a mixture of markers Mx including fractions of E2-M1, E2-M2, E2-M3 and E2-M4 in HP2 (Fig. 2c), as calculated by regression analysis.

[0016] Figs. 3a and 3c illustrate the distillation curves of example E3, in particular the distillation profile of the pure hydrocarbon product HP3 (kerosene) (Fig. 3a), the distillation profiles of the three solutions of the three markers E3-M1, E3-M2 or E3-M3, each dissolved in HP3 (Fig. 3b) and the distillation profiles of the pure hydrocarbon product HP3 and the distillation profile of a mixture of markers Mx including fractions of E3-M1, E3-M2 or E3-M3 in HP3 (Fig. 3c), as calculated by regression analysis. DETAILED DESCRIPTION Definitions

[0017] The following definitions should be used to interpret the meaning of the terms discussed in the description and recited in the claims.

[0018] As used in this document, the article "a" indicates one, as well as more than one, and does not necessarily limit its referent noun to the singular. Petition 870250081200, dated 10 / 09 / 2025, page 21 / 63 9 / 35

[0019] As used in this document, the term "about" means that the quantity or value in question may be the designated value or some other similar value. The sentences are intended to convey that similar values ​​within a range of ± 5% of the indicated value promote equivalent results or effects according to the invention.

[0020] As used in this document, the term at least one is intended to define one or more than one, for example, one or two or three.

[0021] As used in this document, the term and / or means that all or only one of the elements of said group may be present. For example, A and / or B should mean only A, or only B, or both A and B. In the case of only A, the term also covers the possibility that B is absent, that is, only A, but not B.

[0022] The term comprising, as used in this document, is intended to be non-exclusive and open to interpretation. The term comprising also includes, as a particular modality, the more restrictive meanings of essentially consisting of and consisting of.

[0023] When the present description refers to preferred modes / features, combinations of these preferred modes / features should also be considered as disclosed, provided that such combination of preferred modes / features is technically significant.

[0024] Atom means an element (of the periodic table) that can be detected quantitatively by a selected analytical technique. Petition 870250081200, dated 10 / 09 / 2025, page 22 / 63 10 / 35

[0025] A functional group means a chemical fraction that can be quantitatively detected by a selected analytical technique. A functional group contains at least two different atoms.

[0026] Marker means a chemical compound that contains at least one atom and / or functional group.

[0027] Distillation profile is the graphical representation obtained by plotting the percentage of HP distilled at a specific temperature, as shown in the figures.

[0028] T(BpL) is the initial temperature at which the first drops of distillate are obtained when distilling an HP.

[0029] T(BpE) is the final temperature at which the final drops of distillate are obtained when distilling an HP.

[0030] Distillate is the liquid that results from the condensation of vapor produced by heating a liquid to be distilled. It is the product recovered by distillation when heated from T(BpL) to T(BpE).

[0031] Mx is the mixture of markers obtained by mixing at least two markers M1 and M2, wherein the quantities of the individual markers are determined based on the method described in this document.

[0032] The method described in this document has as its main, but not exclusive, objective the marking of a hydrocarbon product (HP). The term HP refers to any liquid hydrocarbon, including, but not limited to, refined or unrefined petroleum products such as crude oil, naphtha, gasoline, diesel, fuel oil. Petition 870250081200, dated 10 / 09 / 2025, page 23 / 63 11 / 35 aviation, kerosene, propane, lubricant (e.g., engine oil), hydraulic fluid, and natural gas. The method described herein can also be used to mark other distillable products.

[0033] The marking method described in this document comprises steps A) - J). In a preferred embodiment, the steps should be performed one after the other, as defined. However, it is within the knowledge of one skilled in the art to rearrange some of the steps or perform them in parallel without losing the essence of the method and where it is logical to do so. For example, steps A) - C) can be performed in a different order without affecting the eventual result.

[0034] The marking method described in this document involves step A), in which the HP to be marked is subjected to distillation to record the distillation profile of the HP. The distillation profile helps to determine, among other things, the temperatures T(BpL) and T(BpE) of the distilled HP. Distillation can be performed using any standard distillation apparatus suitable for the purpose, preferably using the ASTM D-86 standard.

[0035] Step B), which may be performed after Step A), comprises the selection of at least two compatible and distillable markers (M1, M2) to label HP, said markers comprising at least one identical or equal atom and / or functional group to be analyzed by a suitable analytical technique, wherein M1 and M2 have different boiling points and / or different distillation profiles. In a preferred embodiment, more than two markers are selected and, even more preferably, four. Petition 870250081200, dated 10 / 09 / 2025, p. 24 / 63 12 / 35 markers M1 - M4 are selected to mark the HP. It is also possible to have more than four markers, that is, i markers that contain at least one of the same atom and / or functional group.

[0036] The at least two markers containing at least one of the same atoms and / or functional groups are selected such that one of M1 or M2 has a boiling point temperature T(BpM1) lower than T(BpL) or one of M1 or M2 has a boiling point temperature within the HP distillation temperature range [T(BpL) < T(BpM1) < T(BpE)] and is at most 20%, preferably 15%, higher than T(BpL), and wherein one of M1 or M2 has a boiling point temperature T(BpM2) higher than T(BpE) or the other M1 or M2 has a boiling point temperature that is within the HP distillation temperature range [T(BpL) < T(BpM2) < T(BpE)], and is at most 20%, preferably 15%, lower than T(BpL). T(BpE). The selection of at least two markers in such a way ensures that the HP distillation range is covered by at least one marker that contributes at least one of the same atoms and / or functional groups to be analyzed and quantified.

[0037] The at least two markers described in this document must be compatible and distillable with the HP to be marked. Compatibility means that markers that are stable, miscible, and compatible with HP are selected for marking. For example, the markers meet certain requirements, such as being environmentally friendly (i.e., not harmful to the air, to the Petition 870250081200, dated 10 / 09 / 2025, p. 25 / 63 13 / 35 water, soil components, living organisms and the like), non-corrosive, non-volatile, non-toxic, non-reactive with each other or with HP. Furthermore, the markers are capable of being detected and quantified within the quantification range of the hydrocarbon product. Therefore, the nature of the markers and the amount added to the product must allow for the subsequent detection of at least one of the same atoms and / or functional groups contained in the markers using an appropriate analytical technique. The amount of each marker added is preferably calculated to provide a concentration of at least one of the same atoms and / or functional groups greater than the lower limit of quantification (LLQ). The LLQ can be the concentration at which a certain minimum level of certainty can be guaranteed in measuring the concentration of at least one of the same atoms and / or functional groups by the selected analytical technique.

[0038] The detection or analysis method used may be selected from those that have the necessary sensitivity and selectivity according to the type of atom and / or functional group to be detected and quantified. In some cases, optical methods such as fluorescence, surface-enhanced Raman spectroscopy, Fourier transform infrared (FT-IR), or UV spectroscopy may be used. At least one atom and / or functional group may be detectable by mass spectrometry or by atomic absorption spectroscopy using elemental analysis. Suitable methods may be based on mass spectrometry, such as inductively coupled plasma mass spectrometry (ICP-MS), or emission spectroscopy, such as ICP optical emission spectroscopy (ICP-MS). Petition 870250081200, dated 10 / 09 / 2025, page 26 / 63 14 / 35 (OES). A particularly advantageous method is based on X-ray fluorescence spectroscopy (XRF). Another preferred method is the use of FT-IR to detect and quantify the amount of a functional group.

[0039] The at least two markers described in this document contain at least one identical or identical atom and / or functional group that can be analyzed and quantified by a suitable analytical technique. For example, if two different markers are selected, then they contain at least one same atom G and / or at least one same functional group H. In another embodiment, the at least two markers may contain another additional common analyzable atom and / or functional group.

[0040] According to one example, the marker may be based on an alkane, whose formula is CnH2n+2, where n = 1,2,3... At least one hydrogen atom is replaced by an element that can be preferentially detected by an XRF analyzer. The resulting compound has the general formula CnH2n+2-mXm, where n = 1,2,3... and m = 1,2,3... X is any element that can be preferentially detected by an X-ray fluorescence analyzer. A simple example of such an element is lithium (Li), an alkali metal, which forms a covalent bond with a carbon atom. In a preferred embodiment, the element X is a halogen.

[0041] Consequently, the marker can be a halogen compound, such as an alkyl halide with the general formula CnH2n+2-mXm, where n = 1,2,3..., m = 1,2,3... X is a halogen, such as fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). The following are the chemical names and molecular formulas of some suitable examples of the marker in halide form. Petition 870250081200, dated 10 / 09 / 2025, p. 27 / 6 15 / 35 alkyl: 1,1,2,2-tetrachloroethane (C2H2CI4), 1,1,2trichloroethane (C2H3CI3), pentachloroethane (C2HCI5), hexachloroethane (C2CIg), 1,2,4-trichloroethane (CgH9CI3), 1,2,4,5-tetrachlorobenzene (CgH8CI4), ethyliodetho (C2H5I), ethylbromate (C2H5Br), dichloro-1,2-dibromoethane (C2H2Cl2Br2), dichlorotribromoethane (C2HCI2Br3), difluoro-1-chloroethane (C2H3F2CI), difluoro-1,2-dibromoethane (C2H2F2Br2), trifluoro1,2,2-dibromoethane (C2HF3Br2), tribromopropane (C5H7Br3), dibromobenzene (CgH10Br2), dibromoethane (C2H4Br2), npropylbromate (C3H7Br), parabromofluorobenzene (C6H4FBr), butylbromate (C4H9Br) and octylbromate (C8H15Br), 2chloropropane (C3H7Cl), 1-chloropropane (C3H7Cl), chlorohexane (CgH13Cl), iodobenzene (CgH5I), 1,4-diiodobutane (C4H8I2), 1,6-diiodohexane (C4H8I2), 1-iodohexadecane (C16H33I).

[0042] According to another example, the marker may be an organometallic or halogen compound in which at least one metallic element or at least one halogen is bonded to at least one carbon atom of an alkene (olefin), with the general formula (CnH2n-m)Xm where n = 2,3..., m = 1,2,3... X is an alkali metal or a halogen. An example of such a compound is bromoethylene with the molecular formula C2H3Br.

[0043] According to a further example, the marker can be any of the compounds mentioned above, in which silicon (Si), germanium (Ge), and the like replace a carbon atom. For example, diethylsilane (i.e., C4H12Si) is one such compound. It should be noted that silicon is detectable by an X-ray fluorescence analyzer. Consequently, the X elements (i.e., halogens) do not need to appear in the compound if silicon, germanium, and the like serve as the detectable marker element. Petition 870250081200, dated 10 / 09 / 2025, page 28 / 63 16 / 35 by X-ray fluorescence analyzer. For alkanes, the general formula of the compound is Cn-mH2n+2Ym, where n = 1,2,3..., m = 1,2,3..., m <n e onde Y designa o silício, o germânio e similares. Para alcenos (olefinas), a fórmula geral do composto é (Cn-mH2n-m)Ym, em que n = 1,2,3..., m = 1,2,3... e em que Y designa o silício, o germânio e similares.

[0044] Another class of markers that are particularly suitable are alkoxisilanos and alkoxisilanos de alquila, como metiltrimethoxysilano (CAS 1185-55-3), dimethoxydimethylsilano (CAS 1112-39-6), methoxytrimetilsilano (CAS 1825-61-2), ethoxytrimetilsilano (CAS 1825-62-3), triethoxymethylsilano (CAS 2031-67-6), isopropoxytrimetilsilano (CAS 1825-64-5), triethoximetilsilano (CAS 2031-67-6), trimethoxy(octyl)silano (CAS 3069-40-7), trimethoxy(octadecyl)silano (CAS 3069-42-9), hexadecyltrimethoxysilano (CAS 3069-42-9) 16415-12-6), triethoxy(octyl)silano (CAS 2943-75-1), tetraethylorthosilicate (CAS 78-10-4), dicyclopentylmethoxysilane (CAS 126990-35-0), hexamethyldissiloxane (CAS 107-46-0), (3aminopropyl)trimethoxysilane (CAS 13822-56-5), (3aminopropyl)triethoxysilane (CAS 919-30-2), (N,Ndimethylaminopropyl)trimethoxysilane (CAS 2530-86-1), (3mercaptopropyl)trimethoxysilane (CAS 4420-74-0), (3mercaptopropyl)triethoxysilane (CAS 14814-09-6),triethoxy-3-(2-imidazolin-1-yl)propylsilane (CAS 58068-97-6) or cyclomethicones, which are a group of methylsiloxanes with a [(CH3)2SiO]n backbone structure. Suitable non-limiting examples include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, Petition 870250081200, dated 10 / 09 / 2025, page 29 / 63 17 / 35 dodecamethylcyclohexasiloxane, hexamethylcyclotrisiloxane, tetradecamethylcycloheptasiloxane (CAS 107-50-6), hexadecamethylcyclooctasiloxane (CAS 556-68-3), octadecamethylcyclononasiloxane (CAS 556-71-8), eicosamethylcyclodecassiloxane (CAS 18772-36-6), docosamethylcycloundecassiloxane (CAS 18766-38-6), tetracosamethylcyclodecassiloxane (CAS 18919-94-3), hexacosamethylcyclotridecassiloxane (CAS ) or silanol compounds, such as trimethylsilanol (CAS 1066-40-6) or compounds of the silazan family, such as, but not limited to, hexamethyldisilazane (CAS 999-97-3), 1,1,3,3-tetramethyldisilazane (CAS 15933-59-2), 1,3-diethyl-1,1,3,3-tetramethyldisilazane (CAS 17882-94-9), 2,2,4,4,6,6-hexamethylcyclotrisilazane (CAS 1009-93-4) or halogenated silanes, such as, but not limited to, chlorodimethylsilane (CAS 1066-35-9), dichloromethylsilane (CAS 75-54-7), dichlorodimethylsilane (CAS 75-78-5), chloromethyltrimethylsilane (CAS 2344-80-1), bromotrimethylsilane (CAS 2857-97-8), iodomethyl)trimethylsilane (CAS 4206-67-1), chloro(chloromethyl)dimethylsilane (CAS 1719-57-9), trichloro(octadecyl)silane (CAS 112-04-9), trichlorododecylsilane (CAS 4484-72-4), trichloro(octadecyl)silane (CAS 5283-66-9), trichloro(phenethyl)silane (CAS 940-41-0), trichloro(hexyl)silane (CAS 928-65-4), methyltrichlorosilane (CAS 75-79-6), chloro(3-chloropropyl)dimethylsilane (CAS 1060540-0), (3-chloropropyl)trimethoxyxylane (CAS 2530-87-2), (3bromopropyl)trimethoxyxylane (CAS 51826-90-5), (3iodopropyl)trimethoxyxylane (CAS 14867-28-8), Petition 870250081200, 10 / 09 / 2025, pág. 30 / 63 18 / 35 trifluoromethanesulfonate de trimethylsilyla (CAS 27607-778).

[0045] If infrared spectroscopy (FT-) or Raman spectroscopy (surface enhanced) is selected as the analytical technique, suitable detectable and quantifiable functional groups may be used as part of the method described in this document. Some examples are ketones and mixtures thereof, such as, but not limited to, octanone (CAS 106-68-3), 2-nonanone (CAS 821-556), 2-decanone (CAS 693-54-9), 3-hexadecanone (CAS 18787-649), 5-octadecanone (CAS 18276-99-8) or hydrazines and mixtures thereof, such as, but not limited to, 1,2-dimethylhydrazine (CAS 540-73-8), 1,2-diethylhydrazine (CAS 1615-80-1), 1,2-dipropylhydrazine (CAS 1615-83-4), 1,2-bis(1-methylethyl)hydrazine (CAS 3711-34-0), 1,2-dibutylhydrazine (CAS 1744-71-4), N,N-dimethylhydrazine (CAS 57-14-7), 1-aminopiperidine (CAS 2213-43-6), 1-amino-4-methylpiperazine (CAS 6928-85-4) or nitro compounds and mixtures thereof, such as, but not limited to, 1-nitroethane (CAS 79-24-3), 1-nitropropane (CAS 108-03-2),1-nitrobutane (CAS 627-05-4), nitrobenzene (CAS 98-95-3) or cyclic esters and mixtures thereof, such as, but not limited to, δ-undecalactone (CAS 710-04-3), γ-undecalactone (CAS 104-67-6), δ-dodecalactone (CAS 713-95-1), δ-tridecalactone (CAS 7370-92-5), δ-tetradecalactone (CAS 2721-22-4) or ethers and mixtures thereof, such as, but not limited to, dimethoxymethane (CAS ), diethyl ether (CAS 60-29-7), diisopropyl ether (CAS 108-203), di-tert-butyl ether (CAS 6163-66-2), dibutyl ether (CAS 142-96-1), dihexyl ether (CAS 112-58-3), tert-butyl methyl ether (CAS 1634-04-4), 1-methoxyhexane (CAS 4747-07 Petition 870250081200, dated 10 / 09 / 2025, page 31 / 63, 19 / 35 3) diethyl acetal formaldehyde (CAS 462-95-3).

[0046] Step C) involves selecting a Ct value for the total atom concentration, where the Ct value is selected based on the analytical technique and the presence of at least one atom and / or functional group to be analyzed by said analytical technique, selected in step B). The Ct value can range from about 10 ppm to about 2000 ppm, preferably from about 10 ppm to about 1000 ppm. The selection of the Ct value should be made in such a way that reliable quantification of at least one atom and / or functional group can be obtained by the selected analytical technique.

[0047] To determine the individual distillation profile for at least two markers M1 and M2, step D) comprises the preparation of individual solutions n1 and n2, respectively, in the HP to be labeled. The concentration of at least one atom and / or functional group can be freely selected, but it is preferable that it be close to the Ct value itself, and may even be lower than the Ct value. In a preferred embodiment, the concentration of at least one atom and / or functional group is selected to be equivalent to the Ct value. Before performing the fractional distillation of solutions n1 and n2 individually, the initial concentration and initial mass of at least one atom and / or functional group are determined by the analytical technique selected in step B).

[0048] Step E) involves performing separate fractional distillation of solutions n1 and n2 to obtain fractions F1-X and F2-X, respectively. For example, if 10 fractions are collected for solution n1, they will be Petition 870250081200, dated 10 / 09 / 2025, page 32 / 63 20 / 35 designated as F1-1 to F1-10. Distillation can be carried out using any standard distillation apparatus suitable for the purpose, preferably using the ASTM D-86 standard.

[0049] The concentration and total mass of at least one of the same atom and / or functional group in each F1-X fraction are determined by the analytical technique selected in step B) above. The same operation is performed on the F2-X fractions of the n2e solution for any additional My marker in a corresponding ny solution prepared as described in this document.

[0050] Step G) involves calculating the percentage of the atom's mass quantity (%) relative to the initial total mass of at least one of the same atoms and / or functional groups determined in step D) for each fraction FX. As shown in Table 3, column 4, when the initial mass of the atom is 1.11 mg (as detected in the undistilled sample n1, step D) and fraction F1-1 contains 0.073 mg of the detected and quantified atom and / or functional group, the percentage of the atom's mass quantity (%) in fraction F1-1 can be calculated as 0.073 / 1.11 * 100 = 6.58%. Similarly, the remaining fractions can be calculated to determine the percentage values ​​(%) of the atom's mass quantity.

[0051] Step G) also involves calculating the cumulative percentage of the atom's mass quantity (%) for each fraction F.Thus, as shown in Table 3, last column, the cumulative percentage of the atomic mass (%) is the total percentage of the atomic mass (%) in each fraction F. It is clear to one skilled in the art that, for the first fraction, the cumulative percentage... Petition 870250081200, dated 10 / 09 / 2025, page 33 / 63 21 / 35 of the atomic mass (%) will be equal to the total percentage of the atomic mass (%). However, fraction F1-2 would contain a percentage of the total atomic mass (%) from the previous fraction F1-1, as well as F1-2. Similarly, fraction F1-3 would contain the cumulative percentage of the atomic mass from fractions F1-3 and the previous fraction F1-2. Thus, the value of the cumulative percentage of the atomic mass (%) can be determined for all fractions in this way. It should be noted that, due to unavoidable errors when performing fractional distillation (e.g., temperature regulation, fraction collection mechanism), it is possible that the percentage of the cumulative atomic mass (%) may deviate from the ideal value of 100%. However, this deviation does not affect the eventual analysis in step H).

[0052] Step H) comprises the determination of an atom portion (e.g., a percentage) originating from individual markers M1 and M2 in a mixture of markers Mx by performing a regression analysis to determine a relationship between the cumulative percentage of the atom mass for each fraction F as determined in step G) for each of the solutions n1 and n2 and the HP distillation profile determined in step A) for at least part of the HP distillation temperature range. In particular, the regression analysis allows fitting a weighted sum of the percentage of the cumulative atom mass for each fraction F, as determined in step G) for each of the solutions n1 and n2 to the HP distillation profile. In other words, if the percentage of the cumulative atom mass of each marker M1 and M2, respectively, Petition 870250081200, dated 10 / 09 / 2025, page 34 / 63 22 / 35 has a weighting coefficient b1 and b2, the regression analysis adjustment allows determining the coefficients b1 and b2 so that the sum of b1 multiplied by the percentage of the cumulative mass of the atom for solution n1 and b2 multiplied by the percentage of the cumulative mass of the atom for solution n2 approximates as closely as possible the HP distillation profile. The regression analysis allows determining the weights b1 and b2 of the weighted sum. The regression analysis preferably allows reducing a difference between the HP distillation profile and the weighted sum of the percentage of the cumulative mass of the atom for each fraction F, as determined in step G) for each of the solutions n1 and n2.Regression analysis can be any mathematical tool that allows such fitting and may, in particular, include a calculation of a mean absolute deviation, a maximum absolute deviation, a mean absolute deviation of the worst-case scenario, and / or a least squares median. Regression analysis may include any convex programming in which a cost function is well-defined (as is the case, for example, in least squares analysis). Regression analysis may be a least squares optimization analysis, preferably a constrained least squares convex optimization analysis. Fitting (which may also be referred to as difference minimization) may be performed over the entire HP distillation temperature range (referred to as integral minimization) or in sections thereof (referred to as partial minimization).Preferably, distinct partial minimizations are performed for different temperature sections, in order to jointly cover the entire temperature range. Petition 870250081200, dated 10 / 09 / 2025, page 35 / 63 23 / 35 HP distillation. This last example allows for better adjustment of each temperature section and is particularly safe against a use case where an attacker attempts to distill small portions of the mixture. Step H) allows determining a value for the atom and / or functional group portion for each atom marker M1 and M2.

[0053] Based on the atom and / or functional group portion value determined in step H) for each atom marker M1 and M2, step I) comprises calculating a marker mixture composition Mx based on the weight fraction of each atom and / or functional group in each marker M1 and M2 and the purity of markers M1 and M2. As shown in Table 4, the marker concentration R4 of the E1-M1 marker in the Mx marker mixture for an overall concentration of 10 ppm of atom and / or functional group can be calculated as R4 = R1 * (100 / R2) * (100 / R3), where R1 is the atom and / or functional group ratio for a 10 ppm atom concentration of the E1-M1 marker, R2 is the atom and / or functional group weight ratio in the E1-M1 marker, and R3 is the purity of the E1M1 marker.

[0054] The final step J) comprises the preparation of the marker mixture Mx by mixing the quantities of markers determined in step I) and adding it to the hydrocarbon product HP around the value of Ct.

[0055] HP can be marked by a manual or automatic marking process. Manual marking of petroleum hydrocarbons is conventionally achieved by distributing a marker solution into the petroleum hydrocarbon contained in a petroleum hydrocarbon compartment of petroleum hydrocarbon transport vehicles (by Petition 870250081200, dated 10 / 09 / 2025, page 36 / 63 24 / 35 example, trucks).

[0056] The labeling method described in this document provides, among other advantages, the fact that the presence of markers containing at least one of the same atoms and / or functional groups does not alter the distillation profile of the labeled HP. Furthermore, each marker distills independently of the other, according to its own distillation behavior. Thus, the distillation profile of the weighted mixture of at least two markers in the labeled HP is equivalent to the corresponding weighted sum of the distillation profile of the (isolated) marker in the labeled HP. The method described in this document offers the advantage that the ratio of at least two markers containing at least one of the same atoms and / or functional groups is such that the distillation profile of the detected and analyzed atom and / or functional group corresponds substantially to that of the labeled HP. Thus, if 50% of the labeled HP is distilled, approximately 50% of the detected and analyzed atom and / or functional group will also be distilled.This allows for an evaluation that is not only qualitative but also quantitative of the marked HP.

[0057] Another approach is directed to a method for detecting adulteration in a hydrocarbon (HP) product which comprises the following steps: a) sampling of a labeled HP according to the method described in this document, said HP having a predetermined Ct value; b) detection and calculation of the Ct value in the HP sample using an appropriate analytical technique; c) assessment of potential HP adulteration by comparing the Ct value determined in step b) with the Ct value Petition 870250081200, dated 10 / 09 / 2025, page 37 / 63 25 / 35 predetermined from step a).

[0058] Labeled HP can be sampled at any suitable sampling point in the HP supply chain, for example, at the service station or storage location. Although not required, but preferably, the quantity of at least one of the same atoms and / or functional groups is detected and analyzed using the same analytical technique used in the HP labeling method described in this document. The calculated quantity in the sampled HP is compared to the predetermined Ct value, i.e., the concentration at which the HP was initially labeled before entering the supply chain. A significant reduction in the quantity of the predetermined Ct value may indicate that the labeled HP has been adulterated at some point in the supply chain.

[0059] Another modality is directed to a method of detecting adulteration in a hydrocarbon (HP) product which comprises the steps of: a) sampling of a first HP; b) detection and, if present, quantification of an atom and / or functional group by means of an appropriate analytical technique; c) determination of the quantity of a second labeled HP according to the method described in this document, in the first HP, based on the atom and / or functional group quantified in step b).

[0060] In this embodiment, it is expected that the first HP sampled at the sampling point will not be labeled. However, if an atom and / or functional group is detected by a suitable analytical technique, such as those described in this document, this indicates that a second Petition 870250081200, dated 10 / 09 / 2025, pp. 38 / 63 26 / 35 A HP labeled preferably according to the method described in this document was added to the first HP, resulting in adulteration. In this case, the detected atom and / or functional group can be quantified, and the quantified quantity of the atom and / or functional group is directly related to the quantity of the second HP, labeled according to the method described in this document, that was mixed or added to the first HP.

[0061] Those skilled in the art may contemplate various modifications to the specific embodiments described above, without departing from the spirit of the present invention. These modifications are covered by the present invention.

[0062] Furthermore, any documents referred to throughout this descriptive report are incorporated herein by reference in their entirety, as set forth in full herein. EXAMPLES

[0063] The present invention is now described in more detail with reference to non-limiting examples. The examples below provide further details on the method, in particular on the calculation of the composition of a marker mixture and the method for labeling a hydrocarbon product with the marker mixture. Determination of the distillation curve of pure hydrocarbon product HP

[0064] Three HP1 - 3 hydrocarbon products were selected: SOCAR 95 Suisse gasoline (E1) and SOCAR Suisse diesel (E2), both from SOCAR Energy Switzerland, and Total Energies A1 jet kerosene (E3).

[0065] A 100 ml sample of each product of Petition 870250081200, dated 10 / 09 / 2025, page 39 / 63 27 / 35 hydrocarbon was distilled independently according to ASTM D-86. The temperature at the start of distillation T(BpL) was recorded. 10 ml fractions were collected and the temperature ranges at which each fraction was collected were recorded; the temperature of the last fraction collected was the temperature T(BpE). The distillation profiles obtained for each pure hydrocarbon product HP1 - 3 are shown in Figs. 1a, 2a and 3a, respectively.

[0066] The distillation temperature range for each HP hydrocarbon product is shown in Table 1: Table 1: Hydrocarbon products to be labeled and their boiling point range Example: Hydrocarbon product (HP) T(BpL) [°C] T(BpE) [°C] E1 Gasoline (HP1) 44 165 E2 Diesel (HP2) 174 340 E3 Kerosene (HP3) 135 244 Selection of markers from example E1 - E3

[0067] The markers for examples E1 - E3 were selected as revealed in table 2: Table 2: List of markers used in examples E1 - E3 Marker IUPAC Name ω OS > lo MW [g / m ol] AM / M Ratio W3) [%] Pe [°C] 1) Purity E1-M1 2-Chloropropane 75 78.5 4 45.1 35.7 TCI, > 99% Petition 870250081200, dated 10 / 09 / 2025, page 40 / 63 28 / 35 Marker Name IUPAC Ui os > 10 MW [g / m ol] AM / M Ratio W3) [%] Pe [°C] 1) Purity E1-M2 1-Chloropentane 54 3- 59 106, 59 33.2 107, 8 Thermo Scientf ic, 98% E1-M3 Chlorohexane 54 4- 120, 62 29.4 135 Fluka, 99% E2-M1 lodobenzene 59 1- 50 -4 204, 01 62.2 188, 4 Sigma Aldrich, 99% E2-M2 1,4-Diiodobutane 62 8- 21 -7 309, 92 81.9 246 °C 2) Sigma Aldrich, 98% E2-M3 1,6-Diiodohexane 62 9- 09 -4 337, 97 75.1 307 2) Sigma Aldrich, 98% E2-M4 1-Iodohexadecane 54 4- 77 -4 352, 34 36.0 357 2) Sigma Aldrich, 95% E3-M1 Octamethylcyclotetrasiloxane 55 6- 67 -2 296.62 37.9 175 Sigma-Aldrich, 98% Petition 870250081200, dated 10 / 09 / 2025, page 41 / 63 29 / 35 Brand Name IUPAC no MW Ratio Pe Purity pain CA [g / mo [°C] S ol] AM / M 1) W3) [%] 54 Decamethylcyclo 1- 370, Acros, E3-M2 pentasiloxane 02 77 37.9 210 97% -6 54 Dodecamethylcyclohex 0- 444, TCI, >9 E3-M3 asiloxane 97 92 37.9 245 7% -6 1) Boiling point temperatures of markers according to SciFinder® 2) Boiling point temperatures of markers according to SDS 3) Percentage of atomic weight relative to the molecular weight of each marker Example E1 Determining the composition of the marker mixture

[0068] Three solutions (100 ml) were produced independently by individually mixing the markers E1-M1, E1-M2, and E1-M3 in HP1 gasoline in a volumetric flask and manually shaking the three solutions for 1 minute at room temperature (step D). The amount of markers was selected so that the atom concentration was within the range of the desired total concentration Ct (e.g., for example E1, Ct was approximately 10 ppm). The exact concentration of the Cl atom was determined by XRF analysis and was Petition 870250081200, dated 10 / 09 / 2025, pp. 42 / 63 30 / 35 of approximately 10 ppm (10 mg per liter) in each of the three solutions (step D) (see table 3).

[0069] A 100 ml sample of each of the three solutions was distilled individually and 10 ml fractions were collected (step E).

[0070] The concentration of the Cl atom in each fraction was determined by XRF analysis, and the mass content of the Cl atom in each fraction, as well as the percentage of the mass quantity of the Cl atom in each fraction relative to the total mass of chlorine atom in the initial 100 ml sample, and the percentages of the cumulative mass quantity of distilled chlorine atom were calculated (see Table 3, for example, for the E1-M3 solution in HP1; the E1M1 and E1-M2 solutions in HP1 are measured and calculated analogously). For each of the three solutions, the percentages of cumulative mass quantity of distilled Cl atom were reported relative to the distillation temperature (Fig. 1b).

[0071] For the analysis, a SPECTROCUBE ED-XRF (SPECTRO Analytical Instruments GmbH, Kleve, Germany) was used.The analysis conditions were selected for heavy elements (3 keV < E < 6 keV), and a tube voltage of 22.5 kV with 1 mA was set with the current regulation setting ON. The analysis time was set to 300 seconds. Each element was calibrated with a 7-point calibration curve, and the extended Compton mathematical model was selected with a logarithmic fit. Table 3 Petition 870250081200, dated 10 / 09 / 2025, pp. 43 / 63 31 / 35 Fraction No. F1-X Cumulative distilled volume (ml) Distillation temperature range of the fraction (°C) Atom concentration (ppm) Atom mass (mg) Percentage of atom mass (%)1) Cumulative percentage of atom mass (%)2) 0 0 11.1 1.1 1 1-1 10 44 - 56 7.3 0.0 73 6.58 6.58 1-2 20 56 - 65 3.1 0.0 31 2.79 9.37 1-3 30 65 - 73 3.6 0.0 36 3.24 12.61 1-4 40 73 - 85 5 0.0 5 4.50 17.11 1-5 50 85 - 95 5.8 0.0 58 5.22 22.33 1-6 60 95 - 105 8 0.0 8 7.21 29.54 1-7 70 105 - 115 12.8 0.1 28 11.53 41.07 1-8 80 115 - 128 20.9 0.2 09 18.82 59.89 Petition 870250081200, dated 10 / 09 / 2025, pp. 44 / 63 32 / 35 Fraction No. F1-X Cumulative distilled volume (ml) Distillation temperature range of the fraction (°C) Atom concentration (ppm) Atom mass (mg) Percentage of atom mass (%)1) Cumulative percentage of atom mass (%)2) 1-9 90 128 - 145 28.3 0.2 83 25.49 85.38 1-10 100 145 - 165 19.6 0.1 96 17.65 103.03 4) 1) For example, to calculate the percentage of the atom's mass quantity for the fraction F1-1: 100 / 1.11 * 0.073 = 6.58%. 2) For example, to calculate the percentage of the cumulative mass of atoms for fraction F1-2: 6.58 + 2.79 = 9.37%

[0072] The ideal composition of the marker mixture (E1M1, E1-M2 and E1-M3) was calculated, based on the three distillation profiles, using constrained convex least squares optimization as an example for regression analysis, so that the distillation profile of the marker mixture M1 (based on the contribution of each marker atom) substantially overlaps the distillation profile of the pure hydrocarbon product HP1 (Fig. 1c) (step H). The resulting weight percentage of the atom and / or functional group of each marker E1-M1, E1-M2 and E1-M3 in the marker mixture M1 Petition 870250081200, dated 10 / 09 / 2025, pp. 45 / 63 33 / 35 obtained from the constrained least squares convex optimization are reported in Table 4. The composition of the derived marker was calculated taking into account the ratio of the atomic mass of Cl to the molecular weight of each marker El-Ml, E1-M2 and E1-M3 and their respective purity (Table 4). Table 4 Marker or Atom Ratio [%] Atom ratio for an atom concentration Ct of 10 ppm 2) (R1) [ppm] AM / MW Ratio (R2) [%] Purity (R3) [%] Marker concentration for an atom concentration Ct of 10 ppm 3) (R4) [ppm] Percentage of markers in the marker mixture [% by weight] El-M1 22.7 2.27 45.1 99 5.08 16.9 El-M2 46.8 4.68 33.2 98 14.38 47.9 El-M3 30.5 3.05 29.4 98 10.58 35.2 Total 100 10 30.04 100 1) Percentage (%) of each marker atom in the marker mixture, as calculated using constrained least squares convex optimization. 2) Concentration ratio of each marker atom in the marker mixture for a marker mixture concentration of 10 ppm. 3) Marker ratio in the marker mixture, after correction based on the percentage of atomic weight relative to the molecular weight of each marker (Table 2) and purity. Petition 870250081200, dated 10 / 09 / 2025, pp. 46 / 63 34 / 35 of each marker (table 2). Calculated as: R4 = RI *(100 / R2) * (100 / R3).

[0073] Examples E2 and E3 were calculated in a similar manner. The results are shown in Tables 5 and 6. Table 5: Example E2 (hydrocarbon product HP2) Marker or Atom Ratio [%] Atom ratio for an atom concentration Ct of 10 ppm (R1) [ppm] AM / MW Ratio (R2) [%] Purity (R3) [%] Marker concentration for an atom concentration Ct of 10 ppm (R4) [ppm] Percentage of markers in the marker mixture [% by weight] E2-M1 12.2 1.22 62.2 99 1.96 10.46 E2-M2 39.6 3.96 81.9 98 4.93 26.29 E2-M3 13.7 1.37 75.1 98 1.86 9.92 E2-M4 34.5 3.45 36.3 95 10.00 53.33 Total 100 10 100 Table 6: Example E3 (hydrocarbon product HP3) Petition 870250081200, dated 10 / 09 / 2025, page 47 / 63 35 / 35 Marker or Atom Ratio [%] Atom ratio for an atom concentration Ct of 1000 ppm (R1) [ppm] AM / MW Ratio (R2) [%] Purity (R3) [%] Marker concentration for an atom concentration Ct of 1000 ppm (R4) [ppm] Percentage of markers in the marker mixture [% by weight] E3-M1 47.3 473 37.9 98 1273.49 47.04 E3-M2 24.4 244 37.9 97 663.71 24.52 E3-M3 28.3 283 37.9 97 769.80 28.44 Total 100 10004) 100 4) For E3, Ctdo Si was selected.

Claims

1 / 5 CLAIMS 1. Method for labeling a hydrocarbon product (HP) characterized by comprising the steps of: A. selecting an HP to be labeled and recording the distillation profile of the HP to determine the initial temperature (TBpL) and the final temperature (TBpE) at which distillation occurs; B.Selection of at least two compatible and distillable markers (M1, M2) to label the HP, wherein said markers comprise at least one of the same atom and / or functional group to be analyzed by a suitable analytical technique, wherein M1 and M2 individually have different boiling points and / or different distillation profiles, wherein one of M1 or M2 has a boiling point temperature T(BpM1) being lower than T(BpL) or one of M1 or M2 has a boiling point temperature within the distillation temperature range of the HP [T(BpL) < T(BpM1) < T(BpE)], and being at most 20% higher than T(BpL), and wherein one of M1 or M2 has a boiling point temperature T(BpM2) higher than T(BpE) or the other M1 or M2 has a boiling point temperature that is within the distillation temperature range of the HP. [T(BpL) < T(BpM2) < T(BpE)], and being at most 20% smaller than T(BpE); W.selection of a Ct value for total atom concentration, where the Ct value is selected based on Petition 870250081200, dated 10 / 09 / 2025, page 59 / 63 2 / 5 analytical technique and on at least one same atom and / or functional group to be analyzed by said analytical technique, selected in step B); D. preparation of individual solutions n1 and n2 of markers M1 and M2 in the HP, respectively, preferably at the Ct value, and determining, before fractional distillation, the initial concentration and initial total mass of at least one same atom and / or functional group in n1 and n2 by the analytical technique selected in step B); E. performing separate fractional distillation of solutions n1 and n2 to obtain fractions F; F. determination of the concentration and total mass of at least one same atom and / or functional group in each fraction F by the analytical technique selected in step B); G.Calculation of the percentage of the atom's mass quantity (%) in relation to the initial total mass of at least one same atom and / or functional group determined in step D) in each fraction F and determining the cumulative percentage of the atom's mass quantity for each fraction F; H. Determination of an atom portion originating from individual markers M1 and M2 in a mixture of markers Mx, performing a regression analysis to determine a relationship between the cumulative percentage of the atom's mass quantity for each fraction F as determined in step G) for each of the solutions n1 and n2 and the HP distillation profile determined in step A) for at least part of the HP distillation temperature range; I.Calculation of a marker mixture composition Mx based on the atom portion determined in step H) for each marker M1 and M2, the weight fraction of each atom and / or functional group in each marker M1 and M2, and the purity of markers M1 and M2; J. Preparation of the marker mixture Mx by mixing the quantities of markers determined in step I) and adding it to the hydrocarbon product HP around the Ct value.

2. Method for labeling a hydrocarbon product (HP), according to claim 1, characterized in that one of M1 or M2 has a boiling point temperature T(BpM1) being lower than T(BpL) or one of M1 or M2 has a boiling point temperature within the distillation temperature range of HP [T(BpL) < T(BpM1) < T(BpE)], and being at most 15% higher than T(BpL), and in that one of M1 or M2 has a boiling point temperature T(BpM2) higher than T(BpE) or the other M1 or M2 has a boiling point temperature that is within the distillation temperature range of HP [T(BpL) < T(BpM2) < T(BpE)], and being at most 15% lower than T(BpE).

3. Method for labeling a hydrocarbon (HP) product according to claim 1 or 2, characterized in that at least four markers M1 - M4 are selected in step B).

4. Method for labeling a hydrocarbon (HP) product according to claim 1 or 2, characterized in that the markers i are selected in step B) Petition 870250081200, dated 10 / 09 / 2025, page 61 / 63 4 / 5 and wherein i > 4.

5. Method for labeling a hydrocarbon product (HP), according to claim 1 or 3, characterized in that at least two labels M1 and M2 comprise an atom.

6. Method for labeling a hydrocarbon product (HP), according to claims 1 to 3, characterized in that at least two labels M1 and M2 comprise a halogen atom.

7. Method for labeling a hydrocarbon (HP) product according to claims 1 to 6, characterized in that the analytical technique selected in step B) is based on X-ray fluorescence.

8. Method for labeling a hydrocarbon (HP) product according to claims 1 to 7, characterized in that the Ct value in step C) is between 10 and 2000 ppm, preferably between 10 and 1000 ppm.

9. Method according to claims 1 to 8, characterized in that the hydrocarbon product (HP) is a fuel, preferably diesel, kerosene or gasoline.

10. A method for detecting adulteration in a hydrocarbon product (HP) characterized by comprising the steps of: a) sampling a labeled HP as defined in claims 1 to 9, said HP having a predetermined Ct value; b) detecting and calculating the Ct value in the HP sample by means of a suitable analytical technique; c) evaluating the potential adulteration of the fuel by comparing the Ct value determined in step b) with the predetermined Ct value of step a).

11. A method for detecting adulteration in a hydrocarbon product (HP) characterized by comprising the steps of: a) sampling a first HP; b) detecting and, if present, quantifying an atom and / or functional group by means of a suitable analytical technique; c) determining the quantity of a second HP labeled as defined in claims 1 to 9 in the first HP, based on the atom and / or functional group from step b). Petition 870250081200, dated 10 / 09 / 2025, p. 63 / 63

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