WO2021122929A1

WO2021122929A1 - Composition marking

Info

Publication number: WO2021122929A1
Application number: PCT/EP2020/086684
Authority: WO
Inventors: Emmanuel GOMEZ; Simon PONDAVEN; Nikola Babic; Hervé VEZIN
Original assignee: Total Se; Centre National De La Recherche Scientifique; Université de Lille
Priority date: 2019-12-17
Filing date: 2020-12-17
Publication date: 2021-06-24
Also published as: EP4077602B1; FR3104607A1; FR3104607B1; EP4077602A1

Abstract

The present application relates to the use of a radical compound in a composition comprising at least one hydrocarbon or in an additive composition intended to be added to a composition comprising at least one hydrocarbon, to mark said hydrocarbon mixture.

Description

Composition marking

The present invention relates to the labeling of compositions comprising at least one hydrocarbon and of an additive composition intended to be added to compositions comprising at least one hydrocarbon.

In order to combat counterfeit products and protect a company's know-how, it is increasingly important to be able to quickly determine whether a product belongs to that company or not.

In the event of an accident, for example leakage of a composition and possible contamination of the environment, it is imperative to be able to determine the origin of the compositions.

Finally, it is advantageous to be able to have an indicator, in a final composition, making it possible to trace the preparation process and therefore guarantee the quality of said composition. In the field of fuels, it is important to guarantee homogeneity of the compositions, in particular during the additivation of fuels, and thus to be able to trace the preparation process.

There are currently compounds added to the compositions which can be detected by analysis and therefore allow the determination of the origin of the compositions. However, the compounds currently used for such labeling require laboratory analysis on sophisticated devices. It is therefore not possible to have the necessary analyzes quickly and simply on site.

There is an interest in providing a process for labeling compositions comprising at least one hydrocarbon or compositions of additives intended to be added to compositions comprising at least one hydrocarbon or compositions comprising water and urea used in the preparation. automotive field, in particular in exhaust gas aftertreatment devices.

An objective of the present invention is to provide a marking making it possible to detect the origin of a composition comprising at least one hydrocarbon or of a composition comprising water and urea and used in the automotive field.

Another objective of the present invention is to provide a marking making it possible to trace the manufacturing process of a composition comprising at least one hydrocarbon and to ensure the quality of the process. An objective of the invention is to provide such a marking which is simple to use and which can be carried out on site without the need for large equipment.

Other objects will become apparent from the following description of the invention.

These objectives are fulfilled by the present invention, which relates to the use of a radical compound in a composition comprising at least one hydrocarbon or in an additive composition intended to be added to a composition comprising at least one hydrocarbon, or in a composition comprising water and urea and intended for use in the automotive field to mark said compositions, the marking being followed by Electronic Paramagnetic Resonance (EPR) (by detection of the radical compound).

Radical compounds are compounds which can be detected in small quantities by Electronic Paramagnetic Resonance (EPR). There are portable RPE devices.

Thus, in a particularly advantageous manner, the invention makes it possible, by adding a small amount, in particular of the order of ppm, of radical compound in a composition comprising at least one hydrocarbon, to mark said composition, the analysis of this composition being able to be carried out quickly and in the field, in particular by Electronic Paramagnetic Resonance (RPE) (by detection of the radical compound).

The present invention therefore advantageously makes it possible to quickly obtain knowledge of the origin of the composition comprising at least one hydrocarbon and, for example, to detect any counterfeits.

The present invention also advantageously makes it possible to quickly obtain knowledge of the origin of a composition comprising water and urea and intended for use in the automotive field, for example in post-repair devices. treatment of vehicle exhaust gases to reduce polluting emissions.

In a particularly advantageous manner, the invention makes it possible, by adding a known quantity of radical compound in an additive composition intended to be added to a composition comprising at least one hydrocarbon, to be able to determine the quantity of additive composition added to the mixture. composition comprising at least one hydrocarbon and thus check whether this quantity corresponds to the usual quantities and meets the quality criteria of the manufacturing process, the analysis to determine the quantity of additive composition added to the composition comprising at least one hydrocarbon and thus check whether this quantity corresponds to the usual quantities and meets the quality criteria of the manufacturing process is carried out by RPE (by detection of the radical compound).

Thus, the present invention allows the marking of a composition comprising at least one hydrocarbon and of a composition comprising water and urea and intended for use in the automotive field and the marking of the process for preparing a composition comprising at least less one hydrocarbon, the labeling being followed by RPE (by detection of the radical compound) and the tracing carried out by RPE (by detection of the radical compound).

The radical compound can be chosen from all the radical compounds known to those skilled in the art. In particular, the radical compound must not react with the constituents of the composition comprising at least one hydrocarbon or with the composition of additives.

The radical product is preferably colorless.

Preferably, the radical compound has no influence on the properties of the composition comprising at least one hydrocarbon or the composition of additives.

The radical compound should preferably be stable, preferably stable for at least 3 months, preferably at least 6 months, preferably at least 12 months.

In the context of the present invention, the term “stable” is understood to mean a radical compound whose RPE intensity of a composition comprising this compound after aging varies by at most 10% relative to the RPE intensity of a composition. comprising this compound without aging (fresh composition). The aging conditions for the compositions comprising at least one hydrocarbon is storage for at least 3 months, preferably at least 6 months, preferably at least 12 months, at room temperature. The aging conditions for the additive compositions correspond to storage at a temperature between 30 and 50 ° C for at least 3 months, preferably at least 6 months, preferably at least 12 months.

Examples of radical compounds are, for example, nitroxides (nitroxide radicals), trityl radicals, radicals stabilized by a polycyclic aromatic structure (for example asphaltenes) or conjugated systems (dilithium phthalocyanine), phenyl radicals and sterically hindered isoindolines . Preferably, the radical compound is added in an amount of between 0.1 and 100 mM, preferably between 5 and 50 mM.

At these low concentrations, the radical compound can only be detected by RPE and by no other analysis (RPE being a very sensitive analysis).

In the context of the present invention, the term “hydrocarbon” or “hydrocarbons” is understood to mean aromatic compounds of the benzene family, alkenes, alkanes and cycloalkanes.

In the context of the present invention, the term “compositions comprising at least one hydrocarbon” is understood to mean compositions such as, for example, base oils, lubricants, fuels (gasoline, diesel, biofuel), bitumens, and the like.

In the context of the present invention, the term “composition comprising water and urea and intended for use in the automotive field” is understood to mean compositions which can be used in particular in post-treatment devices. exhaust gases, more particularly SCR devices to limit polluting emissions. These compositions can also include additives as defined in patent EP2129452. By way of example, mention may be made of AdBlue® marketed by the company Total or Clearnox® marketed by the company Total.

In the context of the present invention, the term “additive composition intended to be added to compositions comprising at least one hydrocarbon” means compositions comprising additives generally used in the petroleum field, in particular in lubricants, base oils, fuels, bitumens, etc. By way of example, the additive compositions can comprise at least one of the following additives:

Thickeners whose role is to increase the viscosity of the composition, both hot and cold, or viscosity index (VI) improving additives. Preferably, these additives are most often low molecular weight polymers, on the order of 2000 to 50,000 Dalton (Mn). They can be chosen from PIB (of the order of 2000 Dalton), Poly-Acrylate or Poly Methacrylates (of the order of 30,000 Dalton), Olefin-copolymers, Olefin and Alpha olefin copolymers, EPDM, Polybutenes , High molecular weight Poly-Alphaolefins (viscosity 100 ° C> 150), Styrene-Olefin copolymers, hydrogenated or not;

Anti-wear and extreme pressure additives. Antiwear additives and extreme pressure additives protect friction surfaces by forming a film protector adsorbed on these surfaces. There is a wide variety of antiwear additives. Preferably for the lubricating composition according to the invention, the anti-wear additives are chosen from phospho-sulfur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTP. The preferred compounds are of formula Zn ((SP (S) (OR3) (OR4)) 2, in which R3 and R4, identical or different, independently represent an alkyl group, preferably an alkyl group comprising from 1 to 18 carbon atoms Amine phosphates are also anti-wear additives which can be used in the lubricating composition according to the invention. However, the phosphorus provided by these additives can act as a poison in the catalytic systems of automobiles because these additives generate ash. These effects can be minimized by partially substituting the amine phosphates with additives which do not provide phosphorus, such as, for example, polysulphides, in particular sulfur-containing olefins;

The dispersants. Dispersants are well known additives used in the formulation of lubricating composition, in particular for application in the marine field. Their primary role is to maintain in suspension the particles initially present or appearing in the lubricating composition during its use in the engine. They prevent their agglomeration by playing on steric hindrance. They can also exhibit a synergistic effect on neutralization. Dispersants used as lubricant additives typically contain a polar group, associated with a relatively long hydrocarbon chain, generally containing from 50 to 400 carbon atoms. The polar group typically contains at least one nitrogen, oxygen or phosphorus element. Compounds derived from succinic acid are dispersants particularly used as lubricating additives. Use is made in particular of succinimides, obtained by condensation of succinic anhydrides and amines, succinic esters obtained by condensation of succinic anhydrides and alcohols or polyols. These compounds can then be treated with various compounds including sulfur, oxygen, formaldehyde, carboxylic acids and compounds containing boron or zinc to produce, for example, borated succinimides or succinimides blocked with zinc. Mannich bases, obtained by polycondensation of phenols substituted with alkyl groups, formaldehyde and primary or secondary amines, are also compounds used as dispersants in lubricants. For example, there may be mentioned succinimide PIB, for example borated or blocked with zinc;

Anti-foam additives, for example polar polymers such as polymethylsiloxanes, polyacrylates,

Antioxidant additives in / or anti-rust. The antioxidant additive generally makes it possible to delay the degradation of the lubricating composition in service. This degradation can be reflected in particular by the formation of deposits, by the presence of sludge or by an increase in the viscosity of the lubricating composition. Among the antioxidant additives commonly used, there may be mentioned antioxidant additives of phenolic type, antioxidant additives of amine type, phosphosulfurized antioxidant additives. Some of these antioxidant additives, for example phosphosulfurized antioxidant additives, can generate ash. The phenolic antioxidant additives can be ash free or in the form of neutral or basic metal salts. The antioxidant additives can in particular be chosen from sterically hindered phenols, sterically hindered phenol esters and sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted with at least one C1-C12 alkyl group, N, N '-dialkyl-aryl-diamines and mixtures thereof. Preferably according to the invention, the sterically hindered phenols are chosen from compounds comprising a phenol group of which at least one carbon vicinal of the carbon carrying the alcohol function is substituted by at least one C1-C10 alkyl group, preferably an alkyl group. C1-C6, preferably a C4 alkyl group, preferably by the tert-butyl group. Amino compounds are another class of antioxidant additives that can be used, optionally in combination with phenolic antioxidant additives. Examples of amino compounds are aromatic amines, for example aromatic amines of formula NR5R6R7 in which R5 represents an aliphatic group or an aromatic group, optionally substituted, R6 represents an aromatic group, optionally substituted, R7 represents a hydrogen atom, an alkyl group, an aryl group or a group of formula R8S (0) zR9 in which R8 represents an alkylene group or an alkenylene group, R9 represents an alkyl group, an alkenyl group or an aryl group and z represents 0, 1 or 2 Sulfurized alkyl phenols or their alkali and alkaline earth metal salts can also be used as antioxidant additives. Another class of antioxidant additives is that of copper compounds, for example copper thio- or dithiophosphates, copper salts and carboxylic acids, dithiocarbamates, sulphonates, phenates, copper acetylacetonates. Copper I and II salts, salts of succinic acid or anhydride can also be used. Friction modifier additives. The friction modifier additive can be chosen from a compound providing metallic elements and an ash-free compound. Among the compounds providing metallic elements, mention may be made of transition metal complexes such as Mo, Sb, Sn, Fe, Cu, Zn, the ligands of which may be hydrocarbon compounds comprising oxygen, nitrogen or carbon atoms. sulfur or phosphorus. The ash-free friction modifying additives are generally of organic origin and can be chosen from fatty acid monoesters and polyols, alkoxylated amines, alkoxylated fatty amines, fatty epoxides, borate fatty epoxides; fatty amines or fatty acid glycerol esters. According to the invention, the fatty compounds comprise at least one hydrocarbon group comprising from 10 to 24 carbon atoms.

Pour point improvers. By slowing the formation of paraffin crystals, pour point depressant additives generally improve the cold behavior of the lubricating composition according to the invention. As an example of pour point depressant additives, there may be mentioned polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes, alkylated polystyrenes. ;

Detergents. Detergent additives generally make it possible to reduce the formation of deposits on the surface of metal parts by dissolving the by-products of oxidation and combustion. The detergent additives which can be used are generally known to those skilled in the art. The detergent additives can be anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophilic head. The associated cation can be a metal cation of an alkali or alkaline earth metal. The detergent additives are preferably chosen from alkali metal or alkaline earth metal salts of carboxylic acids, sulphonates, salicylates, naphthenates, as well as salts of phenates. The alkali metals and alkaline earth metals are preferably calcium, magnesium, sodium or barium. These metal salts generally include the metal in stoichiometric amount or else in excess, therefore in an amount greater than the stoichiometric amount. These are then overbased detergent additives; the excess metal providing the overbased character to the detergent additive is then generally in the form of a metal salt insoluble in oil, for example a carbonate, a hydroxide, an oxalate, an acetate, a glutamate, preferably a carbonate .

In the context of the present invention, the term “base oil” is understood to mean oils of mineral, synthetic or vegetable origin, as well as their mixtures. The mineral or synthetic oils generally used in the application belong to one of the classes defined in the API classification as summarized in the table below.

Group 1 mineral oils can be obtained by distillation of selected naphthenic or paraffinic crudes followed by purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreatment or hydrogenation.

The oils of Groups 2 and 3 are obtained by more stringent purification processes, for example a combination of hydrotreatment, hydrocracking, hydrogenation and catalytic dewaxing.

The synthetic base oils of Groups 4 and 5 can be chosen from esters, silicones, glycols, polybutene, polyalphaolefins (PAO), alkylbenzene or alkylnaphthalene. The polyalphaolefins used as base oils are for example obtained from monomers comprising from 4 to 32 carbon atoms, for example from octene or decene, and whose viscosity at 100 ° C is between 1, 5 and 15 mm ² . s ^-1 according to ASTM D445. Their average molecular mass is generally between 250 and 3000 according to the ASTM D5296 standard.

The base oils can also be oils of natural origin, for example esters of alcohols and carboxylic acids, which can be obtained from natural resources such as sunflower oil, rapeseed oil, palm oil, soybeans etc.

These base oils can be used alone or as a mixture. Mineral oil can be combined with synthetic oil.

The present invention also relates to a method for marking and / or tracing, in particular marking and / or tracing detectable by RPE, of a composition comprising at least one hydrocarbon comprising the addition of a radical compound to said composition comprising at least one hydrocarbon or to an additive composition intended to be added to the composition comprising at least one hydrocarbon, said method also comprises a step of detecting the marking and / or tracing (and therefore of the radical compound) by RPE.

The present invention also relates to a method of labeling, in particular labeling detectable by RPE, of a composition comprising at least one hydrocarbon comprising the addition to said composition of a radical compound, said method also comprises a step of detecting the labeling (and therefore the radical compound) by RPE.

The present invention also relates to a method of traceability of the process for preparing a composition comprising at least one hydrocarbon and an additive composition comprising the addition of a radical compound to the additive composition intended to be added to the composition. comprising at least one hydrocarbon, said method also comprising a step of detecting said radical compound by RPE.

Indeed, knowing the amount of radical compound in the additive composition and the dilution of the additive composition in the composition comprising at least one hydrocarbon, it is possible, by analyzing the RPE spectrum, to know the amount of radical compound. in the composition comprising at least one hydrocarbon and (since the radical compound is stable) determining whether the correct amount of additive composition has been added to meet the quality standards.

The present application also relates to a method of labeling, in particular labeling detectable by RPE, of a composition comprising water and urea intended for use in the automotive field, comprising the addition of a radical compound. to said composition, said method also comprises a step of detecting the labeling by RPE.

The present invention also relates to a composition comprising at least one hydrocarbon and one radical compound.

The present invention also relates to an additive composition intended to be added to a composition comprising at least one hydrocarbon, said additive composition comprising a radical compound.

The present invention also relates to a composition comprising water and urea, and optionally an additive, intended for use in the automotive field, said composition comprising a radical compound.

The definitions of the compositions, of the radical compound and of the amount of radical compound are as defined above.

The present application will now be described with the aid of the following non-limiting examples.

Figure 1 shows the strength of the RPE signal as a function of time for B7 diesel compositions supplemented with 10mM of nitroxide.

Figure 2 shows the RPE spectra of a base oil sample comprising 10mM nitroxide at T0, T0 + 4 months and TO + 6 months.

Example 1

An additive composition for a diesel composition B7 comprising 8.3 mM of nitroxide is prepared. The nitroxide content is chosen so as to have after dilution of the additive composition (1200 ppm) in the diesel composition B7, the nitroxide is present in a content of 10 mM (1.9 ppm).

The additive composition is separated into several samples:

A sample is left at room temperature and then at different times is formulated for RPE analysis, each RPE spectrum is repeated three times (A, B and C) A sample is left at 50 ° C then at different times is formulated for RPE analysis, each RPE spectrum is repeated three times (A 50, B 50 and C 50) The formulation for RPE analysis is as follows: The additive composition comprising the nitroxide is diluted in a diesel composition B7 at the nominal nitroxide concentration of 10 mM. Samples are prepared for RPE measurement then the spectra are carried out at room temperature on a continuous X-band spectrometer with a field center at the factor g of 2.005 and a magnetic field window of 100 G. The acquisition of the spectra takes 15 s. Signal strength is measured as the height of the nitroxide peak and is compared to the value at tO (fresh sample).

The results of the spectra are given in Figure 1.

These results show the possibility of using free radical markers in compositions comprising at least one free radical compound. Example 2

A nitroxide solution (10 mM) is added to a base oil. The composition obtained is added in a 5 mm tube for RPE. An RPE spectrum is carried out at room temperature under the same conditions as in Example 1. The spectrum is carried out at tO (just after the preparation of the composition) then at tO + 4 months and tO + 6 months.

The results of the spectra are given in figure 2.

These results show fully superimposable spectra proving that the radical compound is stable in the base oil and can therefore be used as a marker or tracer in the process for preparing a composition comprising at least one hydrocarbon.

Claims

1. Use of a radical compound in a composition comprising at least one hydrocarbon or in a composition comprising water and urea and intended for use in the automotive field or in an additive composition intended to be added. to a composition comprising at least one hydrocarbon, for marking said compositions, said marking being followed by electronic paramagnetic resonance (EPR).

2. Use according to claim 1, wherein the radical compound should preferably be stable, preferably stable for at least 3 months, preferably at least 6 months, preferably at least 12 months.

3. Use according to claim 1 or 2, in which the radical compound is chosen from nitroxides (nitroxyl radicals), trityl radicals, radicals stabilized by a polycyclic aromatic structure (for example asphaltenes) or conjugate systems (phthalocyanine of dilithium), sterically hindered phenyl and isoindoline radicals.

4. Use according to any one of claims 1 to 3, wherein the radical compound is added in an amount of 0.1 and 100 mM, preferably between 5 and 50 mM.

5. Method for labeling and / or tracing a composition comprising at least one hydrocarbon comprising the addition of a radical compound to said composition comprising at least one hydrocarbon or to an additive composition intended to be added to the composition comprising at least a hydrocarbon, said method using electronic paramagnetic resonance (EPR).

6. Method for traceability of the process for preparing a composition comprising at least one hydrocarbon and an additive composition comprising the addition of a radical compound to the additive composition intended to be added to the composition comprising at least one. hydrocarbon, said method using electronic paramagnetic resonance (EPR).

7. Method for labeling a composition comprising water and urea intended for use in the automotive field comprising the addition of a radical compound to said composition, said method using electronic paramagnetic resonance ( RPE).

8. A composition comprising water and urea, and optionally an additive, intended for use in the automotive field, said composition comprising a radical compound.