WO2023218148A1

WO2023218148A1 - Fuel composition with a low impact on co2 emissions, and use thereof in particular in new vehicles

Info

Publication number: WO2023218148A1
Application number: PCT/FR2023/050682
Authority: WO
Inventors: Lisa SERVE
Original assignee: Totalenergies Onetech
Priority date: 2022-05-12
Filing date: 2023-05-12
Publication date: 2023-11-16
Also published as: FR3135463A1

Abstract

The present invention relates to a fuel composition comprising: (i) from 85% to 98% by weight of a mixture of hydrocarbons comprising: a) from 8% to 40% by weight of aromatic compounds; b) from 50% to 90% by weight of noncyclic paraffins containing at least 4 carbon atoms; and c) from 2% to 15% by weight of naphthenes: and (ii) from 2% to 15% by weight of ethanol, this composition having a density at 15°C, measured according to the standard EN ISO 12185, within the range extending from 720 to 745 kg/m3. This composition is useful for powering a spark-ignition engine, and in particular as an "OEM" fuel for vehicles equipped with new engines.

Description

DESCRIPTION

TITLE: Fuel composition with low impact on CO2 emissions, and its use in particular in new vehicles

The subject of the present invention is a fuel composition intended for vehicles comprising a spark ignition engine (or gasoline engine), and which has particular properties.

The invention also relates to the use of such a composition to power a spark ignition engine, both in a conventional vehicle, in particular an automobile, and in a competition vehicle. The invention is particularly aimed at the use of this composition as the first fuel in a new engine.

Petrol-type fuels marketed in Europe and usable in spark-ignition engines, particularly those of motor vehicles, must meet the specifications of standard EN 228 which defines a certain number of criteria such as, for example, an engine octane number ( or MON, from English Motor Octane Number) greater than 85 and a research octane number (or RON, from English Research Octane Number) of a minimum of 95. In a manner well known in itself, the index Octane gauge measures the resistance of a fuel used in a spark-ignition engine to self-ignition.

These fuels are suitable for the vast majority of automobile engines.

However, specific requirements arise when the gasoline fuel is a so-called "first fill fuel", that is to say a fuel intended to power a new engine. such as typically an engine fitted to a new vehicle.

By new engine we mean an engine which has not yet been used after its manufacture.

Particularly when leaving motor vehicle assembly lines, the tanks of new vehicles are filled in all or part of an original equipment fuel, which corresponds to the very first fuel which powers the engine when the vehicle is put into circulation.

These original equipment fuels must meet very specific technical requirements.

A first set of requirements is imposed by the numerous starts and stops of vehicles carried out without rolling the vehicle leaving the assembly lines, and which must be done without generating any fouling of the engine. Under these conditions, original equipment fuels must protect new engines, guarantee their cleanliness and proper functioning until delivery of the vehicle to the first customer.

In addition, motor vehicles after their manufacture are often stored and shipped around the world before they are first put on the road. Original equipment fuel is thus stored for long periods, often several months, in the vehicle before being consumed by the end user of the vehicle. Original equipment fuel must therefore have excellent long-term storage stability, and in particular perfect oxidation stability.

Furthermore, the vehicle is often put into circulation in a place of marketing very far from its place of manufacture: these may be on different continents, with fundamentally different climatic conditions. However, starting the vehicle by the end user should not pose any difficulty. For this, the original equipment fuel must allow immediate starting and good running of the vehicle regardless of where it is sold, both in hot regions and very cold countries.

Finally, as engines are started and stopped several times on assembly lines until their final marketing, operators working on assembly lines are particularly exposed to emissions generated by fuel combustion. For this reason, it is also important that the original equipment fuel has a high level of safety. In particular, the constraints in terms of hygiene, safety and environment imposed by some car manufacturers can be high in order to avoid any toxicity of the fuel for operators who have to handle it regularly.

Thus, original equipment fuels are subject to technical, logistical and environmental requirements that are much higher than conventional fuels sold at service stations.

Furthermore, for all vehicles and in particular those intended for general public applications, we are increasingly seeking to use fuels formulated from bases of plant origin, and in particular so-called "biosourced" bases, in order to meet environmental concerns and limit the use of fossil resources. Thus, current environmental concerns are pushing consumers to seek more environmentally friendly fuels.

However, the use of fuel compositions from biosourced bases must not be to the detriment of fuel performance.

There is therefore a need to develop new fuel compositions intended to power spark ignition engines which make it possible to meet the requirements of modern vehicles, while being formulated from bases and/or compounds of renewable origin, also called biosourced compounds.

There is also a need to formulate fuels meeting the specific requirements of original equipment fuels, which can also be formulated from biosourced bases.

In a manner well known in the prior art, additives improving the octane number (or octane boosters) are typically added to gasoline type fuel compositions. Organometallic compounds comprising in particular iron, lead or manganese are well-known octane number improvers.

Thus, tetraethyl lead (TEL) has been widely used as a very effective octane improver. However, in most parts of the world, TEL and other organometallic compounds can now only be used in fuels in very small quantities, if at all, because they can be toxic, damage the engine, and are harmful to the environment.

Non-metal based octane improvers include oxygenates (e.g. ethers and alcohols) and aromatic amines. However, these additives also suffer from various disadvantages. For example, N-methylaniline (NMA), an aromatic amine, must be used at a relatively high processing rate (1.5 to 2% by weight of additive/mass of fuel base) to have a significant effect on the octane number of the fuel. NMA can also be toxic.

By way of example, document US-A-4812146 describes compositions of unleaded gasoline fuels for competition engines which comprise at least four components chosen from butane, isopentane, toluene, MTBE (methyl tert -butyl ether) and an alkylate.

Document W02010/014501 describes unleaded gasoline fuel compositions comprising at least 45% by volume of branched paraffins, at most 34% by volume of one or more mono- and di-alkylated benzenes, from 5 to 6% by volume at least one linear paraffin having 3 to 5 carbon atoms (denoted C3-C5), one or more alkanols having 2 to 4 carbon atoms (denoted C2-C4), in sufficient quantity to increase the AKI ( from the English Anti Knock Index) i.e. (RON+MON)/2 of at least 93. These compositions are presented as having high torque and maximum power.

Thus, we are looking for fuel compositions having good intrinsic properties, that is to say without it being necessarily necessary to add additives improving the octane number such as those described above. .

Continuing its research into the development of fuel formulations for gasoline engines, the Applicant has now discovered a composition which makes it possible to meet the above objectives.

The subject of the present invention is therefore a fuel composition comprising:

(i) from 85 to 98% by mass of a mixture of hydrocarbons comprising: a) from 8 to 40% by mass of aromatic compounds; b) from 50 to 90% by mass of non-cyclic paraffins containing at least 4 carbon atoms; and c) from 2 to 15% by mass of naphthenes; And

(ii) from 2 to 15% by mass of ethanol, this composition having a density at 15°C, measured according to standard EN ISO 12185, included in the range from 720 to 745 kg/m ³ .

These compositions are intended to power spark ignition engines (or gasoline engines). These engines can be present in any vehicle equipped with a thermal engine, including conventional vehicles as well as rechargeable and non-rechargeable hybrid electric vehicles, mixed fuel vehicles. The compositions according to the invention are also useful for powering a mixed carburetion compression ignition engine (or “dual fuel” engine).

The fuel compositions according to the invention comply with the specifications of standard EN 228. In particular, they have high RON and MON octane numbers.

The compositions according to the invention are particularly suitable for uses in which the constraints and requirement levels are extremely high, for example in uses in vehicles equipped with new engines. Thus, the compositions according to the invention constitute particularly efficient so-called original equipment fuels.

They are extremely stable in storage and withstand very significant temperature variations. They can be used in very diverse climatic conditions ranging from hot to very cold regions. They do not clog the engines and are very safe.

The composition according to the invention also has significant advantages for uses other than in vehicles equipped with new engines, such as for example so-called general public uses, in particular for light vehicles (or LVs). Where applicable, it must meet the specifications of standard EN 228. According to a particularly advantageous embodiment, the composition according to the invention can be, in whole or in part, prepared from biomass and in particular from bases and/or compounds of plant origin(s). In particular, the composition according to the invention may contain at least 30% by mass of one or more biosourced bases, preferably at least 50% by mass, more preferably at least 80% by mass and better still at least 90%. in mass of one or more biosourced bases. According to a particular embodiment, the composition according to the invention is entirely composed of biosourced bases (content greater than 99.9% by mass).

Thus, it allows a very substantial gain in carbon dioxide (CO2) equivalent compared to a fossil base, of the order of at least 20% compared to a conventional fuel not containing hydrocarbons from biomass. such as a fuel based on hydrocarbons of fossil (petroleum) origin.

This gain in CO2 equivalent is calculated over the entire life cycle of the fuel composition, from its manufacture to its use. It corresponds to a reduction in greenhouse gas emissions and can be determined by life cycle analysis, in accordance with standard ISO 14040-44.

The invention also relates to the use of the fuel composition defined above to power a spark ignition engine.

According to a particularly advantageous embodiment, the composition according to the invention is used as first filling fuel for a new engine, that is to say as “original equipment” fuel. In other words, the composition is used to power a new engine of a motor vehicle.

Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and examples which follow.

In what follows, and unless otherwise indicated, the limits of a domain of values are included in this domain, particularly in the expressions: "between... and...", "in the range from... to...", and "ranging from... to...".

Furthermore, the expressions “at least one” and “at least” used in this description are respectively equivalent to the expressions “one or more” and “greater or equal”.

Finally, in a manner known per se, the term CN compound means a compound containing N carbon atoms in its chemical structure.

Fuel composition

The composition according to the invention contains a mixture (i) of hydrocarbons containing: a) from 8 to 40% by mass of aromatic compounds; b) from 50 to 90% by mass of non-cyclic paraffins containing at least 4 carbon atoms; and c) 2 to 15% by mass of naphthenes.

These contents are expressed in mass, relative to the mass of the mixture (i) of hydrocarbons.

The mixture (i) of hydrocarbons represents 85 to 98% by mass, relative to the total mass of the fuel composition, preferably 88 to 95% by mass, relative to the total mass of the fuel composition. .

The aromatic compound(s) (i)a) are preferably chosen from alkylbenzenes comprising from 7 to 12 carbon atoms. By alkyl-benzenes we designate in a manner known per se the benzene derivatives in which one or more hydrogen atoms are replaced by one or more alkyl groups.

The aromatic compound(s) may in particular be chosen from toluene, ethylbenzene, xylenes (and in particular 1,2-dimethylbenzene or ortho-xylene, 1,3-dimethylbenzene or meta-xylene and 1,4- dimethylbenzene or para-xylene), l-ethyl-3-methylbenzene, mesitylene (1,3,5-trimethylbenzene), l-ethyl-3,5-dimethylbenzene, and mixtures of these compounds.

We particularly prefer mixtures of aromatic compounds, and more particularly mixtures of alkyl-benzenes comprising from 8 to 10 carbon atoms such as ethylbenzene, xylenes (and in particular 1,2-dimethylbenzene or ortho-xylene, 1,3-dimethylbenzene or meta-xylene and 1,4-dimethylbenzene or para-xylene), 1-ethyl-3-methylbenzene, mesitylene ( 1,3,5-trimethylbenzene), and 1-ethyl-3,5-dimethylbenzene.

The content of the aromatic compounds (i)a) represents 8 to 40% by mass, preferably 10 to 30% by mass, and better still 12 to 25% by mass, relative to the mass of the hydrocarbon mixture ( i).

The composition according to the invention also contains non-cyclic paraffins (i)b) containing at least 4 carbon atoms.

By “paraffins” we designate in a manner known per se branched alkanes (also called iso-paraffins or iso-alkanes) and unbranched alkanes (also called n-paraffins or n-alkanes).

The paraffins are preferably chosen from those comprising from 5 to 12 carbon atoms, more preferably from 5 to 9 carbon atoms.

The paraffins can be chosen from n-paraffins (or normal-paraffins, i.e. linear alkanes) and isoparaffins (i.e. branched alkanes).

We particularly prefer mixtures of n-paraffins and iso-paraffins chosen from those described above, preferably comprising a major proportion of iso-paraffins, with a mass ratio of the quantity of iso-paraffins to the quantity of n-paraffins greater than or equal to 6, preferably greater than or equal to 8 and better still greater than or equal to 10. According to a preferred embodiment, this ratio is included in the range from 8 to 20, preferably from 10 to 18, and better still from 12 to 15.

The mixture of hydrocarbons (i) advantageously contains from 3 to 10% by mass of n-paraffins and from 40 to 87% by mass of iso-paraffins.

Preferably, the content of the paraffins (i)b) ranges from 60 to 90% by mass, more preferably from 70 to 85% by mass, relative to the mass of the hydrocarbon mixture (i).

The composition according to the invention also contains naphthenes

(i)c). By “naphthenes” we designate in a manner known per se cyclic alkanes (or cycloalkanes) containing from 5 to 12 carbon atoms. Preferably, the naphthenes are chosen from cyclic alkanes containing from 5 to 12 carbon atoms, and more preferably from 6 to 9 carbon atoms.

Preferably, the content of naphthenes (i) c) ranges from 2 to 10% by mass, more preferably from 3 to 6% by mass, relative to the mass of the mixture of hydrocarbons (i).

According to a preferred embodiment, the mixture (i) of hydrocarbons comes at least 20% by mass from the transformation of plant raw materials. Thus, the mixture (i) advantageously consists entirely or partly of biosourced hydrocarbons, and preferably entirely of biosourced hydrocarbons. The raw materials of plant origin can for example be chosen from cereals (wheat, corn), rapeseed, sunflower, soya, palm oil, sugar cane, beets, plant waste such as for example wood waste, straw, bagasse, grape marc, used vegetable cooking oils, algae, lignocellulosic materials.

The composition according to the invention also contains ethanol.

According to a preferred embodiment, ethanol of plant origin, also called bioethanol, is used.

Bioethanol can, for example, be produced from the fermentation of sugars, mainly glucose, using classic or genetically modified yeast strains. Different plant raw materials can be used for the production of bioethanol, such as sugar cane, corn, barley, potato waste, sugar beet, wine residues such as grape marc.

The composition has an ethanol content ranging from 2 to 15% by mass, preferably from 5 to 12% by mass, relative to the total mass of the fuel composition.

According to an advantageous embodiment, the composition according to the invention comprises at most 2% by mass of olefins, preferably at plus 1.5% by weight of olefins, more preferably at most 1% by weight of olefins, even more preferably at most 0.5% by weight of olefins, relative to the total mass of the fuel composition.

According to a preferred embodiment, the composition according to the invention comprises at most 0.1% by mass of benzene. In other words, its benzene content is less than or equal to 0.1% by mass, relative to the total mass of the composition.

The composition according to the invention may also comprise one or more ethers. Ethers, also called ether-oxides or alkoxy-alkyls, are compounds of formula R-O-R', in which R and R', identical or different, represent an alkyl radical, typically a C to C5 radical.

Mention will be made in particular of the following ethers, which are often incorporated into fuel compositions: methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), methyl tert-amyl ether (TAME) , tertio-amyl ethyl ether (TAEE), and mixtures of these compounds.

The composition has a density at 15°C, measured according to standard EN ISO 12185, in the range from 720 to 745 kg/m ³ . Preferably, the density is in the range from 720 to 730 kg/m ³ .

According to a preferred embodiment, the composition according to the invention has a distillation end point, measured according to standard EN ISO 3405, greater than 190°C, preferably greater than or equal to 195°C.

The composition as described above generally has a research octane index (RON index) greater than or equal to 95, preferably greater than or equal to 99, and more preferably greater than or equal to 100, the RON being measured according to the standard EN ISO 5164.

It generally has an engine octane number (MON index) greater than or equal to 85, preferably greater than or equal to 88, and more preferably greater than or equal to 90, the MON being measured according to standard EN ISO 5163. The above values relate to the intrinsic octane index of the composition, that is to say without adding additional compounds such as in particular octane booster additives.

In addition to the basic compounds described above, the fuel composition according to the invention may also comprise one or more additives, chosen from those usually used in gasoline fuels.

In particular, the composition according to the invention may comprise at least one detergent additive ensuring the cleanliness of the intake circuit. Such an additive can for example be chosen from the group consisting of succinimides optionally substituted by a polyisobutylene group, polyetheramines, betaines, Mannich bases and quaternary ammonium salts, for example those described in documents US4171959 and WO2006135881 .

The composition may also comprise at least one lubricating additive or anti-wear agent, in particular (but not limited to) chosen from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and derivatives of mono- and polycyclic carboxylic acids. Examples of such additives are given in the following documents: EP680506, EP860494, WO98/04656, EP915944, FR2772783, FR2772784.

Other additives can also be incorporated into the fuel composition according to the invention, such as anti-valve recession additives and anti-oxidant additives, additives improving the octane number where appropriate.

The additives described above can be added in quantities ranging, for each of them, from 10 to 5000 ppm by mass, preferably from 50 to 1000 ppm by mass in the fuel composition.

According to a preferred embodiment, the composition comprises a package of additives, that is to say a combination of at least two different additives, advantageously chosen from detergent additives, lubricating additives, anti-recession additives valves and anti-oxidant additives. These additives are advantageously chosen from those cited above. The fuel compositions according to the invention have a lead content generally less than or equal to 5 mg/L (present for example in the form of tetraethyl lead) and, preferably, are lead-free, that is to say they do not contain lead or lead-containing compounds.

Preparation of fuel composition

The composition according to the invention can be prepared by simply mixing its constituents.

A non-limiting embodiment comprises the following steps:

1) preparation of a mixture of hydrocarbons (i) comprising from 8 to 40% by mass of aromatic compounds, from 50 to 90% by mass of non-cyclic paraffins containing at least 4 carbon atoms and from 2 to 15% in mass of naphthenes; Then

2) mixture of 85 to 98% by mass of said mixture (i) with 2 to 15% by mass of ethanol.

The mixture of hydrocarbons (i) preferably comprises one or more biosourced bases at least 20% by mass, that is to say that at least 20% by mass of the hydrocarbons have been obtained from plant raw materials. . More preferably, the mixture of hydrocarbons (i) comprises one or more biosourced bases at least 30% by mass, more preferably at least 50% by mass and better still at least 70% by mass. These quantities are expressed in relation to the total mass of the hydrocarbon mixture (i).

The mixture of hydrocarbons (i) may further comprise non-biosourced hydrocarbons, such as hydrocarbons of fossil (petroleum) origin, preferably in a minority quantity, typically less than 80% by mass, preferably less than 70% by weight. mass, more preferably less than 50% by mass, better still less than 30% by mass. These quantities are expressed in relation to the total mass of the hydrocarbon mixture (i).

According to a particularly preferred embodiment, the mixture of hydrocarbons (i) is entirely made up of one or more biosourced bases. As preferred biosourced bases, one can use in particular those produced from biomass, converted into bio-hydrocarbons by known catalytic conversion processes.

Likewise, ethanol is preferably bioethanol.

Thus, the composition according to the invention can be entirely prepared from raw materials of plant origin.

Uses

The invention also relates to the use of the composition as described above to power a spark ignition engine. The engine can be of the direct injection or indirect injection type.

The fuel composition can be advantageously used both to power an engine of a conventional automobile vehicle (known as “general public”) and a high-power spark ignition engine, such as a motor racing vehicle engine. It may in particular be an atmospheric or turbocharged engine used in a competition vehicle (circuits or rallies), or even a hybrid engine, that is to say a thermal engine coupled to an electric motor, of the rechargeable type ( or PHEV vehicle for “Plug-in Hybrid Electric Vehicle”) or non-rechargeable vehicle (or HEV vehicle for “Hybrid Electric Vehicle”).

According to a preferred embodiment, the composition according to the invention is used as “original equipment” fuel, that is to say as first filling fuel in a vehicle comprising a new engine. In other words, the composition is used to power a new engine of a vehicle, in particular a motor vehicle or not (heavy goods vehicle, public transport vehicle or other), preferably a motor vehicle.

The invention also relates to the use of the composition as described above to reduce equivalent carbon dioxide emissions, measured by life cycle analysis in accordance with standard ISO 14040-44. This reduction is typically determined in relation to a fossil reference, in particular an equivalent fuel composition of petroleum origin. The examples below are intended solely to illustrate the invention, and cannot be interpreted as limiting its scope.

Example

The example below was carried out using a base B comprising 22% by mass of biosourced hydrocarbons resulting from the transformation of bio-alcohol itself resulting from the transformation of biomass.

Base B has the following composition:

[Table 1]

A fuel composition C was prepared, by mixing:

- 89.58% by base mass B, and

- 10.42% by mass of bioethanol.

This composition has a density at 15°C, measured according to standard EN ISO 12185, of 722 kg/m ³ .

Its end point of distillation, measured according to EN ISO 3405, is 195°C.

It has a research octane number (RON, measured according to the EN ISO 5164 standard) of 100.4 and an engine octane number (MON, measured according to the EN ISO 5163 standard) of 91.5.

Compared to an equivalent fuel composition of petroleum origin (that is to say comprising 89.58% by mass of fossil hydrocarbons and 10.42% by mass of bioethanol), the composition C described above has allowed a gain of 21% in CO2 equivalents. This gain was calculated by life cycle analysis, in accordance with standard ISO 14040-44.

Claims

1. Fuel composition comprising:

2. Composition according to the preceding claim, characterized in that the mixture (i) of hydrocarbons represents 88 to 95% by mass, relative to the total mass of the fuel composition.

3. Composition according to any one of the preceding claims, characterized in that the aromatic compounds (i)a) are chosen from alkylbenzenes comprising from 7 to 12 carbon atoms, and preferably from mixtures of alkyl- benzenes comprising 8 to 10 carbon atoms.

4. Composition according to any one of the preceding claims, characterized in that the content of the aromatic compounds (i)a) ranges from 10 to 30% by mass, preferably from 12 to 25% by mass, relative to the mass of the hydrocarbon mixture (i).

5. Composition according to any one of the preceding claims, characterized in that the non-cyclic paraffins (i)b) consist of a mixture of n-paraffins and iso-paraffins with a mass ratio of the quantity d 'iso-paraffins on the quantity of n-paraffins greater than or equal to 6, preferably greater than or equal to 8 and better still greater than or equal to 10.

6. Composition according to the preceding claim, characterized in that the mass ratio of the quantity of iso-paraffins to the quantity of n-paraffins is included in the range going from 8 to 20, preferably from 10 to 18, and better still 12 to 15.

7. Composition according to any one of the preceding claims, characterized in that the content of the paraffins (i)b) ranges from 60 to 90% by mass, preferably from 70 to 85% by mass, relative to the mass of the mixture of hydrocarbons (i).

8. Composition according to any one of the preceding claims, characterized in that the naphthenes (i)c) are chosen from cyclic alkanes containing from 5 to 12 carbon atoms, and more preferably from 6 to 9 carbon atoms.

9. Composition according to any one of the preceding claims, characterized in that the content of the naphthenes (i)c) ranges from 2 to 10% by mass, preferably from 3 to 6% by mass, relative to the mass of the mixture of hydrocarbons (i).

10. Composition according to any one of the preceding claims, characterized in that its ethanol content ranges from 5 to 12% by mass, relative to the total mass of the fuel composition.

11. Composition according to any one of the preceding claims, characterized in that it comprises at most 2% by mass of olefins, preferably at most 1.5% by mass of olefins, more preferably at most 1% by mass mass of olefins, and even more preferably at most 0.5% by mass of olefins, relative to the total mass of the fuel composition.

12. Composition according to any one of the preceding claims, characterized in that its benzene content is less than or equal to 0.1% by mass, relative to the total mass of the fuel composition.

13. Composition according to any one of the preceding claims, characterized in that the mixture of hydrocarbons (i) comes at least 20% by mass from the transformation of plant raw materials.

14. Use of the composition as defined in any one of the preceding claims to power a spark ignition engine.

15. Use of the composition as defined in any one of claims 1 to 13, as primary fuel filling in a vehicle comprising a new engine, preferably a motor vehicle.

16. Use of the composition as defined in any one of claims 1 to 13 to reduce equivalent carbon dioxide emissions, measured by life cycle analysis in accordance with standard ISO 14040-44.