Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
  • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
  • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
  • C10L2200/0254—Oxygen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
  • C10L2200/0259—Nitrogen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/02—Specifically adapted fuels for internal combustion engines
  • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/14—Injection, e.g. in a reactor or a fuel stream during fuel production
  • C10L2290/141—Injection, e.g. in a reactor or a fuel stream during fuel production of additive or catalyst
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/24—Mixing, stirring of fuel components

Definitions

• Methanol-based engine fuel containing a combustion improvement additive Methanol-based engine fuel containing a combustion improvement additive.
• the field of the invention is that of fuels for combustion engines.
• the fuel of the invention is one of the new fuels with reduced impact on the environment, for example those commonly called “e-fuels” when they are made from low-carbon electricity, hydrogen with a low carbon footprint, and/or from CO 2 . They are considered a solution for the decarbonization of transport.
• the fuel of the invention is essentially (at least 98%) composed of methanol and is therefore one of the ecological alternatives for replacing fossil fuels.
• the invention relates to an additive which, when incorporated into methanol, provides better ignition and faster combustion of fuel in the engine.
• Methanol of the “e-fuel” type represents a credible alternative with low environmental impact to soon replace fossil fuels and biofuels for combustion engines.
• the combustion of this methanol thus produced leads to a neutral CO 2 balance.
• Methanol as a fuel has a usable energy density in combustion engines but has a low cetane number. Its ignition in compression ignition diesel engines is problematic, especially at low engine speeds. Different means for improving the ignition of methanol in a compression ignition engine have been described.
• the first method is the co-injection into the engine of a pilot fuel or an additive with methanol.
• patent application CN 214944586 describes the co-injection of a diesel-type pilot fuel with methanol as the main fuel.
• the scientific article “Effect of Cetane Improvers on Gasoline, Ethanol, and Methanol Reactivity and the Implications for RCCI Combustion” (SAE International Journal of Fuels and Lubricants Vol. 6, No. 1 (April 2013), pp. 170-187) describes the co-injection of 2-ethylhexyl nitrate (NEH) with a fuel composed essentially of methanol.
• NHE 2-ethylhexyl nitrate
• the second way is a mixture of fuels with methanol. It is known to mix in a minority or majority proportion of alcohols, such as methanol or ethanol, with fossil or synthetic diesel fuels of the dimethyl ether (DME) type or with gasolines. In this case again, the CO 2 emission balance has a negative impact on the environment.
• alcohols such as methanol or ethanol
• DME dimethyl ether
• the third means is the incorporation of an ignition improvement additive mixed with methanol, possibly also mixed with diesel fuel.
• an ignition improvement additive mixed with methanol possibly also mixed with diesel fuel.
• Numerous patent applications such as patent applications CN 103865592 and CN 104232180, describe the incorporation of a cocktail of multifunctional additives mixed in methanol, possibly also mixed with a fuel oil. These additives have, for example, conservation, anti-corrosion, combustion improvement and detergency functions. These additives generally represent at least 10% of the mass of the fuel.
• the proportion of methanol in the fuel is between 30% and 90% by mass depending on the mass percentages of additives and diesel fuel present in the fuel. The combined effects of these additives are only observed globally without precisely measuring the necessary quantities. It is therefore not a fuel essentially composed of methanol.
• 2-ethylhexyl nitrate has been known for a long time as a cetane improvement additive for diesel fuel.
• a higher cetane value ensures lower fuel consumption, reduced particulate matter and NOx emissions, faster cold engine starting, reduced engine knock and noise, and reduced engine wear.
• the reaction mechanism of NEH in the presence of a hydrocarbon diesel fuel was studied for example in the scientific publication “The Autoignition Behavior of Surrogate Diesel Fuel Mixtures and the Chemical Effects of 2-Ethylhexyl Nitrate (2-EHN) Cetane Improver” (vol 108, section 4: Journal of fuels and lubricants (1999), pp. 1029-1045).
• the present invention provides a solution for improving the ignition of methanol in combustion engines. This improvement is obtained by adding in a very low mass proportion the NEH additive alone mixed with the methanol fuel. More broadly, other alkyl nitrates, whose power to improve the cetane index is known in a manner similar to NEH for a diesel fuel, are also recommended in the context of the present invention to improve the methanol inflammation. It is unexpected that additives known to increase the cetane number of a diesel or hydrocarbon biodiesel can also be used effectively, at a very low mass percentage, to improve the ignition of an alcohol such as methanol.
• the invention relates to a fuel comprising from 98.0% to 99.9% by mass of methanol for an engine by auto-ignition by compression or by spark ignition, and from 0.01% to 2.0% by mass of a compound to improve the ignition delay of methanol.
• Said compound is an alkyl nitrate.
• Said compound has the advantage of being liquid at room temperature, not very flammable, non-toxic and produced industrially.
• Said compound at these low levels in the presence of methanol fuel, is therefore conventionally considered a fuel additive.
• liquid compound is carried out as a mixture with methanol in the liquid state to form the fuel according to the invention in a tank. It can also be stored separately and mixed with the methanol to form the fuel according to the invention prior to its injection into the engine, or co-injected to form the fuel according to the invention in a premixing chamber of the engine.
• Said compound, of the alkyl nitrate type, previously reserved for improving the cetane index of fossil diesel or biodiesel hydrocarbon fuels, is therefore used effectively and surprisingly as additives for improving the inflammation of the methanol.
• Figure 1 shows the effect of alkyl nitrates on the cetane number of standard diesel fuel.
• Figure 6 shows the ignition delay of a methanol-based fuel containing different quantities of NEH, for a richness (air/fuel) of 1, at a compression pressure Pc of 30 bars, over a temperature range going from 850K to 1000K.
• Figure 7 is an enlarged view of Figure 6 over the temperature range from 900K to 1000K.
• the present disclosure relates to a fuel for a motor (in particular for a combustion engine) which comprises about 98.0% to about 99.9% by mass of methanol and about 0.01% to about 2.0% by mass of a compound consisting of an alkyl nitrate.
• the fuel comprises about 0.05% to about 1.5% by weight of said compound.
• the fuel comprises about 0.1% to about 1.0% by mass of said compound.
• the fuel comprises about 0.1% to less than 1.0% ( ⁇ 1.0%) by mass of said compound.
• the fuel of the invention consists of methanol and said compound (and in this case, the quantity of compound in the fuel is at least 0.1% by mass).
• the fuel when the sum of the methanol amount and the compound amount does not equal 100% by mass, the fuel may contain one or more other additives to supplement the fuel to 100%, such as for example additives with conservation, anti-corrosion or detergency functions.
• Said compound added to methanol is chosen from one or more linear, branched or cyclic alkyl nitrates.
• Said compound is more particularly chosen from linear alkyl nitrates comprising 4 to 36, advantageously 4 to 24 carbon atoms, branched alkyl nitrates comprising 4 to 36, advantageously 4 to 24 carbon atoms, alkyl nitrates cyclic (or cycloalkyl nitrates) containing 5 to 18 carbon atoms, and mixtures thereof.
• said compound is chosen from 2-ethylhexyl nitrate, cyclohexyl nitrate, dodecyl nitrate, n-nonyl nitrate, 2-tetradecyl-l-octadecyl nitrate, hexyl nitrate, 2-octyl nitrate, isononyl nitrate, 2-propylheptyl nitrate, a mixture of C9-C13 branched alkyl nitrates, and mixtures thereof.
• the alkyl nitrate is 2-ethylhexyl nitrate alone or mixed with one or more other alkyl nitrates as defined above, advantageously the alkyl nitrate is 2 nitrate -ethylhexyl alone.
• C9-C13 branched alkyl nitrates can be obtained from corresponding mixtures of C9-C13 branched alcohols, for example the alcohols available from the company Exxon under the trade name ExxalTM.
• a mixture of at least two branched alcohols chosen from a C 9 branched alcohol, a C i0 branched alcohol, a Cn branched alcohol, a C i2 branched alcohol and a C branched alcohol can be prepared. i3 , then synthesize the corresponding mixture of alkyl nitrates.
• said compound and the methanol are stored separately, and brought into contact with each other in an injector, thus forming the fuel according to the invention before it is conveyed into the fuel chamber. engine combustion.
• said compound is stored separately from the methanol and is coinjected with the methanol to form the fuel according to the invention in a premixing chamber of the engine.
• the present disclosure also relates to the use of an alkyl nitrate (as defined above), in the proportions defined above, as an agent for improving the ignition of a fuel based (consisting of) of methanol.
• the present disclosure also relates to a method for improving the ignition of a fuel based (consisting of) methanol in an engine (in particular a combustion engine), the method comprising the addition to methanol of an alkyl nitrate ( as defined above), in the proportions defined above.
• the alkyl nitrate and methanol are mixed in an injector.
• the alkyl nitrate and methanol are mixed in a premix chamber of the engine.
• the present disclosure also relates to an engine (in particular a combustion engine) of a vehicle (such as a car, heavy goods vehicle, tractor, etc.) or a ship (such as an oil tanker, container ship, etc.) containing a fuel as defined above.
• a vehicle or vessel comprising an engine as defined above.
• the improvement in the ignition delay of methanol was measured under test conditions equivalent to those described in the scientific article “Ignition delay times of NH 3 /DME blends at high pressure and low DME fraction: RCM experiments and simulations” (Combustion and Flame Volume 227, May 2021, Pages 120-134).
• the test laboratory engine is a rapid compression machine equivalent to that described in this scientific article. This is a rapid compression machine used to measure the auto-ignition time of a mixture. This machine allows the mixture to be compressed in a very short time in order to obtain pre-established pressure and temperature conditions.
• the admission of liquids into the tank is done through an orifice different from that of the admission of gases, the quantities of liquids are measured using a syringe and a precision balance.
• the ignition delay dAI is defined according to the following formula in which Pc is the pressure applied to the injected fuel:
• the ignition times were determined as a function of the injection temperature (between 800K and 1000K), at a pressure Pc of 30 bars, of a fuel according to the invention consisting of 99.8% by mass of methanol and of 0.2% by mass of NEH and for respectively a richness of 0.5, 1 and 1.5 of mixing with air.
• the results are shown in Figures 2, 3 and 4 along with the ignition delay reference points for methanol alone.
• a significant reduction, by approximately a factor of 5 to 10 in fuel ignition times is observed when the latter contains NEH, compared to methanol alone. This reduction in ignition delay compared to that of methanol alone is all the more significant as the temperature is low.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Output Control And Ontrol Of Special Type Engine (AREA)

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• 2022
  • 2022-06-23 FR FR2206260A patent/FR3137104B1/fr active Active
• 2023
  • 2023-03-10 US US18/119,919 patent/US12152209B2/en active Active
  • 2023-03-10 CA CA3192534A patent/CA3192534A1/fr active Pending
  • 2023-06-22 PE PE2024003070A patent/PE20251092A1/es unknown
  • 2023-06-22 EP EP23744847.7A patent/EP4544007A1/de active Pending
  • 2023-06-22 CN CN202380049208.XA patent/CN119563009A/zh active Pending
  • 2023-06-22 WO PCT/FR2023/050937 patent/WO2023247901A1/fr not_active Ceased
  • 2023-06-22 KR KR1020257000681A patent/KR20250034079A/ko active Pending
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