EP3399008B1 - Essence potentiellement neutre en co2 et écologique bassée sur la chimie c1 - Google Patents

Essence potentiellement neutre en co2 et écologique bassée sur la chimie c1 Download PDF

Info

Publication number
EP3399008B1
EP3399008B1 EP18153578.2A EP18153578A EP3399008B1 EP 3399008 B1 EP3399008 B1 EP 3399008B1 EP 18153578 A EP18153578 A EP 18153578A EP 3399008 B1 EP3399008 B1 EP 3399008B1
Authority
EP
European Patent Office
Prior art keywords
volume
vol
spark
engine fuel
ignition engine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP18153578.2A
Other languages
German (de)
English (en)
Other versions
EP3399008A1 (fr
Inventor
Thomas Wilharm
Philipp Seidenspinner
Eberhard Jacob
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asg Analytik-Service GmbH
Original Assignee
Asg Analytik-Service GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asg Analytik-Service GmbH filed Critical Asg Analytik-Service GmbH
Publication of EP3399008A1 publication Critical patent/EP3399008A1/fr
Application granted granted Critical
Publication of EP3399008B1 publication Critical patent/EP3399008B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines

Definitions

  • the invention relates to an environmentally friendly and potentially CO 2 -neutral petrol based on C1 chemistry, as well as its use and its production.
  • e-Fuels are made from a synthesis gas (mixture of CO, CO 2 and H 2 ), which is produced from recycled industrial exhaust gases with high levels of CO 2 and CO and sustainably produced H 2 (eH 2 ).
  • synthesis gas can also be obtained by high-temperature gasification of biomass. It is also conceivable to extract CO 2 from the air as a C source.
  • the C1 oxygenates methanol (M) and dimethyl ether (DME) allow simple and inexpensive production from sustainable synthesis gas.
  • the H 2 requirement is low compared to the production of hydrocarbons, since only one of the O atoms of CO 2 is subject to the reduction with H 2 .
  • methanol is an excellent gasoline, but its toxic and organ-damaging properties require a lot of protective measures for its handling.
  • Use as a petrol station fuel is therefore questionable in countries with high consumer protection standards.
  • the EN 228 standard for petrol allows the admixture of up to 3% by volume of methanol, but this is mostly not used in the EU refineries, e.g. since, according to the GHS labeling requirement, a methanol-containing gasoline would also have to be classified as toxic.
  • DME is a fuel that is only suitable for diesel engines, but as a liquefied gas requires a special supply structure.
  • OME 2-6 For internal combustion engines with auto-ignition, ie for diesel engines, the C1 ethers OME 2-6 have been used to describe a fuel that enables soot-particle-free combustion in engines with internal mixture formation (direct fuel injection).
  • OME is characterized by rapid biodegradability and is less toxic as a pure substance.
  • Sustainable OME E-Diesel
  • CN 101434874 A discloses a fuel based on methanol and dimethyl ether and 35-56 liters of methanol, 4-10 liters of ethanol, 1-15 liters of C5 distillate, 10-37 liters of dimethyl ether, 3-11 liters of water, 6-12 liters of gasoline, 8- Contains 15 liters of diesel, 6-8 liters of dimethyl carbonate and 6-8 liters of dimethoxymethane.
  • This fuel is based on dimethyl ether, which is gaseous at room temperature, and is therefore only suitable as a fuel because of its high vapor pressure if pressure tanks are used.
  • WO 01/53436 A1 discloses a gasoline containing hydrocarbons, ethanol and adjuvants for adjusting the DVPE.
  • EP 0082688 A2 a fuel intended for use in spark ignition internal combustion engines comprising a hydrocarbon fuel and a dialkyl carbonate.
  • Fenken Wang et al describe in "Surface Tensions of Mixtures of Diesel Oil or Gasoline and Dimethoxymethane, Dimethyl Carbonate, or Ethanol", Energy & Fuels., Vol. 20, no. 6, ISSN 0887-0624, pp. 2471-2474 , Mixtures of diesel or gasoline with dimethoxymethane, dimethyl carbonate, or ethanol.
  • the EP 0501097 A1 describes a fuel for spark ignition internal combustion engines which contains a fraction of hydrocarbons and boiling in the range from 30 to 200 ° C contains in particular 1.0 to 50.0% by volume of methyl formate.
  • the EP 0112172 A1 describes the production of dihydrocarbyl carbonates and their suitability as additives in fuels for internal combustion engines.
  • the CN 103952194 A describes a composition containing 88 to 95 parts by weight of dimethoxymethane as a mixed fuel for a vehicle.
  • An object of this invention is to find an OME analog for spark ignition internal combustion engines, ie a gasoline fuel, which burns largely without soot particles. It is also advantageous if the fuel is classified as less toxic and / or not environmentally hazardous.
  • This petrol should preferably be used both for engines with external mixture formation (intake manifold injection) and for engines with internal mixture formation (direct injection, DI).
  • soot particle emissions currently exists in petrol DI engines. For this reason, legislators in the EU indirectly require the installation of a particle filter for cars by lowering the particle number limit to 6x10 11 # / km from October 2018. A fuel with which these extremely low particle emissions can be achieved without the use of particle filters is particularly desirable.
  • An advantageous embodiment of the present invention therefore sets itself the goal of providing such a fuel.
  • the invention sets itself the goal of providing a sustainable fuel that can be produced on the basis of C1 chemistry and can therefore be produced entirely from recycled or air-derived CO 2 and sustainably produced hydrogen or from biomass.
  • the present invention provides a composition in which dimethyl carbonate (DMC) and methyl formate (MF) and / or dimethoxymethane (DMM) are major components of a petrol.
  • DMC dimethyl carbonate
  • MF methyl formate
  • DMM dimethoxymethane
  • the motor suitability of this fuel can be further improved by the optional addition of methanol (MeOH) and / or ethanol (EtOH).
  • the desired properties of this composition include, in particular, adequate cold resistance and a corresponding volatility, characterized by a volatility index (Vapor Lock Index, VLI) that meets the requirements of the EN standard for petrol fuels DIN EN 228: 2013 (preferably DIN EN 228: 2017 ) and thus guarantees a cold start for carburettor engines at - 30 ° C and the build-up of a grease vapor bell in the tank as explosion protection.
  • VLI volatility index
  • the C1 ester dimethyl carbonate is an important component of the composition and is preferably the main component (the component with the largest volume fraction in comparison to all other individual components).
  • Dimethyl carbonate is a prototype for a green solvent. It is rapidly biodegradable and less toxic and can be produced from methanol and CO 2 in a 2-step process (C1 chemistry). So far, the use of dimethyl carbonate has only become known as a blend component for fuels, primarily for diesel fuels, based on hydrocarbons.
  • dimethyl carbonate not only as an admixture to conventional fuels is advantageous, but in the special mixture with MF and / or DMM and optionally MeOH and / or EtOH is also suitable as petrol without hydrocarbon-based fuel admixtures.
  • Dimethyl carbonate for example, has a melting point of 2 to 4 ° C and therefore requires an additive in order to obtain a liquid fuel even at low temperatures.
  • all-season fuel in Germany should remain liquid down to around -25 ° C, in special cases down to -30 ° C. It is also desirable that the engine can be operated at an ambient temperature of up to 50 ° C.
  • the C1-ester methyl formate (MF) has an mp of -100 ° C and is therefore particularly suitable for lowering the fixed point of a fuel based on DMC.
  • a cold resistance required for a fuel can be achieved by mixing the C1 ester methyl formate (MF) with dimethyl carbonate (DMC).
  • DMC dimethyl carbonate
  • MF has a boiling point of 31.5 ° C and is therefore well suited to raising the low steam pressure of the DMC to the legally prescribed values (EN228).
  • EN228 legally prescribed values
  • the addition of the very volatile MF significantly improves the mixture formation in the combustion chamber of the engine and thus prevents the formation of fat pockets with local oxygen deficiency, which lead to the formation of soot particles.
  • Methyl formate also has the particular advantage that it can be produced very cheaply from methanol and carbon monoxide (CO). In addition, methyl formate burns as a C1 ester (free of CC bonds) without soot particle formation (cf. Härtl et.al MTZ 07/08 (2017 )).
  • DCM dimethoxymethane
  • methyl formate has a purity of 97%.
  • the rest consists mainly of methanol, which is a GHS classification as toxic and organ-damaging Fabric required.
  • Pure methyl formate (with a methanol content ⁇ 0.3%) has so far not been available on an industrial scale.
  • the inventors were able to determine that sufficiently pure methyl formate can be produced from technical methyl formate by simple distillation. Pure methyl formate, as a non-toxic and non-environmentally hazardous substance, is only stable in the long term if it is completely water-free.
  • esters DMC and MF are kinetically stable against hydrolysis in a neutral medium.
  • a solution of MF in water is already susceptible to hydrolysis.
  • EtOH denatured in this way can also be used in the present fuel at least up to an ethanol content of 10% by volume, preferably up to 5% by volume, without any appreciable deterioration in the soot formation tendency.
  • preferably undenatured EtOH especially EtOH which contains at least no Bitrex
  • ethanol with a composition according to EN15376 can be used.
  • An admixture (total proportion in the petrol) of 5% bioethanol (possibly in addition to ethanol produced elsewhere) is in accordance with the currently valid European directives and is therefore preferred.
  • the proportion of bioethanol in the petrol is preferably in a range from 4 to 10% by volume, more preferably 5 to 10% by volume, or 5-8% by volume.
  • composition of the present invention provides a petrol that can potentially be produced directly from the recycled CO 2 and environmentally friendly hydrogen produced using C1 chemistry.
  • the fuel also enables a significant reduction in soot particle emissions and can at best achieve sub-zero emissions, in which fewer pollutants of a certain type leave the vehicle than are supplied with the combustion air.
  • the petrol may also contain components C and / or D, the content of component D being at most 10% by weight and the sum of the contents of components A, B, C and D being 100% by weight.
  • the total content of methanol in the petrol is at most 1.75% by volume.
  • the petrol contains at least 40 vol.% And at most 70 vol.% Of component A and at least 30 vol.% And at most 40 vol.% Of component B.
  • Dimethyl carbonate (DMC) has a very high octane number (> 110) and can be produced from renewable sources, but has insufficient vapor pressure and insufficient cold resistance for a petrol. Only the combination with methyl formate (MF) - a substance with a very high octane number (RON: 115; MOZ: 114.8) - or dimethoxymethane (DMM) enables a fuel that has a sufficiently high vapor pressure and good to very good cold resistance owns. Dimethoxymethane lowers the octane number and can therefore be used to adjust the mixture octane number in order to obtain octane numbers for e.g. B. to realize the Superplus level (RON 98) and the Super level (RON 95). However, the petrol of the present invention preferably has an octane number (RON) of 100 or more, preferably 105 or more.
  • gasoline of the present invention can help reduce soot particle formation without sacrificing octane rating.
  • the petrol preferably has a soot point according to ASTM D 1322 (2015) of at least 45 mm.
  • the soot point is preferably at least 50 mm, at least 55 mm, at least 60 mm, or more than 60 mm.
  • the petrol may contain an optional component D, the sum of components A, B, C and D being 100% by weight.
  • the component D is not necessarily a pure substance and can be a mixture of substances.
  • the content of the component D is 10% by weight or less, preferably 5% by weight or less and particularly preferably 2% by weight or less.
  • component D is an additional constituent and therefore naturally does not contain any of dimethyl carbonate, methyl formate, dimethoxymethane, ethanol and methanol.
  • Component D like component C, is optional; it can therefore also not be present (content of 0% by weight).
  • the component D can contain auxiliary substances or additives or functional additives. These include, for example, oxidation inhibitors, rust inhibitors, lubricants and also dyes, some of which are highly viscous or are present as solids.
  • auxiliary substances or additives or functional additives include, for example, oxidation inhibitors, rust inhibitors, lubricants and also dyes, some of which are highly viscous or are present as solids.
  • PAGE polyalkylene glycol ethers
  • Polypropylene glycol (10-50% by weight) alkyl ethers can be added in concentrations up to 1% by weight. Commercial representatives are e.g. B.
  • Synalox 40-D700 (manufacturer: Dow Chemical Co; copolymer made from polyethylene glycol- 60% by weight polypropylene glycol- 40% by weight ether) and Ucon 75-H-450 (manufacturer: Dow Chemical Co; copolymer made from polyethylene glycol- 75 wt .-% polypropylene glycol- 25 wt .-% ether), which are preferably etherified using ethylene glycol.
  • Component D may also contain contaminants such as water.
  • the high solubility of water in the present gasoline fuel means that there is no risk of water separation, particularly in the presence of component C. This also applies to temperatures down to -25 ° C and sometimes below. There were no ice deposits at water concentrations of max. 2% by volume observed. Since water in particular increases the tendency to hydrolysis, the water content is preferably 4.0% by volume or less, more preferably 2.0% by volume or less, 1.0% by volume or less, 0 , 5 vol.% Or below, at 0.2 vol.% Or below or at 0.1 vol.% Or below.
  • Component D may also contain other fuels, such as hydrocarbons (or mixtures thereof), a conventional gasoline fuel and / or a renewable fuel.
  • the content of methanol is 0.17% by weight or less
  • the content of water is 0.2% by weight or less
  • the content of C3 and C4 oxygenates e.g. acetone and Methyl ethyl ketone
  • the hydrocarbon content total content
  • the content of the component D is limited.
  • a fuel which contains larger amounts of a component D for example also a mixture of the present fuel with gasoline and / or - less suitably - diesel in any mixing ratio
  • the inventors have set themselves the goal of developing a fuel that is as soot-free as possible. Therefore, the proportion of a component D is limited and In particular, constituents (D) with CC bonds should only be contained in small amounts.
  • the petrol preferably contains at least 10% by volume of component A.
  • the content of component A (DMC) is preferably at least 20% by volume, at least 25% by volume, at least 30% by volume, at least 35% by volume. -%, at least 40% by volume or at least 45% by volume.
  • the content of component A is preferably at most 90% by volume, at most 80% by volume, at most 75% by volume, at most 70% by volume, at most 65% by volume or at most 60% by volume.
  • Component A shows good combustion properties and is characterized by an almost perfect environmental compatibility. It is therefore preferred that this component represents the largest proportion (% by volume) of all individual components (i.e. none of the individual components B, C and D is present in a larger amount (% by volume) than component A).
  • % refers to "volume%” (v / v). The volumes are determined at a temperature of 15 ° C. Unless stated otherwise, percentages refer to the composition (e.g. petrol) as a whole.
  • Component B in particular methyl formate, can be produced comparatively inexpensively.
  • the petrol contains at least 30% by volume and at most 40% by volume of component B.
  • a content of 35 ⁇ 2% by volume is particularly preferred, in particular if component B consists of MF.
  • component B Due to its comparatively high vapor pressure, component B contributes significantly to the formation of a grease vapor bell (avoiding the risk of explosion) over the fuel and gives the fuel a satisfactory cold start ability.
  • the Dry Vapor Pressure Equivalent (DVPE) value increases from 10.8 kPa for dimethyl carbonate to 39.5 kPa (20 vol.% MF) or 49.9 kPa (30 vol. -% MF) for the mixtures of dimethyl carbonate and methyl formate (MF).
  • DVPE Dry Vapor Pressure Equivalent
  • DMM dimethoxymethane
  • MF MF
  • octane number of the fuel This can be advantageous in order to achieve the values of 90 to 100 (RON) which are common for commercial fuels, since both DMC and MF have octane numbers of well over 100.
  • the petrol preferably contains at least 2 vol.%, More preferably at least 3 vol.%, At least 4 vol.%, Or at least 5 vol.% Of component C.
  • the petrol preferably contains at most 20 vol. more preferably at most 15 vol.%, at most 10 vol.%, at most 8 vol.% or at most 6 vol.% of component C.
  • the content of component C can be in a range from 0 to 12 vol. -%, preferably 0 to 10 vol .-%.
  • Component C can not only contribute to a further reduction in the melting point of the mixture, but also gives the petrol long-term stability.
  • both ethanol (EtOH) and methanol (MeOH) are able to reduce or prevent hydrolysis of methyl formate (MF).
  • the ratio is in a range from 5: 1 to 2: 1, preferably in a range from 9: 2 or below, or 4: 1 or below, also preferably 3: 1 or above or 7: 2 or above.
  • the petrol may preferably contain component C in an amount of 0 to 10% by volume, including the possibility that component C may not is available.
  • component C in an amount of 0 to 10% by volume, including the possibility that component C may not is available.
  • the content of the component can also be low or Component C can be omitted.
  • the gasoline have at most 10.0 vol%, preferably at most 5.0 vol%, at most 3.0 vol%, at most 2.0 vol%, at most 1.0 vol. -%, at most 0.1 vol .-% or at most 100 ppm (v / v) contains hydrocarbons.
  • Hydrocarbons can be included as component D. However, it is preferred to keep the hydrocarbon content low. Hydrocarbons are particularly preferably not present or only present as unavoidable impurities. Hydrocarbons, which are commonly used in petrochemicals, tend to evaporate and thus pollute the environment. In addition, conventional hydrocarbons contribute significantly to the formation of soot particles during combustion. Surprisingly, it was found that even small amounts of hydrocarbons in the mixtures of the present invention result in a significant increase in soot particle formation.
  • hydrocarbons are compounds which consist of carbon and hydrogen.
  • the petrol contains at most 0.5 vol.%, At most 0.2 vol.%, At most 0.1 vol.% Or at most 100 ppm (v / v) aromatics.
  • aromatics are all compounds with at least one aromatic ring and thus include optionally substituted hydrocarbon-based aromatics as well as optionally substituted heteroaromatics. The lowest possible proportion of aromatics is desirable both with regard to the direct environmental and health hazard and with regard to the formation of soot particles during combustion.
  • the total content of dimethoxymethane (DMM) in the petrol is preferably at most 40% by volume, particularly preferably at most 30.0% by volume, at most 25.0% by volume, at most 20.0% by volume .-%, at most 15.0 vol .-%, at most 10.0 vol .-% or at most 8.0 vol .-%.
  • Dimethoxymethane can be used advantageously to adjust the octane number and to increase the vapor pressure.
  • DMM is currently more expensive to produce than methyl formate, so that the proportion of DMM should be kept rather low for economic reasons.
  • component C preferably in an amount of at least 5% by volume, more preferably at least 10% by volume, at least 15% by volume or at least 20 vol .-%) are used.
  • components B and possibly C and a high proportion of component A allow the petrol to meet certain minimum requirements for resistance (long-term stability), corrosion resistance, vapor pressure and cold resistance.
  • petrol fuels are also preferred which contain 0-40% by volume (preferably 5-40% by volume) of ethanol.
  • the petrol preferably has a total content of compounds with a direct CC bond, with the exception of ethanol, of at most 10.0 vol.%, Preferably at most 5.0 vol.%, At most 2.5 vol. -%, at most 1.0% by volume, at most 0.5% by volume, at most 0.2% by volume or at most 0.1% by volume or at most 100 ppm (v / v).
  • the content is calculated from the content of compounds with at least one direct C-C bond minus the content of ethanol.
  • a direct C-C bond includes any direct bond between two carbon atoms, e.g. B. a C-C single bond, a C-C double bond or a C-C triple bond. Due to a strong tendency to form soot, especially compounds with C-C multiple bonds should be avoided.
  • the petrol preferably consists essentially of components A, B and possibly C.
  • the sum of the amount of components A, B and C is preferably at least 95% by volume, particularly preferably at least 97% by volume, at least 98% by volume .-%, at least 99 vol .-% or 100 vol .-%.
  • a fuel that primarily contains the components mentioned can be produced as e-fuel, i.e. completely or almost completely from recycled CO 2 and sustainably produced H 2 . In addition, such a fuel is hardly prone to soot formation and is therefore advantageous in several respects from an environmental point of view.
  • component C preferably contains at least 50% by volume, particularly preferably at least 70% by volume, at least 80% by volume, at least 90% by volume, at least 95% by volume, at least 97% by volume. % or at least 99 vol% Ethanol.
  • component B can contain at least 70 vol.%, At least 80 vol.%, At least 90 vol.%, At least 95 vol.%, At least 97 vol.%, At least 99 vol.% Or 100 vol. -% contain methyl formate. Methyl formate is very inexpensive to produce and is therefore preferred as component B.
  • the total content of methanol in the petrol is at most 1.75 vol.%, Preferably at most 1.20 vol.%, At most 1.00 vol.%, At most 0.70 vol.%, At most 0.50 vol .-%, at most 0.20 vol .-%, at most 0.15 vol .-% or at most 0.10 vol .-%.
  • the hazard symbols GHS06 and GHS08 can be omitted for mixtures with a content of 1.75% methanol and below. Such a fuel therefore does not currently have to be labeled with these potentially deterrent hazardous substance symbols.
  • the fuel of the present invention is said to have a total methanol content of 1.75% by volume to be harmful to health and to avoid appropriate labeling where possible. With regard to future tightening of labeling requirements, but also with regard to protecting users, smaller amounts of methanol should also be preferred.
  • Absolute ethanol (99.6%) is preferably used as the component C.
  • methanol can be contained as an unavoidable impurity (e.g. from the addition of methyl formate or as impurity of the ethanol itself; absolute ethanol as a mixed component for conventional petrol contains max. 0.1% methanol).
  • the petrol preferably has a volatile index (VLI) of 1150 or less.
  • VLI volatile index
  • the VLI is a key figure for describing the suitability of a fuel for certain climatic conditions (especially in the transition period).
  • a VLI of 1150 or less ensures that the fuel does not evaporate excessively during storage (e.g. in the tank) during the transition period.
  • the petrol preferably has a DVPE of 90 kPa or less. This value is particularly advantageous for winter fuels. A DVPE of 60 kPa should not be exceeded in summer. In both cases, the fuel should have an E70 value of 52 vol.% Or less. It is particularly preferred that the petrol of the present invention meets the requirements of a winter fuel according to DIN EN 228 (status: 2017-08) and / or a summer fuel according to DIN EN 228 (status: 2017-08).
  • the petrol should preferably have a filterability limit (CFPP) of -20 ° C or below.
  • the CFPP is more preferably -25 ° C or below, -30 ° C or below, -35 ° C or below or -40 ° C or below.
  • higher values are permissible, for example 0 ° C and below or -10 ° C and below.
  • the Cold Filter Plugging Point (CFPP, German: temperature limit of filterability or filterability limit) describes the temperature in ° C at which a test filter clogs according to EN 116.
  • the measuring method comes from the Characterization of diesel fuels and is normally not used for conventional petrol. However, it is useful and necessary with the existing substance mixtures in order to be able to make reliable statements. It is also preferred if the petrol is still liquid at a temperature of -25 ° C, ie no solid components are observed at this temperature.
  • the present invention also relates to the use of the gasoline described above as a fuel for the operation of internal combustion engines with spark ignition.
  • the present invention also relates to a method for producing a petrol, comprising the mixing of dimethyl carbonate with at least one of methyl formate and dimethoxymethane and optionally with at least one of ethanol and methanol and also optionally with further constituents.
  • the mixed components can contain the impurities described above.
  • methyl formate can contain methanol as an impurity
  • ethanol can contain methanol and water as an impurity.
  • Ethanol denatured can also be used and thus contain the denaturants permitted according to EN15376 (isobutanol, isopropanol, Bitrex, methyl t-butyl ether, ethyl t-butyl ether).
  • No methanol is preferably added during the mixing. Specifically, this means that methanol is not added deliberately, but is only introduced as an impurity.
  • the method may also include mixing other ingredients. These constituents correspond to constituent D of the above mixture and the addition amounts are accordingly preferably corresponding to the respective content of the mixture indicated above.
  • the method preferably produces a gasoline fuel as defined above.
  • the petrol of the present invention can be made primarily from C1 materials from sustainably sourced materials.
  • the fuel burns with little soot particle formation, which makes it particularly interesting with regard to smog formation and fine dust pollution.
  • the mixture C60F35E5 shows particularly good properties with regard to DVPE and E70.
  • the flash points of all mixtures are at a minimum of -13 ° C higher than those of gasoline (flash point: ⁇ -25 ° C) and therefore offer a little more safety with regard to undesired ignition.
  • Table 2-2 C50F50 C50F40E10 C55F40E5 C60F40 Oxygen content % By weight 53.5 51.62 52.56 53.5 Lower heating value kWh / kg 4.39 4,695 4.54 4.39 Air requirement, stoichiom.
  • compositions were prepared analogously to Example 1 and tested for their resistance to hydrolysis and their tendency to corrode. For this purpose, water was added to the samples so that the total water content was 2% by volume. The samples were then stored together with a coil spring (material according to EN 10270-1 type SH) in a closed glass vessel at 50 ° C for 4 weeks.
  • a coil spring material according to EN 10270-1 type SH
  • the coil spring was examined after the 4 weeks and in the absence of visible corrosion (caused by formic acid formed during the hydrolysis) the sample was rated as "passed".
  • the samples rated "passed” can thus be regarded as highly hydrolysis-resistant, since the extreme conditions of the test cannot be expected in real operation.
  • the water content of conventional petrol is usually below 0.1% by volume (usually between 600 and 800 ppm (m / m)).
  • compositions were prepared analogously to Example 1 and examined for their vapor pressure.
  • the petrol can therefore be adjusted so that it is suitable for use in summer as well as in winter and in the transition period.
  • compositions were prepared analogously to Example 1 and tested for their cold resistance.
  • Fig. 4 The dates of the 1 to 3 are in Fig. 4 summarized, whereby only data points rated "passed" are shown.
  • a circle represents the cold resistance
  • a cross represents the hydrolysis resistance
  • a square represents a vapor pressure range of 45-60 kPa.
  • compositions shown contain the constituents DMC ("C”), MF (“P”) and EtOH (“E”) each in increments of a full 5.0% by volume, that is, for. B. 0%, 5.0%, 10.0%, 15.0% etc.
  • Example 2 Analogously to Example 1, a composition of 50% by volume DMC, 40% by volume DMM and 10% by volume EtOH (DMC50-DMM40-EtOH10) was prepared. The mixture had a cold resistance of at least -25 ° C (ie no solid components were observed at -25 ° C, CFPP is -40 ° C). The flash point is -16 ° C. Although the DVPE is quite low at around 45 kPa at 37.8 ° C, a relatively high E70 value is found at 54.2%. The properties of the composition of Example 5 are summarized in Table 3.
  • a selected gasoline of the present invention namely DMC60-MF35-EtOH5 (60% by volume DMC, 35% by volume MF, 5% by volume EtOH), and several mixtures of DMC with a conventional E5 were used to investigate the formation of soot particles Petrol prepared according to EN 228.
  • the soot point was determined in accordance with ASTM D 1322 (2015). The higher the soot point, the less soot formation. From a soot point of over 60 mm, it is assumed that no soot particle formation takes place. In such a case, trace amounts of soot in the combustion gases can be recognized by a yellow flame color. The results are shown in Table 4. Table 4: Sample No.
  • composition Soot point (mm) 1 E5 petrol (EN 228) 14 2nd E5 petrol (EN 228) + 20 vol.% DMC 14 3rd E5 petrol (EN 228) + 50 vol.% DMC 22 4th E5 petrol (EN 228) + 80 vol.% DMC 24th 5 DMC60-MF35-EtOH5 > 60

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Claims (15)

  1. Carburant automobile, qui est constitué par les constituants A et B suivants, éventuellement le constituant C suivant et éventuellement jusqu'à 10 % en poids d'un ou de plusieurs constituants D supplémentaires, la somme des teneurs des constituants A, B, C et D étant de 100 % en poids :
    - constituant A : le carbonate de diméthyle,
    - constituant B : le formiate de méthyle ou un mélange de formiate de méthyle et de diméthoxyméthane, le constituant B contenant au moins 50 % en volume de formiate de méthyle,
    - constituant C : l'éthanol, le méthanol ou un mélange d'éthanol et de méthanol,
    la teneur totale en méthanol dans le carburant automobile étant d'au plus 1,75 % en volume,
    le carburant automobile contenant au moins 40 % en volume et au plus 70 % en volume du constituant A,
    le carburant automobile contenant au moins 30 % en volume et au plus 40 % en volume du constituant B.
  2. Carburant automobile selon la revendication 1, dans lequel la teneur du constituant D est de 5 % en poids ou moins, de préférence de 2 % en poids ou moins.
  3. Carburant automobile selon la revendication 1 ou 2, dans lequel la teneur totale en méthanol dans le carburant automobile est d'au plus 1,00 % en volume, de préférence d'au plus 0,50 % en volume, d'au plus 0,20 % en volume ou d'au plus 0,10 % en volume.
  4. Carburant automobile selon l'une quelconque des revendications 1 à 3, qui présente un indice de volatilité (VLI) de 1 150 ou moins, l'indice de volatilité étant calculé à partir du DVPE, Dry Vapour Pressure Equivalent, mesuré selon DIN EN 13016-1 à 37,8 °C en kPa, et de la quantité évaporée à 70 °C, E70, mesurée selon DIN EN ISO 3405 en % (v/v), selon la formule suivante : VLI = 10*DVPE + 7*E70.
  5. Carburant automobile selon l'une quelconque des revendications 1 à 4, qui présente un DVPE, mesuré selon DIN EN 13016-1 à 37,8 °C, de 90 kPa ou moins, de préférence de 60 kPa ou moins.
  6. Carburant automobile selon l'une quelconque des revendications 1 à 5, dans lequel le constituant B contient au moins 70 % en volume, au moins 80 % en volume, au moins 90 % en volume, au moins 95 % en volume, au moins 97 % en volume, au moins 99 % en volume ou 100 % en volume, de formiate de méthyle.
  7. Carburant automobile selon l'une quelconque des revendications 1 à 6, qui contient au moins 45 % en volume et au plus 65 % en volume du constituant A.
  8. Carburant automobile selon l'une quelconque des revendications 1 à 7, qui présente une température limite de filtrabilité (CFPP) selon EN 116 de -20 °C ou moins, de préférence de -25 °C ou moins, -30 °C ou moins, -35 °C ou moins, ou -40 °C ou moins.
  9. Carburant automobile selon l'une quelconque des revendications 1 à 8, qui contient 0 à 10 % en volume du constituant C.
  10. Carburant automobile selon l'une quelconque des revendications 1 à 9, qui contient au plus 1,0 % en volume, de préférence au plus 100 ppm (v/v) d'hydrocarbures.
  11. Carburant automobile selon l'une quelconque des revendications 1 à 10, dans lequel la teneur totale en composés contenant une liaison C-C directe, à l'exception de l'éthanol, est d'au plus 10,0 % en volume, de préférence d'au plus 5,0 % en volume, d'au plus 2,5 % en volume, d'au plus 1,0 % en volume, d'au plus 0,2 % en volume, d'au plus 0,2 % en volume ou d'au plus 0,1 % en volume.
  12. Carburant automobile selon l'une quelconque des revendications 1 à 11, qui présente :
    une teneur en eau d'au plus 0,5 % en volume, de préférence d'au plus 0,2 % en volume ou d'au plus 0,1 % en volume ; et/ou
    une teneur en essence d'au plus 1 % en poids, de préférence d'au plus 0,5 % en poids ou d'au plus 0,1 % en poids ; et/ou
    une teneur en carburants diesels, tels que par exemple le diesel EN590, le diesel paraffinique EN15490 et l'éther diméthylique, d'au plus 0,2 % en poids.
  13. Carburant automobile selon l'une quelconque des revendications 1 à 12, qui présente un indice d'octane, ROZ, d'au moins 90, de préférence d'au moins 95, d'au moins 98, d'au moins 100 ou d'au moins 105.
  14. Utilisation du carburant automobile selon l'une quelconque des revendications 1 à 13 en tant que carburant pour l'exploitation de moteurs à combustion à allumage externe.
  15. Procédé de fabrication d'un carburant automobile, comprenant le mélange de carbonate de diméthyle avec au moins du formiate de méthyle et éventuellement du diméthoxyméthane, ainsi qu'éventuellement avec de l'éthanol et/ou du méthanol et éventuellement avec d'autres constituants, de manière à obtenir un carburant automobile selon l'une quelconque des revendications 1 à 13.
EP18153578.2A 2017-05-02 2018-01-26 Essence potentiellement neutre en co2 et écologique bassée sur la chimie c1 Active EP3399008B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102017109320 2017-05-02

Publications (2)

Publication Number Publication Date
EP3399008A1 EP3399008A1 (fr) 2018-11-07
EP3399008B1 true EP3399008B1 (fr) 2020-03-18

Family

ID=61054202

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18153578.2A Active EP3399008B1 (fr) 2017-05-02 2018-01-26 Essence potentiellement neutre en co2 et écologique bassée sur la chimie c1

Country Status (1)

Country Link
EP (1) EP3399008B1 (fr)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU9142782A (en) * 1981-12-22 1983-06-30 British Petroleum Company Plc, The Fuel composition
CA1218670A (fr) * 1982-12-15 1987-03-03 The British Petroleum Company P.L.C. Preparation de carbonates de dihydrocarbyle; leur emploi comme additifs pour les carburants; compositions-carburants qui en renferment
AT404596B (de) * 1991-02-26 1998-12-28 Oemv Ag Treibstoff für verbrennungsmotoren und verwendung von methylformiat
AU3684800A (en) 2000-01-24 2001-07-31 Angelica Golubkov Motor fuel for spark ignition internal combustion engines
CN101434874A (zh) 2007-11-16 2009-05-20 上海欧罗福企业（集团）有限公司 一种清洁液体燃料
CN103952194B (zh) * 2014-04-29 2016-05-11 成都天丰清洁能源发展有限公司 作为车用掺烧燃料的二甲氧基甲烷组合物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP3399008A1 (fr) 2018-11-07

Similar Documents

Publication Publication Date Title
DE102008032254B4 (de) Rußarme Dieselkraftstoffe, enthaltend einen Kraftstoffzusatz, deren Verwendung sowie die Verwendung des Kraftstoffzusatzes zur Herstellung von rußarmen Dieselkraftstoffen
DE60024474T3 (de) Treibstoff für diesel-, gasturbinen- und turboeinspritzmotoren mit mindestens vier verschiedenen sauerstoff enthaltenden funktionellen gruppen wie alkohole, ether, aldehyde, ketone, ester, anorganische ester, azetate, epoxide und peroxide
DE69535651T2 (de) Unverbleite treibstoffzusammensetzungen
DE3116734C2 (de) Vergaserkraftstoff
EP0078249B1 (fr) Additif améliorant la combustion et réduisant la formation de noir de fumée des huiles combustibles, carburant diesel et autres combustibles et carburants liquides ainsi que ce combustible et carburant liquide en soi
US20190016982A1 (en) Mesitylene as an octane enhancer for automotive gasoline, additive for jet fuel, and method of enhancing motor fuel octane and lowering jet fuel carbon emissions
DE102008008818A1 (de) Kraftstoffe für Otto-Motoren
DE102009035503A1 (de) Verwendung von Polyoxymethylendi(alkylpolyglykol)ethern als Zusatz zu Dieselkraftstoffen zur Verminderung der Rußemission in Selbstzündungsmotoren
DE102009015347A1 (de) Dieselkraftstoff auf Ethanol-Basis
TW200409811A (en) Fuel compositions
DE69931014T2 (de) Grundöl für Dieselbrennstoff und dieses enthaltende Zusammensetzungen
DE102010019986A1 (de) Synthetische Dieseltreibstoffzusammensetzungen
EP3399008B1 (fr) Essence potentiellement neutre en co2 et écologique bassée sur la chimie c1
EP2759588B1 (fr) Carburant pour moteurs à allumage par compression à base de monooxyméthylènediméthyléther
EP2780435B1 (fr) Hydroperoxyde de tertiobutyle (tbhp) comme additif diesel
WO1999040166A1 (fr) Additifs solides pour carburants
EP0166096B1 (fr) Combustibles pour moteurs
EP2106434A1 (fr) Carburants liquides présentant la forme d'un mélange de carburants diesel ou de fioul de chauffage léger
EP1923453A1 (fr) Additifs et leur utilisation comme agent pour améliorer la solubilité dans les combustibles
DE69033497T3 (de) Neuer kohlenwasserstoff-brennstoff, methode zur herstellung und verwendung
DE3422506C2 (de) Motor-Kraftstoffe auf Basis niederer Alkohole
WO2016016336A1 (fr) Essence synthétique et son utilisation
US20160168499A1 (en) Mesitylene as an octane enhancer for automotive gasoline, additive for jet fuel, and method of enhancing motor fuel octane and lowering jet fuel carbon emissions
DE102016223056A1 (de) Kraftstoffadditiv
DE3044687A1 (de) Verfahren zur herstellung einer ersatzbrennstoff-zusammensetzung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17P Request for examination filed

Effective date: 20190506

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

17Q First examination report despatched

Effective date: 20190614

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C10L 1/02 20060101AFI20190829BHEP

Ipc: C10L 1/19 20060101ALI20190829BHEP

Ipc: C10L 1/18 20060101ALI20190829BHEP

Ipc: C10L 10/02 20060101ALI20190829BHEP

Ipc: C10L 1/182 20060101ALI20190829BHEP

Ipc: C10L 1/185 20060101ALI20190829BHEP

INTG Intention to grant announced

Effective date: 20191001

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502018000958

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1245906

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200415

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200618

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200619

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200618

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200812

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200718

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502018000958

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 502018000958

Country of ref document: DE

Representative=s name: TBK, DE

Ref country code: DE

Ref legal event code: R081

Ref document number: 502018000958

Country of ref document: DE

Owner name: ASG ANALYTIK-SERVICE AG, DE

Free format text: FORMER OWNER: ASG ANALYTIK-SERVICE GESELLSCHAFT MBH, 86356 NEUSAESS, DE

26N No opposition filed

Effective date: 20201221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20210617 AND 20210623

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210126

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210131

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210126

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20180126

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1245906

Country of ref document: AT

Kind code of ref document: T

Effective date: 20230126

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230126

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230126

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240129

Year of fee payment: 7

Ref country code: GB

Payment date: 20240124

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20240131

Year of fee payment: 7

Ref country code: FR

Payment date: 20240124

Year of fee payment: 7