EP3399008B1 - Potentially co2-neutral and ecological gasoline based on c1-chemistry - Google Patents

Description

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.

Technical field

A primary motivation for the development of fuels of the future is to stop the part of the increase in the concentration of CO ₂ in the atmosphere caused by the transport sector. The climate protection legislation requires electrification of the drives, especially for cars. Due to the low storage density of batteries, hybrid drives in particular have the advantage of a longer range due to the combustion engine. The full penetration of e-mobility, as the legislation is aiming for in 2050, is prevented by the use of fossil fuel in the hybrid vehicles. The use of "electric fuels" (e-fuels) would remove this obstacle. These e-fuels are required as gasoline for hybrid vehicles, which are mainly equipped with spark ignition engines (spark ignition engines) and should preferably be year-round compatible. The use of e-fuels for vehicles with internal combustion engines generally falls under the generic term e-mobility as an indirect drive type and will replace the use of fossil fuels in the coming decades.

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 ). Sustainably produced 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 .

From the point of view of combustion technology, 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.

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) can be produced from methanol from CO ₂ and eH ₂ .

Describe like this Härtl et al., "Oxymethylene ether as a potential CO2-neutral fuel for clean diesel engines, part 1", MTZ (78) 02/2017, pp. 52-58 and Jacob et al., "Oxymethylene ether as a potential CO2 neutral fuel for clean diesel engines, part 2", MTZ (78) 03/2017, pp. 54-61 Fuels for diesel engines with largely soot particle-free combustion based on e.g. B. oxymethylene ethers.

Appropriate fuels for gasoline engines (gasoline fuels) are not yet available.

Wen et al, "The effect of adding dimethylcarbonate (DMC) and ethanol to unleaded gasoline on exhaust emission", Applied Energy 87 (2010), pp. 115-121 disclose dimethyl carbonate or ethanol in amounts of up to 15% as an additive for hydrocarbon-based petrol.

Yang et al., "Impacts of dimethyl carbonate blends on gaseous and particulate emissions from heavy-duty diesel engine", Fuel (184), Nov. 15, 2016, pp. 681-688 disclose the reduction in soot particle mass in diesel fuel by admixing up to 30% dimethyl carbonate.

Kocis et al., "Effects of Dimethoxymethane and Dimethylcarbonate on Soot Production in an Optically-accessible DI Diesel Engine", SAE (2000), 2000-01-2795 disclose admixture of dimethoxymethane (DMM) and dimethyl carbonate (DMC) to hydrocarbon-based diesel fuel up to an oxygen content of 4% by weight.

Pacheco et al., Review of Dimethyl Carbonate (DMC) Manufacture and its Characteristics as a Fuel Additive ", Energy & Fuels 1997 (11), pp. 2-29 disclose up to 4% DMC as an additive to petrol.

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.

Furthermore describes the 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.

Disclosure of the invention

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). The problem of 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.

In a further advantageous embodiment, 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.

Summary of the invention

• Bestandteil A: Dimethylcarbonat
• Bestandteil B: Methylformiat oder ein Gemisch aus Methylformiat und Dimethoxymethan, wobei der Bestandteil B zumindest 50 Vol.-% Methylformiat enthält
• Bestandteil C: Ethanol, Methanol oder ein Gemisch aus Ethanol und Methanol,

wobei der Ottokraftstoff zumindest 40 Vol.-% und höchstens 70 Vol.-% des Bestandteils A enthält, und der Ottokraftstoff zumindest 30 Vol.-% und höchstens 40 Vol.-% des Bestandteils B enthält.The invention relates to a petrol, its use and its manufacture. The petrol consists of the following constituents A, B and C, and up to 10% by weight of one or more further constituents D, the constituents C and D being optional and the total methanol content in the petrol being at most 1.75 Vol .-%, and, the sum of the contents of the components A, B, C and D is 100 wt .-%:

• Component A: dimethyl carbonate
• Component B: methyl formate or a mixture of methyl formate and dimethoxymethane, component B containing at least 50% by volume of methyl formate
• Component C: ethanol, methanol or a mixture of ethanol and methanol,

wherein the petrol contains at least 40 vol.% and at most 70 vol.% of component A, and the petrol contains at least 30 vol.% and at most 40 vol.% of component B.

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. 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.

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.

The inventors of the present invention surprisingly found that 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.

In order to enable the use of DMC as petrol, however, some hurdles had to be overcome. 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. In particular, 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). At the same time there is an increase in vapor pressure. For example, 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). 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 )).

In addition to MF, dimethoxymethane (DMM) can also be used to lower the melting point and increase the vapor pressure.

However, there are problems with using MF. Commercial 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. However, 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.

In particular, the esters DMC and MF are kinetically stable against hydrolysis in a neutral medium. In the case of MF, this applies to a solution of water in MF (maximum solubility approx. 4% by volume). In contrast, a solution of MF in water is already susceptible to hydrolysis.

The hydrolysis of MF is as follows and is catalyzed by the presence of acids or bases (including those generated by autoprotolysis or in situ ):

MF + H ₂ O → HCOOH + CH ₃ OH

As a result of extensive research, the inventors found that both methanol (MeOH) and ethanol (EtOH) are suitable for stabilizing MF against hydrolysis.

Specifically, it was found that additions of methanol and ethanol to a DMC-MF mixture increase the solubility of water and thus the possibility of water droplets (possibly in the form of a dispersion / emulsion) in the fuel, in which a quicker hydrolysis can take place, shift to higher water concentrations. The maximum solubility of water in the DMC / MF mixtures is increased by adding ethanol or methanol, e.g. B. with DMC60MF35EtOH5 three times (at -25 ° C) compared to DMC65MF35 (the numbers after the substance names indicate the content of the respective substance in vol .-%), as can be seen from the following Table 1. <b> Table 1: </b> Mixing ratio (vol .-%) Water solubility (vol .-%) at -25 ° C Water solubility (vol .-%) at +25 ° C DMC65-MF35 1.2 4.2 DMC60-MF40 0.66 5.0 DMC50-MF50 1.1 5.6 DMC60-MF35-EtOH5 3.6 8.7 DMC55-MF40-EtOH5 3.2 9.1 DMC55-MF35-EtOH10 4.9 11.7 DMC50-MF40-EtOH10 5.0 14.3

The addition of ethanol causes a slight increase in soot particle emissions. This can also be seen from the increasingly yellow flame color when ethanol is added to the CF mixtures (DMC65-MF35 burns with a pale blue flame). An ethanol concentration of over 10% by volume should therefore be avoided in order to obtain a fuel that burns as free of soot as possible.

For ethanol addition, absolute ethanol should be used as far as possible without the denaturing additives required by law for end-user preparations (see Commission Implementing Regulation (EU) 2017/1112 of June 22, 2017 amending Regulation (EC) No. 3199/93). Bitrex with a molecular weight of 447 in particular is a possible source of particle emissions. From August 1, 2017, freely traded ethanol in the EU must contain 1.0 liter of isopropyl alcohol (propan-2-ol) (IPA), 1.0 liter of methyl ethyl ketone (butan-2-one) (MEK) and 1 per 100 liters of alcohol , 0 grams of denatonium benzoate (Bitrex) can be added. 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. In general, and especially with EtOH contents above 10% by volume, preferably undenatured EtOH (especially EtOH which contains at least no Bitrex) should be used, even if denatured EtOH can be used even with ethanol contents above 10% by volume. Alternatively, 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.

The 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.

1. 1. Ottokraftstoff, der aus den folgenden Bestandteilen A und B, optional dem folgenden Bestandteil C und optional bis zu 10 Gew.-% eines oder mehrerer weiterer Bestandteile D besteht, wobei die Summe der Gehalte der Bestandteile A, B, C und D 100 Gew.-% beträgt:
   • Bestandteil A: Dimethylcarbonat
   • Bestandteil B: Methylformiat oder ein Gemisch aus Methylformiat und Dimethoxymethan
   • Bestandteil C: Ethanol, Methanol oder ein Gemisch aus Ethanol und Methanol,
     wobei der Gesamtgehalt an Methanol in dem Ottokraftstoff höchstens 1,75 Vol.-% beträgt.
2. 2. Ottokraftstoff gemäß Punkt 1, wobei der Gehalt des Bestandteils D 5 Gew.-% oder weniger, bevorzugt 2 Gew.-% oder weniger beträgt.
3. 3. Ottokraftstoff gemäß Punkt 1 oder 2, wobei der Gesamtgehalt an Methanol in dem Ottokraftstoff höchstens 1,00 Vol.-%, bevorzugt höchstens 0,50 Vol.-%, höchstens 0,20 Vol.-% oder höchstens 0,10 Vol.-% beträgt.
4. 4. Ottokraftstoff gemäß einem der Punkte 1 bis 3, bei dem der Bestandteil C zumindest 50 Vol.-%, bevorzugt zumindest 70 Vol.-%, zumindest 80 Vol.-%, zumindest 90 Vol.-%, zumindest 95 Vol.-%, zumindest 97 Vol.-% oder zumindest 99 Vol.-% Ethanol enthält.
5. 5. Ottokraftstoff gemäß einem der Punkte 1 bis 4, bei dem der Bestandteil B zumindest 70 Vol.-%, bevorzugt zumindest 80 Vol.-%, zumindest 90 Vol.-%, zumindest 95 Vol.-%, zumindest 97 Vol.-%, zumindest 99 Vol.-% oder 100 Vol.-% Methylformiat enthält.
6. 6. Ottokraftstoff gemäß einem der Punkte 1 bis 5, der eine Flüchtigkeitskennziffer (VLI) von 1150 oder weniger aufweist, wobei die Flüchtigkeitskennziffer berechnet wird aus dem Dry Vapour Pressure Equivalent, DVPE, gemessen nach DIN EN 13016-1 bei 37,8 °C in kPa, und der verdampften Menge bei 70 °C, E70, gemessen nach DIN EN ISO 3405 in %(v/v), gemäß folgender Formel: VLI = 10^∗DVPE + 7^∗E70.
7. 7. Ottokraftstoff gemäß einem der Punkte 1 bis 6, der ein DVPE, gemessen nach DIN EN 13016-1 bei 37,8 °C, von 90 kPa oder weniger aufweist.
8. 8. Ottokraftstoff gemäß einem der Punkte 1 bis 7, der einen E70 Wert von 52 Vol.-% oder weniger.
9. 9. Ottokraftstoff gemäß einem der Punkte 1 bis 8, der ein DVPE von 60 kPa oder weniger aufweist.
10. 10. Ottokraftstoff gemäß einem der Punkte 1 bis 9, der einen Wassergehalt von höchstens 0,5 Vol.-%, bevorzugt höchstens 0,2 Vol.-% oder höchstens 0,1 Vol.-% aufweist.
11. 11. Ottokraftstoff gemäß einem der Punkte 1 bis 10, wobei der Gesamtgehalt an Dimethoxymethan in dem Ottokraftstoff höchstens 40,0 Vol.-%, bevorzugt höchstens 30 Vol.-%, höchstens 25 Vol.-%, höchstens 22,0 Vol.-%, höchstens 20,0 Vol.-%, höchstens 15,0 Vol.-%, höchstens 10,0 Vol.-% oder höchstens 8,0 Vol.-% beträgt.
12. 12. Ottokraftstoff gemäß einem der Punkte 1 bis 11, wobei der Ottokraftstoff einen Rußpunkt nach ASTM D1322 von zumindest 45 mm, bevorzugt zumindest 55 mm, weiter bevorzugt zumindest 60 mm aufweist.
13. 13. Ottokraftstoff gemäß einem der Punkte 1 bis 12, der zumindest 45 Vol.-% des Bestandteils A enthält.
14. 14. Ottokraftstoff gemäß einem der Punkte 1 bis 13, der zumindest 50 Vol.-%, oder zumindest 55 Vol.-% des Bestandteils A enthält.
15. 15. Ottokraftstoff gemäß einem der Punkte 1 bis 14, der höchstens 65 Vol.-% des Bestandteils A enthält.
16. 16. Ottokraftstoff gemäß einem der Punkte 1 bis 15, der zumindest 2 Vol.-% des Bestandteils C enthält.
17. 17. Ottokraftstoff gemäß einem der Punkte 1 bis 16, der zumindest 3 Vol.-%, bevorzugt zumindest 4 Vol.-% oder zumindest 5 Vol.-% des Bestandteils C enthält.
18. 18. Ottokraftstoff gemäß einem der Punkte 1 bis 17, der höchstens 20 Vol.-%, bevorzugt höchstens 15 Vol.-%, höchstens 10 Vol.-%, höchstens 8 Vol.-%, oder höchstens 6 Vol.-% des Bestandteils C enthält.
19. 19. Ottokraftstoff gemäß einem der Punkte 1 bis 18, der 0 bis 10 Vol.-% des Bestandteils C enthält.
20. 20. Ottokraftstoff gemäß einem der Punkte 1 bis 19, wobei die Summe der Gehalte der Bestandteile A, B und C zumindest 95 Vol.-%, bevorzugt zumindest 97 Vol.-%, zumindest 98 Vol.-%, zumindest 99 Vol.-% oder 100 Vol.-% beträgt.
21. 21. Ottokraftstoff gemäß einem der Punkte 1 bis 20, der höchstens 10,0 Vol.-%, bevorzugt höchstens 5,0 Vol.-%, höchstens 3,0 Vol.-%, höchstens 2,0 Vol.-% oder höchstens 1,0 Vol.-% Kohlenwasserstoffe enthält.
22. 22. Ottokraftstoff gemäß einem der Punkte 1 bis 21, der höchstens 100 ppm (v/v) Kohlenwasserstoffe enthält.
23. 23. Ottokraftstoff gemäß einem der Punkte 1 bis 22, der höchstens 10,0 Vol.-%, bevorzugt höchstens 5,0 Vol.-%, höchstens 2,0 Vol.-%, höchstens 1,0 Vol.-%, besonders bevorzugt höchstens 0,5 Vol.-%, höchstens 0,2 Vol.-% oder höchstens 0,1 Vol.-% Aromaten enthält.
24. 24. Ottokraftstoff gemäß einem der Punkte 1 bis 23, der höchstens 100 ppm (v/v) Aromaten enthält.
25. 25. Ottokraftstoff gemäß einem der Punkte 1 bis 24, wobei der Gesamtgehalt an Verbindungen mit einer direkten C-C-Bindung, mit Ausnahme von Ethanol, höchstens 10,0 Vol.-%, bevorzugt höchstens 5,0 Vol.-%, höchstens 2,5 Vol.-%, höchstens 1,0 Vol.-%, höchstens 0,5 Vol.-%, höchstens 0,2 Vol.-% oder höchstens 0,1 Vol.-% beträgt.
26. 26. Ottokraftstoff gemäß einem der Punkte 1 bis 25, der
    • 35-65 Vol.-% des Bestandteils A,
    • 30-40 Vol.-% des Bestandteils B und
    • 10-20 Vol.-% des Bestandteils C enthält.
27. 27. Ottokraftstoff gemäß einem der Punkte 1 bis 25, der
    • 45-60 Vol.-% des Bestandteils A,
    • 30-40 Vol.-% des Bestandteils B und
    • 10-15 Vol.-% des Bestandteils C enthält.
28. 28. Ottokraftstoff gemäß einem der Punkte 1 bis 25, der
    • 50-60 Vol.-% des Bestandteils A,
    • 30-40 Vol.-% des Bestandteils B und
    • 10-15 Vol.-% des Bestandteils C enthält.
29. 29. Ottokraftstoff gemäß einem der Punkte 1 bis 25, der
    • 60-70 Vol.-%, bevorzugt 63-67 Vol.-% des Bestandteils A und
    • 30-40 Vol.-%, bevorzugt 33-37 Vol.-% des Bestandteils B enthält.
30. 30. Ottokraftstoff gemäß einem der Punkte 1 bis 25, der
    • 55-65 Vol.-%, bevorzugt 58-62 Vol.-% des Bestandteils A,
    • 30-40 Vol.-%, bevorzugt 33-37 Vol.-% des Bestandteils B und
    • 1-9 Vol.-%, bevorzugt 3-7 Vol.-% des Bestandteils C enthält.
31. 31. Ottokraftstoff gemäß einem der Punkte 1 bis 25, der
    • 50-60 Vol.-%, bevorzugt 53-57 Vol.-% des Bestandteils A,
    • 30-40 Vol.-%, bevorzugt 33-37 Vol.-% des Bestandteils B und
    • 5-15 Vol.-%, bevorzugt 8-12 Vol.-% des Bestandteils C enthält.
32. 32. Ottokraftstoff gemäß einem der Punkte 1 bis 25, der
    • 55-65 Vol.-% des Bestandteils A,
    • 30-40 Vol.-% des Bestandteils B und
    • 0-10 Vol.-% des Bestandteils C enthält.
33. 33. Ottokraftstoff gemäß einem der Punkte 1 bis 25, der
    • 55-65 Vol.-% des Bestandteils A,
    • 30-40 Vol.-% des Bestandteils B und
    • 2-10 Vol.-% des Bestandteils C enthält.
34. 34. Ottokraftstoff gemäß einem der Punkte 1 bis 25, der
    • 55-65 Vol.-% des Bestandteils A,
    • 30-40 Vol.-% des Bestandteils B und
    • 3-7 Vol.-% des Bestandteils C enthält.
35. 35. Ottokraftstoff gemäß einem der Punkte 1 bis 34, der einen Gehalt an Benzin und/oder Diesel von höchstens 1,0 Vol.-%, bevorzugt höchsten 0,5 Vol.-% oder höchstens 0,1 Vol.-% aufweist.
36. 36. Ottokraftstoff gemäß einem der Punkte 1 bis 35, der einen Gehalt an Dimethylether von höchstens 1,0 Vol.-%, bevorzugt höchsten 0,5 Vol.-% oder höchstens 0,1 Vol.-% aufweist.
37. 37. Ottokraftstoff gemäß einem der Punkte 1 bis 36, der einen Gehalt an Dimethoxymethan (DMM) von höchstens 1,0 Vol.-%, bevorzugt höchsten 0,5 Vol.-% oder höchstens 0,1 Vol.-% aufweist.
38. 38. Ottokraftstoff gemäß einem der Punkte 1 bis 37, der eine Filtrierbarkeitsgrenze (CFPP) von -20 °C oder darunter, bevorzugt -25 °C oder darunter, -30 °C oder darunter, -35 °C oder darunter, oder -40 °C oder darunter aufweist.
39. 39. Ottokraftstoff gemäß einem der Punkte 1 bis 38, der gemäß UN-ECE R83/R49 ohne Verwendung eines Rußpartikelfilters eine Rußpartikelanzahl von 6x10¹¹ Partikel/km oder weniger erreicht.
40. 40. Verwendung des Ottokraftstoffs gemäß einem der Punkte 1 bis 39 als Kraftstoff für den Betrieb von Verbrennungsmotoren mit Fremdzündung.
41. 41. Verwendung des Ottokraftstoffs gemäß einem der Punkte 1 bis 40 als Kraftstoff für den Betrieb von Fahrzeugen mit Verbrennungsmotoren mit Fremdzündung, die bevorzugt ohne Ottopartikelfilter (OPF) ausgerüstet sind, wobei besonders bevorzugt der Partikelanzahlgrenzwert von 6x10¹¹ Partikel/km auch ohne Einsatz eines ohne Ottopartikelfilters unterschritten wird.
42. 42. Verfahren zur Herstellung eines Ottokraftstoffs, umfassend das Mischen von Dimethylcarbonat mit zumindest Methylformiat und optional Dimethoxymethan sowie optional mit zumindest einem aus Ethanol und Methanol und optional mit weiteren Bestandteilen, so dass ein Ottokraftstoff nach einem der Punkte 1 bis 39 erhalten wird.
43. 43. Verfahren gemäß Punkt 42, wobei die weiteren Bestandteile in einer Menge von höchstens 10 Gew.-%, bevorzugt höchstens 5 Gew.-% oder höchstens 2 Gew.-%, bezogen auf den hergestellten Ottokraftstoff, eingemischt werden.
44. 44. Verfahren gemäß Punkt 42 oder 43, wobei bei dem Mischen kein Methanol zugegeben wird.

The invention is defined in the appended claims. Specifically, the invention relates to one or more of the following:

1. 1. petrol which consists of the following components A and B, optionally the following component C and optionally up to 10% by weight of one or more further components D, the sum of the contents of components A, B, C and D 100 % By weight is:
   • Component A: dimethyl carbonate
   • Component B: methyl formate or a mixture of methyl formate and dimethoxymethane
   • Component C: ethanol, methanol or a mixture of ethanol and methanol,
     the total content of methanol in the petrol being at most 1.75% by volume.
2. 2. Petrol according to item 1, the content of component D being 5% by weight or less, preferably 2% by weight or less.
3. 3. Petrol according to item 1 or 2, the total content of methanol in the petrol being at most 1.00 vol.%, Preferably at most 0.50 vol.%, At most 0.20 vol.% Or at most 0.10 vol .-%.
4. 4. Gasoline according to one of items 1 to 3, in which the component C is at least 50% by volume, preferably at least 70% by volume, at least 80% by volume, at least 90% by volume, at least 95% by volume. %, contains at least 97% by volume or at least 99% by volume of ethanol.
5. 5. Gasoline according to one of items 1 to 4, in which component B is at least 70% by volume, preferably at least 80% by volume, at least 90% by volume, at least 95% by volume, at least 97% by volume. %, contains at least 99% by volume or 100% by volume of methyl formate.
6. 6. Gasoline according to one of items 1 to 5, which has a volatility index (VLI) of 1150 or less, the volatility index being calculated from the Dry Vapor Pressure Equivalent, DVPE, measured according to DIN EN 13016-1 at 37.8 ° C in kPa, and the amount evaporated at 70 ° C, E70, measured according to DIN EN ISO 3405 in% (v / v), according to the following formula: VLI = 10 ^∗ DVPE + 7 ^∗ E70.
7. 7. Gasoline according to one of items 1 to 6, which has a DVPE, measured according to DIN EN 13016-1 at 37.8 ° C, of 90 kPa or less.
8. 8. Gasoline according to any one of items 1 to 7, which has an E70 value of 52% by volume or less.
9. 9. Gasoline according to any one of items 1 to 8, which has a DVPE of 60 kPa or less.
10. 10. Petrol according to one of items 1 to 9, which has a water content of at most 0.5 vol.%, Preferably at most 0.2 vol.% Or at most 0.1 vol.%.
11. 11. Gasoline according to one of items 1 to 10, the total content of dimethoxymethane in the gasoline being at most 40.0 vol.%, Preferably at most 30 vol.%, At most 25 vol.%, At most 22.0 vol. %, at most 20.0 vol%, at most 15.0 vol%, at most 10.0 vol% or at most 8.0 vol%.
12. 12. Petrol according to one of items 1 to 11, the petrol having a soot point according to ASTM D1322 of at least 45 mm, preferably at least 55 mm, more preferably at least 60 mm.
13. 13. Gasoline according to one of items 1 to 12, which contains at least 45% by volume of component A.
14. 14. Gasoline according to one of items 1 to 13, which contains at least 50% by volume or at least 55% by volume of component A.
15. 15. Petrol according to one of items 1 to 14, which contains at most 65 vol .-% of component A.
16. 16. Gasoline according to one of items 1 to 15, which contains at least 2 vol .-% of component C.
17. 17. Gasoline according to one of items 1 to 16, which contains at least 3% by volume, preferably at least 4% by volume or at least 5% by volume of component C.
18. 18. Gasoline according to one of the items 1 to 17, which contains at most 20% by volume, preferably at most 15% by volume, at most 10% by volume, at most 8% by volume, or at most 6% by volume of the component C contains.
19. 19. Gasoline according to one of items 1 to 18, which contains 0 to 10% by volume of component C.
20. 20. Gasoline according to one of items 1 to 19, the sum of the contents of the components A, B and C at least 95% by volume, preferably at least 97% by volume, at least 98% by volume, at least 99% by volume. % or 100% by volume.
21. 21. Gasoline according to one of the items 1 to 20, which is at most 10.0 vol.%, Preferably at most 5.0 vol.%, At most 3.0 vol.%, At most 2.0 vol.% Or at most Contains 1.0 vol .-% hydrocarbons.
22. 22. Petrol according to one of items 1 to 21, which contains a maximum of 100 ppm (v / v) hydrocarbons.
23. 23. Gasoline according to one of the items 1 to 22, which is at most 10.0 vol.%, Preferably at most 5.0 vol.%, At most 2.0 vol.%, At most 1.0 vol.%, Particularly preferably contains at most 0.5% by volume, at most 0.2% by volume or at most 0.1% by volume of aromatics.
24. 24. Petrol according to one of items 1 to 23, which contains a maximum of 100 ppm (v / v) aromatics.
25. 25. petrol according to any one of items 1 to 24, the total content of compounds with a direct CC bond, with the exception of ethanol, not more than 10.0% by volume, preferably not more than 5.0% by volume, not more than 2, 5 vol.%, At most 1.0 vol.%, At most 0.5 vol.%, At most 0.2 vol.% Or at most 0.1 vol.%.
26. 26. Gasoline according to one of items 1 to 25, the
    • 35-65% by volume of component A,
    • 30-40% by volume of component B and
    • Contains 10-20 vol .-% of component C.
27. 27. Gasoline according to one of items 1 to 25, the
    • 45-60% by volume of component A,
    • 30-40% by volume of component B and
    • Contains 10-15% by volume of component C.
28. 28. Gasoline according to one of items 1 to 25, the
    • 50-60% by volume of component A,
    • 30-40% by volume of component B and
    • Contains 10-15% by volume of component C.
29. 29. Gasoline according to one of items 1 to 25, the
    • 60-70% by volume, preferably 63-67% by volume of component A and
    • 30-40 vol .-%, preferably 33-37 vol .-% of component B.
30. 30. Gasoline according to one of items 1 to 25, the
    • 55-65% by volume, preferably 58-62% by volume of component A,
    • 30-40 vol .-%, preferably 33-37 vol .-% of component B and
    • Contains 1-9 vol .-%, preferably 3-7 vol .-% of component C.
31. 31. Gasoline according to one of items 1 to 25, the
    • 50-60% by volume, preferably 53-57% by volume of component A,
    • 30-40 vol .-%, preferably 33-37 vol .-% of component B and
    • 5-15 vol .-%, preferably 8-12 vol .-% of component C.
32. 32. Petrol according to one of items 1 to 25, the
    • 55-65% by volume of component A,
    • 30-40% by volume of component B and
    • Contains 0-10% by volume of component C.
33. 33. Petrol according to one of items 1 to 25, the
    • 55-65% by volume of component A,
    • 30-40% by volume of component B and
    • Contains 2-10 vol .-% of component C.
34. 34. Petrol according to one of items 1 to 25, the
    • 55-65% by volume of component A,
    • 30-40% by volume of component B and
    • Contains 3-7% by volume of component C.
35. 35. Petrol according to one of the items 1 to 34, which has a gasoline and / or diesel content of at most 1.0% by volume, preferably at most 0.5% by volume or at most 0.1% by volume.
36. 36. Petrol according to one of items 1 to 35, which has a dimethyl ether content of at most 1.0% by volume, preferably at most 0.5% by volume or at most 0.1% by volume.
37. 37. Petrol according to one of items 1 to 36, which has a dimethoxymethane (DMM) content of at most 1.0% by volume, preferably at most 0.5% by volume or at most 0.1% by volume.
38. 38. Petrol according to one of items 1 to 37, which has a filterability limit (CFPP) of -20 ° C or below, preferably -25 ° C or below, -30 ° C or below, -35 ° C or below, or -40 ° C or below.
39. 39. Petrol according to one of the items 1 to 38, which according to UN-ECE R83 / R49 reaches a number of soot particles of 6x10 ¹¹ particles / km or less without using a soot particle filter.
40. 40. Use of the petrol according to one of items 1 to 39 as fuel for the operation of internal combustion engines with spark ignition.
41. 41.Use of the petrol according to one of the items 1 to 40 as fuel for the operation of vehicles with internal combustion engines with spark ignition, which are preferably equipped without a gasoline particle filter (OPF), with the particle number limit of 6x10 ¹¹ particles / km being particularly preferred even without the use of one Below the gasoline particle filter.
42. 42. A method for producing a petrol, comprising the mixing of dimethyl carbonate with at least methyl formate and optionally dimethoxymethane and optionally with at least one of ethanol and methanol and optionally with other constituents, so that a petrol according to one of items 1 to 39 is obtained.
43. 43. The method according to item 42, the further constituents being mixed in in an amount of at most 10% by weight, preferably at most 5% by weight or at most 2% by weight, based on the petrol produced.
44. 44. The method according to item 42 or 43, wherein no methanol is added during the mixing.

Brief description of the drawings

• Fig. 1 shows a Gibbs diagram ternary mixtures of dimethyl carbonate ("C"), methyl formate ("P") and ethanol ("E"), which are characterized in terms of their hydrolysis resistance.
• Fig. 2 shows a Gibbs diagram of ternary mixtures of dimethyl carbonate ("C"), methyl formate ("F") and ethanol ("E"), which are characterized in terms of their vapor pressure.
• Fig. 3 shows a Gibbs diagram ternary mixtures of dimethyl carbonate ("C"), methyl formate ("P") and ethanol ("E"), which are characterized in terms of their low temperature resistance (-25 ° C).
• Fig. 4 issues the data 1 to 3 summarized.

Detailed description of the invention

• Bestandteil A: Dimethylcarbonat
• Bestandteil B: Methylformiat oder ein Gemisch aus Methylformiat und Dimethoxymethan.

The petrol of the present invention contains at least the following components A and B:

• Component A: dimethyl carbonate
• Component B: methyl formate or a mixture of methyl formate and dimethoxymethane.

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.

In addition, all components A, B and C, with the exception of ethanol, burn largely without the formation of soot particles. Even with the combustion of ethanol, the soot particle formation is far behind that of conventional petrol. Therefore, the 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.

In addition to components A, B and optionally C, 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.

The 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. For example, to increase the lubricity and resistance to hydrolysis, polyalkylene glycol ethers (PAGE) in the form of high molecular weight copolymers made from polyethylene glycol (50-90% by weight) 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.

It is particularly preferred if 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) is 0.3% by weight or less, and / or the hydrocarbon content (total content) is 0.1% by weight or less.

In the gasoline of the present invention, the content of the component D is limited. The inventors found that even 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) results in a reduction in the tendency to build up soot Has. However, 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. Furthermore, 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).

Unless otherwise stated, all percentages ("%") refer 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.

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 (at 37.8 ° C) 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). Furthermore, by mixing the C1 ester methyl formate (MF) with dimethyl carbonate (DMC) one for a fuel desirable cold resistance achieved. The mixture remains liquid even when it cools down to -25 ° C. No fixed phase is formed (see Fig. 3 ).

In addition to MF, dimethoxymethane (DMM) can also be used to increase the vapor pressure and reduce the melting point. However, the effect of DMM to reduce the melting point of the mixture is not as pronounced as that of MF, which is why it is advisable to add component D if DMM is used predominantly or exclusively as component B. In addition, the manufacturing costs of DMM are higher than those of MF. The invention thus relates to mixtures which contain at least MF. However, DMM is able to reduce the 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. Likewise, 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. In particular, 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. In particular, both ethanol (EtOH) and methanol (MeOH) are able to reduce or prevent hydrolysis of methyl formate (MF). In mixtures of dimethyl carbonate, methyl formate and one or both of methanol and ethanol, it is preferred that the ratio (amount of methyl formate: total amount of methanol and ethanol) 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. Especially in non-corrosive environments (e.g. when using non-corrosive materials) as well as in mixtures with low water content (e.g. 0.10% by volume and below) the content of the component can also be low or Component C can be omitted.

It is desirable that 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.

For the purposes of the present invention, hydrocarbons are compounds which consist of carbon and hydrogen.

In addition, it is particularly desirable that 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. In the context of the invention, 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.

In the present invention, 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. However, DMM is currently more expensive to produce than methyl formate, so that the proportion of DMM should be kept rather low for economic reasons. In addition, when using DMM as component B (ie without using MF), 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.

• 35-65 Vol.-% des Bestandteils A, 20-45 Vol.-% des Bestandteils B und 10-20 Vol.-% des Bestandteils C, wobei erfindungsgemäß zumindest 30 Vol.-% und höchstens 40 Vol.-% des Bestandteils B enthalten sind
• 45-60 Vol.-% des Bestandteils A, 30-40 Vol.-% des Bestandteils B und 10-15 Vol.-% des Bestandteils C
• 50-60 Vol.-% des Bestandteils A, 30-40 Vol.-% des Bestandteils B und 10-15 Vol.-% des Bestandteils C
• 50-60 Vol.-% des Bestandteils A, 30-40 Vol.-% des Bestandteils B und 10-15 Vol.-% des Bestandteils C
• 60-70 Vol.-%, bevorzugt 63-67 Vol.-% des Bestandteils A und 30-40 Vol.-%, bevorzugt 33-37 Vol.-% des Bestandteils B
• 55-65 Vol.-%, bevorzugt 58-62 Vol.-% des Bestandteils A, 30-40 Vol.-%, bevorzugt 33-37 Vol.-% des Bestandteils B und 1-9 Vol.-%, bevorzugt 3-7 Vol.-% des Bestandteils C
• 50-60 Vol.-%, bevorzugt 63-67 Vol.-% des Bestandteils A, 30-40 Vol.-%, bevorzugt 33-37 Vol.-% des Bestandteils B und 5-15 Vol.-%, bevorzugt 8-12 Vol.-% des Bestandteils C
• 55-65 Vol.-% des Bestandteils A, 30-40 Vol.-% des Bestandteils B und 0-10 Vol.-% des Bestandteils C
• 55-65 Vol.-% des Bestandteils A, 30-40 Vol.-% des Bestandteils B und 2-10 Vol.-% des Bestandteils C
• 55-65 Vol.-% des Bestandteils A, 30-40 Vol.-% des Bestandteils B und 3-7 Vol.-% des Bestandteils C

Gasoline fuels that have components A and B, optionally C (and optionally another component D) in the following areas have proven to be particularly advantageous:

• 35-65% by volume of component A, 20-45% by volume of component B and 10-20% by volume of component C, according to the invention at least 30% by volume and at most 40% by volume of the component B are included
• 45-60% by volume of component A, 30-40% by volume of component B and 10-15% by volume of component C
• 50-60% by volume of component A, 30-40% by volume of component B and 10-15% by volume of component C.
• 50-60% by volume of component A, 30-40% by volume of component B and 10-15% by volume of component C.
• 60-70% by volume, preferably 63-67% by volume of component A and 30-40% by volume, preferably 33-37% by volume of component B
• 55-65% by volume, preferably 58-62% by volume of component A, 30-40% by volume, preferably 33-37% by volume of component B and 1-9% by volume, preferably 3 -7% by volume of component C
• 50-60% by volume, preferably 63-67% by volume of component A, 30-40% by volume, preferably 33-37% by volume of component B and 5-15% by volume, preferably 8 -12% by volume of component C
• 55-65% by volume of component A, 30-40% by volume of component B and 0-10% by volume of component C
• 55-65% by volume of component A, 30-40% by volume of component B and 2-10% by volume of component C
• 55-65% by volume of component A, 30-40% by volume of component B and 3-7% by volume of component C

Certain minimum amounts of components B and possibly C and a high proportion of component A, as defined by the above compositions, allow the petrol to meet certain minimum requirements for resistance (long-term stability), corrosion resistance, vapor pressure and cold resistance.

In the present invention, petrol fuels are also preferred which contain 0-40% by volume (preferably 5-40% by volume) of ethanol.

In the present invention, 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. For the purposes of the invention, 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. In particular, 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.

In the gasoline fuel, 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. The higher the ethanol content of component C, the lower the methanol content. This helps to reduce the health hazard of the fuel.

Likewise, 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 .-%. According to the current GHS labeling requirements, 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. Although methanol works well as a gasoline fuel, and even higher amounts of methanol would not significantly degrade the engine properties of the gasoline fuel of the present invention, 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.

In this regard, it should be noted that commercially available technical methyl formate (purity 97%) contains approx. 3% methanol. This can therefore be used in mixtures with approx. 58 vol.% Methyl formate and below in order to comply with the limit value of a total methanol content of 1.75 vol.%. If a significant reduction in the methanol content is desired, the methyl formate must be freed from methanol. In this regard, the inventors found that by distillation methyl formate (99.9%) with a max. 0.1% methanol can be obtained.

Absolute ethanol (99.6%) is preferably used as the component C. However, 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. The Vapor Lock Index (VLI, German: volatility index) is calculated from the Dry Vapor Pressure Equivalent (DVPE, German: vapor pressure), measured according to DIN EN 13016-1 at 37.8 ° C in kPa and the evaporated amount at 70 ° C (E70), measured according to DIN EN ISO 3405 in% (v / v) according to the following formula: VLI = 10 ^∗ DVPE + 7 ^∗ E70. 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).

To ensure adequate suitability for low temperatures, 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. Depending on the area of application (e.g. for summer fuels), 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. Specifically, methyl formate can contain methanol as an impurity and 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. In particular, 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. In addition the fuel burns with little soot particle formation, which makes it particularly interesting with regard to smog formation and fine dust pollution.

Examples

The present invention is explained in more detail below with the aid of examples. It should be noted that the examples only represent embodiments of the invention and the invention is not limited to these specific embodiments. Nevertheless, the compositions and also the amounts of individual constituents disclosed in the examples can be used in particular in order to give new ranges of composition together with broader definitions in the general description.

Examples 1:

Composition of dimethyl carbonate (DMC, in Fig. "C", purity ≥99.8%), methyl formate (MF, in Fig. "F", purity> 97%, balance methanol) and possibly ethanol (EtOH, in "E", purity 99%) were prepared by mixing the components in the proportions shown in Table 2 (vol .-%) and their properties were determined. The results are shown in Table 2 ("-" indicates that the value in question has not been determined). Table 2-1: C45F35E20 C55F35E10 C60F35E5 C65F35 Oxygen content % By weight 49.75 51.62 52.56 53.5 Lower heating value kWh / kg 5.00 4,695 4.54 4.39 Air requirement, stoichiom. kg / kg 5.53 5.08 4.86 4.64 Density at 15 ° C kg / m ³ 975.0 1011 1024 1041 Energy density at 15 ° C kWh / l 4.88 4.75 4.64 4.57 CFPP ° C -54 -45 -35 -33 Heat of vaporization kWh / kg 0.1481 0.1344 0.1276 0.1207 Flash point ° C -13 -13 -10 -9 RON / MOZ - > 110/100 > 110/100 > 110/100 > 110/100 Surface span at 20 ° C mN / m 25.8 26.0 25.8 25.7 Kin. Viscosity at 20 ° C mm ² / s 0.578 0.568 0.473 0.472 DVPE at 37.8 ° C kPa 60 59.8 59.2 57.2 E70, evaporates at 70 ° C Vol .-% 56.2 51 46.8 43.3 Vapor Lock Index (VLI) - 993 955 920 875 Average molar mass g / mol 70.767 75.168 77.368 79,577

As can be seen from Table 2-1, the mixture C60F35E5 shows particularly good properties with regard to DVPE and E70. In general, 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. kg / kg 4.64 5.08 4.86 4.64 Density at 15 ° C kg / m ³ 1027 1007 1022 1036 Energy density at 15 ° C kWh / l - 4.72 4.64 - CFPP ° C <-40 -52 <-40 <-30 Flash point ° C -15 -13 -13 -12 Kin. Viscosity at 20 ° C mm2 / s - 0.555 0.464 - DVPE at 37.8 ° C kPa 73.6 65.1 63.8 64.9 E70, evaporates at 70 ° C Vol .-% 61.2 58.9 50.3 50.9 Vapor Lock Index (VLI) - 1164 1063 990 1005

Example 2:

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.

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. In particular, the water content of conventional petrol is usually below 0.1% by volume (usually between 600 and 800 ppm (m / m)).

The results are shown in a three-component diagram according to Gibbs ( Fig. 1 ), where an empty triangle stands for "passed" and a filled triangle stands for "failed".

It has been found that optimum resistance to hydrolysis can be ensured with an ethanol content of 10% by volume, provided that the methyl formate content does not exceed 40% by volume. The binary mixtures C50F50 and C60F40 have a somewhat reduced hydrolysis stability (first slight signs of corrosion after 1 week, after 3 weeks rust formation clearly visible under the measuring conditions).

Example 3:

Compositions were prepared analogously to Example 1 and examined for their vapor pressure.

The results are shown in a three-component diagram according to Gibbs ( Fig. 2 ), whereby an empty square stands for a vapor pressure (DVPE at 37.8 ° C) of 45-60 kPa (as required by EN 228 class A for summer fuels; as "Passed" denotes) and a filled square stands for a vapor pressure of 60-90 kPa (EN 228 class D1).

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.

Example 4:

Compositions were prepared analogously to Example 1 and tested for their cold resistance.

The results are shown in a three-component diagram according to Gibbs ( Fig. 3 ), with an empty circle representing a cold resistance of -25 ° C or less (solids, ie the appearance of a solid phase or partial freezing are already observed in the mixture above or at a temperature of -25 ° C) and a filled circle stands for a cold resistance of more than -25 ° C (at a temperature of -25 ° C - or below - no solids are observed in the mixture).

It shows that there is excellent cold resistance over a wide range of compositions.

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 and a square represents a vapor pressure range of 45-60 kPa.

In the 1 to 4 The 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 5:

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. Table 3: Density at 15 ° C kg / m ³ 965 CFPP ° C -40 DVPE at 37.8 ° C kPa 44.6 E70, evaporates at 70 ° C Vol .-% 54.2 Vapor Lock Index (VLI) - 825

Example 6:

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

It can be seen from Table 3 that an addition of 50% by volume of DMC to conventional fuel brings about a significant reduction in the tendency towards soot formation. From further experiments (not shown), it was found that this effect is not or not significantly worsened by the presence of EtOH, MeOH, MF and / or DMM. At most when adding more than 10 vol .-% EtOH (denatured) shows a reduction in the effect. In the case of sample No. 5 according to the invention, no soot formation could be detected using the method used.

Claims (15)

1. Spark-ignition engine fuel composed of the following constituents A and B, optionally the following constituents C and optionally up to 10% by weight of one or more further constituents D, wherein the sum of the contents of the constituents A, B, C and D is 100% by weight:

   - constituent A: dimethyl carbonate

   - constituent B: methyl formate or a mixture of methyl formate and dimethoxymethane, wherein the constituent B contains at least 50% by volume of methyl formate,

   - constituent C: ethanol, methanol or a mixture of ethanol and methanol,
   wherein the total content of methanol in the spark-ignition engine fuel is at most 1.75% by volume, the spark-ignition engine fuel contains at least 40% by volume and at most 70% by volume of the constituent A,
   the spark-ignition engine fuel contains at least 30% by volume and at most 40% by volume of the constituent B.
2. Spark-ignition engine fuel according to Claim 1, wherein the content of the constituent D is 5% by weight or less, preferably 2% by weight or less.
3. Spark-ignition engine fuel according to Claim 1 or 2, wherein the total content of methanol in the spark-ignition engine fuel is at most 1.00% by volume, preferably at most 0.50% by volume, at most 0.20% by volume or at most 0.10% by volume.
4. Spark-ignition engine fuel according to any of Claims 1 to 3 which has a volatility index (VLI) of 1150 or less, wherein the volatility index is calculated from the dry vapour pressure equivalent, DVPE, measured according to DIN EN 13016-1 at 37.8°C in kPa and the evaporated fraction at 70°C, E70, measured according to DIN EN ISO 3405 in % (v/v) according to the following formula: VLI = 10*DVPE + 7*E70.
5. Spark-ignition engine fuel according to any of Claims 1 to 4 which has a DVPE measured according to DIN EN 13016-1 at 37.8°C of 90 kPa or less, preferably 60 kPa or less.
6. Spark-ignition engine fuel according to any of Claims 1 to 5, wherein the constituent B contains 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, at least 99% by volume or 100% by volume of methyl formate.
7. Spark-ignition engine fuel according to any of Claims 1 to 6 which contains at least 45% by volume and at most 65% by volume of the constituent A.
8. Spark-ignition engine fuel according to any of Claims 1 to 7 which has a filterability limit (CFPP) according to EN 116 of -20°C or below, preferably -25°C or below, -30°C or below, -35°C or below or -40°C or below.
9. Spark-ignition engine fuel according to any of Claims 1 to 8 which contains 0% to 10% by volume of the constituent C.
10. Spark-ignition engine fuel according to any of Claims 1 to 9 which contains at most 1.0% by volume, preferably at most 100 ppm (v/v) of hydrocarbons.
11. Spark-ignition engine fuel according to any of Claims 1 to 10, wherein the total content of compounds having a direct C-C bond, save for ethanol, is at most 10.0% by volume, preferably at most 5.0% by volume, at most 2.5% by volume, at most 1.0% by volume, at most 0.2% by volume, at most 0.2% by volume or at most 0.1% by volume.
12. Spark-ignition engine fuel according to any of Claims 1 to 11 which has
    a water content of at most 0.5% by volume, preferably at most 0.2% by volume or at most 0.1% by volume; and/or
    a content of gasoline of at most 1% by weight, preferably at most 0.5% by weight or at most 0.1% by weight; and/or
    a content of diesel fuels, such as for instance diesel EN590, paraffin diesel EN15490 and dimethyl ether, of at most 0.2% by weight.
13. Spark-ignition engine fuel according to any of Claims 1 to 12 which has an octane number RON of at least 90, preferably at least 95, at least 98, at least 100 or at least 105.
14. Use of the spark-ignition engine fuel according to any of Claims 1 to 13 as a fuel for the operation of internal combustion engines with externally supplied ignition.
15. Process for producing a spark-ignition engine fuel comprising mixing dimethyl carbonate with at least methyl formate and optionally dimethoxymethane and also optionally with one of ethanol and methanol and optionally with further constituents to obtain a spark-ignition engine fuel according to any of Claims 1 to 13.

Images