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EP2143778B1 - Low-soot diesel fuel containing a fuel additive, and its use in the reduction of soot in diesel fuel combustion - Google Patents

Low-soot diesel fuel containing a fuel additive, and its use in the reduction of soot in diesel fuel combustion Download PDF

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Publication number
EP2143778B1
EP2143778B1 EP09008881.6A EP09008881A EP2143778B1 EP 2143778 B1 EP2143778 B1 EP 2143778B1 EP 09008881 A EP09008881 A EP 09008881A EP 2143778 B1 EP2143778 B1 EP 2143778B1
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EP
European Patent Office
Prior art keywords
diesel fuel
diesel
fuel
fuel according
soot
Prior art date
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Active
Application number
EP09008881.6A
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German (de)
French (fr)
Other versions
EP2143778A2 (en
EP2143778A3 (en
Inventor
Eberhard Jacob
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MAN Truck and Bus SE
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MAN Truck and Bus SE
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Publication of EP2143778A2 publication Critical patent/EP2143778A2/en
Publication of EP2143778A3 publication Critical patent/EP2143778A3/en
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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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/185—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
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • 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
    • 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

Definitions

  • the invention relates to low odor burning diesel fuels containing at least one fuel additive. Furthermore, the invention relates to their use for reducing the formation of soot in the combustion of diesel fuels.
  • hydrocarbon fuels are usually either hydrocarbons, e.g. produced by Fischer-Tropsch synthesis from raw materials such as gas, coal and plant residues, or from alcohols, e.g. can be obtained from sugar cane by fermentation.
  • Hydrocarbon fuels are typically produced using XTL technology, where X is a placeholder for gas (G), coal (C) or biomass (B).
  • G gas
  • C coal
  • B biomass
  • T and L in this context mean that the starting material is converted into a liquid (to liquids).
  • the XTL technology is often based on the Fischer-Tropsch synthesis at low temperature and provides a liquid fuel as a product.
  • Such less sooty combustion is particularly desirable in urban transport and is currently and in the near future by the relevant emission standards such as the commercial vehicle engines according to EU V (EU Directive 2006/51 / EC) and EU VI (EU Directive will be published in 2009) by law limited.
  • EU V EU Directive 2006/51 / EC
  • EU VI EU Directive will be published in 2009
  • XTL fuels consist mainly of aromatics-free alkanes due to the production technique of the Fischer-Tropsch synthesis, the density at 0.735 g / ml (manufacturer: Shell) and 0.765 (manufacturer: Sasol), however, by 7.6 to 13% lower than the standard for diesel fuels (DIN EN 590, issue 3.2004 requires a density of 0.820 - 0.845 g / ml).
  • the boiling point of such a fuel is about 170 ° C, the boiling end at about 330 ° C.
  • a disadvantage in the production of such fuels is also that in the Fischer-Tropsch synthesis predominantly a crude product of straight-chain n-alkanes having up to 60 carbon atoms is formed, which partially reacted in a subsequent cracking and isomerization step to short-chain n-alkanes and isoalkanes Need to become. This further step is necessary because long-chain n-alkanes generally have high benchmarks, which adversely affects the fluidity of the fuels, and can lead to clogging of the fuel filter at cold temperatures, such as in winter.
  • soot Even with XTL diesel fuels, the development of soot can be halved at best.
  • oxygen-containing fuel additives Such additives have the advantage that they lead to a reduction in the average combustion temperature in the cylinder and increase the proportion of premixed combustion.
  • Premixed combustion is understood to mean the combustion of a homogenized mixture of vaporized fuel and air as opposed to diffusion combustion (inhomogeneous combustion of fuel droplets with soot formation). So far, predominantly oxygenates have been tested and used as fuel additives in which the oxidation number of the carbon atoms containing bound oxygen atoms is greater than +1.
  • carbonates such as dimethyl carbonate (DMC) and esters such as dibutyl maleate (DBM) and fatty acid methyl ester (FAME) containing carbonyl groups have been used.
  • DMC dimethyl carbonate
  • DBM dibutyl maleate
  • FAME fatty acid methyl ester
  • acetals and polyacetals such as butylal and methylal were used with a -COCOC skeleton, in which the central carbon atom is bound to two adjacent O atoms
  • dialkyl ethers and other monoethers having 2-24 C atoms ( WO 1995/025153 such as US 5 520 710 ), and ethylene and diethylene glycol dimethyl ethers (SAE Paper 2000-01-2886) as fuel additives for diesel fuels.
  • the described ether oxygenates generally have either a low oxygen content at acceptable boiling points, or a very low boiling point at high oxygen content, such as dimethyl ether or diethyl ether, which makes their use in fuels problematic.
  • many low molecular weight ethers have a pronounced tendency to form peroxides, so that their use in practice is not effective.
  • Alcohols are also less suitable than fuel packs, either because they have very low cetane numbers (such as ethanol or methanol), or at acceptable cetane numbers already too high benchmarks and have only a low oxygen content. In the case of low molecular weight alcohols (1-4 carbon atoms), they are poorly or not miscible with diesel fuels ( Nylund et al. "Alcohols / Ethers as Oxygenates in Diesel Fuel", Report TEC 3/2005 ).
  • the GB 565 465 A discloses a diesel fuel containing polyethylene glycol dialkyl ethers and a diesel fuel containing a mixture of tetraethylene glycol dialkyl ethers and diethylene glycol diethyl ether having a high ignitability.
  • the EP 0 014 992 A1 describes diesel fuels containing a polyether, ethanol and / or methanol, and mineral based diesel fuels which burn with very little soot formation.
  • the GB 1 246 853 A discloses a fuel having reduced smoke properties, comprising a diesel fuel mixed with an ether.
  • the EP 0 903 395 A1 discloses a cetane number increase diesel fuel composition containing dimethoxypropane and optionally higher dialkoxyalkanes.
  • the EP 1 178 101 A2 discloses a fuel based on an ethylene glycol compound mixed with a liquid hydrocarbon.
  • the US Pat. No. 3,594,138 discloses a fuel composition comprising a liquid hydrocarbon, a Group II metal salt, an alkanoic acid and an alkyl ether.
  • the JP 59 232176 A describes fuels for diesel engines containing polyethers which burn with reduced soot formation.
  • EP 0 861 882 A1 discloses fuel compositions for diesel engines comprising as a major component a mineral oil and also dialkyl phthalate compounds and glycol ethers.
  • the US 5,425,790 A discloses fuel compositions consisting of hydrocarbons, aromatics and polyethers.
  • DE 697 33 363 T2 describes diesel fuel additives which comprise a polyether derivative and serve to reduce emissions of white smoke.
  • the invention is therefore based on the object to develop the diesel fuels described above so that the disadvantages of known diesel fuels are largely excluded.
  • the diesel fuels should have a reduced formation of soot and lead to a reduction in the combustion temperature and thus the formation of NO x and be substantially free of toxic components.
  • the additives contained in the diesel fuel for soot reduction during combustion should have the highest possible oxygen content.
  • the oxygen content of the fuel should be kept just as low as the soot-reducing effect requires in order to allow the lowest possible volumetric calorific value loss compared to diesel fuel according to DIN EN 590.
  • the boiling points of the additives used should preferably be such that they meet the requirements of international standardization for diesel fuels (eg according to DIN EN 590 only 5% of the components may boil higher than 360 ° C). Furthermore, the diesel fuel should have a good low-temperature behavior (CFPP according to the test method EN 116 in DIN EN 590) and thus allow a good filtration capacity in the cold. The diesel fuel should preferably approach the density requirements of the EN 590 standard. Finally, the ignition properties of the diesel fuels should remain at a high level (cetane number> 50). The flash point should be ⁇ 55 ° C as with diesel fuel.
  • a diesel fuel containing a fuel additive comprising at least one poly-oxa-alkane of the general formula (I): R 1 (-O-CH 2 -CHR 2 ) m -OR 3 (I), where R 1 is a straight-chain or branched alkyl radical, R 2 is a straight-chain or branched alkyl radical or H, R 3 is a straight-chain or branched alkyl radical, and wherein the fuel additive is free of toxic constituents, toxic being poisonous according to the Ordinance on Hazardous Substances (GefStoffV 23.12 2004, BGBI., I p. 3758), and wherein the diesel fuel contains 5 to 20% by volume of fatty acid methyl ester (FAME), and where m ⁇ 4, and wherein the diesel fuel contains up to 10% by volume of polyoxa contains alkane.
  • a fuel additive comprising at least one poly-oxa-alkane of the general formula (I): R 1 (-O-CH 2 -C
  • At least one poly-oxa-alkane expressly includes mixtures of poly-oxa-alkanes.
  • Toxic is understood as toxic according to the Ordinance on Hazardous Substances (GefStoffV 23.12.2004, BGBI. IS 3758).
  • Toxic components should also include teratogenic components.
  • the diesel fuels according to the invention have a significantly reduced soot formation.
  • a diesel fuel in particular a hydrogenated vegetable oil, preferably NexBTL or an XTL diesel fuel
  • a hydrogenated vegetable oil preferably NexBTL or an XTL diesel fuel
  • the air requirement of the engine is lowered by up to one third.
  • the cylinder filling ratio (quotient of boost pressure and air pressure) can be reduced by up to one third compared to an engine operation with XTL fuel. Accordingly, the cost of charging (compression) of the charge air decreases, which means that can be dispensed with an expensive two-stage charging and a cheaper one-stage Aufladeoli can be used.
  • the amount of exhaust gas produced is also about one third lower when the air demand for diesel engine combustion is one third lower.
  • the catalytic exhaust aftertreatment then saves almost a third of catalyst volume and can be intensified and simplified.
  • the poly-oxa-alkanes are derived from alkanes in which more CH 2 groups are replaced by oxygen atoms.
  • the radical R 1 preferably denotes an alkyl radical having a chain length of 1 to 4 carbon atoms, more preferably a straight-chain alkyl radical, since such increase the cetane numbers of the oxygenates.
  • Methyl, ethyl and n-butyl radicals can also be produced biogenically. This is a possibility to supply the bioalcohols methanol, ethanol and n-butanol to a refinement, since their direct use as diesel fuels is made very difficult especially by their low ignitability.
  • the cetane numbers of methanol, ethanol and n-butanol are 3, 8 and 17, respectively.
  • the radical R 2 preferably denotes a straight-chain or branched alkyl radical having 1 to 4 carbon atoms or H, more preferably a straight-chain alkyl radical or H.
  • R 2 is preferably H.
  • the radical R 3 likewise preferably denotes a straight-chain or branched alkyl radical having 1 to 4 carbon atoms, more preferably a straight-chain alkyl radical or H.
  • R 1 and R 3 are a methyl, an ethyl and / or a butyl radical.
  • m is ⁇ 4, in particular 4-16 and particularly preferably 4 to 12. Such compounds are particularly cost-effective.
  • the polyoxaalkane is preferably free of carbon atoms having an oxidation number> +1, more preferably free of carbon atoms having an oxidation number> 0.
  • the polyalkylene glycol dialkyl ether is selected from the group consisting of tetraethylene glycol ethyl methyl ether, tetraethylene glycol butyl methyl ether, dipropylene glycol dimethyl ether, and polypropylene glycol dimethyl ether with 4-5 propylene units.
  • the polyoxaalkane is particularly preferably a polyethylene glycol dibutyl ether, in particular a polyethylene glycol dibutyl ether having an average molecular weight of about 300, such as polyglycol BB 300 (available from Clariant Kunststoff GmbH).
  • a polyethylene glycol dibutyl ether having an average molecular weight of about 300, such as polyglycol BB 300 (available from Clariant Kunststoff GmbH).
  • the boiling point of the poly-oxa-alkane is preferably between about 100 ° C and about 450 ° C, more preferably between about 150 and about 375 ° C, and most preferably between about 170 and about 330 ° C.
  • this increases the proportion of premixed, low-carbon combustion and at the same time reduces the proportion of soot-forming diffusion combustion of the non-evaporable fuel droplets.
  • the polyoxaalkane has a melting point of less than about -10 ° C, preferably less than about -20 ° C. This has the advantage that the CFFP value required in the standard DIN EN 590 can be achieved when mixing with n-alkanes (high fixed point).
  • the polyoxaalkane has a density of from about 0.8 to about 1.1 g / ml, preferably from about 0.85 to about 1.0 g / ml.
  • a high density has the advantage that it can compensate for the possibly lower density of a diesel fuel, so that the diesel fuel according to the invention fulfills the EN 590 standard or approaches this standard.
  • the flash point of the poly-oxa-alkane is greater than about 55 ° C. This has the advantage that the DIN EN 590 is met.
  • any diesel fuel can be used.
  • the diesel fuel used is preferably substantially free of aromatic constituents, since such constituents are generally responsible for increased soot formation.
  • Hydrogenated vegetable oil, in particular NexBTL, or XTL diesel fuels are particularly preferably used as diesel fuels.
  • XTL as used herein is intended to encompass fuels that have been prepared by a gas to liquids (GTL) coal to liquids (CTL) or biomass to liquids (BTL) process. Most preferred is the use of GTL diesel fuel.
  • GTL gas to liquids
  • CTL coal to liquids
  • BTL biomass to liquids
  • the diesel fuel used preferably has a density of about 0.7 to about 0.8 g / ml, in order not to allow the density to drop too much below the standardized value of 0.82 g / ml and thus also the volumetric calorific value drops only slightly ,
  • the diesel fuels, ie fuel additives, according to the invention preferably have a density of from about 0.8 to about 0.845 g / ml in order to approximately meet the standard (EN 590).
  • the diesel fuel of the present invention is preferably substantially free of components having a boiling point greater than about 450 ° C to meet diesel fuel standardization in boiling behavior.
  • the diesel fuel of the invention contains less than 5% by volume of components having a boiling point greater than about 360 ° C (EN590).
  • the proportion of poly-oxa-alkane in the diesel fuel according to the invention is up to 10% by volume, and more preferably up to 5% by volume.
  • the calorific value reduction of the diesel fuel according to the invention is even lower.
  • the diesel fuel according to the invention contains 5 to 20% by volume of fatty acid methyl ester (FAME).
  • FAME fatty acid methyl ester
  • the diesel fuel according to the invention preferably contains 5 to 10% by volume of FAME.
  • the present invention also relates to the use of a diesel fuel to reduce soot formation in the combustion of diesel fuels.
  • any of the aforementioned diesel fuels can be used.
  • the used special also each of the aforementioned diesel fuels are used.
  • the diesel fuel used is preferably a fuel that is free of aromatic constituents, and more preferably a hydrogenated vegetable oil, especially NexBTL, or an XTL diesel fuel.
  • Also disclosed is a process for homogenizing diesel fuel / alkanol mixtures which comprises admixing polyoxaalkanes of general formula (I) as solubilizers and cetane improvers, the same restrictions being imposed on R 1 , R 2 and R 3 , m and on Fuel additive should apply as described above for diesel fuels.
  • any of the aforementioned diesel fuels can be used.
  • Hemogenization as used herein describes the conversion of a multiphase mixture to a single phase mixture.
  • the alcohol used herein is preferably a primary alcohol, more preferably a primary alcohol having 1 to 6 carbon atoms, and most preferably ethanol or n-butanol.
  • Ethanol is an alternative fuel to mineral oil-based fuels that can be produced inexpensively from organic sources by fermentation.
  • n-Butanol has the advantage that in the future it can be produced from cellulose by a biochemical process and thus does not compete with food production.
  • Diesel fuel / alkanol mixtures are of interest in view of the increasing scarcity of mineral oil-based fuels because, in particular, ethanol can be obtained by fermentation from renewable raw materials. Such bio-ethanol can be produced very cheaply, for example, in Brazil and increase the total amount of fuel by admixture with conventional diesel fuel.
  • diesel fuel / alkanol mixtures can generally not be used as fuel because the two components are immiscible or only in small proportions. This is especially true for the low molecular weight alkanols methanol and ethanol.
  • polyoxaalkanes of the general formula (I) diesel fuel / alkanol mixtures can be prepared which are single-phase at the temperature of use and which at the same time permit the admixture of large quantities of alkanol with the diesel fuel.
  • the amount of adjuvant added is preferably at least about 4%, more preferably at least about 5 to 11%.
  • the amount of alkanol component is usually about ⁇ 10%, preferably about ⁇ 20%, and most preferably about ⁇ 30%.
  • Polyglycol BB 300 is a polyethylene glycol dibutyl ether with an average molecular weight of about 300 (manufacturer Clariant Products GmbH, 84504 Burgmün).
  • Polyglycol DME 250 or DME 500 are polyethylene glycol dimethyl ether having an average molecular weight of about 250 or 500 (manufacturer Clariant products GmbH, 84504 Burgmaschinen).
  • diesel fuel / ethanol blends with poly-oxa-alkanes have been prepared as solubilizers.
  • diesel / ethanol mixtures were prepared with the highest possible ethanol content of ⁇ 30 wt .-%.
  • diesel fuel GTL were from Sasol / FM no. 243 with a density at 20 ° C of 0.7656 g / cm 2 and Aral Ultimate with a density at 20 ° of 0.8236 g / cm 2 and ethanol with a density at 20 ° of 0.7893 g / cm 2 used .
  • the densities and the corresponding oxygen contents of the corresponding mixtures are given in Table 2.

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

Description

Die Erfindung betrifft rußarm verbrennende Dieselkraftstoffe, die zumindest einen Kraftstoffzusatz enthalten. Weiterhin betrifft die Erfindung deren Verwendung zur Verminderung der Rußbildung bei der Verbrennung von Dieselkraftstoffen.The invention relates to low odor burning diesel fuels containing at least one fuel additive. Furthermore, the invention relates to their use for reducing the formation of soot in the combustion of diesel fuels.

Aufgrund des in den letzten Jahren stark ansteigenden Bedarfs an Öl und der damit verbundenen starken Preissteigerung haben synthetische Kraftstoffe und Kraftstoffe aus nachwachsenden Rohstoffen immer größere Bedeutung erlangt. Solche Kraftstoffe bestehen in der Regel entweder aus Kohlenwasserstoffen, die z.B. mit Hilfe der Fischer-Tropsch-Synthese aus Rohstoffen wie Gas, Kohle und Pflanzenresten hergestellt werden, oder aus Alkoholen, die z.B. aus Zuckerrohr durch Vergärung gewonnen werden können. Kohlenwasserstoff-Kraftstoffe werden in der Regel mit Hilfe der XTL-Technologie hergestellt, wobei X ein Platzhalter für Gas (G), Kohle (C) oder Biomasse (B) ist. Die Buchstaben T und L bedeuten in diesem Zusammenhang, dass das Ausgangsprodukt in eine Flüssigkeit umgewandelt wird (to liquids). Die XTL-Technologie basiert häufig auf der Fischer-Tropsch-Synthese bei niedriger Temperatur und liefert einen flüssigen Kraftstoff als Produkt.Due to the rapidly increasing demand for oil in recent years and the associated strong price increase, synthetic fuels and fuels from renewable raw materials have become increasingly important. Such fuels are usually either hydrocarbons, e.g. produced by Fischer-Tropsch synthesis from raw materials such as gas, coal and plant residues, or from alcohols, e.g. can be obtained from sugar cane by fermentation. Hydrocarbon fuels are typically produced using XTL technology, where X is a placeholder for gas (G), coal (C) or biomass (B). The letters T and L in this context mean that the starting material is converted into a liquid (to liquids). The XTL technology is often based on the Fischer-Tropsch synthesis at low temperature and provides a liquid fuel as a product.

Auf diese Weise synthetisch hergestellte XTL-Dieselkraftstoffe führen gegenüber Mineralöl basierenden Kraftstoffen zu einer um etwa 20 % rußärmeren Verbrennung ( J. Krahl et.al., 5th Internat. Colloquium Fuels, Jan.12-13,2005, Edt.: W.J. Bartz, TAE Ostfildern, S.207/212 ). Eine solche rußärmere Verbrennung ist besonders im innerstädtischen Verkehr erwünscht und wird derzeit und in naher Zukunft durch die maßgeblichen Abgasnormen z.B. bei den Nutzfahrzeugmotoren gemäß EU V (EU-Richtlinie 2006/51/EC) und EU VI (EU-Richtlinie erscheint 2009), gesetzlich eingeschränkt. Eine analoge Gesetzgebung existiert in USA und Japan. Weiterhin erlauben es solche Dieselkraftstoffe, die AGR-Raten (AGR=Abgasrückführung) der Dieselmotoren deutlich zu erhöhen, um so die NOx Emissionen abzusenken, ohne dass die Rußemission und der Kraftstoffverbrauch ansteigen. XTL-Kraftstoffe bestehen aufgrund der Herstellungstechnik über die Fischer-Tropsch-Synthese fast ausschließlich aus aromatenfreien Alkanen, deren Dichte mit 0,735 g/ml (Hersteller: Shell) und 0,765 (Hersteller: Sasol) jedoch um 7,6 bis 13 % niedriger ist als die Norm für Dieselkraftstoffe vorschreibt (DIN EN 590, Ausgabe 3.2004 erfordert eine Dichte von 0,820 - 0,845 g/ml). Der Siedebeginn eines solchen Kraftstoffs liegt bei ca. 170°C, das Siedeende bei ca. 330°C. Ein Nachteil bei der Herstellung solcher Kraftstoffe ist ebenfalls, dass bei der Fischer-Tropsch-Synthese überwiegend ein Rohprodukt aus geradkettigen n-Alkanen mit bis zu 60 Kohlenstoffatomen entsteht, die in einem nachfolgenden Crackungs- und Isomerisierungsschritt partiell zu kurzkettigen n-Alkanen und Isoalkanen umgesetzt werden müssen. Dieser weitere Schritt ist erforderlich, weil langkettige n-Alkane in der Regel hohe Festpunkte aufweisen, was die Fließfähigkeit der Kraftstoffe negativ beeinflusst, und bei kalten Temperaturen, wie beispielsweise im Winter, zu einer Verstopfung der Kraftstofffilter führen kann. Durch die Beimischung von Isoalkanen zu der Fraktion von n-Alkanen kann eine Filtrationsfähigkeit auch in der Kälte (Cold Filter Plugging Point, CFPP nach DIN EN 590 im Winter: -20°C) gewährleistet werden, weil Isoalkane in der Regel geringere Festpunkte haben und so die Fließfähigkeit des Gemischs verbessert wird. Neben dem notwendigen Isomerisierungsschritt hat dieses Vorgehen jedoch noch einen weiteren Nachteil. Die Beimischung von Isoalkanen zu den n-Alkanen führt auch zu einem Absinken der Cetanzahl des Kraftstoffs, so dass sich die Zündfähigkeit des Fischer-Tropsch-Kraftstoffs ebenfalls vermindert.Synthetically produced XTL diesel fuels lead to an approximately 20% less soot-burning compared to mineral oil-based fuels ( J. Krahl et.al., 5th Internat. Colloquium Fuels, Jan.12-13,2005, Ed .: WJ Bartz, TAE Ostfildern, p.207 / 212 ). Such less sooty combustion is particularly desirable in urban transport and is currently and in the near future by the relevant emission standards such as the commercial vehicle engines according to EU V (EU Directive 2006/51 / EC) and EU VI (EU Directive will be published in 2009) by law limited. An analogous legislation exists in USA and Japan. Furthermore, such diesel fuels make it possible to significantly increase the EGR (EGR) rates of the diesel engines so as to lower NO x emissions without increasing soot emission and fuel consumption. XTL fuels consist mainly of aromatics-free alkanes due to the production technique of the Fischer-Tropsch synthesis, the density at 0.735 g / ml (manufacturer: Shell) and 0.765 (manufacturer: Sasol), however, by 7.6 to 13% lower than the standard for diesel fuels (DIN EN 590, issue 3.2004 requires a density of 0.820 - 0.845 g / ml). The boiling point of such a fuel is about 170 ° C, the boiling end at about 330 ° C. A disadvantage in the production of such fuels is also that in the Fischer-Tropsch synthesis predominantly a crude product of straight-chain n-alkanes having up to 60 carbon atoms is formed, which partially reacted in a subsequent cracking and isomerization step to short-chain n-alkanes and isoalkanes Need to become. This further step is necessary because long-chain n-alkanes generally have high benchmarks, which adversely affects the fluidity of the fuels, and can lead to clogging of the fuel filter at cold temperatures, such as in winter. By the admixture of isoalkanes to the fraction of n-alkanes, a filtration capacity can be ensured even in the cold (Cold Filter Plugging Point, CFPP according to DIN EN 590 in winter: -20 ° C), because isoalkanes usually have lower fixed points and so the flowability of the mixture is improved. However, besides the necessary isomerization step, this procedure has a further disadvantage. The addition of isoalkanes to the n-alkanes also leads to a decrease in the cetane number of the fuel, so that the ignitability of the Fischer-Tropsch fuel also decreases.

Auch durch XTL-Dieselkraftstoffe lässt sich die Rußentwicklung bestenfalls halbieren. Alternativ zu deren Verwendung wurde bereits mehrfach nachgewiesen, dass sich eine deutliche Verminderung der Rußbildung auch durch sauerstoffhaltige Kraftstoffzusätze erzielen lässt. Solche Zusätze haben den Vorteil, dass sie zu einer Absenkung der mittleren Verbrennungstemperatur im Zylinder führen und den Anteil an vorgemischter Verbrennung erhöhen. Unter vorgemischten Verbrennung versteht man die Verbrennung eines homogenisierten Gemisches aus verdampften Kraftstoff und Luft im Gegensatz zur Diffusionsverbrennung (Inhomogene Verbrennung von Kraftstofftröpfchen unter Rußbildung). Bisher sind überwiegend Oxygenate als Kraftstoffzusätze erprobt und verwendet worden, bei denen die Oxidationszahl der Kohlenstoffatome, die gebundene Sauerstoffatome enthalten, größer als +1 ist. Insbesondere wurden Carbonate z.B. Dimethylcarbonat (DMC) und Ester z.B. Dibutylmaleat (DBM) und Fettsäuremethylester (FAME) verwendet, die Carbonylgruppen enthalten. Weiterhin wurden Acetale und Polyacetale z.B. Butylal und Methylal mit einem -C-O-C-O-C- Grundgerüst verwendet, bei dem das zentrale C-Atom an zwei benachbarte O-Atome gebunden istEven with XTL diesel fuels, the development of soot can be halved at best. As an alternative to their use has been repeatedly demonstrated that a significant reduction in soot formation can also be achieved by oxygen-containing fuel additives. Such additives have the advantage that they lead to a reduction in the average combustion temperature in the cylinder and increase the proportion of premixed combustion. Premixed combustion is understood to mean the combustion of a homogenized mixture of vaporized fuel and air as opposed to diffusion combustion (inhomogeneous combustion of fuel droplets with soot formation). So far, predominantly oxygenates have been tested and used as fuel additives in which the oxidation number of the carbon atoms containing bound oxygen atoms is greater than +1. In particular, carbonates such as dimethyl carbonate (DMC) and esters such as dibutyl maleate (DBM) and fatty acid methyl ester (FAME) containing carbonyl groups have been used. Furthermore, acetals and polyacetals such as butylal and methylal were used with a -COCOC skeleton, in which the central carbon atom is bound to two adjacent O atoms

(A. Bertola, K. Boulouchos, SAE Paper 2000-01-2885). In diesen Fällen sind die Oxidationsstufen des Sauerstoff tragenden C-Atoms mit ≥+2 bereits sehr hoch was zu einer entsprechenden Verminderung des Brennwertes führt. Bei Estern mit -C=O(-OR)-Gruppen führt deren Verbrennung zu einer Decarboxylierung unter lokaler CO2-Abspaltung, so dass der enthaltende Sauerstoff wenig zur Absenkung der Rußbildung beitragen kann. Die Verwendung von solchen Fettsäuremethylestern (FAME nach EN 14214:2003) als Kraftstoff, die ca. 11 % Sauerstoff enthalten, führt zur Absenkung der Partikelemissionen gegenüber Dieselkraftstoff von 40 - 60 % ( J. Krahl et.al., 5th Internat. Colloquium Fuels, Jan. 12-13, 2005, Edt.: W.J. Bartz, TAE Ostfildern, S.207/212 ).(A. Bertola, K. Boulouchos, SAE Paper 2000-01-2885). In these cases, the oxidation states of the oxygen-carrying carbon atom with ≥ + 2 are already very high, which leads to a corresponding reduction in the calorific value. For esters with -C = O (-OR) groups, their combustion leads to a decarboxylation with local CO 2 cleavage, so that the oxygen contained can contribute little to reducing soot formation. The use of such fatty acid methyl esters (FAME according to EN 14214: 2003) as fuel, which contain about 11% oxygen, leads to the reduction of particle emissions compared to diesel fuel from 40 to 60% ( J. Krahl et.al., 5th Internat. Colloquium Fuels, Jan. 12-13, 2005, Ed .: WJ Bartz, TAE Ostfildern, p.207 / 212 ).

Darüber hinaus wurden ebenfalls Dialkylether und andere Monoether mit 2 - 24 C-Atomen ( WO 1995/025153 sowie US 5 520 710 ), sowie Ethylen- und Diethylenglykol-Dimethylether (SAE Paper 2000-01-2886) als Kraftstoffzusätze für Dieselkraftstoffe beschrieben. Die beschriebenen Etheroxygenate haben jedoch in der Regel entweder nur einen geringen Sauerstoffgehalt bei akzeptablen Kochpunkten, oder bei hohem Sauerstoffgehalt einen sehr niedrigen Kochpunkt, wie etwa Dimethylether oder Diethylether, was deren Verwendung in Kraftstoffen problematisch macht. Hinzu kommt dass viele niedermolekulare Ether eine ausgeprägte Neigung zur Bildung von Peroxiden aufweisen, so dass ihre Verwendung in der Praxis nicht zielführend ist. Die bisher beschriebenen Diethylenglykol-Dialkylether, insbesondere Cetaner®, ein Gemisch aus 20% 1,2-Dimethoxyethan und 80% Diethylenglykoldimethylether, weisen eine stark rußsenkende Wirkung auf. Bei beiden Komponenten von Cetaner® handelt es sich jedoch um ausgesprochen giftige Stoffe, deren allgemeine Verwendung als Kraftstoff oder Kraftstoffzusatz nicht genehmigungsfähig ist. Ein weiterer Nachteil ist, dass beide Substanzen relativ leicht flüchtig sind, was im Zusammenhang mit ihrer Giftigkeit zusätzlich problematisch ist.In addition, dialkyl ethers and other monoethers having 2-24 C atoms ( WO 1995/025153 such as US 5 520 710 ), and ethylene and diethylene glycol dimethyl ethers (SAE Paper 2000-01-2886) as fuel additives for diesel fuels. However, the described ether oxygenates generally have either a low oxygen content at acceptable boiling points, or a very low boiling point at high oxygen content, such as dimethyl ether or diethyl ether, which makes their use in fuels problematic. In addition, many low molecular weight ethers have a pronounced tendency to form peroxides, so that their use in practice is not effective. The diethylene glycol dialkyl ether described so far, in particular Cetaner ®, a mixture of 20% 1,2-dimethoxyethane and diethylene glycol dimethyl ether 80%, have a highly rußsenkende effect. However, both components of Cetaner ® are extremely toxic substances whose general use as a fuel or fuel additive is not approvable. Another disadvantage is that both substances are relatively volatile, which is additionally problematic in connection with their toxicity.

Alkohole eignen sich ebenfalls weniger als Kraftstoffsätze, weil sie entweder sehr niedrige Cetanzahlen aufweisen (wie Ethanol oder Methanol), oder aber bei akzeptablen Cetanzahlen schon zu hohe Festpunkte und nur einen geringen Sauerstoffgehalt haben. Bei den niedermolekularen Alkoholen (1-4 Kohlenstoffatome) kommt hinzu, dass sie nur schlecht oder gar nicht mit Dieselkraftstoffen mischbar sind ( Nylund et al. "Alcohols /Ethers as Oxygenates in Diesel Fuel", Report TEC 3/2005 ).Alcohols are also less suitable than fuel packs, either because they have very low cetane numbers (such as ethanol or methanol), or at acceptable cetane numbers already too high benchmarks and have only a low oxygen content. In the case of low molecular weight alcohols (1-4 carbon atoms), they are poorly or not miscible with diesel fuels ( Nylund et al. "Alcohols / Ethers as Oxygenates in Diesel Fuel", Report TEC 3/2005 ).

Die GB 565 465 A offenbart einen Dieselkraftstoff, enthaltend Polyethylenglykoldialkylether und einen Dieselkraftstoff, enthaltend eine Mischung von Tetraethylenglykoldialkylether und Diethylenglykoldiethylether mit einer hohen Zündfähigkeit. Die EP 0 014 992 A1 beschreibt Dieselkraftstoffe, enthaltend einen Polyether, Ethanol und/oder Methanol, und Dieselkraftstoffe auf Mineralbasis, die unter sehr geringer Rußbildung verbrennen. Die GB 1 246 853 A offenbart einen Kraftstoff mit reduzierten Raucheigenschaften, umfassend einen Dieselkraftstoff gemischt mit einem Ether. In der EP 0 903 395 A1 wird eine Dieselkraftstoffzusammensetzung zur Cetanzahlerhöhung, enthaltend Dimethoxypropan und gegebenenfalls höhere Dialkoxyalkane, offenbart. Die EP 1 178 101 A2 offenbart einen Kraftstoff auf Basis einer Ethylenglykolverbindung gemischt mit einem flüssigen Kohlenwasserstoff. Die US 3 594 138 A offenbart eine Kraftstoffzusammensetzung, umfassend einen flüssigen Kohlenwasserstoff, ein Gruppe-II-Metallsalz, eine Alkansäure und einen Alkylether. Die JP 59 232176 A beschreibt Kraftstoffe für Dieselmotoren, enthaltend Polyether, die unter verminderter Rußbildung verbrennen. In der EP 0 861 882 A1 werden Kraftstoffzusammensetzungen für Dieselmotoren offenbart, die als Hauptkomponente ein Mineralöl und außerdem Dialkylphtalat-Verbindungen und Glykolether umfassen. Die US 5 425 790 A offenbart Kraftstoffzusammensetzungen bestehend aus Kohlenwasserstoffen, Aromaten und Polyethern. DE 697 33 363 T2 beschreibt Dieselkraftstoffzusätze (Additive), welche ein Polyetherderivat umfassen und der Verringerung der Emissionen von weißem Rauch dienen.The GB 565 465 A discloses a diesel fuel containing polyethylene glycol dialkyl ethers and a diesel fuel containing a mixture of tetraethylene glycol dialkyl ethers and diethylene glycol diethyl ether having a high ignitability. The EP 0 014 992 A1 describes diesel fuels containing a polyether, ethanol and / or methanol, and mineral based diesel fuels which burn with very little soot formation. The GB 1 246 853 A discloses a fuel having reduced smoke properties, comprising a diesel fuel mixed with an ether. In the EP 0 903 395 A1 discloses a cetane number increase diesel fuel composition containing dimethoxypropane and optionally higher dialkoxyalkanes. The EP 1 178 101 A2 discloses a fuel based on an ethylene glycol compound mixed with a liquid hydrocarbon. The US Pat. No. 3,594,138 discloses a fuel composition comprising a liquid hydrocarbon, a Group II metal salt, an alkanoic acid and an alkyl ether. The JP 59 232176 A describes fuels for diesel engines containing polyethers which burn with reduced soot formation. In the EP 0 861 882 A1 discloses fuel compositions for diesel engines comprising as a major component a mineral oil and also dialkyl phthalate compounds and glycol ethers. The US 5,425,790 A discloses fuel compositions consisting of hydrocarbons, aromatics and polyethers. DE 697 33 363 T2 describes diesel fuel additives which comprise a polyether derivative and serve to reduce emissions of white smoke.

Der Erfindung liegt daher die Aufgabe zugrunde, die eingangs beschriebenen Dieselkraftstoffe so weiterzuentwickeln, dass die Nachteile bekannter Dieselkraftstoffe weitgehend ausgeschlossen werden. Dabei sollen die Dieselkraftstoffe insbesondere eine verminderte Rußbildung aufweisen und zu einer Absenkung der Verbrennungstemperatur und damit der NOx-Bildung führen sowie im Wesentlichen frei von giftigen Bestandteilen sein. Ferner sollen die im Dieselkraftstoff zur Rußverminderung bei der Verbrennung enthaltenen Zusatzstoffe einen möglichst hohen Sauerstoffgehalt aufweisen. Der Sauerstoffgehalt des Kraftstoffs sollte andererseits gerade so niedrig gehalten werden, wie es die rußsenkende Wirkung erfordert, um einen möglichst geringen volumetrischen Brennwertverlust gegenüber Dieselkraftstoff nach DIN EN 590 zu ermöglichen. Die Siedepunkte der verwendeten Zusatzstoffe sind vorzugsweise so zu wählen, dass sie den Anforderungen der internationalen Normung für Dieselkraftstoffe (z.B. dürfen nach DIN EN 590 nur 5% der Komponenten höher als 360°C sieden) entsprechen.. Ferner soll der Dieselkraftstoff ein gutes Kälteverhalten (CFPP nach der Prüfmethode EN 116 in der DIN EN 590) besitzen und damit eine gute Filtrationsfähigkeit in der Kälte ermöglichen. Der Dieselkraftstoff sollte sich vorzugsweise den Dichteanforderungen der Norm EN 590 nähern. Schließlich sollten die Zündeigenschaften der Dieselkraftstoffe auf hohem Niveau (Cetanzahl >50) verbleiben. Der Flammpunkt sollte wie bei Dieselkraftstoff <55°C betragen.The invention is therefore based on the object to develop the diesel fuels described above so that the disadvantages of known diesel fuels are largely excluded. In particular, the diesel fuels should have a reduced formation of soot and lead to a reduction in the combustion temperature and thus the formation of NO x and be substantially free of toxic components. Furthermore, the additives contained in the diesel fuel for soot reduction during combustion should have the highest possible oxygen content. On the other hand, the oxygen content of the fuel should be kept just as low as the soot-reducing effect requires in order to allow the lowest possible volumetric calorific value loss compared to diesel fuel according to DIN EN 590. The boiling points of the additives used should preferably be such that they meet the requirements of international standardization for diesel fuels (eg according to DIN EN 590 only 5% of the components may boil higher than 360 ° C). Furthermore, the diesel fuel should have a good low-temperature behavior ( CFPP according to the test method EN 116 in DIN EN 590) and thus allow a good filtration capacity in the cold. The diesel fuel should preferably approach the density requirements of the EN 590 standard. Finally, the ignition properties of the diesel fuels should remain at a high level (cetane number> 50). The flash point should be <55 ° C as with diesel fuel.

Erfindungsgemäß wird diese Aufgabe dadurch gelöst, dass ein Dieselkraftstoff, enthaltend einen Kraftstoffzusatz, umfassend zumindest ein Poly-oxa-alkan der allgemeinen Formel (I):

        R1(-O-CH2-CHR2)m-O-R3     (I),

wobei R1 ein geradkettiger oder verzweigter Alkylrest ist, R2 ein geradkettiger oder verzweigter Alkylrest oder H ist, R3 ein geradkettiger oder verzweigter Alkylrest ist, und wobei der Kraftstoffzusatz frei von giftigen Bestandteilen ist, wobei unter giftig giftig nach der Gefahrstoffverordnung (GefStoffV 23.12.2004, BGBI. I S. 3758) verstanden wird, und wobei der Dieselkraftstoff 5 - 20 Vol.-% Fettsäuremethylester (FAME) enthält, und wobei m ≥ 4 ist, und wobei der Dieselkraftstoff bis zu 10 Vol.% Poly-oxa-alkan enthält.According to the invention this object is achieved in that a diesel fuel containing a fuel additive comprising at least one poly-oxa-alkane of the general formula (I):

R 1 (-O-CH 2 -CHR 2 ) m -OR 3 (I),

where R 1 is a straight-chain or branched alkyl radical, R 2 is a straight-chain or branched alkyl radical or H, R 3 is a straight-chain or branched alkyl radical, and wherein the fuel additive is free of toxic constituents, toxic being poisonous according to the Ordinance on Hazardous Substances (GefStoffV 23.12 2004, BGBI., I p. 3758), and wherein the diesel fuel contains 5 to 20% by volume of fatty acid methyl ester (FAME), and where m ≥ 4, and wherein the diesel fuel contains up to 10% by volume of polyoxa contains alkane.

Der Begriff "zumindest ein Poly-oxa-alkan" schließt Gemische von Poly-oxa-alkanen ausdrücklich ein.The term "at least one poly-oxa-alkane" expressly includes mixtures of poly-oxa-alkanes.

Unter giftig wird giftig nach der Gefahrstoffverordnung (GefStoffV 23.12.2004, BGBI. I S 3758) verstanden. Beispielsweise enthält der erfindungsgemäße Dieselkraftstoff keine Polyethylenglykoldimethylether der Formel CH3O(C2H4O)nCH3 mit n = 1-3. Giftige Bestandteile sollen auch teratogene Bestandteile umfassen.Toxic is understood as toxic according to the Ordinance on Hazardous Substances (GefStoffV 23.12.2004, BGBI. IS 3758). For example, the diesel fuel according to the invention contains no polyethylene glycol dimethyl ether of the formula CH 3 O (C 2 H 4 O) n CH 3 where n = 1-3. Toxic components should also include teratogenic components.

Die erfindungsgemäßen Dieselkraftstoffe weisen eine deutlich verminderte Rußbildung auf.The diesel fuels according to the invention have a significantly reduced soot formation.

Des Weiteren führt der Kraftstoffzusatz in Verbindung mit einem Dieselkraftstoff, insbesondere einem hydrierten Pflanzenöl, vorzugsweise NexBTL, oder einem XTL-Dieselkraftstoff, zu einer Erhöhung der Dichte und damit einer Kompensation der volumetrischen Heizwertverminderung, die beim Ersatz von CH2 Gruppen in langkettigen Alkanen durch -O-Gruppen eintritt.Furthermore, the addition of fuel in combination with a diesel fuel, in particular a hydrogenated vegetable oil, preferably NexBTL or an XTL diesel fuel, leads to an increase in the density and thus a compensation of the volumetric calorific value reduction which occurs when replacing CH 2 groups in long-chain alkanes, O groups enters.

Ferner wird der Luftbedarf des Motors bis zu einem Drittel abgesenkt. Dies hat eine Reihe von Vorteilen: Der Zylinderfüllungsgrad (Quotient aus Ladedruck und Luftdruck) kann bis zu einem Drittel gegenüber einem Motorenbetrieb mit XTL-Kraftstoff verringert werden. Entsprechend sinkt der Aufwand für die Aufladung (Kompression) der Ladeluft, was dazu führt, dass auf eine teure zweistufige Aufladung verzichtet werden kann und eine billigere einstufige Aufladegruppe eingesetzt werden kann. Weiterhin ist die produzierte Abgasmenge ebenfalls um ca. ein Drittel niedriger wenn der Luftbedarf zur dieselmotorischen Verbrennung um ein Drittel niedriger ist. Die katalytische Abgasnachbehandlung spart dann fast ein Drittel an Katalysatorvolumen und kann intensiviert und vereinfacht werden.Furthermore, the air requirement of the engine is lowered by up to one third. This has a number of advantages: The cylinder filling ratio (quotient of boost pressure and air pressure) can be reduced by up to one third compared to an engine operation with XTL fuel. Accordingly, the cost of charging (compression) of the charge air decreases, which means that can be dispensed with an expensive two-stage charging and a cheaper one-stage Aufladegruppe can be used. Furthermore, the amount of exhaust gas produced is also about one third lower when the air demand for diesel engine combustion is one third lower. The catalytic exhaust aftertreatment then saves almost a third of catalyst volume and can be intensified and simplified.

Die Poly-oxa-alkane leiten sich von Alkanen ab, in denen mehrere CH2-Gruppen durch Sauerstoffatome ersetzt sind.The poly-oxa-alkanes are derived from alkanes in which more CH 2 groups are replaced by oxygen atoms.

Der Rest R1 bezeichnet bevorzugt einen Alkylrest mit einer Kettenlänge von 1 - 4 Kohlenstoffatomen, besonders bevorzugt einen geradkettigen Alkylrest, da solche die Cetanzahlen der Oxygenate ansteigen lassen. Methyl-, Ethyl und n-Butylreste können auch biogen hergestellt werden. Dies ist eine Möglichkeit die Bioalkohole Methanol, Ethanol und n-Butanol einer Veredlung zuzuführen, da deren direkter Einsatz als Dieselkraftstoffe insbesondere durch deren geringe Zündfähigkeit sehr erschwert ist. Die Cetanzahlen von Methanol, Ethanol und n-Butanol liegen bei 3, 8 bzw. 17.The radical R 1 preferably denotes an alkyl radical having a chain length of 1 to 4 carbon atoms, more preferably a straight-chain alkyl radical, since such increase the cetane numbers of the oxygenates. Methyl, ethyl and n-butyl radicals can also be produced biogenically. This is a possibility to supply the bioalcohols methanol, ethanol and n-butanol to a refinement, since their direct use as diesel fuels is made very difficult especially by their low ignitability. The cetane numbers of methanol, ethanol and n-butanol are 3, 8 and 17, respectively.

Der Rest R2 bezeichnet bevorzugt einen geradkettigen oder verzweigten Alkylrest mit 1 - 4 Kohlenstoffatomen oder H, besonders bevorzugt einen geradkettigen Alkylrest oder H. DerThe radical R 2 preferably denotes a straight-chain or branched alkyl radical having 1 to 4 carbon atoms or H, more preferably a straight-chain alkyl radical or H. Der

Rest R2 enthält, besonders bevorzugt 0 bis 2 Kohlenstoffatome und ganz besonders bevorzugt 0 bis 1 Kohlenstoffatome. Wenn der Rest R2 keine Kohlenstoffatome enthält ist R2 = H.R 2 contains, more preferably 0 to 2 carbon atoms and most preferably 0 to 1 carbon atoms. When the radical R 2 contains no carbon atoms, R 2 = H.

Aus Kostengründen ist R2 vorzugsweise H.For cost reasons, R 2 is preferably H.

Der Rest R3 bezeichnet ebenfalls bevorzugt einen geradkettigen oder verzweigten Alkylrest mit 1 - 4 Kohlenstoffatomen, besonders bevorzugt eine geradkettige Alkylrest oder H.The radical R 3 likewise preferably denotes a straight-chain or branched alkyl radical having 1 to 4 carbon atoms, more preferably a straight-chain alkyl radical or H.

In einer weiteren bevorzugten Ausführungsform sind R1 und R3 ein Methyl-, ein Ethyl- und/oder ein Butylrest. Der Einsatz derartiger Verbindungen führt zu einer verbesserten Löslichkeit des Poly-oxa-alkans im Dieselkraftstoff, d. h. die Mischbarkeit wird erhöht.In a further preferred embodiment, R 1 and R 3 are a methyl, an ethyl and / or a butyl radical. The use of such compounds leads to an improved solubility of the poly-oxa-alkane in diesel fuel, ie, the miscibility is increased.

m ist, wie erwähnt, ≥ 4, insbesondere 4 - 16 und besonders bevorzugt 4 bis 12. Derartige Verbindungen sind besonders kostengünstig.As mentioned, m is ≥ 4, in particular 4-16 and particularly preferably 4 to 12. Such compounds are particularly cost-effective.

Das Poly-oxa-alkan ist bevorzugt frei von Kohlenstoffatomen mit einer Oxidationszahl > +1, besonders bevorzugt frei von Kohlenstoffatomen mit einer Oxidationszahl > 0.The polyoxaalkane is preferably free of carbon atoms having an oxidation number> +1, more preferably free of carbon atoms having an oxidation number> 0.

In einer bevorzugten Ausführungsform ist das zumindest eine Poly-oxa-alkan ein Polyalkylenglykoldiethylether, insbesondere ein Polyethylenglykoldimethylether der allgemeinen Formel CH3O(C2H4O)mCH3 ist, wobei m=4 oder ein Gemisch von m=4 bis m=12, vorzugsweise von m=4 bis m=8, ist.In a preferred embodiment, the at least one poly-oxa-alkane is a Polyalkylenglykoldiethylether, in particular a polyethylene glycol dimethyl ether of the general formula CH 3 O (C 2 H 4 O) m CH 3 , where m = 4 or a mixture of m = 4 to m = 12, preferably from m = 4 to m = 8.

In einer weiteren bevorzugten Anfertigungsform wird der Polyalkylenglykoldialkylether ausgewählt aus der Gruppe bestehend aus Tetraethylenglykolethylmethylether, Tetraethylenglykolbutylmethylether, Dipropylenglykoldimethylether, und Polypropylenglykoldimethylether mit 4-5 Propyleneinheiten.In a further preferred preparation form, the polyalkylene glycol dialkyl ether is selected from the group consisting of tetraethylene glycol ethyl methyl ether, tetraethylene glycol butyl methyl ether, dipropylene glycol dimethyl ether, and polypropylene glycol dimethyl ether with 4-5 propylene units.

Besonders bevorzugt ist das Poly-oxa-alkan ein Polyethylenglykoldibutylether, insbesondere ein Polyethylenglykoldibutylether mit einem mittleren Molekulargewicht von etwa 300, wie Polyglykol BB 300 (erhältlich von Clariant Produkte GmbH). Mit diesem Poly-oxa-alkan ist die Formulierung von Dieselkraftstoffen möglich, die bei entsprechend hohem Gehalt den Dichteanforderungen der DIN EN 590 genügen.The polyoxaalkane is particularly preferably a polyethylene glycol dibutyl ether, in particular a polyethylene glycol dibutyl ether having an average molecular weight of about 300, such as polyglycol BB 300 (available from Clariant Produkte GmbH). With this poly-oxa-alkane, the formulation of diesel fuels is possible, which meet the density requirements of DIN EN 590 with a correspondingly high content.

Der Siedepunkt des Poly-oxa-alkans liegt vorzugsweise zwischen etwa 100°C und etwa 450°C, besonders bevorzugt zwischen etwa 150 und etwa 375°C und ganz besonders bevorzugt zwischen etwa 170 und etwa 330°C. Wenn der Siedepunkt des Polyoxaalkans gleich oder weniger also ca. 330 °C ist, wird dadurch der Anteil der vorgemischten, rußarmen Verbrennung erhöht und gleichzeitig der Anteil der rußbildenden Diffusionsverbrennung der nicht verdampfbaren Kraftstofftröpfchen erniedrigt.The boiling point of the poly-oxa-alkane is preferably between about 100 ° C and about 450 ° C, more preferably between about 150 and about 375 ° C, and most preferably between about 170 and about 330 ° C. When the boiling point of the polyoxaalkane is the same or less than about 330 ° C, this increases the proportion of premixed, low-carbon combustion and at the same time reduces the proportion of soot-forming diffusion combustion of the non-evaporable fuel droplets.

In einer weiteren bevorzugten Ausführungsform hat das Poly-oxa-alkan einen Schmelzpunkt von weniger als etwa -10°C, vorzugsweise von weniger als etwa -20°C. Dies hat den Vorteil, dass der in der Norm DIN EN 590 geforderte CFFP-Wert beim Mischen mit n-Alkanen (hoher Festpunkt) erreicht werden kann.In a further preferred embodiment, the polyoxaalkane has a melting point of less than about -10 ° C, preferably less than about -20 ° C. This has the advantage that the CFFP value required in the standard DIN EN 590 can be achieved when mixing with n-alkanes (high fixed point).

In einer weiteren bevorzugten Ausführungsform hat das Poly-oxa-alkan eine Dichte von etwa 0,8 bis etwa 1,1 g/ml, bevorzugt von etwa 0,85 bis etwa 1.0 g/ml. Eine hohe Dichte hat den Vorteil, dass dadurch die eventuell niedrigere Dichte eines Dieselkraftstoffs ausgeglichen werden kann, so dass der erfindungsgemäße Dieselkraftstoff die EN 590 Norm erfüllt oder sich dieser Norm annähert.In a further preferred embodiment, the polyoxaalkane has a density of from about 0.8 to about 1.1 g / ml, preferably from about 0.85 to about 1.0 g / ml. A high density has the advantage that it can compensate for the possibly lower density of a diesel fuel, so that the diesel fuel according to the invention fulfills the EN 590 standard or approaches this standard.

In einer weiteren bevorzugten Ausführungsform ist der Flammpunkt des Poly-oxa-alkans größer als etwa 55°C. Dies hat den Vorteil, dass die DIN EN 590 erfüllt wird.In a further preferred embodiment, the flash point of the poly-oxa-alkane is greater than about 55 ° C. This has the advantage that the DIN EN 590 is met.

Als Ausgangssubstanz für den erfindungsgemäßen Dieselkraftstoff kann jeder Dieselkraftstoff verwendet werden. Bevorzugt ist der verwendete Dieselkraftstoff jedoch im Wesentlichen frei von aromatischen Bestandteilen, da solche Bestandteile in der Regel für eine verstärkte Rußbildung verantwortlich sind. Besonders bevorzugt werden als Dieselkraftstoffe hydriertes Pflanzenöl, insbesondere NexBTL, oder XTL-Dieselkraftstoffe verwendet. XTL, wie hier verwendet, soll Kraftstoffe umfassen, die über ein gas to liquids (GTL) coal to liquids (CTL) oder biomass to liquids (BTL) -Verfahren hergestellt wurden. Am meisten bevorzugt ist die Verwendung von GTL-Dieselkraftstoff.As starting material for the diesel fuel according to the invention, any diesel fuel can be used. However, the diesel fuel used is preferably substantially free of aromatic constituents, since such constituents are generally responsible for increased soot formation. Hydrogenated vegetable oil, in particular NexBTL, or XTL diesel fuels are particularly preferably used as diesel fuels. XTL as used herein is intended to encompass fuels that have been prepared by a gas to liquids (GTL) coal to liquids (CTL) or biomass to liquids (BTL) process. Most preferred is the use of GTL diesel fuel.

Der verwendete Dieselkraftstoff hat bevorzugt eine Dichte von etwa 0,7 bis etwa 0,8 g/ml, um die Dichte nicht zu stark unter den genormten Wert von 0,82 g/ml absinken zu lassen und damit auch der volumetrische Heizwert nur geringfügig absinkt.The diesel fuel used preferably has a density of about 0.7 to about 0.8 g / ml, in order not to allow the density to drop too much below the standardized value of 0.82 g / ml and thus also the volumetric calorific value drops only slightly ,

Die erfindungsgemäßen, d. h. Kraftstoffzusatz enthaltenden, Dieselkraftstoffe weisen bevorzugt eine Dichte von etwa 0,8 bis etwa 0,845 g/ml auf, um die Norm (EN 590) annähernd zu erfüllen.The diesel fuels, ie fuel additives, according to the invention preferably have a density of from about 0.8 to about 0.845 g / ml in order to approximately meet the standard (EN 590).

Der erfindungsgemäße Dieselkraftstoff ist bevorzugt im Wesentlichen frei von Komponenten mit einem Siedepunkt von über etwa 450°C, um die Dieselkraftstoffnormung bezüglich des Siedeverhaltens zu erfüllen.The diesel fuel of the present invention is preferably substantially free of components having a boiling point greater than about 450 ° C to meet diesel fuel standardization in boiling behavior.

Vorzugsweise enthält der erfindungsgemäße Dieselkraftstoff weniger als 5 Vol.% Komponenten mit einem Siedepunkt von über etwa 360°C (EN590).Preferably, the diesel fuel of the invention contains less than 5% by volume of components having a boiling point greater than about 360 ° C (EN590).

Der Anteil des Poly-oxa-alkans im erfindungsgemäßen Dieselkraftstoff beträgt bis 10 Vol.%, und besonders bevorzugt bis 5 Vol.%. Umso niedriger der Anteil des Zusatzstoffes ist, umso kostengünstiger ist der erfindungsgemäße Dieselkraftstoff. Zudem fällt die Heizwertabsenkung des erfindungsgemäßen Dieselkraftstoffs umso geringer aus.The proportion of poly-oxa-alkane in the diesel fuel according to the invention is up to 10% by volume, and more preferably up to 5% by volume. The lower the proportion of the additive, the more cost-effective is the diesel fuel according to the invention. In addition, the calorific value reduction of the diesel fuel according to the invention is even lower.

Der erfindungsgemäße Dieselkraftstoff enthält 5 bis 20 Vol.% Fettsäuremethylester (FAME). Dies hat den Vorteil, dass die biogenen Bestandteile des Dieselkraftstoffes erhöht werden, was im Übrigen in vielen Ländern gesetzlich vorgeschrieben ist. Darüber hinaus besitzt FAME die Eigenschaft, als Lösungsvermittler zu dienen. Dies hat den Vorteil, dass mehr Poly-oxa-alkan der allgemeinen Formel (I) in dem Dieselkraftstoff in Lösung gebracht werden kann. Vorzugsweise enthält der erfindungsgemäße Dieselkraftstoff 5 bis 10 Vol.% FAME. Dies hat den Vorteil, dass dadurch bis zu 10 Vol.% Poly-oxa-alkan, insbesondere Polyethylenglykoldimethylether der allgemeinen Formel CH3O(C2H4O)mCH3, wobei m = 4 bis m = 8, ist, in Lösung gebracht werden können.The diesel fuel according to the invention contains 5 to 20% by volume of fatty acid methyl ester (FAME). This has the advantage that the biogenic components of the diesel fuel are increased, which is otherwise required by law in many countries. In addition, FAME has the property of serving as a solubilizer. This has the advantage that more poly-oxa-alkane of the general formula (I) can be brought into solution in the diesel fuel. The diesel fuel according to the invention preferably contains 5 to 10% by volume of FAME. This has the advantage that up to 10 vol.% Poly-oxa-alkane, in particular polyethylene glycol dimethyl ether of the general formula CH 3 O (C 2 H 4 O) m CH 3 , where m = 4 to m = 8, in Solution can be brought.

Die vorliegende Erfindung betrifft auch die Verwendung eines Dieselkrafstoffes zur Verminderung der Rußbildung bei der Verbrennung von Dieselkraftstoffen.The present invention also relates to the use of a diesel fuel to reduce soot formation in the combustion of diesel fuels.

Bei der Verwendung kann insbesondere auch jeder der vorgenannten Dieselkraftstoffe verwendet werden. Der verwendete sondere auch jeder der vorgenannten Dieselkraftstoffe verwendet werden. Der verwendete Dieselkraftstoff ist jedoch bevorzugt ein Kraftstoff, der frei von aromatischen Bestandteilen ist, und besonders bevorzugt ein hydriertes Pflanzenöl, insbesondere NexBTL, oder ein XTL-Dieselkraftstoff.In use, in particular, any of the aforementioned diesel fuels can be used. The used special also each of the aforementioned diesel fuels are used. However, the diesel fuel used is preferably a fuel that is free of aromatic constituents, and more preferably a hydrogenated vegetable oil, especially NexBTL, or an XTL diesel fuel.

Außerdem offenbart wird ein Verfahren zur Homogenisierung von Dieselkraftstoff/AlkanolGemischen, das die Beimischung von Poly-oxa-alkanen der allgemeinen Formel (I) als Lösungsvermittler und Cetanzahlverbesserer umfasst, wobei die gleichen Einschränkungen für R1, R2 und R3, m und den Kraftstoffzusatz gelten sollen wie vorstehend für Dieselkraftstoffe beschrieben. Bei der Anwendung des Verfahrens kann auch jeder der vorgenannten Dieselkraftstoffe verwendet werden.Also disclosed is a process for homogenizing diesel fuel / alkanol mixtures which comprises admixing polyoxaalkanes of general formula (I) as solubilizers and cetane improvers, the same restrictions being imposed on R 1 , R 2 and R 3 , m and on Fuel additive should apply as described above for diesel fuels. In the application of the method, any of the aforementioned diesel fuels can be used.

"Homogenisierung", wie hier verwendet, beschreibt die Umwandlung eines mehrphasigen Gemischs in ein Gemisch mit nur einer Phase. Der dabei verwendete Alkohol ist bevorzugt ein primärer Alkohol, besonders bevorzugt ein primärer Alkohol mit 1 bis 6 Kohlenstoffatomen und am meisten bevorzugt Ethanol oder n-Butanol. Ethanol ist ein Alternativkraftstoff zu Mineralöl basierenden Kraftstoffen, der kostengünstig aus organischen Ausgangsstoffen durch Vergärung hergestellt werden kann. n-Butanol hat den Vorteil, dass es zukünftig nach einem biochemischen Verfahren aus Cellulose hergestellt werden kann und damit nicht in Konkurrenz zur Nahrungsmittelherstellung steht."Homogenization" as used herein describes the conversion of a multiphase mixture to a single phase mixture. The alcohol used herein is preferably a primary alcohol, more preferably a primary alcohol having 1 to 6 carbon atoms, and most preferably ethanol or n-butanol. Ethanol is an alternative fuel to mineral oil-based fuels that can be produced inexpensively from organic sources by fermentation. n-Butanol has the advantage that in the future it can be produced from cellulose by a biochemical process and thus does not compete with food production.

Dieselkraftstoff/Alkanol-Gemische sind im Hinblick auf die zunehmende Knappheit von auf Mineralöl basierenden Kraftstoffen interessant, weil insbesondere Ethanol durch Vergärung aus nachwachsenden Rohstoffen gewonnen werden kann. Solches Bio-Ethanol kann beispielsweise in Brasilien sehr kostengünstig erzeugt werden und durch Beimischung zu konventionellem Dieselkraftstoff die Gesamtkraftstoffmenge erhöhen.Diesel fuel / alkanol mixtures are of interest in view of the increasing scarcity of mineral oil-based fuels because, in particular, ethanol can be obtained by fermentation from renewable raw materials. Such bio-ethanol can be produced very cheaply, for example, in Brazil and increase the total amount of fuel by admixture with conventional diesel fuel.

Als Zwei-Komponenten-Gemisch können Dieselkraftstoff/Alkanol-Gemische aber in der Regel nicht als Kraftstoff verwendet werden, weil die beiden Komponenten nicht oder nur in geringen Anteilen miteinander mischbar sind. Dies gilt im besonderen Maße für die niedermolekularen Alkanole Methanol und Ethanol. Durch die Beimischung von Poly-oxa-alkanen der allgemeinen Formel (I) können jedoch Dieselkraftstoff/Alkanol-Gemische hergestellt werden, die bei der Verwendungstemperatur einphasig sind und die gleichzeitig die Beimischung großer Mengen Alkanol zum Dieselkraftstoff erlauben. In solchen drei Komponentengemischen von Dieselkraftstoff/Alkanol und Zusatzstoff, beträgt die Menge an beigefügtem Zusatzstoff bevorzugt mindestens etwa 4 %, besonders bevorzugt mindestens etwa 5 bis 11 %. Die Menge der Alkanol Komponente beträgt in der Regel etwa ≥ 10 %, bevorzugt etwa ≥ 20 % und am meisten bevorzugt etwa ≥ 30 %.As a two-component mixture, however, diesel fuel / alkanol mixtures can generally not be used as fuel because the two components are immiscible or only in small proportions. This is especially true for the low molecular weight alkanols methanol and ethanol. By admixing polyoxaalkanes of the general formula (I), however, diesel fuel / alkanol mixtures can be prepared which are single-phase at the temperature of use and which at the same time permit the admixture of large quantities of alkanol with the diesel fuel. In such three component blends of diesel fuel / alkanol and additive, the amount of adjuvant added is preferably at least about 4%, more preferably at least about 5 to 11%. The amount of alkanol component is usually about ≥ 10%, preferably about ≥ 20%, and most preferably about ≥ 30%.

Im Folgenden wird die Erfindung anhand von Beispielen weiter illustriert. Die Beispiele sollen jedoch in keiner Weise limitierend oder beschränkend für die vorliegende Erfindung sein.In the following, the invention will be further illustrated by way of examples. However, the examples are not intended to be limiting or limiting in any way for the present invention.

Beispiel 1example 1

Erzeugung einer stabilen Lösung von GTL-Dieselkraftstoff und Oxygenat.Generation of a stable solution of GTL diesel fuel and oxygenate.

Als GTL-Kraftstoff wurde GTL von Sasol/FM/Nr. 243 mit einer Dichte bei 20°C von 0,7656 g/cm2 verwendet. Der Sauerstoffgehalt in der Endmischung betrug 11 Gew.-%. Die Dichten der jeweiligen Gemische sind in Tabelle 1 angegeben. Tabelle 1 Dieselkraftstoff (%m/m) Glyme (%m/m) Sauerstoff (%m/m) Dichte bei 20°C (g/cm3) Diethylenglykolethylmethylether 66,46 33,54 11,0 0,8071 Diethylenglykoldiethylether 62,84 37,16 11,0 0,8083 Dipropylenglykoldimethylether 62,84 37,16 11,0 0,8078 Tetraethylenglykoldimethylether 69,44 30,56 Maximale Löslichkeit 6 % Polyglykol BB 300 55,47 44,53 11,0 0,8253 Diethylenglykoldibutylether 50,00 50,00 11,0 0,8176 Polyglykol DME 250 / DME 500 (1:4) 69,53 30,47 Maximale Löslichkeit 2 % As GTL fuel, GTL from Sasol / FM / No. 243 with a density at 20 ° C of 0.7656 g / cm 2 used. The oxygen content in the final mixture was 11% by weight. The densities of the respective mixtures are given in Table 1. Table 1 Diesel fuel (% m / m) Glyme (% m / m) Oxygen (% m / m) Density at 20 ° C (g / cm 3 ) Diethylenglykolethylmethylether 66.46 33.54 11.0 .8071 diethylene glycol diethyl ether 62.84 37.16 11.0 0.8083 dipropylene 62.84 37.16 11.0 .8078 tetraethylene 69.44 30.56 Maximum solubility 6% Polyglycol BB 300 55.47 44.53 11.0 .8253 diethylene glycol dibutyl ether 50,00 50,00 11.0 .8176 Polyglycol DME 250 / DME 500 (1: 4) 69.53 30.47 Maximum solubility 2%

Polyglykol BB 300 ist ein Polyethylenglykoldibutylether mit einem mittleren Molekulargewicht von etwa 300 (Hersteller Clariant Produkte GmbH, 84504 Burgkirchen).
Polyglykol DME 250 bzw. DME 500 sind Polyethylenglykoldimethylether mit einem mittleren Molekulargewicht von etwa 250 bzw. 500 (Hersteller Clariant Produkte GmbH, 84504 Burgkirchen).Polyglycol BB 300 is a polyethylene glycol dibutyl ether with an average molecular weight of about 300 (manufacturer Clariant Products GmbH, 84504 Burgkirchen).
Polyglycol DME 250 or DME 500 are polyethylene glycol dimethyl ether having an average molecular weight of about 250 or 500 (manufacturer Clariant products GmbH, 84504 Burgkirchen).

Aus Tabelle 1 ist ersichtlich, dass sich durch die Beimischung von Poly-oxa-alkanen zu GTL-Dieselkraftstoffen Dieselkraftstoffe herstellen lassen, die eine deutlich höhere Dichte aufweisen als reine GTL-Dieselkraftstoffe. Im Fall von Polyglykol BB 300 erfüllt das Dieselkraftstoff/Glyme-Gemisch auch die Dichtekriterien der EN 590 Norm. Es zeigt sich weiterhin, dass Tetraethylenglykoldimethylether sowie Polyglykol DME 250/DME 500-Gemische nicht zur Formulierung von Dieselkraftstoffen mit einem Sauerstoffgehalt von 11 % geeignet sind. Beide Zusatzstoffe weisen Sauerstoffgehalte von etwa 36 % auf, was dazu führt, dass die Mischbarkeit mit unpolarem GTL-Dieselkraftstoff herabgesetzt ist.From Table 1 it can be seen that can be produced by the addition of poly-oxa-alkanes to GTL diesel fuels diesel fuels, which have a significantly higher density than pure GTL diesel fuels. In the case of Polyglycol BB 300, the diesel fuel / glyme mixture also meets the density criteria of the EN 590 standard. It also shows that tetraethylene glycol dimethyl ether and polyglycol DME 250 / DME 500 mixtures are not suitable for the formulation of diesel fuels with an oxygen content of 11%. Both additives have oxygen contents of about 36%, which results in reduced miscibility with nonpolar GTL diesel fuel.

Beispiel 2Example 2

An einem MAN-Einzylinder-Forschungsmotor mit einem Hubvolumen von 1,75 I, einer Motorleistung von 55 kW, einem Common Rail Einspritzsystem (Raildruck 1800 bar), einer Verdichtung von 20,5, einem Einspritzbeginn vor dem oberen Todpunkt von - 8° Kurbelwinkel und einer AGR-Rate von 20 % wurde eine Kraftstoffmischung aus 95 Vol.% Dieselkraftstoff nach EN 590 und 5 Vol.% Tetraethylenglykoldimethylether getestet.On a MAN single-cylinder research engine with a displacement of 1.75 l, an engine output of 55 kW, a common rail injection system (rail pressure 1800 bar), a compression of 20.5, an injection start before the upper dead center of - 8 ° crank angle and an EGR rate of 20%, a fuel mixture of 95 vol.% Diesel fuel according to EN 590 and 5 vol.% Tetraethylene glycol dimethyl ether was tested.

Die Ergebnisse sind in nachstehender Tabelle 2 zu entnehmen. Als Vergleich diente reiner Dieselkraftstoff nach EN 590. Tabelle 2 Betriebspunkt BP 1 BP 2 BP 3 BP 4 Rußminderung (NOx-Emissionsniveau konstant) % -41,2 -53,1 -52,9 -27,4 Drehzahl U/min 914 1542 1542 1800 Drehmoment Nm 75 200 270 140 Mitteldruck bar 6,3 15,7 20,7 11,7 Luftzahl 3,1 1,35 1,35 1,9 The results are shown in Table 2 below. As a comparison served pure diesel fuel according to EN 590. Table 2 operating point BP 1 BP 2 BP 3 BP 4 Soot reduction (NOx emission level constant)% -41.2 -53.1 -52.9 -27.4 Speed rpm 914 1542 1542 1800 Torque Nm 75 200 270 140 Medium pressure bar 6.3 15.7 20.7 11.7 air ratio 3.1 1.35 1.35 1.9

Dieser Versuch zeigt, dass der Zusatz von Tetraethylenglykoldimethylether zu einer deutlichen Rußminderung führt, die umso höher ausfällt je niedriger der Luftüberschuss bei der Verbrennung ist (siehe Luftzahl in Tabelle 2).This experiment shows that the addition of tetraethylene glycol dimethyl ether leads to a significant reduction in soot, which is the higher the lower the excess air in the combustion (see air ratio in Table 2).

Beispiel 3Example 3

Es wurden mehrere Dieselkraftstoff/Ethanol-Mischungen mit Poly-oxa-alkanen als Lösungsvermittler hergestellt. Dazu wurden Diesel/Ethanol-Mischungen mit einem möglichst hohen Ethanolanteil von ≥ 30 Gew.-% hergestellt. Als Dieselkraftstoff wurden GTL von Sasol/FM-Nr. 243 mit einer Dichte bei 20°C von 0,7656 g/cm2 sowie Aral Ultimate mit einer Dichte bei 20° von 0,8236 g/cm2 und Ethanol mit einer Dichte bei 20° von 0,7893 g/cm2 verwendet. Die Dichten sowie die entsprechenden Sauerstoffgehalte der entsprechenden Mischungen sind in Tabelle 2 angegeben. Tabelle 3 Diesel (%m/m) Glyme (%m/m) Ethanol (%m/m) Sauerstoff (%m/m) Dichte bei 20°C (g/cm3 GTL-Diesel Diethylenglykoldibutylether 68,3 0,7 31,0 nicht mischbar 65,6 3,5 31,0 nicht mischbar 62,1 6,9 31,0 12,3 0,7776 Polyglykol BB 300 65,6 3,5 31,0 nicht mischbar 62,1 6,9 31,0 12,5 0,7797 Aral UltiMate Diesel Diethylenglykoldibutylether 65,5 3,5 31,0 nicht mischbar 62,1 6,9 31,0 12,3 0,8147 Polyglykol BB 300 65,6 3,5 31,0 nicht mischbar 62,1 6,9 31,0 12,5 0,8170 - 83,3 - 16,7 nicht mischbar Several diesel fuel / ethanol blends with poly-oxa-alkanes have been prepared as solubilizers. For this purpose, diesel / ethanol mixtures were prepared with the highest possible ethanol content of ≥ 30 wt .-%. As diesel fuel GTL were from Sasol / FM no. 243 with a density at 20 ° C of 0.7656 g / cm 2 and Aral Ultimate with a density at 20 ° of 0.8236 g / cm 2 and ethanol with a density at 20 ° of 0.7893 g / cm 2 used , The densities and the corresponding oxygen contents of the corresponding mixtures are given in Table 2. Table 3 Diesel (% m / m) Glyme (% m / m) Ethanol (% m / m) Oxygen (% m / m) Density at 20 ° C (g / cm 3 GTL diesel diethylene glycol dibutyl ether 68.3 0.7 31.0 immiscible 65.6 3.5 31.0 immiscible 62.1 6.9 31.0 12.3 .7776 Polyglycol BB 300 65.6 3.5 31.0 immiscible 62.1 6.9 31.0 12.5 .7797 Aral UltiMate Diesel diethylene glycol dibutyl ether 65.5 3.5 31.0 immiscible 62.1 6.9 31.0 12.3 .8147 Polyglycol BB 300 65.6 3.5 31.0 immiscible 62.1 6.9 31.0 12.5 .8170 - 83.3 - 16.7 immiscible

Aus Tabelle 3 wird ersichtlich, dass sich stabile Dieselkraftstoff/Ethanol-Mischungen bei Verwendung von relativ geringen Mengen an Poly-oxa-alkan herstellen lassen.From Table 3 it can be seen that stable diesel fuel / ethanol mixtures can be prepared using relatively small amounts of poly-oxa-alkane.

Claims (11)

  1. A diesel fuel containing a fuel additive, comprising at least one polyoxaalkane of the general formula (I):

            R1(-O-CH2-CHR2)mO-R3     (I),

    where R1 is a straight-chain or branched alkyl group, R2 is a straight-chain or branched alkyl group or H, R3 is a straight-chain or branched alkyl group, and wherein the fuel additive is free of toxic constituents, wherein "toxic" is understood as being toxic according to the German Dangerous Substances Act (GefstoffV 23.12.2004, BGBI. I p. 3758), and wherein the diesel fuel contains 5-20% by volume of fatty acid methyl esters (FAME), and wherein m ≥ 4, and wherein the diesel fuel contains up to 10% by volume of polyoxaalkane.
  2. A diesel fuel according to claim 1, wherein the diesel fuel contains up to 5% by volume of polyoxaalkane.
  3. A diesel fuel according to any one of the preceding claims, wherein m is 4 -16 and is more preferably 4 -12.
  4. A diesel fuel according to claim 3, wherein R2 is H.
  5. A diesel fuel according to any one of the preceding claims, wherein R1 and R3 are a methyl, ethyl and/or a butyl group.
  6. A diesel fuel according to any one of the preceding claims, wherein the diesel fuel is a hydrogenated vegetable oil, especially NexBTL, or an XTL diesel fuel.
  7. A diesel fuel according to any one of the preceding claims, wherein the polyoxaalkane is free of carbon atoms with an oxidation number of > +1.
  8. A diesel fuel according to any one of the preceding claims, wherein the at least one polyoxaalkane is a polyalkylene glycol dialkyl ether.
  9. A diesel fuel according to claim 8, wherein the polyalkylene glycol dialkyl ether is a polyethylene glycol dimethyl ether of the general formula CH3O(C2H4O)mCH3, where m=4 or a mixture of m=4 to m=12, preferably of m=4 to m=8.
  10. A diesel fuel according to claim 8, wherein the polyalkylene glycol dialkyl ether is selected from the group consisting of tetraethylene glycol ethyl methyl ether, tetraethylene glycol butyl methyl ether, and polypropylene glycol dimethyl ether having 4-5 propylene units.
  11. The use of a diesel fuel according to any one of the preceding claims for reducing the formation of soot during the combustion of diesel fuels.
EP09008881.6A 2008-07-09 2009-07-07 Low-soot diesel fuel containing a fuel additive, and its use in the reduction of soot in diesel fuel combustion Active EP2143778B1 (en)

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