DE112010002033B4 - Biohydrofuel compositions - Google Patents

Abstract

A bicontinuous monophasic microemulsion comprising at least one aqueous component (A) comprising 5 to 50% by weight of water and 2 to 20% by weight of ethanol, a hydrophobic component (B) comprising 45 to 90% by weight of the one or more usable as fuel, fuel or fuel, but at least one fuel based on mineral oil and / or at least one based on vegetable oils or their derivatives of power, heating or fuel and / or produced by Fischer-Tropsch synthesis force, heating or fuel, an ionic surfactant component (C) comprising a salt of 1 to 10% by weight of a C6-30 fatty acid and 0.2 to 1.0% by weight of a primary, secondary or tertiary amine base, a nonionic surfactant component ( D) comprising 2 to 15 wt .-% C6-30 fatty acid diethanolamide and / or C6-30 fatty acid diethanolamine and an additive / salt component (E) comprising 0 to 0.5 wt .-% ammonium nitrate, wherein the content of (C) is less than the of (D) and wherein the microemulsion has simultaneously a continuous aqueous phase and a continuous hydrophobic phase.

Description

The invention relates to bicontinuous single-phase microemulsions with a special surfactant composition which can be used as fuels and thereby allow combustion with unprecedented low emissions and efficiency. Furthermore, surfactant concentrates are provided for the preparation of such microemulsions.

Background of the invention

For the prudent and rational use of natural resources, reduction of dependence on oil, saving of transport-related CO ₂ emissions and compliance with the Kyoto Protocol, the European Union requires in Directive 2003/30 / EC of 8 May 2003 the use of Biofuels and other renewable fuels in the transport sector (Directive 2003/30 / EC of the European Parliament and of the Council on the promotion of the use of biofuels or other renewable fuels in the transport sector, Official Journal of the European Union, 8 May 2003, L 123/42). To implement these guidelines, the Biofuels Quota Act was passed by the Bundestag on 18 December 2006 (Bundestag, Biofuels Quota Act, Federal Law Gazette, 2006, Part I, No. 62), which sets out the minimum share of biofuel in the total quantity of gasoline and diesel fuel used in the Traffic is determined. From 2015, this quota will be 8.0 percent, based on energy content. However, the use of biofuel can solve the problem of pollutant emissions, such as B .: Soot and nitrogen oxides of diesel engines are not solved.

One way to simultaneously improve combustion efficiency and pollutant emissions is to use special fuels, especially fuels that consist of a mixture of an aqueous and a non-aqueous phase, such as water in oil (W / O) emulsions or in the Further described microemulsions. Such fuels allow an efficient combustion process despite relatively low combustion temperatures caused by the evaporation of the water due to the high enthalpy of vaporization.

In these particular fuels, the addition of water has a positive effect on the combustion. Lowering the combustion temperature reduces heat loss through the motor walls, which has a positive effect on the efficiency of the engine. When operating with microemulsions, a measurable increase in efficiency can be observed. The reduction of the temperature in the combustion chamber, allows a reduction of NO _x emissions. The addition of the water and an increase in the oxygen content in the fuel by the oxygen contained in the surfactants, alcohols and other oxygen-containing components lead to massive reduction of the soot. Depending on the operating condition of the engine and the amount of water in the fuel, the particulate matter (CO and HC and PM) emissions in the exhaust gases are reduced.

The use of emulsions of oil and water in various combustion processes has already been tested many times. The main disadvantage of such emulsions is their thermodynamic instability, moreover, their water content is not variable and only very small.

Formulations are known which are described as kinetically stabilized microemulsions. The use of thermodynamically stable microemulsions has also been described. These are not optimal microemulsions (W / O) from water-wet micelles present in the fuel. These are therefore microemulsions with exactly one continuous phase. Therefore, the water content in the previously known fuel microemulsions is rather small and often not more than 20%. Microemulsions with higher water contents often have high emulsifier contents. Furthermore, many formulations contain large amounts (up to 20%) of alcohols.

Looking more closely at the composition of the known water-fuel mixtures, they are often not water-fuel emulsions with alcohol but only alcohol-fuel emulsions with small amounts of water. Often, the high fugacity of ethanol causes the additional problem that ethanol, but also other more volatile substances are increasingly driven from the mixture into the gas phase. In addition, the technique for setting the water content of the mixture is arbitrary for combustion optimization.

US 4,744,796 describes water / fuel microemulsions with diesel, gasoline, fuel oil and kerosene as an oil component, which at high salt tolerance over a wide temperature range maximum of -10 ° C. to + 70 ° C stable single phase and clear. The proportion of the aqueous component of water and / or methanol is 3 to 40%. As cosurfactant, tert-butyl alcohol (TBA, 1-20%, with methanol up to 30%) is added to one or more cationic, anionic, amphoteric and nonionic surfactants (2-20%). As amphoteric surfactants betaines with different C-chain lengths (11-17) and as nonionic surfactants ethoxylated alcohols (C _i E _j ), alkylphenols and carboxylates are used. Quaternary ammonium salts are used as cationic and fatty acids as anionic surfactants. These water / fuel microemulsions are non-optimal, non-bicontinuous O / W microemulsions for this purpose. US 4,158,551 describes an emulsion of gasoline, water and nonionic surfactants to minimize polluting emissions during combustion. The mixture contains up to 22% water and is stabilized by 1-3.5% surfactants. The surfactants are essentially ethoxylated alkylphenols with 1.5-30 mol of ethylene oxide per mole of nonylphenol. However, such an emulsion is thermodynamically unstable. US 6,302,929 describes water-rich fuels which, unlike most other known emulsions, rely on biphasic water-continuous (O / W) emulsion systems. These fuels offer the advantage over pure hydrocarbons that they are not flammable outside the combustion chamber. In the mixtures described 20-80% of water can be emulsified. Furthermore, the emulsions contain 2-20% alcohols, small amounts (0.3-1%) of nonionic surfactants (C _i E _j , alkylglucosides, Igepal CO-630), and minor proportions polyorganosiloxanes. The fuel component is gasoline, kerosene, diesel, synthetic and biological fuels, which can be burned more effectively than the pure hydrocarbons. The high water content lowers the combustion temperature so much that the emission of pollutants is reduced (CO: -50%). However, the described preparation of the mixtures is difficult to carry out and the combustion composition is likely to vary considerably in use. In practice, the engines for two-phase mixtures must also be more strongly modified ("rotary engines") than for single-phase mixtures.

EP 0475620 describes temperature-insensitive diesel, gasoline and kerosene microemulsions and their low-emission combustion. In this case, the mixtures contain up to 30% water, which can be partially or completely replaced by methanol, ethanol or propanol. In addition to a variety of additives (for example, ammonium nitrites, nitrates, and halogenates, as well as halogen acids and organic compounds) for improving the combustion parameters, a comprehensive selection of emulsifier systems is described, which are used as combinations of at least two different surfactants. Thus, in addition to numerous ionic surfactants (C ₆ -C ₃₀ chains with and without branching / ring) with various head groups (including alkali metals, -SO ₃ H, -NH ₃ and alkylated, alkanoylated, ethoxylated or sulfonated ammonium) and a number of nonionic surfactants (for example C _i E _j , Igepale, ethoxylated alkylphenols). It is not distinguished by ionic and nonionic, but by hydrophilic and lipophilic surfactants (phase state 2 or 2 at T = 20 ° C, Φ = α = 0.5 and γ = 0.02). In addition, a wide range of cosurfactants (medium-chain alcohols, glycol ethers and ethers) is used. Described are single-phase, transparent microemulsions, wherein no statement about the structuring of the microemulsions is made. The described production process of single-phase microemulsions is sometimes very expensive connected with several heating and cooling processes. The listed mixtures with a low water / surfactant ratio are not sufficiently efficient for economical use.

US 5,669,938 describes single-phase W / O emulsions of diesel and 1-40% water and surfactant for reducing pollutants (CO, NO _x , HC, soot, PM). The central feature is the use of organic alkyl nitrates. The alkyl radicals used are linear hydrocarbons having a chain length of from 5 to 10 carbon atoms and branched hydrocarbons, in particular the 2-ethylhexyl radical.

US 4,451,265 describes single phase, clear fuel / water microemulsions which have high stabilities at low temperatures. In the unexplained microstructure, the existence of W / O micelles is suspected. The blends consist of diesel (34-99%), water (0.1-6%), alcohol (0.5-42%) and a surfactant system (0.5-58%). As alcohols, which make up the much larger portion of the aqueous phase (Ψ _Eth = 70-95%), are mainly used ethanol, but also methanol and propanol. The water content in the microemulsion is limited to a maximum of 6%. Also described are microemulsions with industrial surfactants which have a hydrophilic N, N-dimethylethanolamine head and a hydrophobic fatty acid radical having a carbon chain length of 9 to 22 atoms, in particular fatty acids of soybean.

US 4,451,267 describes microemulsion fuels from vegetable oils. As vegetable oils are mainly soybean oil, but also many other oils, such as rapeseed oil used. The aqueous component of the low-water microemulsions consists largely of methanol, ethanol or propanol (Ψ _Eth = 70-95%). As surfactants are used with long-chain fatty acids trialkylated amines, which are characterized by large Amounts of butanol as cosurfactant (about 20%). Again, W / O micelles are assumed as microstructuring.

US 4,002,435 describes W / O emulsions with gasoline, which are stable in a single phase over a wide temperature range and based on large amounts of alcohol (0.1-20%). The alcohols used are methanol, ethanol and isopropanol. The emulsions contain only a small amount of water (0.1-10%) and a mixture of organic oleate, linolate and stearate salts, oleic acid and phenolated and ethoxylated fatty alcohols.

US 4,599,088 describes gasoline emulsion fuels with 2-10% alcohol, such as methanol, ethanol, isopropanol or TBA. However, the formulations contain only 0.1-0.5% water. The blends contain 0.1-3.0% surfactants, excluding nonionic alkylphenols and C _i E _j surfactants, where i = 9-24 and j = 6-10. The mixtures are referred to as single-phase microemulsions of the W / O type (micelles). In them, however, only a little water can be solved. Larger additions of water lead to a water excess phase in the fuel tank.

US 5,104,418 describes microemulsion systems of water, diesel, glycolipid (surfactant) and aliphatic alcohols (cosurfactant). The microemulsions are stably monophasic between 0 ° C and 80 ° C. The specification includes glycolipids of the form AXR, wherein the hydrophilic surfactant heads A may be glucose, mono-, di-, tri- and tetra-saccharides. Hydrophobic radicals R are called saturated, mono- and polyunsaturated, linear and branched hydrocarbon chains having a carbon chain length of 10 to 24 atoms, which are bonded to the surfactant head via the functional groups X = ether, ester, acetal and hemiacetal. The microemulsions are defined as thermodynamically stable colloidal dispersion. Again, with large diesel shares (60-90%), the water content is 1-10% small. The cosurfactant content (butanol, pentanol, hexanol) is very high at 6.3-21%, the glycolipid content is 1.7-9%. US 5,259,851 describes similar water-fuel glycolipid cosurfactant microemulsions with the same glycolipids and similar mixing ratios. Here, however, other cosurfactants, namely aliphatic diols, and used in addition to diesel gasoline, fuel oil, kerosene and other oils.

US 4,465,494 and EP 0058605 describe microemulsions of water, fuel (also fuel oil), surfactant and additive (special alcohols and amines), which are stable single phase between -20 ° C and + 100 ° C (sometimes only between -10 ° C and + 20 ° C). These mixtures contain, besides 1-27% alcohol (methanol, ethanol, isobutanol and ethyl-2-hexanol) only 1-10% water. Benzylamines and phenoxyalkylated organic acid salts (counterion: metal ion or organic base) of different C chain lengths are used as surfactants. The microemulsions are efficient with a surfactant content of 1-10%. If, however, relative to the alcohol, small amounts of water are considered, these microemulsions must be classified as alcohol-fuel microemulsions with small amounts of water. In addition to a process for the preparation of the microemulsions further described is the reduction of emissions during their combustion. The CO emissions are reduced by 80% and NO _x by 75% in relation to 100 driven kilometers compared to conventional fuels.

US 6,017,368 describes microemulsions containing water, fuel, anionic and nonionic surfactants, unsaturated fatty acids, aliphatic alcohols and ethanol or methanol. These are water-in-oil micelles with a low water content of 1 to 10%. These microemulsions are stable over a wide temperature range, have a low viscosity and reduce pollutant emissions during combustion. As fuels are used in addition to diesel, gasoline and fuel oil. The proportion of water-soluble alcohols is 6 to 14% greater than the water content. The water-insoluble alcohols (1 to 10%) have a carbon chain length of 5 to 9 atoms. The anionic surfactants used (2 to 10%) are based on ammonium-neutralized unsaturated fatty acids, for example from soybean oil. As nonionic surfactants (1 to 5%), only non-ethoxylated compounds are used because ethoxylated compounds in the opinion of US 6,017,368 have poor combustion properties. Mentioned as nonionic surfactant is only 2,4,7,9-tetramethyl-5-decyne-4,7-diol.

EP 1101815 describes diesel-water microemulsions containing an emulsifier and an emulsifiable agent, in particular sorbitan monooleate and nonylphenol ethoxylate. However, the water content is limited to a small concentration range (100-145 parts water based on 1000 parts diesel).

WO 00/31216 and EP 1137743 describe a diesel fuel composition consisting of diesel fuel, (hydrous) ethanol, a polymeric stabilizing additive, and optionally an alkyl ester of a fatty acid and / or a co-solvent such as, for example; B. eleven short chain alkyl alcohol. Indeed the water content of the ethanol used is at most 5 wt .-% based on the amount of ethanol in the mixture.

DE 10003105 . WO 01/55282 and EP 1252272 describe fuel-water emulsions in which an alkoxylated polyisobutene is used as the emulsifier. The emulsion preferably contains 10-25% by weight of water and 0.2-10% by weight of emulsifier. WO 03/064565 and WO 03/065479 disclose unstable two-phase mixtures of two microemulsions, namely a mixture of a water-in-oil microemulsion with an oil-in-water microemulsion.

From the WO 2005/012466 a bicontinuous monophasic microemulsion is known, comprising at least one aqueous component consisting of water and alcohol-water mixtures, a hydrophobic component containing one or more usable as Kraft, Treibstoff or fuel materials and an amphiphilic component containing at least one nonionic surfactant as an essential component and optionally further surfactant components including ionic surfactants, the microemulsion having simultaneously a continuous aqueous phase and a continuous hydrophobic phase. The microemulsion described here can be used as fuel in internal combustion engines, preferably in reciprocating engines, rotary engines and turbine engines.

Finally, from the WO 2008/083724 Dispersions are known for improving the cold flow properties of paraffinic mineral oils containing a soluble polymer as a cold flow improver, an alkanolamine salt of a polycyclic carboxylic acid, water and an organic, water immiscible solvent.

The known microemulsions are still in need of improvement in terms of stability, water content, efficiency and pollutant development during combustion.

Brief description of the invention

It has now been found that microemulsions with ionic surfactants as an essential constituent of the emulsifier component are particularly suitable biofuels. The invention offers the possibility not only to minimize CO ₂ emissions by adding biogenic substances, but also to significantly reduce pollutant emissions, but above all the emissions of NO _x , CO, incompletely burned hydrocarbons (HC) and soot particles compared to conventional fuels , The essence of the invention is the efficient solubilization of water in conventional fuels, such as diesel, biodiesel, BTL, GTL using low concentrations of novel emulsifier mixtures of residue-free burning surfactants, cosurfactants and other additives. It is taken into account that the surfactants, cosurfactants and additives are produced on the basis of biogenic substances. The novel fuels are microemulsions formulated on the basis of fossil fuels such as diesel and first generation biofuels such as biodiesel and second generation biofuels such as BTL. In contrast to existing emulsions, our mixtures are characterized by their thermodynamic stability and their single phase, which is present over wide temperature ranges, but at least between -10 ° C and + 90 ° C. According to the invention, the combustion of the optimized nano-fuels shows a clear reduction of pollutant emissions. Thus, the main object of the invention is also compared to conventional fuels more efficient combustion of nano-fuels, which provides a significant reduction in the consumption of oil worldwide in prospect and thus allows a meaningful implementation of the legislation.

• (1) eine Bikontinuierliche einphasige Mikroemulsion, bestehend mindestens aus einer wässrigen Komponente (A) umfassend 5 bis 50 Gew.-% Wasser und 2 bis 20 Gew.-% Ethanol, einer hydrophoben Komponente (B) umfassend 45 bis 90 Gew.-% die einen oder mehrere als Kraft-, Treib- oder Brennstoff einsetzbare Stoffe, jedoch mindestens einen Kraftstoff auf Mineralölbasis und/oder mindestens einen auf pflanzlichen Ölen oder deren Derivaten basierenden Kraft-, Heiz- oder Brennstoff und/oder durch Fischer-Tropsch Synthese hergestellten Kraft-, Heiz- oder Brennstoff enthält, einer ionischen Tensidkomponente (C) umfassend ein Salz aus 1 bis 10 Gew.-% einer C_6-30 Fettsäure und 0,2 bis 1,0 Gew.-% einer primären, sekundären oder tertiären Aminbase, einer nichtionischen Tensidkomponente (D) umfassend 2 bis 15 Gew.-% C_6-30 Fettsäurediethanolamid und/oder C_6-30 Fettsäurediethanolamin und einer Additiv/Salzkomponente (E) umfassend 0 bis 0,5 Gew.-% Ammoniumnitrat, wobei der Gehalt an (C) kleiner als der von (D) ist und wobei die Mikroemulsion gleichzeitig eine kontinuierliche wässrige Phase und eine kontinuierliche hydrophobe Phase aufweist;
• (2) eine spezielle bikontinuierliche einphasige Mikroemulsion, bestehend mindestens aus einer wässrigen Komponente (A) umfassend 5 bis 50 Gew.-% Wasser und 2 bis 20 Gew.-% Ethanol, einer hydrophoben Komponente (B) umfassend 50 bis 90 Gew.-% Diesel, einer ionischen Tensidkomponente (C) umfassend ein Salz aus 1 bis 10 Gew.-% Ölsäure und 0,2 bis 1,0 Gew.-% Ethanolamin, einer nichtionischen Tensidkomponente (D) umfassend 2 bis 15 Gew.-% Ölsäurediethanolamid und einer Additiv/Salzkomponente (E) umfassend 0,01 bis 0,5 Gew.-% Ammoniumnitrat, wobei der Gehalt an (C) kleiner als der von (D) ist und wobei die Mikroemulsion gleichzeitig eine kontinuierliche wässrige Phase und eine kontinuierliche hydrophobe Phase aufweist;
• (3) die Verwendung der in (1) oder (2) definierten Mikroemulsionen (i) als Kraftstoff in Verbrennungskraftmaschinen, bevorzugt in Hubkolbenmotoren, Drehkolbenmotoren und Turbinenmotoren; und/oder (ii) als Kraftstoff in Schubtriebwerken, bevorzugt in Strahltriebwerken, Turbinenstrahltriebwerken und Raketentriebwerken; und/oder (iii) als Brennstoff in Feuerungsanlagen, bevorzugt in Heizungsanlagen und Dampferzeugungsanlagen; und/oder (iv) in Zündverfahren; und/oder (v) in Sprengstoffen; und
• (4) ein Verfahren zur Herstellung der in (1) oder (2) definierten Mikroemulsionen umfassend das Vermischen eines Emulgatorkonzentrats, umfassend die ionischen Tensidkomponente (C), und eine nichtionischen Tensidkomponente (D), wie in (1) oder (2) definiert, mit entsprechenden Mengen der wässrigen Komponente (A) und der hydrophoben Komponente (B).

Stable microemulsion systems based on the following fuels - conventional diesel, biodiesel and BTL fuel (Biopar) - were formulated in a wide temperature range from 0 ° C to 95 ° C single phase microemulsion systems. The proportion of water can be varied from 5 to 50 percent, the addition of higher proportions of water requires a higher proportion of emulsifier mixture for the formation of a stable in a wide temperature range single-phase microemulsion. The percentages given below refer to the total microemulsion unless otherwise indicated. The invention thus relates

• (1) a bicontinuous monophasic microemulsion consisting of at least one aqueous component (A) comprising 5 to 50% by weight of water and 2 to 20% by weight of ethanol, a hydrophobic component (B) comprising 45 to 90% by weight the one or more usable as Kraft, fuel or fuel materials, but at least one fuel based on mineral oil and / or at least one based on vegetable oils or their derivatives of power, heating or fuel and / or produced by Fischer-Tropsch synthesis force -, heating or fuel, an ionic surfactant component (C) comprising a salt of 1 to 10 wt .-% of a C _6-30 fatty acid and 0.2 to 1.0 wt .-% of a primary, secondary or tertiary amine base . a nonionic surfactant component (D) comprising from 2 to 15% by weight C _6-30 fatty acid diethanolamide and / or C _6-30 fatty acid diethanolamine and an additive / salt component (E) comprising 0 to 0.5% by weight ammonium nitrate, the content at (C) is less than that of (D), and wherein the microemulsion has simultaneously a continuous aqueous phase and a continuous hydrophobic phase;
• (2) A special bicontinuous monophasic microemulsion consisting of at least one aqueous component (A) comprising 5 to 50% by weight of water and 2 to 20% by weight of ethanol, a hydrophobic component (B) comprising 50 to 90% by weight. % Diesel, an ionic surfactant component (C) comprising a salt of 1 to 10% by weight of oleic acid and 0.2 to 1.0% by weight of ethanolamine, a nonionic surfactant component (D) comprising 2 to 15% by weight of oleic diethanolamide and an additive / salt component (E) comprising 0.01 to 0.5% by weight of ammonium nitrate, wherein the content of (C) is less than that of (D), and wherein the microemulsion is simultaneously a continuous aqueous phase and a continuous hydrophobic Phase has;
• (3) the use of the microemulsions (i) defined in (1) or (2) as fuel in internal combustion engines, preferably in reciprocating engines, rotary engines and turbine engines; and / or (ii) as fuel in thrusters, preferably in jet engines, turbine jet engines and rocket engines; and / or (iii) as fuel in combustion plants, preferably in heating systems and steam generation plants; and / or (iv) in ignition processes; and / or (v) in explosives; and
• (4) a process for producing the microemulsions defined in (1) or (2) comprising mixing an emulsifier concentrate comprising the ionic surfactant component (C) and a nonionic surfactant component (D) as defined in (1) or (2) , with appropriate amounts of the aqueous component (A) and the hydrophobic component (B).

Brief description of the figures

1 shows the T-γ cut in the pseudoternary system 1 "water / ethanol-diesel-ethanolaminoleate / oleic acid / oleylamine polyglycol ether (degree of ethoxylation about 2 mol)".

2 shows the T-γ cut in the pseudoternary system 2 "water / ethanol-RME-ethanolamine oleate / oleic acid / Oleylaminpolyglykolether (degree of ethoxylation about 2 mol)".

3 shows the T-γ cut in pseudo-ternary system 3 "water / ethanol-BTL (BioPar) ethanolamine oleate / oleic acid / oleylamine polyglycol ether (degree of ethoxylation about 2 moles)".

4 shows the T-γ cut in the pseudoternary system 4 "water / ethanol-diesel-ammonium oleate / oleic acid / sorbitan monooleate".

5 shows the T-γ cut in the pseudoternary system 5 "water / ethanol-diesel-ammonium oleate / oleic acid".

6 shows the T-γ cut in the pseudoternary system 6 "water / ethanol-biodiesel-ammonium oleate / oleic acid".

7A and B show T-γ sections in the pseudoternary system 7 "water / NH ₄ NO ₃ / ethanol-biodiesel-ammonium oleate / oleic acid / Wallamid OD / E".

8th : The influence of the water content in the microemulsified fuel (Diesel (Reference) → ME 5.4% by weight H ₂ O → ME 10.8% by weight H ₂ O → ME 15.8% by weight H ₂ O) on the carbon black (left , measured as FSN) and NO _x - (right, specific emission, moisture corrected) emissions at the variation of the EGR rate. 1 cylinder diesel engine, Actros series, OM 450, speed 1175 min ^-1 , p _e = 0.8 MPa, p _inj. = 120 MPa, pilot and main injection.

9 : The influence of the water content in the microemulsified fuel (diesel (reference) → ME 5.4% by weight H ₂ O → ME 10.8% by weight H ₂ O → ME 15.8% by weight H ₂ O) on the HC (left ) and CO- (right, specific emission) emissions at the variation of the EGR rate. 1 cylinder diesel engine, Actros series, OM 450, speed 1175 min ^-1 , p _e = 0.8 MPa, p _inj. = 120 MPa, pilot and main injection.

10 : The influence of the water content in the microemulsified fuel (Diesel (Reference) → ME 5.4% by weight H ₂ O → ME 10.8% by weight H ₂ O → ME 15.8% by weight H ₂ O) on the CO ₂ emission in the variation of the EGR rate. 1 cylinder diesel engine, Actros series, OM 450, speed 1175 min ^-1 , p _e = 0.8 MPa, p _inj. = 120 MPa, pilot and main injection.

11 : The influence of the water content in the microemulsified fuel (Diesel (Reference) → ME 5.4% by weight H ₂ O → ME 10.8% by weight H ₂ O → ME 15.8% by weight H ₂ O) on the carbon black (left , measured as FSN) and NO _x - (right, specific emission, moisture corrected) Emissions due to variation of injection pressure. 1-cylinder diesel engine, Actros series, OM 450, rotation speed 1175 min ^-1, p _s = 0.8 MPa, the pilot and main injection.

12 : The influence of the water content in the microemulsified fuel (diesel (reference) → ME 5.4% by weight H ₂ O → ME 10.8% by weight H ₂ O → ME 15.8% by weight H ₂ O) on the HC (top left), CO (top right, specific emission) and CO ₂ - (bottom) emissions with variation of injection pressure. 1-cylinder diesel engine, Actros series, OM 450, rotation speed 1175 min ^-1, p _s = 0.8 MPa, the pilot and main injection.

13 : The influence of the water content in the microemulsified fuel (Diesel (Reference) → ME 5.4% by weight H ₂ O → ME 10.8% by weight H ₂ O → ME 15.8% by weight H ₂ O) on the carbon black (left , measured as FSN) and NO _x - (right, specific emission, moisture corrected) Emissions due to variation of injection pressure. 1 cylinder diesel engine, Actros series, OM 450, speed 1175 min ^-1 , p _e = 1.2 MPa, main injection.

14 : The influence of the water content in the microemulsified fuel (diesel (reference) → ME 5.4% by weight H ₂ O → ME 10.8% by weight H ₂ O → ME 15.8% by weight H ₂ O) on the HC (left ) and CO (right, specific emission) emissions at the variation of the injection pressure. 1 cylinder diesel engine, Actros series, OM 450, speed 1175 min ^-1 , p _e = 1.2 MPa, main injection.

15 : The influence of the water content in the microemulsified fuel (Diesel (Reference) → ME 5.4% by weight H ₂ O → ME 10.8% by weight H ₂ O → ME 15.8% by weight H ₂ O) on the CO ₂ emissions in the variation of the injection pressure. 1 cylinder diesel engine, Actros series, OM 450, speed 1175 min ^-1 , p _e = 0.8 MPa, main injection.

16 : The influence of the water content in the microemulsified fuel (Diesel (Reference) → ME 5.4% by weight H ₂ O → ME 10.8% by weight H ₂ O → ME 15.8% by weight H ₂ O) on the carbon black (left , measured as FSN) and NO _x - (right, specific emission, moisture-corrected) Emissions at the variation of injection start. 1-cylinder diesel engine, Actros series, OM 450, rotation speed 1175 min ^-1, p _s = 0.8 MPa, the pilot and main injection.

17 : The influence of the water content in the microemulsified fuel (diesel (reference) → ME 5.4% by weight H ₂ O → ME 10.8% by weight H ₂ O → ME 15.8% by weight H ₂ O) on the HC (left ) and CO (right, specific emission) emissions at the start of injection variation. 1 cylinder diesel engine, Actros series, OM 450, speed 1175 min ^-1 , p _e = 0.8 MPa, p _inj. = 120 MPa, pilot and main injection.

18 : The influence of the water content in the microemulsified fuel (Diesel (Reference) → ME 5.4% by weight H ₂ O → ME 10.8% by weight H ₂ O → ME 15.8% by weight H ₂ O) on the CO ₂ emission in the variation of the start of injection. 1 cylinder diesel engine, Actros series, OM 450, speed 1175 min ^-1 , p _e = 0.8 MPa, p _inj. = 120 MPa, pilot and main injection.

19 : Full load characteristic of diesel engine PSA4HX and operating points.

20 : Relative comparison of soot emissions (measured as FSN) in% to diesel operation (0-line) with fuels: diesel-surfactant mixture, microemulsions with 13/20 wt% water with and without diesel oxidation catalyst (DOC) in Dependence of the operating point.

21 : Relative comparison of soot emissions (gravimetric measurements) in% to diesel operation (0-line) with fuels: diesel-surfactant mixture, microemulsions with 13/20 wt .-% water with and without diesel oxidation catalyst (DOC) depending of the operating point.

22 : Particle analysis following the gravimetric measurement.

23 : Relative comparison of percentage of SOF (soluble organic fraction) emissions to diesel (0-line) with fuels: diesel-surfactant mixture, microemulsions with 13/20 wt% water with and without diesel oxidation catalyst (DOC ) depending on the operating point.

24 : Relative comparison of the proportion of ISF (insoluble fraction) emissions to diesel operation (0-line) with fuels: diesel-surfactant mixture, microemulsions with 13/20 wt% water with and without diesel oxidation catalyst (DOC) in Dependence of the operating point.

25 : Relative comparison of percentage of soluble inorganic fraction (SIOF) emissions to diesel (0-line) with fuels: diesel-surfactant mixture, microemulsions with 13/20 wt% water with and without diesel oxidation catalyst (DOC ) depending on the operating point.

26 : Relative comparison of HC emissions in% to diesel operation (0-line) with fuels: diesel-surfactant mixture, microemulsions with 13/20 wt .-% water with and without diesel oxidation catalyst (DOC) as a function of the operating point.

27 : Relative comparison of% CO emissions to diesel (0-line) with fuels: diesel-surfactant mixture, microemulsions with 13/20 wt% water with and without diesel oxidation catalyst (DOC) as a function of operating point ,

28 : Relative comparison of the percentage of NO _x emissions with diesel (0-line) with fuels: diesel-surfactant mixture, microemulsions with 13/20 wt% water with and without diesel oxidation catalyst (DOC) depending on operating point.

29 : Absolute comparison of soot emissions (measured as FSN) with fuels: diesel, diesel-surfactant mixture, microemulsions with 13/20 wt% water with and without diesel oxidation catalyst (DOC) as a function of operating point.

30 : Absolute comparison of soot emissions (gravimetric measurements) with fuels: diesel, diesel-surfactant mixture, microemulsions with 13/20 wt% water with and without diesel oxidation catalyst (DOC) as a function of the operating point.

31 : Absolute comparison of the fraction of SOF (soluble organic fraction) emissions with fuels: diesel, diesel-surfactant mixture, microemulsions with 13/20 wt .-% water with and without diesel oxidation catalyst (DOC) as a function of the operating point.

32 : Absolute comparison of the fraction of ISF (insoluble fraction) emissions with fuels: diesel, diesel-surfactant mixture, microemulsions with 13/20 wt% water with and without diesel oxidation catalyst (DOC) as a function of the operating point.

33 : Absolute comparison of the proportion of SIOF (soluble inorganic fraction) emissions with fuels: diesel, diesel-surfactant mixture, microemulsions with 13/20 wt% water with and without diesel oxidation catalyst (DOC) as a function of operating point.

34 : Absolute comparison of HC emissions with fuels: diesel, diesel-surfactant mixture, microemulsions with 13/20 wt% water with and without diesel oxidation catalyst (DOC) depending on the operating point.

35 : Absolute comparison of CO emissions with fuels: diesel, diesel-surfactant mixture, microemulsions with 13/20 wt .-% water with and without diesel oxidation catalyst (DOC) as a function of the operating point.

36 : Absolute comparison of NO _x emissions with fuels: diesel, diesel-surfactant mixture, microemulsions with 13/20 wt .-% water with and without diesel oxidation catalyst (DOC) as a function of the operating point.

Detailed description of the invention

The microemulsions of the present invention defined in (1) and (2) above can be used as a final formulation in internal combustion engines and turbines.

In addition, starting from the microemulsion formulation, the above defined concentrates (4) of the invention can be derived. The particular concentrate consists mainly of emulsifiers, wherein emulsifier mixture consists of a mixture of ionic and nonionic surfactants. Other ingredients of the microemulsion may be added to the emulsifier mixture of the concentrate, including fuel, alcohol, water, additives and salts. The addition of fuel and / or alcohols improves the flowability of the concentrate.

The concentrate and alcohol can be completely mixed with the respective fuel. With a lower water concentration (up to 10 percent) or without added water, such a mixture can absorb external water and eliminate the problem of residual water in the tank.

In calculated doses (see below), the concentrate in combination with fuel and water has a microemulsion-forming effect. One of the possible uses of the derived concentrates is the preparation of the microemulsion and / or at lower than for the preparation of the microemulsion concentrations of the emulsion. The addition of low concentrations of the emulsifier mixture to the water-diesel mixture greatly reduces the interfacial tension between the polar and nonpolar phases (Kahlweit, M. et al., Langmuir, 4: 785 (1988)), which leads to the production of a very high can lead to finely structured emulsion.

The use of the concentrate in conjunction with an on-board mixing and / or emulsifying system enables the preparation of a microemulsion and at lower concentrations of the concentrate of an emulsion. In both cases, an efficient and pollution reducing combustible mixture with variable proportions of water may be prepared on-board before the injection system and / or directly in the injection system, in front of the injection nozzle and / or in the injection nozzle. Regardless of the place of manufacture or method, the ability of the emulsifier mixture to exploit the interfacial tension is utilized. Associated with this is a minimal input of energy (for example: shearing forces, ultrasound, cavitation) for the production of a fine emulsion and / or microemulsion.

The use of microemulsion fuels herein in existing diesel engines, without changes in engine parameters or interventions in the exhaust aftertreatment system, drastically reduces pollutant emissions such as soot, oxides of carbon, carbon monoxide, and unburned hydrocarbons and reduces specific fuel consumption.

A further improvement, in terms of pollutant emissions and specific consumption, can be achieved by targeted adjustment of the internal engine parameters, such. B .: final injection time, pressure, duration, optimization of the geometry of the combustion chamber and the design of the injectors, change the exhaust gas recirculation rate, optimization of the settings of the turbocharger, etc., are achieved to the new microemulsion fuels. In addition, water content in the fuel can be adapted to the respective operating point of the engine. The amount of water can be varied as desired in the microemulsion fuel. Since the formation of the microemulsion occurs spontaneously, the fuel component and water component can be combined in the shortest distance, without the action of shear forces, and form a thermodynamically stable single-phase mixture. The surfactant component may be added to the fuel or water, or dosed from a third supply line.

definitions

wobei der Kraftstoff als Öl bezeichnet wird und m_i die Masse eines Stoffes bezeichnet.

dies ist der Neutralisationsgrad. Er ist für die Teilchenzahl n definiert und richtet sich nach dem stöchiometrischen Verhältnis, der aus der jeweiligen Neutralisationsreaktion abgeleitet werden kann.

Generelles System: Wasser/Alkohol/Salz-Kraftstoff-Tensidmischung (ionisches, nichtionisches, amphoteres).

wherein the fuel is referred to as oil and m _i denotes the mass of a substance.

this is the degree of neutralization. It is defined for the particle number n and depends on the stoichiometric ratio which can be derived from the respective neutralization reaction.

General system: water / alcohol / salt-fuel-surfactant mixture (ionic, nonionic, amphoteric).

Surfactants, additives, salts: if available, surfactants and additives based on renewable raw materials should be used. This implies a broad distribution of the carbon chain length and the number of double bonds in the hydrophobic carbon chain, especially for surfactants that are produced from vegetable and animal fats and oils, including hydroxy groups on the carbon chain (eg: ricinoleic acid residue). As combustion-improving additives, organic and inorganic nitrates and / or organic and inorganic peroxides can be used. These may be present both as a solution and as a salt and be soluble in the oil or water component.

Alcohol: Alcohols of short-chain and / or long-chain, branched and / or unbranched alkanes, more specifically alcohols with a C number of 1 to 20, especially ethanol. Polyhydric alcohols, such as ethylene glycol, glycerol and polyalcohols. There are also mixtures of these alcohols possible.

Fuel: All fossil fuels and first generation biofuels such as biodiesel and second generation biofuels such as BTL (Biomass to Liquid), GTL (Gas to Liquid), and their mixtures are possible and meant.

Ionic surfactant: residue-free combustible ionic surfactants consisting of the atomic species C, H, O, N, more precisely salts of long-chain branched and / or unbranched organic acids (C ₆ -C ₃₀ ) or the acids or salts of long-chain branched and unbranched alkylamines (C ₆ -C ₃₀ ) and the amines, especially ammonium or amine salts of fatty acids and the pure fatty acids or nitrates or acetates of alkylamines (C ₆ -C ₃₀ branched and unbranched) and the amines. There are also mixtures used.

In particular, the ionic surfactant of fatty acids can be prepared in situ by neutralization of the respective organic acid with ammonia (gas or aqueous solution) or an amine base. Primary, secondary and tertiary amine bases can be used. The substitution groups on the nitrogen atom can be derived from the pure short-chain alkanes (C ₁ -C ₄ ) (for example: mono-, di-, trimethylamine), and from short-chain alcohols (C ₁ -C ₄ ) (for example: Mono-, di-, trimethanolamine) are derived. Symmetrically and asymmetrically substituted amines are conceivable. In addition, bicyclic amine bases such. B. DABCO, or 1,4-diazabicyclo [2.2.2] octane can be used, which can lead to the formation of surfactants with two alkyl chains in the reaction with organic acids due to the divalent nature.

By changing the degree of neutralization, the surfactant properties can be tailored to the particular fuel and the nonionic or amphoteric cosurfactant. In particular, the change in the degree of neutralization greatly influences the temperature position of the phase boundaries of the single-phase region in the vertical T-γ section through the pseudoternary phase prism. In the case of incomplete neutralization, the greatest possible widening of the single-phase region and thus the temperature invariance of the resulting microemulsion system which is advantageous for the application are achieved.

• 1) Fettsäureaminpolyglykolether: primäre, sekundäre und tertiäre unsymmetrisch substituierte Amine mit einer langen hydrophoben gesättigten oder teilweise ungesättigten C-Kette (C₆-C₃₀) und 2–10 Ethylenoxid- und oder Propylenoxideinheiten. Allgemeinen Strukturformel R-N R'R'', wobei R eine lange hydrophobe gesättigte oder teilweise ungesättigte C-Kette (C₆-C₃₀) darstellt und R' = R'' = H bei primären Aminen; R' ≠ H, R'' = H bei sekundären Aminen und R' ≠ H, R'' ≠ H bei teriären Aminen ist. R' und/oder R'' können von kurzkettigen Alkoholen mit der (C₁-C₄) und/oder bis zu 10 Ethylenoxid- und/oder Propylenoxideinheiten abgeleitet werden. Es sind auch Mischungen aus nichtionischen stickstoffhaltigen Tensiden einsetzbar.
• 2) Fettsäureamide: Fettsäureamide und mit der allgemeinen Strukturformel (R-C=O)-N R'R'', wobei R eine lange hydrophobe gesättigte oder teilweise ungesättigte C-Kette (C₆-C₃₀) darstellt und R' = R'' = H bei primären Carbonsäureamiden; R' ≠ H, R'' = H bei sekundären Carbonsäureamiden und R' ≠ H, R'' ≠ H bei teriären Carbonsäureamiden ist. R' und/oder R'' können von den reinen kurzkettigen Alkanen (C₁-C₄), und von kurzkettigen Alkoholen (C₁-C₄) und 1–10 Ethylenoxid- und/oder Propylenoxideinheiten abgeleitet werden.
• 3) Sorbitanfettsäureester mit 0–10 Ethylenoxid- und oder Propylenoxideinheiten.
• 4) Ethoxylate (E) und/oder Propoxylate (P) von Alkoholen (C_i(E/P)_j) mit i = 6–30 und j = 0–10, speziell: i = 10–18 und j = 2–8 ersetzt sein.

Nonionic surfactant: residue-free combustible nonionic surfactants, consisting of the atomic species C, H, O, N, more precisely:

• 1) fatty acid amine polyglycol ethers: primary, secondary and tertiary unsymmetrically substituted amines having a long hydrophobic saturated or partially unsaturated C chain (C ₆ -C ₃₀ ) and 2-10 ethylene oxide and / or propylene oxide units. General structural formula RN R'R ", where R represents a long hydrophobic saturated or partially unsaturated C chain (C ₆ -C ₃₀ ) and R '= R" = H in primary amines; R '≠ H, R "= H in secondary amines and R' ≠ H, R" ≠ H in teriary amines. R 'and / or R "may be derived from short chain alcohols having the (C ₁ -C ₄ ) and / or up to 10 ethylene oxide and / or propylene oxide units. It is also possible to use mixtures of nonionic nitrogen-containing surfactants.
• 2) Fatty acid amides: Fatty acid amides and having the general structural formula (RC = O) -N R'R ", where R is a long hydrophobic saturated or partially unsaturated C chain (C ₆ -C ₃₀ ) and R '= R" = H for primary carboxylic acid amides; R '≠ H, R''= H for secondary carboxylic acid amides and R' ≠ H, R "≠ H for teriary carboxylic acid amides. R 'and / or R''can be derived from the pure short-chain alkanes (C ₁ -C ₄ ), and from short chain alcohols (C ₁ -C ₄ ) and 1-10 ethylene oxide and / or propylene oxide units.
• 3) Sorbitan fatty acid esters with 0-10 ethylene oxide and or propylene oxide units.
• 4) Ethoxylates (E) and / or propoxylates (P) of alcohols (C _i (E / P) _j ) with i = 6-30 and j = 0-10, especially: i = 10-18 and j = 2- 8 replaced.

It is also possible to use mixtures of nonionic surfactants.

Amphoteric surfactant: residue-free combustible ionic surfactants, consisting of the atomic species C, H, O, N, more precisely: Alkylamidopropylbetaine. It is also possible to use mixtures of nonionic and amphoteric surfactants. The entire mixture can also contain impurities, more precisely waste products from production processes of the components or additives, especially glycerol, as well as di- and monoglycerides or reaction products of the individual surface-active constituents.

Concentrates: Concentrates are derived from the composition of the microemulsion formulation adapted to the particular fuel. The concentrates are prepared from the complete surfactant mixture (ionic surfactant + nonionic surfactant + amphoteric surfactant). To improve the flow properties, the fuel (5 to 100 percent of the amount of microemulsion formulation used as fuel) may be added to the concentrate. Concentrate may also contain alcohol (5 to 100 percent of the amount of microemulsion formulation used as fuel). Concentrates may be used separately to prepare a microemulsion and / or emulsion, or admixed with the fuel component and / or water component.

The aqueous phase, if it is in the external tank, may be mixed with short chain alcohol from the microemulsion formulation (5 to 100 percent of the amount of the exact microemulsion formulation) with the aim of lowering the freezing point. In order to minimize the germ and fungal exposure of the aqueous phase, bactericides, fungicides and algicides may be added.

Komponente Gew.-% Gew.-% (Präferenz) Gew.-% (bes. Präferenz) Diesel 90.00–50.00 80.00–60.00 71.20–62.30 Ionisches Tensid in situ hergestellt aus Fettsäure und Amin Ölsäure 3.00–20.00 5.00–15.00 6.00–12.00 Ethanolamin 0.50–1.00 0.65–0.90 0.70–1.50 Nichtionisches Tensid: zweifach ethoxyliertes tertiäres Oleylamin (hergestellt aus Ölsäure) Oleylaminpolyglykolether, Ethoxylierungsgrad 2 Mol (Walloxen OA 20) 1.00–10.00 2.00–6.00 3.00–5.00 Ethanol 2.00–15.00 3.00–9.00 3.56–8.34 Wasser (destilliert) 5.00–50.00 10.00–40.00 14.24–35.36 Preferred microemulsions are systems 1 to 7 described below:
System 1: Water / ethanol-diesel-ethanolaminoleate / oleic acid / Oleylaminpolyglykolether (degree of ethoxylation about 2 moles). The T-γ cut in the pseudoternary system "water / ethanol-diesel-ethanolaminoleate / oleic acid / oleylamine polyglycol ether (degree of ethoxylation about 2 moles)" is in 1 shown. Composition System 1:
α = 0.99-0.30 preference: 0.95-0.60, special preference: 0.85-0.70
γ = 0.03-0.30 preference: 0.05-0.20, special preference: 0.05-0.15
δ _{(ionic surfactant)} = 0-0.85 Preference: 0.50-0.75, special preference: 0.60-0.70
ψ = 0-0.30 preference: 0.05-0.25, special preference: 0.15-0.20
N = 0.40-0.80 preference: 0.45-0.65, special preference: 0.50-0.60
In weight percent:

component Wt .-% % By weight (preference) Weight% (esp. Preference) diesel 90.00-50.00 80.00-60.00 71.20-62.30 In situ ionic surfactant made from fatty acid and amine oleic acid 3:00 to 20:00 5:00 to 15:00 6:00 to 12:00 ethanolamine 0:50 to 1:00 0.65-0.90 0.70-1.50 Nonionic surfactant: di-ethoxylated tertiary oleylamine (made from oleic acid) Oleylamine polyglycol ether, degree of ethoxylation 2 mol (Walloxen OA 20) 1:00 to 10:00 2:00 to 6:00 3:00 to 5:00 ethanol 2:00 to 15:00 3:00 to 9:00 3:56 to 8:34 Water (distilled) 5.00-50.00 10.00-40.00 14.24-35.36

Komponente Gew.-% Gew.-% (Präferenz) Gew.-% (bes. Präferenz) Biodiesel (RME) 90.00–50.00 80.00–60.00 70.40–61.60 Ionisches Tensid in situ hergestellt aus Fettsäure und Amin Ölsäure 3.00–20.00 5.00–15.00 7.00–8.00 Ethanolamin 0.50–1.00 0.65–0.90 0.75–0.85 Nichtionisches Tensid: zweifach ethoxyliertes tertiäres Oleylamin (hergestellt aus Ölsäure) Oleylaminpolyglykolether Ethoxylierungsgrad 2 Mol (Walloxen OA 20) 1.00–10.00 2.00–6.00 3.50–4.50 Ethanol 2.00–12.00 4.00–9.00 5.28–7.92 Wasser (destilliert) 5.00–50.00 10.00–40.00 12.32–35.48 System 2: Water / ethanol-RME-ethanolamine oleate / oleic acid / oleylamine polyglycol ether (degree of ethoxylation about 2 moles). The T-γ cut in the pseudoternary system "water / ethanol-RME-ethanolaminoleate / oleic acid / oleylamine polyglycol ether (degree of ethoxylation about 2 mol)" is in 2 shown. Composition System 2:
α = 0.99-0.30 preference: 0.95-0.60, special preference: 0.85-0.65
γ = 0.03-0.30 preference: 0.05-0.20, special preference: 0.08-0.15
δ _{(ionic surfactant)} = 0-0.85 Preference: 0.50-0.75, special preference: 0.60-0.70
ψ = 0-0.35 preference: 0.15-0.30, special preference: 0.20-0.30
N = 0.40-0.80 preference: 0.45-0.65, special preference: 0.45-0.55
In weight percent:

component Wt .-% % By weight (preference) Weight% (esp. Preference) Biodiesel (RME) 90.00-50.00 80.00-60.00 70.40-61.60 In situ ionic surfactant made from fatty acid and amine oleic acid 3:00 to 20:00 5:00 to 15:00 7:00 to 8:00 ethanolamine 0:50 to 1:00 0.65-0.90 0.75-0.85 Nonionic surfactant: di-ethoxylated tertiary oleylamine (made from oleic acid) Oleylamine polyglycol ether degree of ethoxylation 2 mol (Walloxen OA 20) 1:00 to 10:00 2:00 to 6:00 3:50 to 4:50 ethanol 2:00 to 12:00 4:00 to 9:00 5.28-7.92 Water (distilled) 5.00-50.00 10.00-40.00 12.32-35.48

Komponente Gew.-% Gew.-% (Präferenz) Gew.-% (bes. Präferenz) BTL (BioPar) 90.00–50.00 80.00–60.00 70.00–61.25 Ionisches Tensid in situ hergestellt aus Fettsäure und Amin Ölsäure 3.00–20.00 5.00–15.00 7.00–8.00 Ethanolamin 0.50–1.00 0.65–0.90 0.77–0.87 Nichtionisches Tensid: zweifach ethoxyliertes tertiäres Oleylamin (hergestellt aus Ölsäure) Oleylaminpolyglykolether Ethoxylierungsgrad 2 Mol (Walloxen OA 20) 1.00–10.00 2.00–6.00 4.00–4.50 Ethanol 2.00–12.00 4.00–9.00 3.50–5.25 Wasser (destilliert) 5.00–35.00 10.00–40.00 15.00–30.00 System 3: Water / ethanol-BTL (BioPar) ethanolamine oleate / oleic acid / oleylamine polyglycol ether (degree of ethoxylation about 2 moles). The T-γ cut in the pseudo-ternary system "water / ethanol-BTL (BioPar) ethanolamine oleate / oleic acid / oleylamine polyglycol ether (degree of ethoxylation about 2 moles)" is in 3 shown. Composition System 3:
α = 0.99-0.30 preference: 0.95-0.60, special preference: 0.85-0.65
γ = 0.03-0.30 preference: 0.05-0.20, special preference: 0.08-0.15
δ _{(ionic surfactant)} = 0-0.85 Preference: 0.50-0.75, special preference: 0.60-0.70
ψ = 0-0.35 preference: 0.15-0.30, special preference: 0.20-0.30
N = 0.40-0.80 preference: 0.45-0.65, special preference: 0.45-0.55
In weight percent:

component Wt .-% % By weight (preference) Weight% (esp. Preference) BTL (BioPar) 90.00-50.00 80.00-60.00 70.00-61.25 In situ ionic surfactant made from fatty acid and amine oleic acid 3:00 to 20:00 5:00 to 15:00 7:00 to 8:00 ethanolamine 0:50 to 1:00 0.65-0.90 0.77-0.87 Nonionic surfactant: di-ethoxylated tertiary oleylamine (made from oleic acid) Oleylamine polyglycol ether degree of ethoxylation 2 mol (Walloxen OA 20) 1:00 to 10:00 2:00 to 6:00 4:00 to 4:50 ethanol 2:00 to 12:00 4:00 to 9:00 3:50 to 5:25 Water (distilled) 5.00-35.00 10.00-40.00 15.00-30.00

Komponente Gew.-% Gew.-% (Präferenz) Gew.-% (bes. Präferenz) Diesel 90.00–50.00 80.00–60.00 67.60–57.75 Ionisches Tensid in situ hergestellt aus Fettsäure und Ammoniak Ölsäure 5.00–20.00 8.00–15.00 10.00–11.28 Ammoniak 0.20–0.70 0.35–0.50 0.39–0.44 Nichtionisches Tensid: Sorbitan Monooleat (hergestellt aus Ölsäure und Sorbitol) Sorbitan Monooleat (TEGO SMO V) 1.00–10.00 4.00–6.00 5.12–5.78 Ethanol 2.00–12.00 5.00–10.00 6.08–8.91 Wasser (destilliert) 5.00–35.00 10.00–20.00 10.82–13.06 System 4: Water / Ethanol-Diesel-Ammonium Oleate / Oleic Acid / Sorbitan Monooleate. The T-γ cut in the pseudoternary system "water / ethanol-diesel-ammonium oleate / oleic acid / sorbitan monooleate" is in 4 shown. Composition System 4:
α = 0.99-0.30 preference: 0.95-0.60, special preference: 0.85-0.65
γ = 0.03-0.30 preference: 0.05-0.25, special preference: 0.10-0.20
δ _{(ionic surfactant)} = 0-0.85 preference: 0.50-0.75, special preference: 0.60-0.70
ψ = 0.20-0.50 Preference: 0.25-0.45, special preference: 0.30-0.40
N = 0.40-0.80 preference: 0.50-0.70, special preference: 0.60-0.70
In weight percent:

component Wt .-% % By weight (preference) Weight% (esp. Preference) diesel 90.00-50.00 80.00-60.00 67.60-57.75 In situ ionic surfactant made from fatty acid and ammonia oleic acid 5:00 to 20:00 8:00 to 15:00 10 a.m. to 11:28 a.m. ammonia 0.20-0.70 00:35 to 00:50 00:39 to 12:44 Nonionic surfactant: sorbitan monooleate (made from oleic acid and sorbitol) Sorbitan monooleate (TEGO SMO V) 1:00 to 10:00 4:00 to 6:00 5.12-5.78 ethanol 2:00 to 12:00 5:00 to 10:00 6.08-8.91 Water (distilled) 5.00-35.00 10:00 a.m. to 8:00 p.m. 10.82-13.06

Komponente Gew.-% Gew.-% (Präferenz) Gew.-% (bes. Präferenz) Diesel 80.00–40.00 70.00–40.00 50.00–40.00 Ionisches Tensid in situ hergestellt aus Fettsäure und Ammoniak Ölsäure 10.00–25.00 15.00–25.00 22.00–23.00 Ammoniak 0.50–1.00 0.55–0.75 0.65–0.70 Ethanol 8.00–20.00 10.00–15.00 12.00–13.00 Wasser (destilliert) 5.00–35.00 15.00–25.00 15.00–20.00 System 5: Water / ethanol-diesel-ammonium oleate / oleic acid. The T-γ cut in the pseudoternary system "water / ethanol-diesel-ammonium oleate / oleic acid" is in 5 shown. Composition System 5:
α = 0.99-0.3, preference: 0.95-0.70, special preference: 0.70-0.40
γ = 0.10-0.8 preference: 0.12-0.30, special preference: 0.15-0.23
ψ = 0.1-0.9 preference: 0.12-0.45, special preference: 0.15-0.40
N = 0.2-0.9 preference: 0.4-0.8, special preference: 0.5-0.7
In weight percent:

component Wt .-% % By weight (preference) Weight% (esp. Preference) diesel 80.00-40.00 70.00-40.00 50.00-40.00 In situ ionic surfactant made from fatty acid and ammonia oleic acid 10.00-25.00 15.00-25.00 22:00 to 11:00 p.m. ammonia 0:50 to 1:00 0.55-0.75 0.65-0.70 ethanol 8:00 to 20:00 10:00 a.m. to 3:00 p.m. 12:00 to 13:00 Water (distilled) 5.00-35.00 15.00-25.00 3:00 p.m. to 8:00 p.m.

Komponente Gew.-% Gew.-% (Präferenz) Gew.-% (bes. Präferenz) Biodiesel (RME) 80.00–40.00 70.00–50.00 62.00–60.00 Ionisches Tensid in situ hergestellt aus Fettsäure und Ammoniak Ölsäure 10.00–25.00 15.00–25.00 18.00–19.00 Ammoniak 0.40–1.00 0.50–0.65 0.50–0.60 Ethanol 2.00–10.00 2.50–6.00 3.50–4.50 Wasser (destilliert) 5.00–35.00 15.00–25.00 16.00–17.00 System 6: Water / Ethanol Biodiesel Ammonium Oleate / Oleic Acid. The T-γ cut in the pseudoternary system "water / ethanol-biodiesel-ammonium oleate / oleic acid" is in 6 shown. Composition System 6:
α = 0.99-0.3, preference: 0.95-0.70, special preference: 0.85-0.75
γ = 0.10-0.8 preference: 0.12-0.30, special preference: 0.15-0.22
ψ = 0.1-0.9 preference: 0.12-0.40, special preference: 0.15-0.35
N = 0.2-0.9 preference: 0.4-0.8, special preference: 0.45-0.65
In weight percent:

component Wt .-% % By weight (preference) Weight% (esp. Preference) Biodiesel (RME) 80.00-40.00 70.00-50.00 62.00-60.00 In situ ionic surfactant made from fatty acid and ammonia oleic acid 10.00-25.00 15.00-25.00 6:00 p.m. to 7:00 p.m. ammonia 0:40 to 1:00 0.50-0.65 0.50-0.60 ethanol 2:00 to 10:00 2:50 to 6:00 3:50 to 4:50 Water (distilled) 5.00-35.00 15.00-25.00 16:00 to 17:00

Komponente Gew.-% Gew.-% (Präferenz) Gew.-% (bes. Präferenz) Diesel 90.00–50.00 80.00–60.00 70.00–61.25 Ionisches Tensid in situ hergestellt aus Fettsäure und Amin Ölsäure 3.00–20.00 5.00–15.00 7.00–8.00 Ethanolamin 0.50–2.00 0.85–1.5 0.95–1.10 Nichtionisches Tensid (hier Ölsäurediethanolamid) Ölsäurediethanolamid (Wallamid OD/E) 1.00–10.00 3.00–7.00 4.50–5.00 Ethanol 2.00–20.00 4.00–15.00 5.00–12.00 Wasser (destilliert) 5.00–50.00 10.00–40.00 15.00–35.00 NH₄NO₃ 0.01–5.00 0.05–1.50 0.05–1.20 System 7A: Water / NH ₄ NO ₃ / ethanol-diesel-ethanolaminoleate / oleic acid / Wallamid OD / E. A T-γ cut in the pseudoternary system "water / NH ₄ NO ₃ / ethanol-diesel-ammonium oleate / oleic acid / Wallamid OD / E" is in 7A shown. Composition System 7A:
α = 0.99-0.3, preference: 0.90-0.40, special preference: 0.60-0.40
γ = 0.05-0.8 preference: 0.10-0.30, special preference: 0.12-0.18
ψ = 0.01-0.9 preference: 0.05-0.40, special preference: 0.08-0.25
N = 0.2-0.9 preference: 0.4-0.8, special preference: 0.45-0.65
ε = 0.01-0.9 preference: 0.03-0.40, special preference: 0.04-0.15
Composition in weight percent at γ = 0.155:

component Wt .-% % By weight (preference) Weight% (esp. Preference) diesel 90.00-50.00 80.00-60.00 70.00-61.25 In situ ionic surfactant made from fatty acid and amine oleic acid 3:00 to 20:00 5:00 to 15:00 7:00 to 8:00 ethanolamine 0:50 to 2:00 0.85-1.5 0.95-1.10 Nonionic surfactant (here oleic diethanolamide) Oleic acid diethanolamide (Wallamid OD / E) 1:00 to 10:00 3:00 to 7:00 4:50 to 5:00 ethanol 2:00 to 20:00 4:00 to 15:00 5:00 to 12:00 Water (distilled) 5.00-50.00 10.00-40.00 15.00-35.00 NH ₄ NO ₃ 0:01 to 5:00 0:05 to 1:50 0:05 to 1:20

Komponente Gew.-% Gew.-% (Präferenz) Gew.-% (bes. Präferenz) Diesel 90.00–50.00 80.00–60.00 70.00–61.25 Ionisches Tensid in situ hergestellt aus Fettsäure und Amin Ölsäure 1.00–10.00 2.00–8.00 4.00–5.00 Ethanolamin 0.20–1.00 0.30–0.85 0.40–0.55 Nichtionisches Tensid (hier Ölsäurediethanolamid) Ölsäurediethanolamid (Wallamid OD/E) 2.00–15.00 3.00–10.00 4.50–6.00 Ethanol 2.00–20.00 4.00–15.00 5.00–12.00 Wasser (destilliert) 5.00–50.00 10.00–40.00 15.00–35.00 NH₄NO₃ 0.01–5.00 0.05–1.50 0.05–1.20 System 7B: Water / NH ₄ NO ₃ / ethanol-diesel-ethanolaminoleate / oleic acid / Wallamid OD / E. A T-γ cut in the pseudoternary system "water / NH ₄ NO ₃ / ethanol-diesel-ammonium oleate / oleic acid / Wallamid OD / E" is in 7B shown. Composition System 7B:
α = 0.99-0.3, preference: 0.90-0.40, special preference: 0.60-0.40
γ = 0.03-0.35 preference: 0.05-0.30, special preference: 0.09-0.18
ψ = 0.01-0.9 preference: 0.05-0.40, special preference: 0.15-0.25
N = 0.2-0.9 preference: 0.3-0.65, special preference: 0.40-0.55
ε = 0.01-0.9 preference: 0.03-0.40, special preference: 0.04-0.10
Composition in weight percent at γ = 0.105:

component Wt .-% % By weight (preference) Weight% (esp. Preference) diesel 90.00-50.00 80.00-60.00 70.00-61.25 In situ ionic surfactant made from fatty acid and amine oleic acid 1:00 to 10:00 2:00 to 8:00 4:00 to 5:00 ethanolamine 0:20 to 1:00 0.30-0.85 12:40 to 12:55 Nonionic surfactant (here oleic diethanolamide) Oleic acid diethanolamide (Wallamid OD / E) 2:00 to 15:00 3:00 to 10:00 4:50 to 6:00 ethanol 2:00 to 20:00 4:00 to 15:00 5:00 to 12:00 Water (distilled) 5.00-50.00 10.00-40.00 15.00-35.00 NH ₄ NO ₃ 0:01 to 5:00 0:05 to 1:50 0:05 to 1:20

The invention will be explained in more detail with reference to the following examples. However, these do not limit the application in any way.

Examples

Example 1: System H ₂ O / ethanol diesel NH ₄ oleate / oleic acid / TEGO ^® SMO V

The first system with biogenic surfactant components and freezing point H ₂ O / ethanol Diesel (Aral) -NH ₄ oleate / oleic acid (65% neutr.) / TEGO ^® SMO V, with ψ = 12:36; δ = 0.67; α = 0.70 / 0.80 / 0.90 (≙ weight% H ₂ O 15.8 / 10.8 / 5.4) and corresponding γ-values γ = 0.175 / 0.16 / 0.16 was studied at the Faculty of Mechanical Engineering University Karlsruhe (TH) in the working group Prof. Dr .-Ing. U. Spicher in a series of motor, optical and numerical investigations (Eckert, P., Numerical and Experimental Investigation of Water Introduction into Diesel Engine Combustion, Research Reports from the Institute of Piston Engines 2/2008 Karlsruhe: Logos Berlin. , ISBN 978-3-8325-1951-3).

These studies compared on the one hand the emissions of a diesel engine operating with diesel fuel and microemulsion fuels with varying proportions of water and the influence of the variations of the in-engine parameters on diesel fuel and microemulsion fuel operation. Special emphasis should be placed on the positive effect of the microemulsion fuel on the soot NOx trade-off in conjunction with the use of different internal engine measures. The soot NOx trade-off can be broken with hydrous microemulsion fuel and the effect of varying the internal engine parameters can be enhanced.

Variation of exhaust gas recirculation rate (EGR rate): In the following, the influence of internal engine measures on pollutant emissions is discussed. Part of the exhaust gas can be introduced into the combustion chamber via the exhaust gas recirculation, as a result of which the gas mass is increased and the combustion temperature is reduced. With this technique, the formation of the thermal or Zeldovic NO can be lowered. The exhaust gas recirculation rate can be increased up to 40%, with the emissions of soot, unburned hydrocarbons and carbon monoxide increasing in diesel operation. Combining microemulsion operation with exhaust gas recirculation, as the water content of the microemulsion fuel increases, the soot NO _x level off tolerance range becomes significantly wider and the EGR rate can be significantly increased. In the 8th the soot and NO _x emissions are plotted in diesel and microemulsion mode as a function of the EGR rate. With the Microemulsion with 15.8 wt .-% water can increase the EGR rate up to 35% without significant increase in soot and NO _x emissions.

The quality of the combustion process can be read off from the emissions of unburned hydrocarbons and carbon monoxide. 9 shows the dependence of HC and CO emissions on the water content of the microemulsion and the EGR rate. Compared to diesel (red circles), there is a relative increase in HC emissions of up to 25% and CO emissions of up to 80%. Due to the exhaust gas recirculation lower temperatures prevail in the combustion chamber. Water addition leads to a further decrease in temperature and deterioration of the course of the combustion reactions, which is evident from the increasing HC and CO emissions. Nevertheless, the formation of soot can continue to repress, probably with the increased occurrence of OH radicals.

From the CO ₂ emission, taking into account the other carbon sources such as HC and CO, the fuel consumption can be estimated. 10 shows the dependence of CO ₂ emissions on the EGR rate. Noteworthy are the extremely low CO ₂ values that are achieved with the microemulsion fuel with 15.8 wt .-% water, and partially reach the values of pure diesel. The emissions of unburned hydrocarbons are relatively low compared to pure diesel. Although the increase in CO emissions is significant, it can not significantly affect the overall carbon footprint, given the magnitude. There is a clear trend of consumption reduction of the energy equivalent mass of the carbonaceous components of the fuel compared to pure diesel fuel with increasing water content in a microemulsion as a fuel.

Injection Pressure Variation: Next, the influence of injection pressure on the emission performance of the engine in diesel and microemulsion operation was investigated. The increase in the injection pressure influences the penetration length of the injection jet, it is a higher injection depth us thus achieves a better utilization of the air volume in the combustion chamber. The improved oxidation conditions lead to the reduction of soot formation. The variation of the injection pressure was investigated in two operating points, at a speed of 1175 min ^-1 and a mean effective pressure of p = 0.8 _s / 1.2 MPa.

11 shows the emissions of soot and nitrogen oxides at an effective mean pressure of p _e = 0.8 MPa, depending on the injection pressure. The diesel characteristic of the soot emissions shows the expected course, the FSN number becomes smaller with increasing rail pressure. Nitrogen oxide emissions increase with increasing rail pressure, indicating better combustion and higher combustion temperatures. In the microemulsion mode, the dependence on the increasing rail pressure can be tracked, but the soot emissions at low injection pressure with 10.8 wt .-% water in microemulsion fuel only 17% of the emissions of diesel. The carbon black characteristic of the microemulsion with 10.8% by weight of water is below that with a higher water content of 15.8% by weight. A lower proportion of water at this operating point brings better reduction of soot emissions. Nitric oxide emissions were also significantly reduced with microemulsion fuel. At higher injection pressure, the reduction is higher than at lower injection pressures. By better distribution of the fuel in the combustion chamber with increasing penetration length, the water contained in the fuel will achieve more homogeneous distribution of the low-temperature regions during evaporation.

In 12 the emissions of unburned hydrocarbons and carbon monoxide are plotted as a function of rail pressure. It is an opposite behavior with the microemulsion with 15.8 wt .-% water to observe. While emissions of unburned hydrocarbons are below diesel levels at high injection pressures, carbon monoxide emissions rise 3.5-fold. Apparently, the radical degradation of the hydrocarbon chains proceeds relatively well, the low combustion temperature slows down the taking place in the last reaction step oxidation of carbon monoxide to carbon dioxide.

The emissions of carbon dioxide ( 12 below) reach the values of pure diesel at some operating points, indicating an identical fuel consumption of the hydrocarbons. The increase in CO ₂ emissions with increasing water content of the microemulsions is due to the lower calorific values of the fuels.

The influence of the variation of the injection pressure at a higher load point with 1.2 MPa effective medium pressure and without pilot injection shows a lower soot reduction in the microemulsion mode ( 13 , Left). At lower injection pressures, a small increase in soot emissions is observed with increasing water content in the microemulsion fuel. From an injection pressure of 1100 bar, the soot emissions with micro-emulsified fuel fall below the diesel characteristic curve. Ultimately at an injection pressure of 1700 bar increase the soot emissions with microemulsions on the values in the diesel operation. The NO _x emissions ( 13 , right) are slightly lowered with increasing water content of the microemulsion fuel, regardless of the injection pressure. In this operating state, the soot NO _x level off can also be intensified with microemulsion fuel, which can be explained in part by a longer injection time and poorer mixture formation in the combustion chamber.

The emission of unburned hydrocarbons and carbon monoxide is in the 14 shown as a function of injection pressure and water content in microemulsified fuels. With a water content of 15.8 wt .-%, it is possible to reduce the HC emissions at high injection pressures of more than 1100 bar by 10 to 30% compared to diesel fuel. The specific emissions of carbon monoxide are at a minimum in diesel operation and in operation with microemulsions with lower proportions of water, in the microemulsion operation with 15.8 wt .-% water is a dramatic increase in CO emissions recorded. An insufficient combustion temperature for the oxidation of carbon monoxide explains the increase in emissions. The use of an oxidation catalyst would also minimize emissions in this case.

The CO ₂ emissions ( 15 ) are lowered in this operating state with microemulsion fuels, so that the consumption of carbonaceous mass is about the consumption of diesel fuel or lowered.

Start of injection variation: For homogeneous mixture preparation, the start of injection is selected so that sufficient time is available for the mixing of fuel and air. The goal is to have as homogeneous a distribution of fuel and air as possible without accumulating fuel on a combustion wall in order to achieve good emissions and low soot emissions. The variation of the start of injection of the fuel into the combustion chamber is measured in degrees of crankshaft angle, where zero is defined as the point at which the piston reaches top dead center. How to get the charts in 16 can show, the diesel characteristic shows a reduction in soot emissions at advanced injection start and a corresponding increase in NO _x emissions due to the improved mixture formation and homogeneous combustion at higher combustion temperatures. In microemulsion mode, the soot emissions can be significantly reduced at each injection start time, with higher water levels even down to the detection limit. The nitrogen oxide emissions are in the range of the values achieved with diesel fuel. The overall balance shows a reduction in the soot NO _x level off.

At the start of injection variation, the emissions of unburned hydrocarbons and carbon monoxide increase, especially at a later start of injection. The time available for the mixture formation is insufficient in this case, so that in the rich, fuel-rich zones the combustion is incomplete and adversely affects the exhaust behavior of the engine ( 17 ).

The emissions of carbon dioxide in microemulsion show the lowest values at the start of injection at -11 ° CA and -5 ° CA. The start of injection at -5 ° CA was also chosen for the injection pressure variation described above, in which the increase in CO ₂ emissions is particularly moderate ( 18 ). It is interesting that the CO ₂ values can also be lowered during the later injection, which is in line with the drastically increased emissions of unburned hydrocarbons and carbon monoxide.

Example 2: System H ₂ O / ethanol-diesel-ethanolamine / oleic acid / Walloxen OA 20

Investigations of the system H ₂ O / ethanol-diesel (Aral) -ethanolamine-oleate / oleic acid (55% neutral) / Walloxen OA 20 with α = 0.80 / 0.70; (≙ 13.12 (≈ 13) /19.69 ((≈ 20)% by weight of water) ψ = 0.20; δ = 0.67 and γ = 0.11 were studied at the Research Institute for Automotive Engineering of the Dresden University of Applied Sciences (FH) under the direction of Prof. Dr.-Ing G. Zikoridse The evaluation of exhaust gas analysis and analysis of the particles was carried out by Dr. U. Hofmann.

The investigations were carried out on an engine test bench with the following configuration: Test engine: Type: DW12TED4 / L4 FAP, PSA type: 4-stroke diesel engine Number of cylinders: 4 displacement: 2179 cm ³ Rated capacity: 97.5 kW at 4000 min ^-1 Max. Torque: 318 Nm at 2000 min ^-1 Equipment: Exhaust gas turbocharger, charge air cooling 2. Loading device and measuring technology Type: DC machine Max. Removable power: 134 kW torque: 350 Nm Rotation speed: 9000 min ^-1 Test automation: CATS NT (Siemens) Fuel consumption measuring device: 733 S (AVL) Air mass meter: Sensyflow P exhaust gas analyzers: NO _x , NO: CLD 700 ht (Eco Physics) THC, CO, CO ₂ , O ₂ : Advance Optima exhaust gas measuring system, (ABB) Schwärzungszahlmessgerät: Smokemeter 415S (AVL) Gravimetric particle measurement: Microtrol 3 (Nova MMB) Particle number and size distribution: SMPS 3936 (TSI)

In the 19 the course of the full load characteristic of the engine is shown and the operating points approached for the tests. The points were selected in such a way that the entire engine map is approximately covered both in the low load range and in the full load range.

The experiments were carried out with diesel as reference fuel, with diesel-surfactant mixture and with microemulsion fuels with two different water contents of 13 and 20 wt .-%. The addition of the surfactant mixture EthanolaminOleat / oleic acid (55% neutral) / Walloxen OA 20 δ = 0.67 and γ = 0.11 to the diesel fuel should clarify the effect of surfactant components on the exhaust behavior of the engine. In all starting points with different fuels, the engine was operated without the use of exhaust aftertreatment systems. Subsequently, in the microemulsion operation, the composition of the exhaust gas was checked by using a diesel oxidation catalyst (DOC). In the following, the percentage deviations of the measured emission values with different fuel types from the reference measurements with diesel fuel are considered ( 20 - 28 ). The exact concentrations of emissions are in 29 - 36 specified.

Soot emission measurements with a blackening meter provided the expected results ( 20 ). Even with the addition of the surfactant mixture to the diesel fuel, a reduction in soot emissions by up to 64% compared to diesel fuel was achieved. These results can be compared with the reduction of soot emissions by the admixture of the biodiesel in whose molecular structure two oxygen atoms are contained (Cheng, AS et al., Int. J. Engine Res. 7 (4): 297-347 (2006 Kegl, B., NOx and Particulate Matter (PM) Emission Reduction Potential by Biodiesel Usage p., 3310-3316 (2007)).

The surfactants used are derivatives of oleic acid with a similar or higher oxygen content than biodiesel.

The highest reduction in the number of blackening (up to 97%) is achieved with the microemulsion fuel having a water content of 20% by weight. The use of a diesel oxidation catalyst has no influence on the degree of blackening.

The results of the gravimetric measurements of the particle emissions show a decisive difference to the blackening number measurements. While the addition of the surfactant mixture to the diesel fuel entails only an insignificant change in the particle mass, the particle mass increases rapidly in microemulsion operation without the oxidation catalyst in the low-load range ( 21 ). For example, the microemulsion is 20 wt .-% of water on the first operating point at a speed of 3000 min ^-1 and a torque of 30 Nm, an increase in mass of particles of 184% compared to diesel fuel. At the operating points in the higher load range, a reduction of the particle mass is observed even with microemulsion fuel. If the engine is operated with the oxidation catalyst, a decrease in the particle mass takes place in microemulsion operation. The first conclusions that can be drawn from these measurements indicate an increase in the emissions of unburned hydrocarbons, which are minimized in the oxidation catalyst. This also explains the reduction of the particle mass in the rolling test rig investigations. The examined vehicle is equipped as standard with an oxidation catalytic converter.

The emitted particle mass consists of a large number of organic and inorganic substances. The main constituents of the organic substances are carbon black, unburned or incompletely burned fuel and lubricating oil. Inorganic substances include sulfates, water and metal compounds. The metal compounds are both chips and rust particles that originate directly from the engine or the exhaust pipe, as well as remnants of fuel and lubricating oil derivatives. The percentage of these substances in the total particle mass depends on many parameters. In addition to design parameters such as combustion chamber shape and design of the injection system include the operating point (load and speed), the fuel and lubricating oil quality and the state of wear of the engine (Wachter, F. and Cartellieri, WP, ways of future emission limits for truck diesel engines, in 8. Int Vienna Motor Symposium 1987., VDI Verlag: Dusseldorf, pp. 206-239 (1987)).

The particles collected on the filters were U. Hofmann in an extraction procedure ( 22 ) analyzed. First, the soluble organic fraction (SOF, soluble organic fraction) is extracted from the filter with dichloromethane.

Then the filters are weighed and the SOF quantity is determined from the mass difference. The extraction residue is treated in further steps with isopropanol and water. This can be used to determine the amount of soluble inorganic residues (SIOF), which include soluble salts such as sulfates, nitrates, carbonates, acetates, etc., and corresponding acids. The insoluble residue (ISF, insoluble fraction) then consists of carbon black, metals or metal oxides.

In 23 shows the percentage deviations of the mass of the extracted organic compounds compared to the reference value of the emissions in diesel operation. Regardless of the operating point, the increase in SOF in microemulsion operation is observed. With the oxidation catalyst, the emissions of unburned hydrocarbons can be significantly reduced. In accordance with the determined reduction in the degree of blackening ( 24 ), the results of the reduction of insoluble residues (ISF) in the microemulsion operation both with and without the diesel oxidation catalyst. With the diesel oxidation catalyst, the amount of insoluble residues, probably the soot, can be further minimized. The lower percentage of insoluble residue reduction than the reduction in the degree of blackening and the significantly higher reduction of the insoluble particles with the oxidation catalyst indicates the presence of the higher, sparingly soluble hydrocarbons that are degraded in the oxidation catalyst (Shah, SD et al., P.5070 -5076 (2007)).

The emissions of the soluble inorganic components increase as early as the addition of the surfactant mixture to the diesel fuel ( 25 ). The added surfactants contain nitrogen which, when oxidized at high combustion temperatures, presumably forms soluble nitrates emitted in the form of SIOF. When using the microemulsified hydrous fuel, the mass of soluble inorganic species increases with increasing water content. It is likely that the reactions in which inorganic salts (ash, which is an undesirable reaction product of the metallic oxide layer on the surface of the combustion chamber, from the impurities of the diesel fuel, etc.) are formed, preferably in the presence of water. The salts emitted in the hot exhaust probably as approximately dry crystalline or amorphous particles also serve as condensation nuclei for water and lower polar carbon compounds and are only partially degraded in the oxidation catalyst.

The measurements of the emission of unburned hydrocarbons are clear ( 26 ). The lower the load, the more HC's are formed in microemulsion operation. At operating point n = 1200 min ^-1 , M = 88 Nm shows the oxidation catalyst in conjunction with the microemulsion fuel with 20 wt .-% water an insufficient reduction of HC emissions. It is likely that the operating temperature of the oxidation catalyst will drop below that of the reduced temperature of the exhaust gas, which is confirmed by the results of the carbon monoxide emission measurements ( 27 ).

Nitrogen oxide emissions can be reduced by 2 to 25% with hydrous microemulsified fuels at high loads ( 28 ). In the low load range, a significant increase in NO _x values is observed. In part, this slope is explained by the increase in the nitrogen content in the fuel. The formation of thermal NO must be largely minimized due to the lower combustion temperatures, therefore, the radical NO formation mechanism is likely to be significant.

Tabelle B: Abgasemissionen und motorischen Parameter im Betrieb des Motors mit Dieselkraftstoff und mikroemulgierten Kraftstoff mit Variation des Wassergehalts (Diesel (Referenz) → ME 5.4 Gew.-% H₂O → ME 10.8 Gew.-% H₂O → ME 15.8 Gew.-% H₂O) bei der Variation des Einspritzbeginns. 1-Zylinder Dieselmotor, Actros-Baureihe, OM 450, Drehzahl 1175 min^–1, p_e = 0.8 MPa, Pilot und Haupteinspritzung (TU Karlsruhe).

Tabelle C: Abgasemissionen und motorischen Parameter im Betrieb des Motors mit Dieselkraftstoff und mikroemulgierten Kraftstoff mit Variation des Wassergehalts (Diesel (Referenz) → ME 5.4 Gew.-% H₂O → ME 10.8 Gew.-% H₂O → ME 15.8 Gew.-% H₂O) bei der Variation des Raildrucks. 1-Zylinder Dieselmotor, Actros-Baureihe, OM 450, Drehzahl 1175 min^–1, p_e = 0.8 MPa, Pilot und Haupteinspritzung (TU Karlsruhe).

Tabelle D: Abgasemissionen und motorischen Parameter im Betrieb des Motors mit Dieselkraftstoff und mikroemulgierten Kraftstoff mit Variation des Wassergehalts (Diesel (Referenz) → ME 5.4 Gew.-% H₂O → ME 10.8 Gew.-% H₂O → ME 15.8 Gew.-% H₂O) bei der Variation des Raildrucks. 1-Zylinder Dieselmotor, Actros-Baureihe, OM 450, Drehzahl 1175 min^–1, p_e = 1.2 MPa, Haupteinspritzung (TU Karlsruhe).

The Motor tests of the system H ₂ O / ethanol diesel NH ₄ oleate / oleic acid / TEGO ^® SMO V in the following tables A-D that of the system H ₂ O / ethanol diesel ethanolamine / oleic acid / Walloxen OA 20 are in 30 - 37 summarized. Table A: Exhaust emissions and engine parameters during operation of the engine with diesel fuel and microemulsified fuel with variation of water content (Diesel (Reference) → ME 5.4% by weight H ₂ O → ME 10.8 wt .-% H ₂ O → ME 15.8 wt .-% H ₂ O) in the variation of the exhaust gas recirculation rate. 1-cylinder diesel engine, Actros series, OM 450, rotation speed 1175 min ^-1, p _s = 0.8 MPa, pilot injection and main injection (TU Karlsruhe).

Table B: Exhaust emissions and engine parameters during operation of the engine with diesel fuel and microemulsified fuel with variation of water content (Diesel (Reference) → ME 5.4% by weight H ₂ O → ME 10.8% by weight H ₂ O → ME 15.8% by weight) -% H ₂ O) in the variation of the start of injection. 1-cylinder diesel engine, Actros series, OM 450, rotation speed 1175 min ^-1, p _s = 0.8 MPa, pilot injection and main injection (TU Karlsruhe).

Table C: Exhaust emissions and engine parameters during operation of the engine with diesel fuel and microemulsified fuel with variation of water content (Diesel (Reference) → ME 5.4 wt% H ₂ O → ME 10.8 wt% H ₂ O → ME 15.8 wt. -% H ₂ O) in the variation of the rail pressure. 1-cylinder diesel engine, Actros series, OM 450, rotation speed 1175 min ^-1, p _s = 0.8 MPa, pilot injection and main injection (TU Karlsruhe).

Table D: Exhaust emissions and engine parameters during operation of the engine with diesel fuel and microemulsified fuel with variation of water content (Diesel (Reference) → ME 5.4% by weight H ₂ O → ME 10.8% by weight H ₂ O → ME 15.8% by weight) -% H ₂ O) in the variation of the rail pressure. 1-cylinder diesel engine, Actros series, OM 450, rotation speed 1175 min ^-1, p _e = 1.2 MPa, main injection (TU Karlsruhe).

Claims (13)

A bicontinuous monophasic microemulsion comprising at least one aqueous component (A) comprising 5 to 50% by weight of water and 2 to 20% by weight of ethanol, a hydrophobic component (B) comprising 45 to 90% by weight of the one or more usable as fuel, fuel or fuel, but at least one fuel based on mineral oil and / or at least one based on vegetable oils or their derivatives of power, heating or fuel and / or produced by Fischer-Tropsch synthesis force, heating or fuel, an ionic surfactant component (C) comprising a salt of 1 to 10% by weight of a C _6-30 fatty acid and 0.2 to 1.0% by weight of a primary, secondary or tertiary amine base, a nonionic surfactant component (D) comprising 2 to 15 wt .-% C _6-30 fatty acid diethanolamide and / or C _6-30 fatty acid diethanolamine and an additive / salt component (E) comprising 0 to 0.5 wt .-% ammonium nitrate, wherein the content of (C ) smaller than the v on (D) and wherein the microemulsion has simultaneously a continuous aqueous phase and a continuous hydrophobic phase. Microemulsion according to claim 1, consisting at least of an aqueous component (A) comprising 5 to 50% by weight of water and 2 to 20% by weight of ethanol, a hydrophobic component (B) comprising 50 to 90% by weight of diesel, an ionic surfactant component (C) comprising a salt of from 1 to 10% by weight of oleic acid and from 0.2 to 1.0% by weight of ethanolamine, a nonionic surfactant component (D) comprising 2 to 15% by weight of oleic diethanolamide and an additive / salt component (E) comprising from 0.01 to 0.5% by weight of ammonium nitrate, wherein the content of (C) is less than that of (D) and wherein the microemulsion has simultaneously a continuous aqueous phase and a continuous hydrophobic phase. A microemulsion according to claim 1 or 2, which is a fuel. Use of the microemulsion according to claim 1 or 2 as fuel in internal combustion engines. Use according to claim 4, wherein the internal combustion engines are reciprocating engines, rotary engines or turbine engines. Use of the microemulsion according to claim 1 or 2 as fuel in thrusters. Use according to claim 6, the thrusters are jet engines, turbine jet engines or rocket engines. Use of the microemulsion according to claim 1 or 2 as fuel in combustion plants. Use according to claim 8, wherein the firing installations are heating installations or steam generating installations. Use of the microemulsion according to claim 1 or 2 in ignition processes. Use of the microemulsion according to claim 1 or 2 in explosives. Process for the preparation of a bicontinuous monophasic microemulsion, comprising at least one aqueous component (A) comprising 5 to 50% by weight of water and 2 to 20% by weight of ethanol, of a hydrophobic component (B) comprising 45 to 90% by weight the one or more usable as Kraft, fuel or fuel materials, but at least one fuel based on mineral oil and / or at least one based on vegetable oils or their derivatives of power, heating or fuel and / or produced by Fischer-Tropsch synthesis force -, heating or fuel, an ionic surfactant component (C) comprising a salt of 1 to 10 wt .-% of a C _6-30 fatty acid and 0.2 to 1.0 wt .-% of a primary, secondary or tertiary amine base nonionic surfactant component (D) comprising 2 to 15% by weight of C _6-30 fatty acid diethanolamide and / or C _6-30 fatty acid diethanolamine and an additive / salt component (E) comprising 0 to 0.5% by weight of ammonium nitrate, wherein d the content of (C) is less than that of (D), and wherein the microemulsion simultaneously comprises a continuous aqueous phase and a continuous hydrophobic phase, the method comprising mixing an emulsifier concentrate comprising the ionic surfactant component (C), and a nonionic surfactant component ( D) with the aqueous component (A) and / or the hydrophobic component (B) and / or the additive / salt component (E). A method according to claim 12, wherein the emulsifier concentrate comprising for solubilization, portions of the hydrophobic component (B) and / or the alcohol and / or the aqueous component (A) and / or the additive / salt component (E).

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