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United States Patent Application	20040060226
Kind Code	A1
Bongart, Frank ;   et al.	April 1, 2004

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Foreign Application Data

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Date	Code	Application Number
Nov 8, 2000	GB	0027273.2
Nov 8, 2000	GB	0027275.7
Nov 8, 2000	GB	0027270.8

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Claims

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1. A fuel composition which is substantially free of alkanolamides, comprising at least 95% by volume of hydrocarbon-based fuel and from 0.1 to 5% by volume of an additive selected from the groups consisting of: (a) optionally alkoxylated linear or branched saturated or unsaturated C.sub.8-24 monoalcohols, comprising 0 to 20 mol of ethylene oxide or 1 to 5 mol of propylene oxide per mol of alcohol; or (b) C.sub.2-6 polyols, optionally partially esterified with C.sub.12-24 fatty acids; or (c) alkoxylated C.sub.12-24 fatty acids having 4 to 20 mol of ethylene oxide per mol of fatty acid; or (d) ethoxylated dimeric fatty acids.

2. A fuel composition according to claim 1 wherein the hydrocarbon-based fuel comprises an oxygenator.

3. A fuel composition according to claim 2 wherein the oxygenator is an alcohol.

4. A fuel composition according to claim 3 wherein the alcohol is a C.sub.1-6 alkanol.

5. A fuel composition according to claim 4 wherein the alkanol is selected from the group consisting of ethanol, propanol and butanol, and isomers thereof.

6. A fuel composition according to claim 5 wherein the alcohol is ethanol.

7. A fuel composition according to claim 3 wherein the alcohol is present in an amount of from 1 to 10% by volume of the composition.

8. A fuel composition according to claim 1 wherein the fuel composition comprises component (a).

9. A fuel composition according to claim 5 wherein component (a) is a primary aliphatic alcohols of the formula (I) R.sup.1OH, wherein R.sup.1 is an aliphatic, linear or branched C.sub.8-24 hydrocarbon radical having 0, 1, 2 or 3 double bonds.

10. A fuel composition according to claim 9 wherein component (a) is selected from the group consisting of caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and combinations thereof.

11. A fuel composition according to claim 9 wherein component (a) is a C.sub.12-18 fatty alcohol.

12. A fuel composition according to claim 11, wherein the fatty alcohol is selected from the group consisting of coconut fatty alcohol, palm fatty alcohol, palm kernel fatty alcohol or tallow fatty alcohol.

13. A fuel composition according to claim 9 wherein component (a) is oleyl alcohol.

14. A fuel composition according to claim 9 wherein component (a) is a C.sub.12-16 Guerbet alcohol.

15. A fuel composition according to clam 8 wherein component (a) is an alkoxylated alcohol.

16. A fuel composition according to claim 15, wherein the alkoxylated alcohol in an ethoxylated alcohol.

17. A fuel composition according to claim 16 wherein component (a) is octanol, ethoxylated with 8 mol of ethylene oxide.

18. A fuel composition according to claim 1 wherein the fuel additive comprises component (b).

19. A fuel composition according to claim 17 wherein component (b) is an organic compound having 2 to 8 carbon atoms and 2 to 4 hydroxyl functions per molecule.

20. A fuel composition according to claim 17 wherein component (b) is selected from the group consisting of ethylene gylcol, propylene glycol, butylene glycol and their oligomers.

21. A fuel composition according to claim 20 wherein component (b) is an oligomer selected from the group consisting of butylene diglycol, glycerol, and neopentyl compounds.

22. A fuel composition according to claim 21 wherein component (b) is a neopentyl compound selected from the group consisting of pentaerythritol and trimethylopropane.

23. A fuel composition according to claim 18 wherein component (b) is a partially esterified derivative of a polyol.

24. A fuel composition according to claim 18 wherein component (b) is a glycerol mono or diester with C.sub.8-22 fatty acids.

25. A fuel composition according to claim 18 wherein component (b) is a pentaerythrityl ester partially esterified with fatty acids.

26. A fuel composition according to claim 18 wherein component (b) is selected from the group consisting of the partially esterified diethylene glycols, pentaerythritols or trimethylolpropane.

27. A fuel composition according to claim 18 wherein component (b) is glycerol.

28. A fuel composition according to claim 26 wherein the component (b) is diethylene glycol monobutyl ether.

29. A fuel composition according to claim 1 wherein the fuel additive comprises component (c).

30. A fuel composition according to claim 28 wherein component (c) is one or more ethoxylated fatty acids.

31. A fuel composition according to claim 29 wherein the ethoxylates contain exclusively ethylene oxide groups as alkoxides.

32. A fuel composition according to claim 29 wherein the ethoxylates contain between 4 and 20 mol of ethylene oxide per mol of ester.

33. A fuel composition according to claim 28 wherein component (c) is a C.sub.5-30 fatty acid of natural or synthetic origin.

34. A fuel composition according to claim 31 wherein the fatty acid is selected from the group consisting of coconut oil, palm kernel oil, Soya oil, sunflower oil, colza oil, cottonseed oil, fish oil, beef tallow, and lard.

35. A fuel composition according to claim 32 wherein the fatty acid is selected from the group consisting of caprylic, capric, lauric, lauroleic, myristic, palmitic, palmitoleic, oleic, elaidic, arachic, gadoleic, behenic and erucic acid.

36. A fuel composition according to claim 1 wherein the fuel additive comprises component (d).

37. A fuel composition according to claim 35 wherein the fatty acid is dimeric fatty acid with dimer content of from 50 to 99% by weight.

38. A fuel composition according to claim 1 wherein the hydrocarbon based fuel comprises a diesel oil.

39. A fuel composition according to claim 37 wherein the diesel oil is petroleum diesel.

40. A fuel composition according to claim 37 wherein a proportion of the diesel oil is a biodiesel.

41. A fuel composition according to claim 1 wherein the components (a) to (d) each have an HLB value of less than 12.

42. A fuel composition according to claim 1 wherein the diesel oil: additive volume ratio (v/v) is the range of 1,000:0.5 to 1,000:50.

43. A fuel composition according to claim 1 wherein the composition is substantially anhydrous.

44. A fuel composition according to claim 1 wherein the composition comprises water and consists of a substantially stable, clear and substantially homogeneous solution.

45. A fuel composition according to claim 37 wherein the composition consists of 88 to 98.5% by volume of diesel oil, 1 to 10% by volume of ethanol and 0.5 to 2% by volume of additive (a), (b), (c) or (d).

46. A fuel composition according to claim 1 which further comprises a nitrogen source.

47. A fuel composition according to claim 1 which further comprises a cetane booster in amount of from 0.1% v/v to 1.0% v/v, based on the volume of the mixture.

48. A fuel composition according to claim 1 which further comprises a demulsifier in an amount of less than 5% v/v.

49. A process for the preparation of a fuel composition according to claim 37 which comprises mixing the additive selected from groups (a), (b), (c) or (d), in an amount of from 0.1 to 5% by volume with diesel oil and splash blending the mixture into a clear, stable fuel.

50. A process for the preparation of a fuel composition according to claim 3 which comprises (i) dissolving an additive selected from groups (a), (b), (c) or (d) in an amount of from 0.1 to 5% by volume in an alcohol; and (ii) splash blending the solution into a hydrocarbon fuel.

51. A process according to claim 49 wherein the hydrocarbon fuel is diesel oil.

52. A method of running an internal combustion engine comprising the use of a fuel composition according to claim 1.

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Description

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[0001] The present invention relates to fuel compositions which are free of alkanolamides and contain specific selected additives.

[0002] The invention furthermore relates to a process for the preparation of diesel oil/ethanol mixtures and the use of selected individual components as solubilisers for alcohol-containing diesel fuel.

[0003] The use of surfactants as additives for fuels has long been known. Thus, for example, British Patent GB 2 21 72 29 describes an additive which contains 48 parts by volume of an ethoxylated alcohol, 3 to 8 parts of lauric acid diethanolamide, 3 to 8 parts of oleic acid diethanolamide and 1.5 to 4 parts of an ethoxylated oleic acid. Such compositions are suitable as additives which permit the dissolution of water in fuel and thus reduce the corrosion. However, problems arise when, instead of the water, for example short-chain alcohols are to be used as the mixed phase with the fuels. For this purpose, WO 98/17745 describes an alternative composition which contains 25% by volume of diethanolamide, 50% by volume of an ethoxylated alcohol and 25% by volume of a C.sub.14 fatty acid ethoxylated with 7 mol ethylene oxide per mole of fatty acid. The additive is used for improving the solubility of ethanol in diesel, which in the end results in the reduction in the emissions of CO.sub.2 and CO and NO.sub.x and particulate matter (PM) when the fuel is burned in a compression-ignition engine.

[0004] As in the past, the disadvantage is that a large number of individual substances have to be used to achieve the desired effect. There has long been a need for achieving dissolution of alcohol in fuel, preferably in diesel, by using economical additives which are as simple as possible, in order to achieve in this way a noticeable reduction in gaseous reaction products of combustion, in particular NO.sub.x and CO or CO.sub.2 and PM.

[0005] It is an object of the present application to solve the problems described above. Surprisingly, it has now been found that sufficient dissolution of alcohol in fuels, preferably in diesel fuel, can be achieved by using selected individual components.

[0006] According to a first aspect of the invention we provide a fuel composition which is substantially free of alkanolamides, containing at least 95% by volume of a hydrocarbon-based fuel and from 0.1 to 5% by volume of an additive selected from the groups consisting of:

[0007] a) the optionally alkoxylated linear or branched saturated or unsaturated monoalcohols having 8 to 24 C atoms, containing zero or 1 to 20 mol of ethylene oxide and/or 1 to 5 mol of propylene oxide per mol of alcohol, or

[0008] b) the polyols having 2 to 6 carbon atoms, optionally partially esterified with fatty acids having 12 to 24 carbon atoms, or

[0009] c) the alkoxylated fatty acids having 12 to 24 carbon atoms and 4 to 20 mol of ethylene oxide per mol of fatty acid, or

[0010] d) the ethoxylated dimeric fatty acids.

[0011] In the context of this application, fuels are understood as meaning all energy-supplying operating materials whose free combustion energy is converted into mechanical work. These include all types of motor and aviation fuels which are liquid at room temperature and atmospheric pressure. Motor fuels, for example for car or lorry engines, contain as a rule hydrocarbons, e.g. petrol fractions or higher-boiling mineral oil fractions. Diesel fuels are obtained from gas oil by cracking or from tars which are obtained in the low-temperature carbonisation of lignite or hard coal. Customary products have a density of between 0.83 and 0.88 g/cm.sup.3, a boiling point between 170 and 360.degree. C. and flash points between 70 and 100.degree. C. The hydrocarbon fuel may comprise any known hydrocarbon fuel or mixtures thereof, therefore such fuels include but shall not be limited to diesel, e.g. petroleum diesel or biodiesel, gasoline, aviation fuel, alcohol, etc. Preferably, the fuels according to the invention contain petroleum diesel or consist of petroleum diesel. They also include the so-called biodiesel, i.e. a fatty acid methyl ester, preferably the methyl ester of rape seed oil fatty acid.

[0012] The fuels according to the invention are distinguished by the fact that they contain only a single component selected from the classes a) to d) and that consequently no expensive and complicated mixtures of different individual substances are required. The additive classes a) to d) used according to the invention are described in more detail below.

[0013] Thus, according to one aspect of the invention, the fuel composition comprises component a).

[0014] Component a)

[0015] Fatty alcohols are to be understood as a meaning primary aliphatic alcohols of the formula (I)

R.sup.1OH (I)

[0016] in which R.sup.1 represents an aliphatic, linear or branched hydrocarbon radical having 8 to 24 carbon atoms and 0 and/or 1, 2 or 3 double bonds. Typical examples are caproic alcohol, caprylic alcohol, 2-exthylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinly alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their industrial mixtures which are obtained, for example, in the high-pressure hydrogenation of industrial methyl esters based on fats and oils or aldehydes from Roelen's oxo synthesis and as a monomer fraction in the dimerisation of unsaturated fatty alcohols. Industrial fatty alcohols having 12 to 18 carbon atoms, such as, for example, coconut fatty alcohol, palm fatty alcohol, palm kernel fatty alcohol or allow fatty alcohol, are preferred. Oleyl alcohol is particularly preferred. Guerbet alcohols having 12 to 16 carbon atoms are furthermore preferred.

[0017] The use of the alkoxylated, preferably ethoxylated and/or propoxylated derivatives of the fatty alcohols of the formula (I) is also particularly preferred. The preparation of these compounds is known and is carried out, for example, by reacting the fatty alcohols in the presence of acidic or basic catalysts with ethylene oxide and/or propylene oxide. Preferred adducts contain 1 to 20 mol of ethylene and/or 1 to 5 mol of propylene oxide per mol of fatty acid. Alkoxylated alcohols which contain 1 to 20 mol of ethylene oxide per mol of fatty alcohol and are free of propylene oxide are particularly preferred. It is furthermore preferable if the radical R represents unsaturated C.sub.12-18 radical. A fatty alcohol ethoxylated with 8 mol of ethylene oxide is to be regarded as a further particularly preferred compound a).

[0018] According to a second aspect of the invention the fuel additive comprises component b).

[0019] Component b)

[0020] In addition to the mono alcohols, polyols and their esterified derivatives are also suitable additives for the fuel according to the invention. Polyols are organic compounds having 2 to 8 carbon atoms and 2 to 4 hydroxyl functions per molecule. These include, for example, ethylene glycol, propylene glycol, butylene glycol and their oligomers, for example butylene diglycol. Another preferably used polyol is glycerol Furthermore, neopentyl compounds, such as pentaerythritol or trimethylolpropane, are suitable components for group b). The partially esterified derivatives of the polyols, for example glycerol mono-and/or diesters with fatty acids having 8 to 22 carbon atoms, are furthermore preferred. Particularly preferred esters are pentaerythritol esters partially esterified with the fatty acids. Other derivatives, such as ethers, for example diethylene glycol monobutyl ether, are also suitable.

[0021] According to a further aspect of the invention the fuel additive comprises component c).

[0022] Component c)

[0023] The compositions according to the invention contain alkoxylated fatty acids as component c). These fatty acid alkoxylates are known compounds and can be prepared by all methods known to a person skilled in the art. The fatty acid alkoxylates contained in the compositions according to the invention contain exclusively ethylene oxide groups as alkoxides. They preferably contain between 4 and 20 mol of ethylene oxide and in particular 2 to 10 mol of ethylene oxide per mol of ester.

[0024] The fatty acid components used are fatty acids have 5 to 30 C atoms and of natural or synthetic origin, in particular straight-chain, saturated or unsaturated fatty acids, including industrial mixtures thereof, as obtainable by lipolysis from animal and vegetable fats and oils, for example from coconut oil, palm kernel oil, soya oil, sunflower oil, colza oil, cottonseed oil, fish oil, beef tallow, and lard; specific examples are caprylic, capric, lauric, lauroleic, myristic, myristoleic, palmitic, palmitoleic, oleic, elaidic, arachic, gadoleic, behenic, and erucic acid.

[0025] According to a further aspect of the invention the fuel additive comprises component d).

[0026] Component d)

[0027] The oligomerisation of unsaturated fatty acids is a known electrocyclic reaction reported in review articles, for example by A. Behr in Fat Sci, Techno. 93, 340 (1991), G. Spiteller in Fac Sci, Technol 94, 41 (1992) or P. Daute et al, in Fat Sci, Technol, 95, 91 (1993). In the oligomerisation, on average two or three fatty acids combine and form dimers or trimers, which have predominantly cycloaliphatic structures. In addition to the fraction comprising the dimers and trimers, a so-called monomer fraction is obtained, which contains unconverted starting materials and branched monomers which have been formed by isomerisation in the course of the reaction. In addition, there is of course also a fraction of higher oligomers which, however, is generally not very important. The oligomerisation can be carried out thermally or in the presence of noble metal catalysts. Preferably, the reaction is carried out in the presence of clays, such as, for example, montmorillonite. The content of dimers and trimers or the amount of monomer fraction can be regulated by the reaction conditions. Industrial mixtures can finally also be purified by distillation. Suitable starting materials for the oligomerisation are industrial unsaturated fatty acids having 12 to 22, preferably 16 to 18, carbon atoms. Typical examples are palmitoleic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, conjuenic fatty acid, elaeostearic acid, ricinoleic acid, gadoleic acid, erucic acid, and their industrial mixtures with saturated fatty acids. Typical examples of suitable industrial mixtures are unhydrogenated cleavage fatty acids or natural triglycerides having iodine numbers in the range from 40 to 140, such as, for example, palm oil acid, tallow fatty acid, colza fatty acid, sunflower fatty acid and the like. Cleavage fatty acids having a higher content of oleic acid are preferred.

[0028] In addition to the fatty acids , it is possible to dimerise their esters, preferably methyl esters. It is also possible to oligomerise the acid and to convert it into the methyl esters prior to hydrogenation. The conversion of the ester group into the acid group takes place in a manner known per se.

[0029] Dimeric fatty acids, which are particularly preferred in the context of the present invention, are obtained by oligomerisation of industrial oleic acid and preferably have a dimer content of 50 to 99% by weight and a polymer content (including trimer content) of 1 to 50% by weight. The content of monomers may be 1 to 15% by weight and, if required, may be reduced by distillation. Dimeric fatty acids which are obtained by oligomerisation are industrial oleic acid and have a dimer content of 70 to 85% by weight, a polymer content of 10 to 20% by weight and a monomer content of 5 to 15% by weight are particularly preferred. The percentages by weight are based on the total amounts of dimeric fatty acid.

[0030] The additive components a) to d) are preferably chosen so that their HLB value is less than 12. The value is calculated as follows:

HLB=Molecular weight of the hydrophilic chain.times.20/total molecular weight.

[0031] According to a further aspect of the invention, the hydrocarbon-based fuel may include an amount of an alcohol or alcohols. Such alcohols are preferentially C1 to C6 alkanols, such as propanol, butanol or ethanol, and isomers thereof. The most preferred alcohol is ethanol. When the hydrocarbon-based fuel comprises an alcohol, then the amount of alcohol present may vary, but is preferably present in an amount of from 1 to 10% by volume. Thus the fuel composition of the invention may comprise at least 85% by volume of a hydrocarbon-based fuel, from 1 to 10% by volume of an alcohol, such as ethanol and from 0.1 to 5% by weight of an additive selected from the groups a), b), c) and d).

[0032] The fuel compositions according to the invention are prepared by mixing the components a), b), c) or d) individually with a fuel/ethanol mixture. Preferred fuel compositions are those in which the volume ratio (v/v) of fuel, e.g. petroleum diesel to additive is in the range of 1000:0.5 to 1000:50, and preferably of 1000:1 to 1000:50.

[0033] In a preferred embodiment of the invention we provide a fuel composition consisting of 90 to 94.5% by volume of diesel oil, 5 to 8% by volume of alcohol, e.g. ethanol and 0.5 to 2% by volume of an additive a), b), c) or d) according to the above description.

[0034] The use of the additives according to the invention makes it possible to prepare mixtures of fuels with alcohol, e.g. ethanol, preferably petroleum diesel with ethanol, in an economical manner. Preferably, a maximum of 0.5 to 2.0% by volume of additive are added to the diesel oil/ethanol mixture. Water may also be present. It is particularly preferable to use substantially anhydrous ethanol which preferably contains less than 0.5% by volume of water. Furthermore, the total fuel composition is preferably anhydrous, i.e. the water content should be less than 0.2% volume, preferably less than 0.11% by volume.

[0035] A further aspect of the present invention relates to a fuel composition consisting of 88 to 98.5% by volume of diesel oil, 1 to 10% by volume of alcohol, e.g. ethanol and 0.5 to 2% by volume of an additive a), b), c) or d) according to the above description.

[0036] For fuels, ethanol may be produced from fossil fuel feedstocks or by fermentation of sugars derived from grains or other biomass materials. Therefore, ethanol suitable for use in accordance with the fuel compositions of the invention may be fuel grade ethanol derived from yeast or bacterial fermentation of starch-based sugars. Such starch-based sugars may be extracted from corn, sugarcane, tapioca and sugar beet. Alternatively, fuel grade ethanol may be produced via known dilute and/or concentrated acid and/or enzymatic hydrolysis of a particular biomass material, for example, from waste industrial sources include, cellulosic portions of municipal solid waster, waste paper, paper sludge, saw dust. Biomass may also be collected from agricultural residues included, for example, rise husks and paper-mill sludge.

[0037] A suitable fuel grade ethanol for use in accordance with the invention may contain none or only contaminant levels of water. It should be noted that fuels containing, e.g. ethanol, may contain trace amounts of water. Thus, for example, anhydrous ethanol will generally contain up to 0.5% w/w of water. Therefore, hereinafter reference to an anhydrous fuel composition should be understood be a composition which is substantially free of water, but may contain, for example, up to 0.5% w/w of water. Alternatively, a suitable fuel grade ethanol for use in accordance with the invention may contain higher amounts of water, up to 5% w/w (hydrous ethanol).

[0038] Use of ethanol in combination with a diesel fuel has previously posed problems wherein the ethanol/diesel fuel mixture would undesirably separate into two distinct phases, especially when water is present, and render the resultant mixture unsuitable for use as a combustible fuel. The use of the fuel additives of the invention permits hydrous ethanol to be blended satisfactorily with conventional diesel fuel without forming two phases. The use of fuel grade ethanol blended in accordance with the invention imparts desirable combustion characteristics to the overall fuel composition; such as improved fuel stability, lower smoke and particulate matter, lower CO and NOx emissions, improved antiknock characteristics, and/or improved anti-freeze characteristics.

[0039] The presence of the additive of the invention ensures that the fuel composition forms a consistent stable homogenous composition and creates a monolayer simultaneously a result of which leads to a better more complete burn which reduced pollution and increases miles per gallon.

[0040] As a result of a blended fuel, particularly alcohol based, is able to combust more precisely with a cooler charge to reduce the iron-formates present from the aldehyde peracids and peroxide reactions normally attributable to engine degradation.

[0041] We further provide a method of running an internal combustion engine comprising the use of a fuel composition of the invention.

[0042] International Patent Application No. WO99/35215, Wenzel, describes an additive for combustible fuels which includes a nitrogen source, such as urea. Whilst the additive is said to reduce NOx, the compositions are very complex and include numerous ingredients, including:

[0043] a water soluble alcohol,

[0044] a C6 to C12 alcohol

[0045] a C6 to C18 ethoxylated alcohol

[0046] a C10 to C24 fatty acid, and

[0047] a nitrogen source.

[0048] We have now surprisingly found that the fuel composition of the invention can comprise very low fuel: additive ratios in combination with nitrogenous compounds, such as urea.

[0049] Thus according to the invention we provide a fuel composition as hereinbefore described and a nitrogen source.

[0050] The nitrogen compound may be selected from the group consisting of ammonia, hydrazine, alkyl hydrazine, dialkyl hydrazine, urea, ethanolamine, monoalkyl ethanolamine, and dialkyl ethanolamine wherein alkyl is independently selected from methyl, ethyl, n-propyl or isopropyl. Urea is preferred. The nitrogen compound may be an anhydrous compound or a hydrous compound, e.g. an aqueous solution, and may be up to a 5% w/w aqueous solution.

[0051] According to a yet further feature of the invention we provide a method of solubilising a nitrogen compound in a fuel composition which comprises mixing a hydrocarbon fuel, a nitrogen compound and a fuel additive as hereinbefore described. The method of the invention may optionally include the addition of an alcohol, such as ethanol or water, as hereinbefore described.

[0052] We also provide the use of a nitrogen compound in the manufacture of a fuel additive of this aspect of the invention. We especially provide the use of urea in the manufacture of fuel additive of the invention.

[0053] In the fuel composition in this aspect of the invention the nitrogen compound may be added by being incorporated into the fuel additive or may be added separately. Furthermore, the nitrogen compound maybe added as an aqueous solution.

[0054] The fuel composition of the invention may also optionally comprise a cetane booster in amount of from 0.1% v/v to 1.0% v/v, based on the volume of the mixture. When a cetane booster is included in the fuel composition of the invention it may be added as part of the fuel additive of the invention or it may be added separately.

[0055] A suitable cetane booster for use in the mixture is selected from the group comprising, 2-ethylhexyl nitrate, tertiary butyl peroxide, diethylene glycol methyl ether, cyclohexanol, and mixtures thereof. The amount of cetane booster present in the mixture is a function of the cetane value of the particular diesel fuel and the amount of ethanol present in the particular fuel composition. Generally, the lower the diesel fuel cetane value, the higher the amount of the octane booster, similarly, because ethanol typically acts as a cetane depressant, the higher the concentration of ethanol in the solution, the more cetane booster may be necessary in the mixture.

[0056] The fuel additives of the invention are advantageous in that, inter alia, they are more efficient at producing micro emulsions than prior art additives. Therefore, they are capable of more efficiently producing a stable, clear and homogenous solution with a hydrocarbon fuel, e.g. diesel/ethanol, even in the presence of water. Therefore, according to a further feature of the invention we provide a fuel composition as hereinbefore described, which optionally includes an amount of water, and wherein the fuel consists of a substantially stable, clear and substantially homogeneous solution.

[0057] Furthermore, the fuel additive or the fuel composition of the invention may also optionally include a demulsifier in an amount of less than 5% v/v and preferably less than 1% v/v based on the volume of the mixture.

[0058] The effect of the additives is to be understood in the sense that they have a solubilising effect. Accordingly, the use of the components a) to d) as solubilisers for ethanol-containing diesel fuels is also claimed.

[0059] We also provide the use of components a) to d) in the manufacture of a fuel composition as hereinbefore described.

[0060] The invention will now be described by way of example only.

EXAMPLE 1

[0061] The effect of the additives according to the invention was tested by the cold filter plugging point test (CFPP) according to EN 116: 1997.

[0062] According to the test method, the additive-containing fuel was cooled stepwise to -30.degree. C. for this purpose, in each case a sample being taken at 1.degree. C. temperature intervals and being sucked through a standardised filter means at reduced pressure of 2 kPa. The stated temperature value then corresponds to the temperature at which the fuel can no longer flow through the filter means in a specified time. Typical of the results obtained for compounds of the invention, was oleyl alcohol +4.6 EO which gave a CFPP value of -18.degree. C. which corresponds to the value for diesel without additives.

EXAMPLE 2

[0063] Preparation and Compositions

[0064] An additive composition was made up ethoxylated oleic acid and 1% by volume of this composition was added to 7.7% ethanol/92.3% diesel blends, including certification diesel, US No 1 (10% aromatic) diesel containing 0.1% cetane improver, resulting in optically clear and stable micro-emulsion fuels. These were tested as automotive fuels on a 1991 Detroit Diesel Series 60 engine using the EPA (USA Environmental Protection Agency) heavy duty engine certification test as described in the Code of Federal Regulations, Title 40, Part 86, Subpart N.

[0065] Toxic exhaust gas omissions were measured and compared with those of the base un-additised diesel. Significant reductions were obtained of toxic gases CO, CO.sub.2, NOx and particulate matter.

EXAMPLE 3

[0066] A comparison was made of the solubilising efficiency of a typical additive of the invention viz. mono ethoxylated oleic acid and an additive of the prior art, when used to stabilise a fuel blend of hydrous ethanol (7.7% v/v) and diesel (92.3% v/v).

[0067] The prior art additive contained 25% diethanolamide, 50% ethoxylated C9-11 alcohol and 25% of a C14 fatty acid ethoxylated with 7 moles EO.

[0068] Experimentally, ethanol/diesel blends were made up with water contents up to 0.6% v/v and the amount of additive required to produce clear, stable solutions determined volumetrically.

[0069] The solubilising ratio i.e. the volume of prior art additive divided by the volume of the additive of the invention, was plotted against water content (see FIG. 1). The results confirm that the additive of the invention is considerably more effective especially at low water concentrations.

EXAMPLE 4

[0070] Petroleum Diesel/Biodiesel/Ethanol Blend

[0071] A Blend was made of certification diesel, biodiesel and ethanol stabilised with the surfactant additive described in Example 1. Engine exhaust emission tests showed reductions in CO, NOx and particulate matter compared with the base diesel.

EXAMPLE 5

[0072] Petroleum Diesel/Ethanol/Urea Blend

[0073] Example A solution of 0.25% urea in ethanol was blended in a 7.7:92.3 ratio with US No 1 diesel and 1.0% of additive was added to produce a clear micro-emulsion automotive fuel. Tests using this blend showed that toxic gas emissions were again lower than the base fuel, the urea having made a contribution to the reductions obtained.

EXAMPLE 6

[0074] Gasoline/Ethanol Blends

[0075] Blends were made up of EPA and CARD gasolines with various amounts of ethanol e.g. a typical blend contained 90% v/v gasoline and 10% ethanol. Small amounts, typically 1% v/v of the additive of the invention were added to the gasoline/ethanol blends and the resulting fuels tested as automotive fuels and the exhaust emissions compared with those of the base gasolines. The results confirmed that ethanol/gasoline blends combust to give lower levels of toxic gas emissions.

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