Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/12—Inorganic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1857—Aldehydes; Ketones
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1608—Well defined compounds, e.g. hexane, benzene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1691—Hydrocarbons petroleum waxes, mineral waxes; paraffines; alkylation products; Friedel-Crafts condensation products; petroleum resins; modified waxes (oxidised)
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1888—Carboxylic acids; metal salts thereof tall oil
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols

Definitions

• the present invention relates to a fuel composition, and methods and uses of such compositions.
• the present invention relates to compositions which may be used to reduce soot content and ash content of an exhaust of a combustion system for fuel.
• the invention also relates to an essentially hydrocarbon mixture (HC mixture) which burns so as to produce very little soot, particularly heating oil and a corresponding additive concentrate.
• HC mixture essentially hydrocarbon mixture
• Ferrocene and its derivatives are known from the literature. Ferrocene and its manufacture were described for the first time in Nature 168 (1951), Page 1039 . Since then, ferrocene and its derivatives as well as corresponding manufacturing procedures have been the object of numerous patents, e.g. US 2 769 828 , US 2 834 796 , US 2 898 360 and US 3 437 634 .
• DE 34 18 648 names ferrocene (dicyclopentadienyl iron) as a possible additive in order to optimise combustion of heating oil. This optimised combustion encourages complete combustion of the heating oil.
• US 3 925 031 teaches that an additive which contains camphor and naphthalene among others can be added to a gasifier fuel, a diesel fuel or a lubricating oil.
• camphor has been used in fuel to provide a reduction in either fuel consumption or hazardous emissions.
• camphor is not known to reduce soot. Rather, as discussed in US 5 116 390 , a disadvantage of using camphor is that additional soot formation is noted on burning fuel that contains camphor as an additive.
• US 3 925 031 teaches that use of camphor in gasoline in sufficient quantities to increase the effective octane rating of the gasoline also results in a reduction of combustion efficiency and a corresponding increase in the quantity of unburned carbon, leading to sooty exhaust particles.
• CN 1597873 discloses a fuel which includes methanol, hydrogen peroxide, ferrocene and camphor that reduces the harmful emissions.
• CN 1325945A relates to an oil-saving additive for diesel oil prepared from ferrous naphthenate manganese naphthenate, naphthalene, camphor, polymethacryl butanediimide, N-octadecamine oleoxysarocisinate, antioxidant, xylene and butyl acetate.
• RU 2105041 describes fuel composition based on engine fuel - containing additives in form of iron salts of fatty acids and camphor group compounds.
• the present invention alleviates the problems of the prior art.
• the present invention provides a fuel composition as defined in present claim 1.
• the task of the invention is to provide a hydrocarbon mixture which contains an organic iron compound in combination with a further component which leads to a considerable reduction in soot. That is the combination of the iron compound and the further component produces a greater reduction in the amount of soot compared to that observed if the same quantity of iron compound is used alone, or to that observed if the same quantity of the further component is used alone.
• the quantity of the iron compound used in the mixture may be reduced to a level where, if the iron compound were used on its own, its catalytic effect in respect of soot reduction would be minimal.
• This task is fulfilled by means of a hydrocarbon mixture which produces little soot on combustion with at least 0.1 ppm ferrocene and at least 1 ppm camphor added.
• metal compounds such as ferrocene
• metal compounds can improve combustion in a combustion system and reduce carbon deposits leading to a reduction in the amount of soot observed in the exhaust of the combustion system.
• the quantity of iron compound required to produce an adequate reduction in soot also leads to an increased amount of ash being formed.
• organic compounds such as camphor
• do not produce ash but are known to increase the amount of soot observed.
• compositions comprising a metal compound in small quantities, such as ferrocene, and an organic compound, such as camphor, can provide good reductions in soot whilst only producing low amounts of ash.
• such a composition provides significantly better soot reduction than is observed if the same amount of metal compound is used in the absence of the organic compound.
• the metal compound (i) is selected from an iron compound, a manganese compound, a calcium compound, a cerium compound, and mixtures thereof.
• the metal compound (i) is selected from an iron compound, methylcyclopentadienyl manganese tricarbonyl, manganese(II) 2-ethylhexanoate, manganese naphthenate, calcium 2-ethylhexanoate, calcium napthenate, calcium sulfonate, cerium(III) 2-ethylhexanoate, cerium sulfonate, and mixture thereof.
• the metal compound (i) for use in the invention are fuel soluble or dispersible and preferably fuel stable.
• the precise nature of the metal containing compounds is less important.
• manganese carbonyl compounds comprise organomanganese polycarbonyl compounds.
• organomanganese polycarbonyl compounds For best results, use should be made of a cyclopentadienyl manganese tricarbonyl compound of the type described in U.S. Pat. Nos. 2,828,417 and 3,127,351 .
• cyclopentadienyl manganese tricarbonyl methylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, dimethylcyclopentadienyl manganese tricarbonyl, trimethylcyclopentadienyl manganese tricarbonyl, propylcyclopentadienyl manganese tricarbonyl, isopropylcyclopentadienyl manganese tricarbonyl, butylcyclopentadienyl manganese tricarbonyl, pentylcyclopentadienyl manganese tricarbonyl, hexylcyclopentadienyl manganese tricarbonyl, ethylmethylcyclopentadienyl manganese tricarbonyl, dimethyloctylcyclopentadienyl manganese tricarbonyl, dodecylcyclopenta
• the manganese compound is an organomanganese compound.
• a preferred organomanganese compound is cyclopentadienyl manganese tricarbonyl. Particularly preferred for use in the practice of this invention is methylcyclopentadienyl manganese tricarbonyl.
• organomanganese compounds include the acyl manganese tricarbonyls such as methylacetyl cyclopentadienyl manganese tricarbonyl and benzoyl methyl cyclopentadienyl manganese tricarbonyl, described in U.S. Pat No. 2,959,604 ; the aryl manganese pentacarbonyls such as phenyl manganese pentacarbonyl, described in U.S. Pat. 3,007,953 ; and the aromatic cyanomanganese dicarbonyls such as mesitylene cyanomanganese dicarbonyl, described in U.S. Pat. No. 3,042,693 .
• cyclopentadienyl manganese dicarbonyl compounds of the formula RMn(CO) 2 L where R is a substituted or unsubstituted cyclopentadienyl group having 5 to 18 carbon atoms, and L is a ligand, such as an olefin, an amine, a phosphine, SO 2 tetrahydrofuran, or the like.
• R is a substituted or unsubstituted cyclopentadienyl group having 5 to 18 carbon atoms
• L is a ligand, such as an olefin, an amine, a phosphine, SO 2 tetrahydrofuran, or the like.
• Such compounds are referred to, for example in, Herberhold, M., Metal ⁇ -Complexes, Vol. II, Amsterdam, Elsevier, 1967 or Giordano, P.J. and Weighton, M. S., Inorg. Chem., 1977,
• the manganese compound is selected from cyclopentadienyl manganese tricarbonyl and substituted cyclopentadienyl manganese tricarbonyl.
• the manganese compound may be cyclopentadienyl manganese tricarbonyl and substituted cyclopentadienyl manganese tricarbonyl, wherein the substituents can be, for example, one or more C 1-5 alkyl groups, preferably C 1-2 alkyl groups. A combination of such manganese complexes may also be used.
• the manganese compound is selected from cyclopentadienyl manganese tricarbonyl and substituted cyclopentadienyl manganese tricarbonyl.
• the manganese compound is methylcyclopentadienyl manganese tricarbonyl (MMT).
• the calcium compound is calcium sulfonate.
• the cerium compound is selected from cerium(III) 2-ethylhexanoate, cerium sulfonate, and mixtures thereof.
• the metal compound (i) is an iron compound or a mixture of iron compounds.
• the iron compound is an iron complex selected from bis-cyclopentadienyl iron; substituted bis-cyclopentadienyl iron; iron tallate and iron octoate; and mixtures thereof.
• the iron compound is an iron complex selected from bis-cyclopentadienyl iron, substituted bis-cyclopentadienyl iron and mixtures thereof.
• the iron compound is a substituted bis-cyclopentadienyl iron selected from adamantyl bis-cyclopentadienyl iron, bis(dicyclopentadienyl-iron) dicarbonyl and mixtures thereof.
• Bis(dicyclopentadienyl-iron) dicarbonyl is also known as cyclopentadienyliron dicarbonyl dimer.
• the iron compound is an iron complex selected from bis-cyclopentadienyl iron, adamantyl bis-cyclopentadienyl iron, bis(dicyclopentadienyl-iron)dicarbonyl, iron tallate and iron octoate; and mixtures thereof.
• Suitable substituted bis-cyclopentadienyl iron complexes are those wherein the substituents can be, for example, one or more C 1-30 alkyl groups, preferably C 1-20 alkyl groups, preferably C 1-10 alkyl groups, alkyl groups, preferably C 1-2 alkyl groups. A combination of such iron complexes may also be used.
• Suitable alkyl-substituted-dicyclopentadienyl iron complexes are cyclopentadienyl-(methylcyclopentadienyl) iron, cyclopentadienyl(ethyl-cyclopentadienyl) iron, bis-(methylcyclopentadienyl) iron, bis-(ethylcyclopentadienyl) iron, bis-(1,2-dimethylcyclopentadienyl) iron, and bis-(1-methyl-3-ethylcyclo-pentadienyl) iron.
• These iron complexes can be prepared by the processes taught in US-A-2680756 , US-A-2804468 , GB-A-0733129 and GB-A-0763550 .
• Another volatile iron complex is iron pentacarbonyl.
• Suitable iron complexes are bis-cyclopentadienyl iron and/or bis-(methylcyclo-pentadienyl) iron.
• transition metals including iron
• hydrocarbon solvents e.g. diesel fuel
• Substituted bis-cyclopentadienyl complex of iron for use in the invention include those in which substitution may be on either or both of the cyclopentadienyl groups.
• Suitable substituents include, for example, one or more C 1-5 alkyl groups, preferably C 1-2 alkyl groups.
• Particularly suitable alkyl-substituted-dicyclopentadienyl iron complexes include cyclopentadienyl(methylcyclopentadienyl) iron, bis-(methylcyclopentadienyl) iron, bis-(ethylcyclopentadienyl) iron, bis-(1,2-dimethylcyclopentadienyl) iron and 2,2-diethylferrocenyl-propane.
• substituents that may be present on the cyclopentadienyl rings include cycloalkyl groups such as cyclopentyl, aryl groups such as tolylphenyl, and acetyl groups, such as present in diacetyl ferrocene.
• a particularly useful substituent is the hydroxyisopropyl group, resulting in ( ⁇ -hydroxyisopropyl) ferrocene.
• ( ⁇ -hydroxyisopropyl)ferrocene is a room temperature liquid.
• Ferrocenes linked by a "bridge” may be used in the present invention. Suitable compounds are taught in WO 02/018398 and WO 03/020733 . Thus, a suitable "bridge” linking ferrocenes may be a unsubstituted or substituted hydrocarbyl group.
• the term "unsubstituted or substituted hydrocarbyl group” as used herein means a group comprising at least C and H and which may, optionally, comprise one or more suitable substituents. In a preferred embodiment one carbon atom of the "bridge” hydrocarbyl group is attached to two ferrocene moieties, hence, bridging the ferrocenes.
• a typical unsubstituted or substituted hydrocarbyl group is an unsubstituted or substituted hydrocarbon group.
• hydrocarbon means any one of an alkylene group, an alkenylene group, an alkynylene group, which groups may be linear, branched or cyclic, or an aryl group.
• the unsubstituted or substituted hydrocarbon group may be an alkylene, branched alkylene or cycloalkylene group.
• the term hydrocarbon also includes those groups but wherein they have been optionally substituted.
• hydrocarbon is a branched structure having substituent(s) thereon
• substitution may be on either the hydrocarbon backbone or on the branch; alternatively the substitutions may be on the hydrocarbon backbone and on the branch.
• a preferred unsubstituted or substituted hydrocarbon group is an unsubstituted or substituted alkylene group having at least one carbon atom in the alkylene linkage. More preferably, the unsubstituted or substituted hydrocarbon group is an unsubstituted or substituted alkylene group having from 1 to 10 carbon atoms in the alkylene linkage, for example, having at least 2 carbon atoms in the alkylene linkage or having one carbon atom in the alkylene linkage.
• the hydrocarbyl group comprises more than one C then those carbons need not necessarily be linked to each other.
• at least two of the carbons may be linked via a suitable element or group.
• the hydrocarbyl group may contain hetero atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for instance, sulphur, nitrogen and oxygen, for example, oxygen.
• a preferred iron complex is ferrocene (i.e. bis-cyclopentadienyl iron).
• Ferrocene derivatives can be used at least in part instead of ferrocene.
• Ferrocene derivatives are compounds where, starting from a basic ferrocene molecule, further substituents are found on one or both of the cyclopentadienyl rings. Examples could be ethylferrocene, butylferrocene, acetylferrocene and 2,2-bis-ethylferrocenylpropane.
• Geminal bisferrocenylalkanes are also suitable, as described, for example, in DE 201 10 995 and DE 102 08 326 .
• the substituted ferrocenes are preferred iron compounds for use in the invention.
• Ferrocene itself is an especially preferred iron compound on this basis.
• Ferrocene of suitable purity is sold in a range of useful forms as PLUTOcen RTM and as solutions, Satacen RTM both by Innospec GmbH.
• the iron compounds for use in the invention need not feature iron-carbon bonds in order to be fuel compatible and stable. Salts may be used; these may be neutral or overbased. Methods for the preparation of metal soaps are described in The Kirk-Othmer Encyclopaedia of Chemical Technology, 4th Ed, Vol. 8:432-445, John Wiley & Sons, 1993 . Suitable stoichiometric, or neutral, iron carboxylates for use in the invention include the so-called 'drier-iron' species, such as iron tris(2-ethylhexanoate) [19583-54-1].
• the organic compound (ii) is selected from a bicyclic monoterpene, substituted bicyclic monoterpene, adamantane, propylene carbonate and mixtures thereof.
• the organic compound (ii) is selected from a bicyclic monoterpene, substituted bicyclic monoterpene and mixtures thereof.
• Suitable substituted bicyclic monoterpenes are those wherein the substituents can be, for example, one or more of aldehyde, ketone, alcohol, acetate and ether functional groups.
• the organic compound (ii) is a bicyclic monoterpene or substituted bicyclic monoterpene selected from camphor, camphene, isobornyl acetate, dipropyleneglycol-isobornyl ether and mixtures thereof.
• the organic compound (ii) is selected from camphor, camphene, isobornyl acetate, dipropyleneglycol-isobornyl ether, adamantane, propylene carbonate and mixtures thereof.
• the organic compound (ii) is camphor.
• Camphor has the systematic name 1,7,7-trimethylbicyclo[2.2.1]heptan-2-one.
• Camphor has the following structure:
• an additive composition for a fuel comprising:
• the composition comprises less than 10 wt %, preferably less than 5 wt %, preferably less than 2 wt %, preferably less than 1 wt %, preferably less than 0.5 wt %, preferably less than 0.1 wt %, preferably less than 0.05 wt %, preferably less than 0.01 wt % methanol.
• an additive composition for a fuel comprising:
• C1 to C5 alcohol means a straight chain or branched alcohol containing between 1 and 5 carbon atoms, such as methanol, ethanol, propanol, butanol and pentanol.
• An example of a suitable branched alcohol is tertiary butanol.
• substantially free of C1 to C5 alcohol comprises less than 10 wt %, preferably less than 5 wt %, preferably less than 2 wt %, preferably less than 1 w t%, preferably less than 0.5 wt %, preferably less than 0.1 wt %, preferably less than 0.05 wt %, preferably less than 0.01 wt % C1 to C5 alcohol compounds.
• an additive composition for a fuel comprising:
• composition comprises less than 10 wt %, preferably less than 5 wt %, preferably less than 2 wt %, preferably less than 1 w t%, preferably less than 0.5 wt %, preferably less than 0.1 wt %, preferably less than 0.05 wt %, preferably less than 0.01 wt % alcohol.
• an additive composition for a fuel comprising:
• the composition comprises less than 10 wt %, preferably less than 5 wt %, preferably less than 2 wt %, preferably less than 1 wt %, preferably less than 0.5 wt %, preferably less than 0.1 wt %, preferably less than 0.05 wt %, preferably less than 0.01 wt % of hydrogen peroxide.
• the metal compound (i) is bis-cyclopentadienyl iron and the organic compound (ii) is camphor.
• the additive composition further comprises a solvent.
• the additive composition prefferably be added as a solution of the active components in a solvent. It is preferable for such solutions to exhibit a high concentration of the active components in the solvent. Ideal solvents are those in which all the active ingredients dissolve equally well and which form a solution which is stable over prolonged storage periods, and also under cold conditions.
• the solvent is selected from an aromatic compound, a paraffin compound and mixtures thereof.
• paraffin compound includes both straight chain and branched chain compounds.
• the branched chain compounds are also known as iso-paraffins.
• the additive composition for a fuel comprises the metal compound or compounds (i) in an amount sufficient to provide less than 30,000 ppm of the metal; preferably less than 15,000 ppm; preferably less than 6,000 ppm.
• the additive composition for a fuel comprises the metal compound or compounds (i) in an amount sufficient to provide from 3 ppm to 30,000 ppm of the metal; preferably from 15 ppm to 15,000 ppm; preferably from 60 ppm to 6,000 ppm.
• the additive composition for a fuel comprises less than 90,000 ppm of the metal compound (i); preferably less than 45,000 ppm; preferably less than 18,000 ppm.
• the additive composition for a fuel comprises from 10 ppm to 90,000 ppm of the metal compound (i); preferably from 50 ppm to 45,000 ppm; preferably from 200 ppm to 18,000 ppm.
• the additive composition for a fuel comprises at least 100 ppm of the organic compound (ii); preferably at least 500 ppm; preferably at least 1,000 ppm; preferably at least 2,000 ppm; preferably at least 10,000 ppm; preferably at least 50,000 ppm; preferably at least 80,000 ppm; preferably at least 100,000 ppm.
• the additive composition for a fuel comprises from 100 ppm to 700,000 ppm of the organic compound (ii); preferably from 500 ppm to about 350,000 ppm; preferably from about 2,000 ppm to about 140,000 ppm; preferably from about 50,000 ppm to about 130,000 ppm; preferably from about 80,000 ppm to about 120,000 ppm.
• the fuel additives be added as part of a package to the fuel prior to combustion. This may be done at any stage in the fuel supply chain (for example, at the refinery or distribution terminal) or may be added via a dosing device associated with the combustion system, for examples, on-board the vehicle. If a dosing device is used it may dose the additives either to the fuel or even separately direct into the combustion chamber or inlet system.
• the fuel additives may be added to the fuel in the combustion systems' fuel tank by the user, a so-called 'aftermarket' treatment.
• the additive composition is a solution.
• the additive composition is for addition to a fuel.
• Such an additive might be dosed at any stage in the fuel supply chain prior to combustion of the fuel.
• the fuel additives of the invention may be dosed to the fuel at any stage in the fuel supply chain.
• each additive is added to the fuel close to the engine or combustion system, within the fuel storage system for the engine or combustion system at the refinery, distribution terminal or at any other stage in the fuel supply chain, including aftermarket use.
• the additive may be added to the fuel at the refinery or at the distribution terminal.
• the volume of solvent used will be such as to provide a non-viscous solution, suitable for use in a dispenser bottle or syringe pack.
• the solvents to be used should be readily fuel soluble and compatible, including with respect to boiling point range, and preferably will have flash points in excess of 62°C for ease of storage.
• the additive composition for a fuel is an additive concentrate composition.
• the fuel is selected from gasoline, diesel, marine fuel, heating oil, middle distillate oil, ,heavy fuel oil and including such fuels containing renewable or bio-derived components and commonly termed bio-fuel, e.g. bio diesel.
• the fuel is selected from biofuel, diesel, marine fuel, heating oil, middle distillate oil and heavy fuel oil.
• the fuel is selected from diesel, marine fuel, heating oil, middle distillate oil and heavy fuel oil
• the fuel is gasoline.
• the fuel is a fuel for spark ignition engines such as gasoline.
• the fuel is a fuel for a high compression spontaneous ignition engine.
• the fuel is diesel.
• the diesel may be biodiesel, low sulphur diesel and ultra-low sulphur diesel.
• the fuel is marine fuel or bunker fuel.
• the fuel is heating oil, for example, kerosene.
• a light heating oil Preferably, the light heating oil is HEL: Schuöl extracetten according to DIN 51603, Part 1.
• the fuel is a middle distillate oil.
• the fuel is a heavy fuel oil.
• the fuel is a hydrocarbon mixture, preferably, a liquid hydrocarbon mixture.
• the fuel composition comprises at least 0.1 ppm of the metal compound (i).
• the fuel composition comprises 9 ppm or less of the metal compound (i); preferably 8 ppm or less of the metal compound (i).
• the fuel composition comprises the metal compound (i) in from 0.1 ppm to 9 ppm.
• the fuel composition comprises the metal compound (i) in from 0.5 ppm to 8 ppm.
• the metal compound (i) is ferrocene
• 0.1 ppm of ferrocene is an amount sufficient to provide 0.03 ppm of the metal (iron).
• the fuel composition comprises a metal compound (i) in an amount sufficient to provide 0.03 ppm of the metal, it would be present in an equivalent amount to 0.1 ppm of ferrrocene.
• the fuel composition comprises the metal compound (i) in an amount sufficient to provide at least 0.03 ppm of the metal.
• the fuel composition comprises the metal compound (i) in an amount to provide 2.70 ppm or less of the metal.
• the fuel composition comprises the metal compound (i) in an amount to provide 2.40 ppm or less of the metal.
• the fuel composition comprises the metal compound (i) in an amount sufficient to provide from 0.03 ppm to 2.70 ppm of the metal.
• the fuel composition comprises the metal compound (i) in an amount sufficient to provide from 0.15 ppm to 2.40 ppm of the metal.
• the fuel composition comprises 70 ppm or less of the organic compound (ii); preferably 60 ppm or less; preferably 50 ppm or less.
• the fuel composition comprises at least 1 ppm of the organic compound (ii).
• the fuel composition comprises the organic compound (ii) in from 1 ppm to 70 ppm; preferably from 10 ppm to 60 ppm; preferably from 20 ppm to 50 ppm.
• the fuel composition is provided by diluting an additive concentrate composition in the fuel.
• the ratio of additive concentrate composition to fuel is from 1: 100 to 1:10,000; preferably from 1:500 to 1:8,000; preferably from 1:1,000 to 1:5,000; preferably from 1:1,500 to 1:3000.
• the fuel composition is substantially free of methanol.
• the fuel composition is substantially free of C1 to C5 alcohol.
• the fuel composition is substantially free of alcohol.
• the composition is substantially free of hydrogen peroxide.
• the metal compound (i) is bis-cyclopentadienyl iron and the organic compound (ii) is camphor.
• This system may be used in many different application areas.
• the application area is diesel fuel.
• the application area is marine fuels.
• the application area is heating oil.
• the application area is middle distillate oil.
• the application area is heavy fuel oil
• the application area is the regeneration of diesel particulate filters.
• the application area is the reduction of soot content and ash content of an exhaust of a combustion system.
• the application area is the improvement of combustion efficiency of a combustion system.
• the application area is the improvement of fuel economy of a combustion system.
• the present invention provides a hydrocarbon mixture which produces little soot on combustion with at least 0.1 ppm ferrocene and at least 1 ppm camphor added.
• camphor is meant a group of compounds consisting of double-ring-form, monoterpenic hydrocarbons such as camphene or phenzene, or analog aldehydes or monoterpenic ketones, for example phenzione. 1,7,7-trimethylbicyclo[2.2.1]heptan-2-one is preferred.
• a preferred ferrocene concentration therefore does not exceed 9 ppm, but is preferably 8 ppm or less.
• the concentration of camphor should also not exceed 70 ppm and is preferably a maximum of 60 ppm, in particular a maximum of 50 ppm.
• the majority of the hydrocarbons contained in the hydrocarbon mixture are petroleum derived.
• the hydrocarbon mixtures can also contain other natural or renewable materials, such as, for example, rapeseed oil methyl ester.
• Particularly suitable hydrocarbon mixtures consist of middle distillates, as are manufactured in crude oil refineries.
• Such middle distillates are the main component of diesel oils and of heating oils, in particular heating oils with particularly low viscosity.
• the precise specification of such products is laid down in DIN standards.
• heating oils serve, as the name suggests, to provide heat. For this purpose they are burnt using special burners and with the addition of air.
• the advantages of the present invention become particularly clear in such applications, as the present application produces less visible smoke, and less measurable soot.
• a further object of the invention is an additive concentrate for manufacture of a hydrocarbon mixture with additive as described herein in numbered paragraph (1), with a content of 0.1-25 ppm ferrocene or, in relation to iron, an equivalent volume of another organic iron component which can dissolve in hydrocarbon, along with 1 to 80 ppm camphor.
• hydrocarbon mixtures to which no additive has been added can be transformed into hydrocarbon mixtures according to the invention, by adding a corresponding quantity of the concentrate to the hydrocarbon mixture and preferably mixing it so that it is homogeneous. It would also be possible to add corresponding amounts of ferrocene and camphor separately to the mixture. However, it would not only be necessary to ensure correct relation of the concentrate to the hydrocarbon mixture, but also the correct relation of the individual additive components to one another. Therefore it is simpler and more customer-friendly to offer an additive which already contains ferrocene and camphor in the correct relation to one another. Preferably the relation by weight of ferrocene to camphor is 7:40 in the additive concentrate.
• the additive concentrate and/or the fuel may further comprise further additives, such as performance-enhancing additives.
• further additives include corrosion inhibitors, rust inhibitors, gum inhibitors, anti-oxidants, solvent oils, anti-static agents, dyes, anti-icing agents, ashless dispersants and detergents.
• the ratio of metal compound (i) (measured in ppm) to organic compound (ii) (measured in ppm) is from 9:1 to 1:700.
• the ratio of metal compound (i) to organic compound (ii) is from 2:1 to 1:100; preferably from 1:1 to 1:10; preferably from 1:2 to 1:8; preferably from 1:3 to 1:7.
• the ratio of metal provided by the metal compound (i) (measured in ppm) to organic compound (ii) (measured in ppm) is from 27:10 to 3:7000.
• the ratio of metal provided by the metal compound (i) to organic compound (ii) is from 6:10 to 3:1000; preferably from 3:10 to 3:100; preferably from 3:20 to 3:80; preferably from 3:30 to 3:70.
• the present invention provides a method for combustion of a fuel composition in a combustion system, comprising providing a fuel composition as defined in the claims.
• the combustion system is selected from a burner, engine and furnace.
• the combustion system is selected from a burner and a furnace.
• the combustion system is an engine.
• the engine is a compression ignition engine (diesel engine).
• the combustion system is an engine.
• the engine is a spark ignition engine.
• the present invention provides a use as defined in the claims.
• the present invention provides a use of a fuel composition as herein defined for reducing soot content and ash content of an exhaust of a combustion system for fuel.
• the Bacharach soot number is a qualitative measure for evaluating the completeness of combustion, based on the optical absorption of visible light by particles that have been deposited on a filter.
• the Bacharach soot number is part of the required testing procedure for judging the combustion quality of oil burners in countries such as Switzerland.
• a well defined amount of undiluted flue gas is sucked through a white filter, leaving behind a discoloured spot.
• the colour of the spot is compared with a calibrated gray scale reaching from 0 (white) to 9 (black). This number is assessed electronically by measuring the reflectance of visible light shone on the loaded filter. The discolouring of the sample filter is attributed to the presence of black shoot.
• the fuel composition provides a 0.5 reduction in the Bacharach soot number compared with the Bacharach soot number observed with the fuel alone.
• the fuel composition provides a 0.8 reduction in the Bacharach soot number; preferably a 1.0 reduction in the Bacharach soot number; preferably a 1.2 reduction in the Bacharach soot number: preferably a 1.5 reduction in the Bacharach soot number; preferably a 1.8 reduction in the Bacharach soot number; preferably a 2.0 reduction in the Bacharach soot number compared with the Bacharach soot number observed with the fuel alone.
• the fuel composition provides a Bacharach soot number of less than 1.0; preferably, less than 0.9; preferably, less than 0.8; preferably, less than 0.7; preferably, less than 0.6; preferably, less than 0.5.
• the soot content is measured by ASTM test method D-2156.
• the fuel composition provides an ash content of 0.010 wt % or less.
• the fuel composition provides an ash content of 0.009 wt % or less; 0.008 wt % or less; 0.007 wt % or less; 0.006 wt % or less; 0.005 wt % or less; 0.004 wt % or less; 0.003 wt % or less; 0.002 wt % or less; 0.001 wt % or less.
• Ash content may be measured according to the standard method DIN EN 6245.
• the steel hot water boiler was brought up to operating temperature with additive-free heating oil.
• a smoke spot number of approximately 4 was set by throttling the air feed to the burner.
• the duration of the trial was approximately 0.75 hours, and then the smoke spot number was measured.
• camphor is meant a group of compounds consisting of double-ring-form, monoterpenic hydrocarbons such as camphene or phenzene, or analog aldehydes or monoterpenic ketones, for example phenzione. 1,7,7-trimethylbicyclo[2.2.1]heptan-2-one is preferred.

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• Inorganic Chemistry (AREA)
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