JP2009500466A - Composition - Google Patents

Abstract

  The present invention provides fuel additive compositions, fuel compositions, and methods and uses for such compositions. Specifically, the present invention relates to compositions that can be used to reduce soot and ash in the exhaust of fuel combustion systems. Specifically, such a composition comprises (i) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof, and (ii) bicyclic monoterpenes, substituted bicyclic mono Including organic compounds selected from terpenes, adamantanes, propylene carbonates and mixtures thereof.

Description

  The present invention provides fuel additive compositions, fuel compositions, and methods and uses for such compositions. Specifically, the present invention relates to compositions that can be used to reduce soot and ash in the exhaust of fuel combustion systems. The invention also relates to a mixture consisting essentially of hydrocarbons (HC mixture) that burns with little soot formation, in particular heating kerosene and corresponding additive concentrates.

  Ferrocene and its derivatives are well known from the literature. Ferrocene and its products were first described in Nature 168 (1951), Page 1039. Since then, ferrocene and its derivatives have been prepared with a number of corresponding procedures, including, for example, U.S. Pat. No. 2,769,828, U.S. Pat. No. 2,847,796, U.S. Pat. No. 2,898,360 and U.S. Pat. No. 3,437,634. It is a subject of patent.

  In addition to many other compounds, DE 3418648 describes the use of ferrocene (dicyclopentadienyl iron) as a potential additive candidate for optimizing the combustion of heating kerosene. Name it. Such combustion optimization promotes complete combustion of heating kerosene.

  U.S. Pat. No. 4,389,220 describes a two-stage process for regulating a diesel motor. According to this patent, carbon deposits in the combustion chamber can be removed by first charging a large amount of ferrocene, 20-30 ppm, into the diesel fuel, and a layer of catalytic iron oxide is deposited on the combustion surface. be able to. Thereafter, this catalytic iron oxide coating is maintained with a small amount of ferrocene, 10-15 ppm. At the same time, it was found that the fuel consumption can be reduced by up to 5% by such means. Since it is difficult to add an organic iron compound such as ferrocene to a fuel in a solid form, a concentrated solution is generally used.

  DE 3031158 teaches that a mixture of 70-85% by volume of water and 0.1-1% of camphor can be added to the heating kerosene just before combustion.

  DE 2147994 teaches that, among other things, an additive containing camphor can be used in the combustion air of an internal combustion engine.

  U.S. Pat. No. 3,925,031 teaches that additives containing camphor and naphthalene can be added to gasifier fuel, diesel fuel or lubricating oil, among others.

  In the art, camphor is used in fuel to reduce fuel consumption or harmful substance emissions. However, it is well known that camphor does not reduce wrinkles. Rather, as discussed in US Pat. No. 5,116,390, a disadvantage in the use of camphor is that additional soot is generated during the combustion of fuel containing camphor as an additive. Similarly, U.S. Pat. No. 3,925,031 uses a sufficient amount of camphor in gasoline to increase the effective octane number of gasoline, resulting in a reduction in combustion efficiency and the corresponding unburned carbon content. It teaches that it leads to an increase and leads to soot particles in the exhaust.

  It is also known that combustion catalysts can lead to ash production. See, for example, US Pat. No. 6,948,926. Thus, additives that reduce the generation of soot may increase the generation of ash. H. Jungbluth, B. Richter, "Neue Ergebnisse zur Regeneration von Dieselpartikelfiltern mit Additiven", Mineraloltechnik, July 1998; Regeneration von Partikelfiltern mit Additiven, FUELS 1999, 2nd International Colloquium, 20-21.01.1999, page 489-495 When an additive is used in the fuel of a heavy-duty diesel engine, the ash generated by the combustion of the additive increases the peak in the emission.

Chinese Patent No. 1597873 discloses a fuel that reduces harmful emissions, including methanol, hydrogen peroxide, ferrocene and camphor.
US Pat. No. 2,769,828 US Pat. No. 2,834,796 U.S. Pat. No. 2,898,360 U.S. Pat. No. 3,437,634 German Patent No. 3418648 US Pat. No. 4,389,220 German Patent Application No. 3031158 German Patent No. 2147994 US Pat. No. 3,925,031 US Pat. No. 5,116,390 US Pat. No. 6,948,926 Chinese Patent No. 1597873 Specification Nature 168 (1951), Page 1039 H. Jungbluth, B. Richter, "Neue Ergebnisse zur Regeneration von Dieselpartikelfiltern mit Additiven", Mineraloltechnik, July 1998 Regeneration von Partikelfiltern mit Additiven, FUELS 1999, 2nd International Colloquium, 20-21.01.1999, page 489-495

  The present invention alleviates some of the problems of the prior art.

In one aspect, the present invention provides the following fuel additive composition:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof; and
(Ii) A fuel additive composition comprising an organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof,
The additive composition for fuels, wherein the additive composition contains at least 100 ppm of the organic compound (ii).

  In a further aspect, the present invention provides a fuel composition comprising the additive composition of the present invention and a fuel.

In a further aspect, the present invention provides a fuel composition comprising:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof;
(Ii) an organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof; and
(Iii) Fuel selected from biofuel, diesel, marine fuel, heating kerosene, middle distillate oil and heavy oil.

In a further aspect, the invention provides:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof;
(Ii) an organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof; and
(Iii) providing a fuel composition comprising fuel; and
A method of combusting a fuel composition in a combustion system with exhaust comprising the step of combusting the fuel composition to reduce soot and ash in the exhaust.

  In one aspect, the object of the present invention is to provide a hydrocarbon mixture containing an organoiron compound in combination with further components that significantly reduce soot. That is, due to the combination of the iron compound and the additional component, the amount of soot is greater than the amount observed when the same amount of iron compound is used alone, or when the same amount of additional component is used alone. It is greatly reduced from the amount observed. Therefore, the amount of the iron compound used in the mixture may be reduced to some extent, and if the iron compound is used as it is, it may be reduced to such an extent that its catalytic effect on the reduction of soot is minimized. This object is achieved by a hydrocarbon mixture which adds at least 0.1 ppm ferrocene and at least 1 ppm camphor and produces little soot during combustion.

  Thus, metal compounds such as ferrocene can improve combustion in the combustion system and reduce carbon deposits, which can reduce the amount of soot observed in the exhaust of the combustion system. Are known in the art. However, the amount of iron compound required to sufficiently reduce soot also increases the amount of ash generated. In contrast, organic compounds such as camphor are known to increase the amount of soot that is observed, while not producing ash. The present invention surprisingly shows that compositions containing small amounts of metal compounds such as ferrocene and organic compounds such as camphor can significantly reduce soot while producing only a small amount of ash. ing. Surprisingly, the wrinkle reduction that such compositions provide is significantly greater than that observed when the same amount of metal compound is used in the absence of organic compounds.

  Aspects of the invention are defined in the appended claims.

Metal compound (i)
The metal compound (i) is selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof.

  The metal compound (i) is an iron compound, methylcyclopentadienyl manganese tricarbonyl, manganese (II) 2-ethylhexanoate, manganese naphthenate, calcium 2-ethylhexanoate, calcium naphthenate, calcium sulfonate, It is preferably selected from cerium (III) 2-ethylhexanoate, cerium sulfonate and mixtures thereof.

  It is important that the metal compound (i) used in the present invention is fuel soluble or dispersible and preferably fuel stable. Compared to this, the exact nature of the metal-containing compound is less important.

Manganese compound The manganese compound is preferably selected from manganese carbonyl compounds, manganese (II) 2-ethylhexanoate, manganese naphthenate and mixtures thereof.

  The most desirable general type of manganese carbonyl compound utilized in accordance with the present invention is one that includes an organomanganese polycarbonyl compound. For best results, cyclopentadienyl manganese tricarbonyl compounds of the type described in US Pat. No. 2,828,417 and US Pat. No. 3,127,351 should be utilized. Therefore, cyclopentadienyl manganese tricarbonyl, methyl cyclopentadienyl manganese tricarbonyl, ethyl cyclopentadienyl manganese tricarbonyl, dimethyl cyclopentadienyl manganese tricarbonyl, trimethyl cyclopentadienyl manganese tricarbonyl, propyl cyclopentadi Enyl manganese tricarbonyl, isopropylcyclopentadienyl manganese tricarbonyl, butylcyclopentadienyl manganese tricarbonyl, pentylcyclopentadienyl manganese tricarbonyl, hexylcyclopentadienyl manganese tricarbonyl, ethylmethylcyclopentadienyl manganese tricarbonyl , Dimethyloctylcyclopentadienyl manganese tricarbonyl, dodecylcyclopentadienyl Manganese tricarbonyl, compounds such as indenyl manganese tricarbonyl, and cyclopentadienyl moiety may utilize a similar compound containing about 18 carbon atoms at maximum.

  In some embodiments, the manganese compound is an organomanganese compound.

  A preferred organomanganese compound is cyclopentadienyl manganese tricarbonyl. Particularly preferred as that used in the practice of the invention is methylcyclopentadienyl manganese tricarbonyl.

  Methods for the synthesis of cyclopentadienyl manganese tricarbonyls are well documented in the literature. For example, in addition to the above-mentioned US Pat. No. 2,818,417 and US Pat. No. 3,127,351, in particular, US Pat. No. 2,868,816, US Pat. No. 2,898,354, US Pat. No. 2,960,514 and US Pat. See U.S. Pat. No. 2,987,529.

Other organomanganese compounds that may be used include the following: methylacetylcyclopentadienyl manganese tricarbonyl and benzoylmethylcyclopentadienyl manganese tricarbonyl as described in US Pat. No. 2,959,604. Acyl manganese tricarbonyls; aryl manganese pentacarbonyls such as phenyl manganese pentacarbonyl as described in US Pat. No. 3,0079,533; and aromatic cyano manganese such as mesitylene cyano manganese dicarbonyl as described in US Pat. Dicarbonyls. Similarly, in the formula RMn _(CO) 2 L (wherein, R is a substituted or unsubstituted cyclopentadienyl group having 5 to 18 carbon atoms, L is an olefin, an amine, a phosphine, _SO 2, Or a cyclopentadienyl manganese dicarbonyl compound of a ligand such as tetrahydrofuran. Such compounds are mentioned, for example, in Herberhold, M., Metal p-Complexes, Vol. II, Amsterdam, Elsevier, 1967 or Giordano, PJ and Weighton, MS, Inorg. Chem., 1977, 16, 160. ing. Manganese pentacarbonyl dimer (dimanganese decacarbonyl) can also be used if necessary.

  The manganese compound is preferably a manganese complex.

  The manganese compound is preferably selected from cyclopentadienyl manganese tricarbonyl and substituted cyclopentadienyl manganese tricarbonyl.

The manganese compound may be cyclopentadienyl manganese tricarbonyl and substituted cyclopentadienyl manganese tricarbonyl, in which case the substituent is, for example, one or more C _1-5 alkyl groups, preferably C _1-2. It may be an alkyl group. Combinations of such manganese complexes may also be used.

  The manganese compound is preferably selected from cyclopentadienyl manganese tricarbonyl and substituted cyclopentadienyl manganese tricarbonyl.

  The manganese compound is preferably methylcyclopentadienyl manganese tricarbonyl (MMT).

Calcium compound The calcium compound is preferably selected from calcium 2-ethylhexanoate, calcium naphthenate, calcium sulfonate and mixtures thereof.

  The calcium compound is preferably calcium sulfonate.

  Other suitable calcium compounds are disclosed and discussed in GB 2248068 and GB 2254610.

Cerium compound The cerium compound is preferably selected from cerium (III) 2-ethylhexanoate, cerium sulfonate and mixtures thereof.

  Most preferably, the metal compound (i) is an iron compound or a mixture of iron compounds.

Iron compound The iron compound may be an iron complex selected from bis-cyclopentadienyl iron, substituted bis-cyclopentadienyl iron, overbased iron soaps such as iron tartrate and iron octoate, and mixtures thereof. preferable.

  The iron compound is preferably an iron complex selected from bis-cyclopentadienyl iron, substituted bis-cyclopentadienyl iron and mixtures thereof.

  The iron compound is preferably a substituted bis-cyclopentadienyl iron selected from adamantyl bis-cyclopentadienyl iron, bis (dicyclopentadienyl iron) dicarbonyl and mixtures thereof. Bis (dicyclopentadienyliron) dicarbonyl is also known as cyclopentadienyliron dicarbonyl dimer.

  In some embodiments, the iron compound is selected from bis-cyclopentadienyl iron, adamantyl bis-cyclopentadienyl iron, bis (dicyclopentadienyl iron) dicarbonyl, iron tartrate and iron octoate, and mixtures thereof. Iron complex.

For other suitable substituted bis-cyclopentadienyl iron complexes, the substituent is, for example, one or more C _1-30 alkyl groups, preferably C _1-20 alkyl groups, preferably C _1-10 alkyl groups, Preferably, it may be a _C1-5 alkyl group, preferably a _C1-2 alkyl group. Combinations of such iron complexes may be used.

  Suitable alkyl-substituted dicyclopentadienyl iron complexes include cyclopentadienyl (methylcyclopentadienyl) iron, cyclopentadienyl (ethylcyclopentadienyl) iron, bis (ethylcyclopentadienyl) iron, bis (1,2-dimethylcyclopentadienyl) iron and bis (1-methyl-3-ethylcyclo-pentadienyl) iron. These iron complexes are taught in US Pat. No. 2,680,756, US Pat. No. 2,804,468, British Patent Application 0733129, and British Patent Application 0763550. Can be prepared by the process. Another volatile iron complex is iron pentacarbonyl.

  Suitable iron complexes are bis-cyclopentadienyl iron and / or bis (methylcyclopentadienyl) iron.

  Complex chemistry associated with the solubilization of transition metals, including iron, in hydrocarbon solvents such as diesel fuel is well known to those skilled in the art (eg, WO 87/01720 and WO 92/20762). Issue pamphlet).

The iron-substituted bis-cyclopentadienyl complex (substituted ferrocene) used in the present invention includes those in which either or both cyclopentadienyl groups may be substituted. 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 (substituted ferrocenes) include cyclopentadienyl (methylcyclopentadienyl) iron, bis (methylcyclopentadienyl) iron, bis (ethylcyclopentadienyl) There are iron, bis (1,2-dimethylcyclopentadienyl) iron, and 2,2-diethylferrocenyl-propane.

  Other suitable substituents that may be present in the cyclopentadienyl ring include cycloalkyl groups such as cyclopentyl, aryl groups such as tolylphenyl, and acetyl groups as present in diacetylferrocene. A particularly useful substituent is the hydroxyisopropyl group, resulting in (α-hydroxyisopropyl) ferrocene. As disclosed in WO 94/09091, (α-hydroxyisopropyl) ferrocene is a room temperature liquid.

  Ferrocene bonded by “bridge” may be used in the present invention. In WO 02/018398 and WO 03/020733, suitable compounds are taught. Thus, a suitable “bridged” linked ferrocene may be an unsubstituted or substituted hydrocarbyl group. As used herein, the phrase “unsubstituted or substituted hydrocarbyl group” means a group that includes at least C and H, and may optionally include one or more suitable substituents. In a preferred embodiment, one carbon atom of a “bridged” hydrocarbyl group is attached to two ferrocene moieties, thereby ferrocene is bridged. Another ferrocene moiety may be attached via another “bridged” hydrocarbyl group. A typical unsubstituted or substituted hydrocarbyl group is an unsubstituted or substituted hydrocarbon group. Here, the phrase “hydrocarbon” means any of an alkylene group, an alkenylene group, an alkynylene group, or an aryl group, which may be linear, branched or cyclic. For example, the unsubstituted or substituted hydrocarbon group may be an alkylene group, a branched alkylene group, or a cycloalkylene group. The phrase hydrocarbon includes such groups, but substitutions are made as necessary in such groups. When the hydrocarbon has a branched structure having a substituent, the substitution may be performed on either the hydrocarbon skeleton or the branched portion; or the substitution may be performed on the hydrocarbon skeleton and the branched portion. Good. Preferred unsubstituted or substituted hydrocarbon groups are unsubstituted or substituted alkylene groups having at least one carbon atom in the alkylene bond. More preferably, the unsubstituted or substituted hydrocarbon group has 1 to 10 carbon atoms in the alkylene bond, such as having at least 2 carbon atoms in the alkylene bond, or 1 in the alkylene bond. An unsubstituted or substituted alkylene group having a carbon atom. When the hydrocarbyl group contains 2 or more C, these carbons need not necessarily be bonded to each other. For example, at least two carbons may be bonded via a suitable element or group. Thus, the hydrocarbyl group may contain heteroatoms. As will be apparent to those skilled in the art, suitable heteroatoms include, for example, sulfur, nitrogen and oxygen, including oxygen.

Other iron organometallic complexes may be used in the present invention as long as they are fuel soluble and stable. Examples of such complexes include iron pentacarbonyl, di-iron nonacarbonyl, (1,3-butadiene) iron tricarbonyl, and (cyclopentadienyl) iron dicarbonyl dimer. A salt such as ditetralin iron tetraphenylborate (Fe (C ₁₀ H ₁₂ ) ₂ (B (C ₆ H ₅ ) ₄ ) ₂ ) may also be used.

  A preferred iron complex is ferrocene (ie bis-cyclopentadienyl iron).

  In terms of iron content, equivalent amounts of other organoiron compounds that are soluble in the hydrocarbon mixture can be used instead of ferrocene. This applies to all statements and subsequent explanations. Dicyclopentadienyl iron has been found to be particularly suitable. Instead of ferrocene, ferrocene derivatives can be used at least in part. A ferrocene derivative is a compound in which another substituent is found in one or both of the cyclopentadienyl rings based on the basic ferrocene molecule. Examples may include ethyl ferrocene, butyl ferrocene, acetyl ferrocene, and 2,2-bis-ethyl ferrocenyl propane. Geminal bisferrocenylalkanes are also suitable, as described, for example, in German Patent No. 201110995 and German Patent No. 10208326.

  As a result of combining its solubility, stability, high iron content, and above all, volatility, substituted ferrocene is a preferred iron compound for use in the present invention. On this basis, ferrocene itself is a particularly preferred iron compound. Ferrocene of appropriate purity is sold in various useful forms as PLUTOcen® and in solution as Satacen®, both of which are manufactured by Innospec Deutschland GmbH.

  The iron compound used in the present invention does not need to have the feature of an iron-carbon bond in order to obtain fuel compatibility and stability. Salts may be used; these may be neutral or overbased. Thus, for example, overbased soaps such as iron stearate, iron oleate and iron naphthenate may be used. Methods for preparing 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 present invention include so-called “drier-iron” such as iron tris (2-ethylhexanoate) [19583-54-1]. ”Species.

  Iron complexes that do not have the iron-carbon bond characteristics and are not prepared by the above-described method may be used in the present invention if they have sufficient fuel compatibility and stability. Examples include complexes with β-diketonates such as tetramethylheptanedionate.

The following chelate ligand iron complexes are also suitable for use in the present invention:
An aromatic Mannich base such as prepared by reaction of an amine with an aldehyde or ketone followed by a nucleophilic attack on the active hydrogen-containing compound, for example 2 equivalents of (tetrapropenyl) phenol, 2 equivalents of formaldehyde, And a product of reaction of 1 equivalent of ethylenediamine,
-Hydroxy aromatic oximes such as (polyisobutenyl) salicylaldoxime. These may be prepared by reaction of (polyisobutenyl) phenol, formaldehyde and hydroxylamine;
A Schiff base as prepared by a condensation reaction between an aldehyde or ketone (eg (tert-butyl) salicylaldehyde) and an amine (eg dodecylamine). Tetradentate ligands may be prepared using ethylenediamine (half equivalent) at the dodecylamine position;
Substituted phenols such as 2-substituted-8-quinolinols, for example 2-dodecenyl-8-quinolinol or 2-N-dodecenylamino-methylphenol;
A substituted phenol, wherein the substituent is NR ₂ or SR, where R is a long chain (eg, 20-30 C atoms) hydrocarbyl group. In both the α-substituted and β-substituted phenols, the aromatic ring may be further substituted with beneficial hydrocarbyl groups such as lower alkyl groups;
Carboxylic acid esters, in particular succinic acid esters such as those prepared by reaction of an anhydride (eg dodecenyl succinic anhydride) with one equivalent of an alcohol (eg triethylene glycol);
-Acylated amines. These may be prepared by various methods well known to those skilled in the art. However, particularly useful chelates are those prepared by reaction of an alkenyl substituted succinic acid such as dodecenyl succinic anhydride with an amine such as N, N′-dimethylethylenediamine or methyl-2-methylaminobenzoic acid;
Amino acids, such as those prepared by reaction of amines such as dodecylamine with α, β-unsubstituted esters such as methyl methacrylate. If a primary amine is used, it may be acylated later with oleic acid or oleyl chloride;
Hydroxamic acid as prepared by reaction of hydroxylamine with oleic acid;
• Bonded phenols such as those prepared by condensation of alkylated phenols with formaldehyde. Phenol: as formaldehyde ratio of 2: With a ratio of 1, the linking group is a CH _2. Using a ratio of 1: 1, the linking group is CH ₂ OCH ₂ ;
Alkylated substituted pyridines such as 2-carboxy-4-dodecylpyridine;
・ Borated acylated amines. These may be prepared by reaction of a succinic acylating agent such as poly (isobutylene) succinic acid with an amine such as tetraethylenepentamine. This procedure is followed by boronation with boron oxide, boron halide or boronic amide or ester. Similar reactions using phosphonic acids result in the formation of phosphorus-containing acylated amines, which are also suitable for providing oil-soluble iron chelates for use in the present invention;
A pyrrole derivative in which the alkylated pyrrole is substituted in position 2 by OH, NH ₂ , NHR, CO ₂ H, SH or C (O) H. Particularly suitable pyrrole derivatives include 2-carboxy-t-butylpyrrole;
A sulfonic acid such as the formula R ¹ SO ₃ H, wherein R ¹ is a C ₁₀ to about C ₆₀ hydrocarbyl group, eg, dodecylbenzene sulfonic acid;
-Ferrocene, substituted ferrocene, iron naphthenate, iron succinate, stoichiometric or overbased iron soap (carboxylate or sulfonate), iron picrate, iron carboxylate, and iron-diketonate complexes , An organometallic complex of iron.

  Suitable iron picrates for use in the present invention include those described in US Pat. No. 4,370,147, US Pat. No. 4,265,639.

  Other iron-containing compounds used in the present invention include those of formula M (R) x. nL (wherein M is an iron cation; R is a residue of an organic compound RH in which R can be replaced by a metal M and in the R group O, S, P, An organic group containing an active hydrogen atom H bonded to an N or C atom; x is 2 or 3; n is the number of donor ligand molecules that form a coordinate bond with 0 or a metal cation. And L is a species capable of acting as a Lewis base.).

Organic compound (ii)
The organic compound (ii) is selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof.

  The organic compound (ii) is preferably selected from bicyclic monoterpenes, substituted bicyclic monoterpenes and mixtures thereof.

  Suitable substituted bicyclic monoterpenes are those in which the substituents can be, for example, one or more aldehyde, ketone, alcohol, acetate, and ether functional groups.

  The organic compound (ii) is preferably a bicyclic monoterpene or a substituted bicyclic monoterpene selected from camphor, camphene, isobornyl acetate, dipropylene glycol-isobornyl ether and mixtures thereof.

  In some embodiments, the organic compound (ii) is selected from camphor, camphene, isobornyl acetate, dipropylene glycol-isobornyl ether, adamantane, propylene carbonate, and mixtures thereof.

  The organic compound (ii) is preferably camphor. Camellia has the strain name 1,7,7-trimethylbicyclo [2.2.1] heptan-2-one. Camphor has the following structure:

Additive composition In certain embodiments, the present invention provides:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof; and
(Ii) A fuel additive composition comprising an organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof,
Provided is a fuel additive composition provided that the composition is substantially free of methanol.

  The phrase “substantially free of methanol” means that the methanol contained in the composition is less than 10% by weight, preferably less than 5% by weight, preferably less than 2% by weight, preferably less than 1% by weight, Preferably it means less than 0.5 wt%, preferably less than 0.1 wt%, preferably less than 0.05 wt%, preferably less than 0.01 wt%.

In another aspect, the invention provides:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof; and
(Ii) A fuel additive composition comprising an organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof,
Provided is a fuel additive composition provided that the composition is substantially free of C1-C5 alcohol.

  As used herein, the phrase “C1-C5 alcohol” means a linear or branched alcohol containing 1-5 carbon atoms such as methanol, ethanol, propanol, butanol and pentanol. An example of a suitable branched alcohol is tertiary butanol.

  The phrase “substantially free of C1-C5 alcohol” means that the C1-C5 alcohol compound contained in the composition is less than 10% by weight, preferably less than 5% by weight, preferably less than 2% by weight, It means preferably less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0.1% by weight, preferably less than 0.05% by weight, preferably less than 0.01% by weight.

In a further aspect, the invention provides:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof; and
(Ii) A fuel additive composition comprising an organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof,
Provided is a fuel additive composition provided that the composition is substantially free of any alcohol.

  The phrase “substantially free of any alcohol” means that the alcohol contained in the composition is less than 10% by weight, preferably less than 5% by weight, preferably less than 2% by weight, preferably less than 1% by weight. , Preferably less than 0.5 wt%, preferably less than 0.1 wt%, preferably less than 0.05 wt%, preferably less than 0.01 wt%.

In a further aspect, the invention provides:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof; and
(Ii) A fuel additive composition comprising an organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof,
Provided is a fuel additive composition provided that the composition is substantially free of hydrogen peroxide.

  The phrase “substantially free of hydrogen peroxide” means that the hydrogen peroxide contained in the composition is less than 10% by weight, preferably less than 5% by weight, preferably less than 2% by weight, preferably 1 It means less than 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%.

  In a preferred embodiment, the metal compound (i) is bis-cyclopentadienyl iron and the organic compound (ii) is camphor.

  The additive composition preferably further contains a solvent.

  It is convenient to add the additive composition as a solution containing the active ingredient in a solvent. About such a solution, it is preferable that the density | concentration of the active ingredient in a solvent is high. An ideal solvent is one that dissolves all active ingredients equally well and forms a solution that is stable during extended storage periods and even in cold conditions.

  The solvent is preferably selected from aromatic compounds, paraffin compounds and mixtures thereof. As used herein, the phrase “paraffinic compound” is intended to include both straight and branched chain compounds. Branched chain compounds are also known as isoparaffins.

  It is preferred that the fuel additive composition comprises an amount of one or more metal compounds (i) sufficient to provide less than 30,000 ppm, preferably less than 15,000 ppm, preferably less than 6,000 ppm of metal. .

  The fuel additive composition comprises an amount of one or more metal compounds (i) sufficient to provide 3 ppm to 30,000 ppm, preferably 15 ppm to 15,000 ppm, preferably 60 ppm to 6,000 ppm of metal. It is preferable.

  It is preferred that the fuel additive composition comprises less than 90,000 ppm, preferably less than 45,000 ppm, preferably less than 18,000 ppm of the metal compound (i).

  It is preferred that the fuel additive composition comprises 10 ppm to 90,000 ppm, preferably 50 ppm to 45,000 ppm, preferably 200 ppm to 18,000 ppm of the metal compound (i).

  The fuel additive composition is at least 100 ppm, 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 of organic compound (ii).

  The fuel additive composition is 100 ppm to 700,000 ppm, preferably 500 ppm to about 350,000 ppm, preferably about 2,000 ppm to about 140,000 ppm, preferably about 50,000 ppm to about 130,000 ppm, preferably about Preferably, it contains 80,000 ppm to about 120,000 ppm of organic compound (ii).

  The fuel additive of the present invention may be added to the fuel as part of the package prior to combustion. This can be done at any stage of the fuel supply chain (supply process) (eg at the final stage of refining or distribution (terminal facility)), or via an input device associated with the combustion system, for example mounted on the bodywork. May be added. When using a charging device, the additive may be charged into the fuel or may be separately charged directly into the combustion chamber or intake system. A user may add a fuel additive to the fuel in the fuel tank of the combustion system. This is the so-called “aftermarket” procedure.

  The additive composition is preferably a solution. Such an additive composition is for fuel addition. Such additives may be introduced at any stage of the fuel supply chain prior to fuel combustion. The fuel additive of the present invention may be introduced into the fuel at any stage of the fuel supply chain. Each additive is added to the interior of the fuel storage system for the engine or combustion system, in the vicinity of the engine or combustion system, at other stages, including refining the fuel supply chain, final stages of distribution, or aftermarket use. It is preferable to add to the fuel. Additives may be added to the fuel at the final stage of purification or distribution.

  However, if the combination of additives is intended to be added as an “aftermarket” treatment, the amount of solvent used is such that a non-viscous solution suitable for use in a dispenser bottle or syringe pack is provided. Become a quantity. The solvent used must be easily soluble and compatible with the fuel, including the boiling point range, and the flash point must be above 62 ° C to facilitate storage. preferable.

  In some embodiments, the fuel additive composition is an additive concentrate composition.

Fuel In one embodiment of the present invention, the fuel is selected from gasoline, diesel, marine fuel, heating kerosene, middle distillate oil and heavy oil, and is a fuel containing a renewable component or a biological component, Includes fuels commonly referred to as biofuels, such as biodiesel.

  In another aspect, the fuel is preferably selected from biofuel, diesel, marine fuel, heating kerosene, middle distillate oil and heavy oil.

  In another aspect, the fuel is preferably selected from diesel, marine fuel, heating kerosene, middle distillate oil and heavy oil.

  In some embodiments, the fuel is gasoline.

  In some embodiments, the fuel is a spark ignition engine fuel, such as gasoline.

  The fuel is preferably a fuel for a high compression self-ignition engine.

  The fuel is preferably diesel. Such diesel may be biodiesel, low sulfur diesel and ultra low sulfur diesel.

  In another aspect, the fuel is marine fuel or bunker fuel.

  In another aspect, the fuel is heating kerosene, such as kerosene. Preferably, it is light kerosene for heating. Such light kerosene for heating is preferably HEL: Heizol extra leichtflussig described in DIN 51603, Part 1.

  In a further aspect, the fuel is middle distillate oil.

  In a further aspect, the fuel is heavy oil.

  In another aspect, the fuel is a hydrocarbon mixture, preferably a liquid hydrocarbon mixture.

Fuel composition The fuel composition preferably comprises at least 0.1 ppm of metal compound (i).

  The fuel composition preferably contains 9 ppm or less of the metal compound (i), and preferably contains 8 ppm or less of the metal compound (i).

  The fuel composition preferably includes about 0.1 ppm to about 9 ppm of metal compound (i).

  The fuel composition preferably comprises about 0.5 ppm to about 8 ppm of metal compound (i).

  For example, when the metal compound (i) is ferrocene, 0.1 ppm of ferrocene is an amount sufficient to provide 0.03 ppm of metal (iron). Thus, if the fuel composition contains a sufficient amount of metal compound (i) to provide 0.03 ppm of metal, there will be an amount corresponding to 0.1 ppm of ferrocene.

  The fuel composition preferably includes a sufficient amount of the metal compound (i) to provide at least 0.03 ppm of metal. The fuel composition preferably includes an amount of metal compound (i) that provides no more than 2.70 ppm of metal. The fuel composition preferably includes an amount of metal compound (i) that provides no more than 2.40 ppm of metal. The fuel composition preferably includes a sufficient amount of the metal compound (i) to provide 0.03 ppm to 2.70 ppm of metal. The fuel composition preferably includes a sufficient amount of the metal compound (i) to provide 0.15 ppm to 2.40 ppm of metal.

  The organic compound (ii) contained in the fuel composition is preferably 70 ppm or less, preferably 60 ppm or less, and preferably 50 ppm or less.

  The fuel composition preferably contains at least 1 ppm of organic compound (ii).

  The organic compound (ii) contained in the fuel composition is preferably about 1 ppm to about 70 ppm, preferably about 10 ppm to about 60 ppm, and preferably about 20 ppm to about 50 ppm.

  In a further aspect, the fuel composition is provided by diluting the additive enriched composition of the present invention contained in the fuel. The ratio of the additive-enriched composition to the fuel is preferably 1: 100 to 1: 10,000, preferably 1: 500 to 1: 8,000, and 1: 1,000 to 1: It is preferably 5,000, preferably 1: 1,500 to 1: 3,000.

  In a further aspect, the fuel composition is substantially free of methanol.

  In a further aspect, the fuel composition is substantially free of C1-C5 alcohol.

  In a further aspect, the fuel composition is substantially free of alcohol.

  In a further aspect, the fuel composition is substantially free of hydrogen peroxide.

  The meaning of the phrase “substantially free” is as defined above for the additive composition.

  In a preferred embodiment, the metal compound (i) is bis-cyclopentadienyl iron and the organic compound (ii) is camphor.

Application Areas The system may be used in many different application areas.

  In some embodiments, the application field is diesel fuel.

  In another aspect, the application field is marine fuel.

  In another aspect, the application field is heating kerosene.

  In another embodiment, the application area is middle distillate oil.

  In another aspect, the application field is heavy oil.

  In another embodiment, the application field is regeneration of diesel particulate filters.

  In another aspect, the application area is the reduction of soot and ash in the exhaust of the combustion system.

  In another aspect, the application field is improving the combustion efficiency of the combustion system.

  In another aspect, the application field is fuel efficiency improvement in combustion systems.

Hydrocarbon Mixture In some embodiments, the present invention provides a hydrocarbon mixture with at least 0.1 ppm ferrocene and at least 1 ppm camphor added that produces little soot upon combustion. In this embodiment, camphor means a compound group consisting of bicyclic monoterpenes such as camphene or fensen, or similar aldehydes, or monoterpene ketones such as phendione. Preference is given to 1,7,7-trimethylbicyclo [2.2.1] heptan-2-one.

  Good results can be obtained with a hydrocarbon mixture containing 7 ppm ferrocene and 40 ppm camphor.

  In order to minimize the ash generated during combustion, it is desirable to minimize the amount of ferrocene so long as the soot-reducing action of the mixture is not adversely changed. Accordingly, the ferrocene concentration is preferably not more than 9 ppm, but is preferably 8 ppm or less.

  Also for camphor, the concentration should not exceed 70 ppm, preferably at most 60 ppm, specifically at most 50 ppm.

  Most of the hydrocarbons contained in the hydrocarbon mixture are preferably derived from petroleum. However, the hydrocarbon mixture may also contain other natural or renewable materials such as rapeseed oil methyl ester.

  Particularly suitable hydrocarbon mixtures are those consisting of middle distillates produced in crude oil refineries. Such middle distillates are a major component of diesel oil and heating kerosene, especially heating kerosene with very low viscosity. The exact specifications of such products are described in the DIN standard.

  The soot-reducing action is particularly clearly observed in heating kerosene, especially in the so-called HEL: Heizol extra leichtflussig heating kerosene described in DIN 51603, Part 1. Heating kerosene, as its name suggests, provides warmth. For this purpose, the heating kerosene is burned with the addition of air using a special burner. The advantages of the present invention become particularly apparent in such applications. This is because this application reduces the amount of visible smoke and measurable soot generation.

  A further subject of the present invention is an additive concentrate for producing a hydrocarbon mixture comprising the additive described in the paragraph numbered (1) herein. ˜25 ppm ferrocene or an equivalent amount of another organic iron component soluble in hydrocarbons in terms of iron and 1-80 ppm camphor.

  The advantages of such additive concentrates are quite obvious. By adding a corresponding amount of concentrate to the hydrocarbon mixture, preferably mixed to homogeneity, the concentrate is used to convert the mixture with no additive added to the hydrocarbon mixture of the present invention. can do. Corresponding amounts of ferrocene and camphor could be added separately to the mixture. However, it is necessary to ensure an appropriate relative amount not only between the concentrate and the hydrocarbon mixture but also between the individual additive components. Thus, it is easier and more convenient for the customer to provide an additive that already contains the proper relative amounts of ferrocene and camphor. The relative amount of ferrocene and camphor in the additive concentrate is preferably 7:40 in terms of weight.

Additional Additives The additive concentrate and / or fuel may further include additional additives such as additives that enhance performance. Lists of such additional additives include corrosion inhibitors, rust inhibitors, gum inhibitors, antioxidants, solvent oils, antistatic agents, dyes, anti-icing agents, ashless dispersants and A cleaning agent is included, but is not limited to these.

Ratio In certain embodiments, the ratio of metal compound (i) (measured in ppm) to organic compound (ii) (measured in ppm) is preferably 9: 1 to 1: 700.

  The ratio of the metal compound (i) to the organic compound (ii) is preferably 2: 1 to 1: 100, preferably 1: 1 to 1:10, and 1: 2 to 1: 8 It is preferable that it is 1: 3 to 1: 7.

  In a further aspect, the ratio of metal provided by metal compound (i) (measured in ppm) to organic compound (ii) (measured in ppm) is preferably 27:10 to 3: 7000. The ratio of the metal provided by the metal compound (i) to the organic compound (ii) is preferably 6:10 to 3: 1000, preferably 3:10 to 3: 100, and 3:20. ~ 3: 80 is preferable, and 3: 30-3: 70 is preferable.

Method In a further aspect, the invention provides:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof;
(Ii) an organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof; and
(Iii) providing a fuel composition comprising fuel; and
A method of combusting a fuel composition in a combustion system is provided that includes the step of combusting the fuel composition to improve the combustion efficiency of the fuel.

In a further aspect, the invention provides:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof;
(Ii) an organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof; and
(Iii) providing a fuel composition comprising fuel; and
Combustion of the fuel composition in a combustion system is provided that includes the step of combusting the fuel composition to improve fuel economy.

In a further aspect, the present invention provides carbon-based particulates present in the particulate filter,
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof;
(Ii) an organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof; and
(Iii) regenerating the particulate filter located in the exhaust system of the fuel combustion system comprising the step of contacting with a combustion product of a fuel composition comprising fuel; and
A method of burning the fuel composition in a combustion system is provided.

  In a preferred embodiment, the metal compound (i) is bis-cyclopentadienyl iron and the organic compound (ii) is camphor.

Combustion system The combustion system is preferably selected from burners, engines and furnaces.

  The combustion system is preferably selected from burners and furnaces.

  The combustion system is preferably an engine. Such an engine is preferably a compression ignition engine (diesel engine).

  In some embodiments, the combustion system is an engine. Such an engine is preferably a spark ignition engine.

Uses In a further aspect, the present invention provides the following uses to reduce soot and ash in the exhaust of a fuel combustion system:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof; and
(Ii) An organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof.

  In a further aspect, the present invention provides the use of an additive composition as defined herein for reducing soot and ash in the exhaust of a fuel combustion system.

  In a further aspect, the present invention provides the use of a fuel composition as defined herein for reducing soot and ash in the exhaust of a fuel combustion system.

In a further aspect, the present invention provides the following uses to improve the combustion efficiency of fuel:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof; and
(Ii) An organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof.

  In a further aspect, the present invention provides the use of an additive composition as defined herein for improving the combustion efficiency of a fuel.

  In a further aspect, the present invention provides the use of a fuel composition as defined herein for improving the combustion efficiency of a fuel.

In a further aspect, the present invention provides the following use to improve the fuel efficiency of a combustion system:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof; and
(Ii) An organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof.

  In a further aspect, the present invention provides the use of an additive composition as defined herein for improving the fuel consumption of a combustion system.

  In a further aspect, the present invention provides the use of a fuel composition as defined herein for improving the fuel efficiency of a combustion system.

In a further aspect, the present invention provides the following use to reduce the regeneration temperature and / or required regeneration frequency of a particulate filter located in the exhaust system of a combustion system:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof; and
(Ii) An organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof.

  In a further aspect, the present invention provides the use of an additive composition as defined herein for reducing the regeneration temperature and / or required regeneration frequency of a particulate filter located in the exhaust system of a combustion system. I will provide a.

  In a further aspect, the present invention relates to the use of a fuel composition as defined herein for reducing the regeneration temperature and / or required regeneration frequency of a particulate filter located in the exhaust system of a combustion system. provide.

Apportionment Bacharach soot number is a qualitative means of assessing the integrity of combustion based on the absorption of visible light by particles deposited on the filter. Bacharach frequency is part of the inspection procedure required to determine the flammability of oil burners, such as in Switzerland.

  After passing a clearly defined amount of undiluted flue gas through the white filter, a discolored spot remains. The color of this spot is compared with a gray scale with a scale from 0 (white) to 9 (black). This number is assessed electronically by measuring the reflectance of the visible light that shines on the loaded filter. The discoloration of the sample filter is due to the presence of a black shoot.

  In the case of the fuel composition, it is preferred that the bacarac frequency is 0.5 lower than that observed in the case of the fuel alone. Compared to the bacharack frequency observed in the case of fuel alone, in the case of the fuel composition, the bacharac frequency is preferably 0.8 lower, and the bacharac frequency is decreased by 1.0. Preferably, the frequency of the bacharac is preferably 1.2 lower, the frequency of the bacharac is preferably lower by 1.5, the frequency of the bacharac is preferably lower by 1.8, It is preferable that the rack frequency is lowered by 2.0.

  The power of the bacharac produced by the fuel composition is preferably less than 1.0, preferably less than 0.9, preferably less than 0.8, and less than 0.7. Preferably, it is less than 0.6, preferably less than 0.5.

  In some embodiments, apportion is measured by ASTM test method D-2156.

Ash content The ash content provided by the fuel composition is preferably 0.010 wt% or less. Ash content provided by the fuel composition is 0.009% or less, 0.008% or less, 0.007% or less, 0.006% or less, 0.005% or less, 0.004% or less, It is preferable that they are 0.003 weight% or less, 0.002 weight% or less, and 0.001 weight% or less.

  Ash content may be measured according to DIN EN 6245, a standard method.

The following examples further illustrate the present invention.
[Example]

  For testing purposes, in each case 25 liters of heating kerosene was mixed with 0.2 liter of test additive. Various formulations were tested. The challenge in the combustion test using a kerosene hot water boiler equipped with a yellow flame burner was to clarify whether their formulation had a soot reducing effect. For this purpose, the initial smoke spot number of the additive-free heating kerosene was set to about 4 by changing the burner to a place where measurable smoke was generated. Thereafter, in order to measure the action of the additive, the additive was tested using this burner. The frequency was measured by evacuation (extracting a specified amount of partial gas through a filter pad with a manual smoke tester). After measurement, the filter pad was optically determined (by comparison). The average value of the frequency is based on the results of 10 measurements made separately.

Test equipment Steel heating boiler Ruhr Brenner, Model B 4T / 14021kW,
Year of manufacture: 1996
Heat output set to 20 kW Oil burner Ruhr Brenner, Model RH-4, 12-45 kW,
Year of manufacture: 1996
Jet Danfoss Typ H, 0.50 US gallons per hour (1.87 kg / h), 60 ° H
° H is index angle / spraying index, hollow cone shape.
Smoke tester Brigon Smoke Tester

  For testing purposes, one container with heating kerosene containing additives and one container without additives were placed next to the steel heating boiler. The burner pump was set to single row mode. This prevented the kerosene from returning to the container and being heated by the burner pump.

  The change was made from the additive-free kerosene to the additive-containing kerosene by switching at the three-way valve just before the burner. Because of the three-way valve and the one-row circuit, it is guaranteed that no situation can occur in which the measured value is inaccurate due to the residue of the additive in the pipeline. Each of the measuring kites was passed through a Bacharach kite pump and evaluated by visual inspection and measurement with a frequency tester.

Implementation The steel hot water boiler was raised to the operating temperature using an additive-free heating kerosene. The smoke spot power was set to about 4 by suppressing the supply of air to the burner.

  The duration of the test was about 0.75 hours, after which the smoke spot frequency was measured.

  Throughout the series of tests, an additive containing 7 ppm ferrocene / 40 ppm camphor reduced the best result, ie, smoke spot power of less than 2 from smoke spot power of 4 to less than 2 on the scale. Has been brought. Incidentally, a ferrocene concentration of 15-20 ppm would be required to similarly reduce the smoke spot power in the absence of camphor. However, the generation of ash by using 15-20 ppm of ferrocene will increase about 40 times.

  Using the same measurement procedure, various organic compounds (ii) were tested with ferrocene. The results are shown in Table 2 below.

  These results indicate the possibility that the range of the organic compound (ii) was effective.

  Using the same measurement procedure, various metal compounds (i) were tested with camphor. The results are shown in Table 3 below.

  Further aspects of the invention are described in the following numbered paragraphs. In these numbered paragraphs, camphor means a compound group consisting of bicyclic monoterpenes such as camphene or fensen, or similar aldehydes, or monoterpene ketones such as phendione. Preference is given to 1,7,7-trimethylbicyclo [2.2.1] heptan-2-one.

(1) A liquid hydrocarbon mixture (HC mixture) with low levels of soot produced by combustion, with 10 ppm camphor, at least 0.1 ppm ferrocene or another equivalent HC soluble organic in iron equivalent HC mixture to which iron compound is added.

(2) The HC mixture according to paragraph (1), comprising about 7 ppm of ferrocene and about 40 ppm of camphor.

(3) The HC mixture according to any one of paragraphs (1) and (2), wherein at least a major part of HC is composed of a mineral-derived hydrocarbon.

(4) The HC mixture according to any one of paragraphs (1) to (3), wherein the HC mixture is a crude middle distillate.

(5) The HC mixture according to any one of paragraphs (1) to (4), wherein the HC mixture is heating kerosene, particularly HEL (super light kerosene for heating).

(6) An additive concentrate for producing the additive-containing HC mixture according to paragraph (1), wherein HC is equivalent to 0.1 to 25 ppm ferrocene or iron equivalent with 10 to 80 ppm camphor Additive concentrate comprising another organic iron compound that is soluble.

(7) The additive concentrate according to paragraph (6), wherein the weight ratio of ferrocene and camphor is around 7:40.

(8) Additive concentrate according to paragraph (6) or (7), characterized in that it mainly contains aromatics or isoparaffin as a solvent with respect to volume.

(9) Use of the additive concentrate according to paragraphs (6) to (8) for producing the additive-containing HC mixture according to paragraph (1).

(10) A liquid hydrocarbon mixture (HC mixture) with low levels of soot produced by combustion, with at least 10 ppm camphor, at least 0.1 ppm ferrocene or equivalent in iron equivalents, HC soluble HC mixture to which an organic iron compound is added.

All publications mentioned so far in this specification are hereby incorporated by reference. Various modifications and variations of the method and system described in the present invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in terms of certain preferred embodiments, it is to be understood that the invention as claimed should not be unduly limited to such specific embodiments. In particular, various modifications of the described embodiments of the invention described herein which are obvious to those skilled in chemistry or related fields are intended to be within the scope of the appended claims.

Claims (28)

(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof; and
(Ii) A fuel additive composition comprising an organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof,
The additive composition for fuels, wherein the additive composition contains at least 100 ppm of the organic compound (ii). The fuel additive composition according to claim 1, further comprising a solvent. 3. The fuel additive composition according to claim 2, wherein the solvent is selected from aromatic compounds, paraffin compounds, and mixtures thereof. The additive composition for fuel according to any one of claims 1 to 3, wherein the additive composition contains an amount of the metal compound (i) sufficient to provide 3 ppm to 30,000 ppm of metal. . The additive composition for fuel according to any one of claims 1 to 4, wherein the additive composition contains 100 ppm to 700,000 ppm of an organic compound (ii). A fuel composition comprising the additive composition according to any one of claims 1 to 5 and a fuel. The fuel composition according to claim 6, wherein the ratio of the additive composition to the fuel is 1: 100 to 1: 10,000. Fuel composition comprising:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof;
(Ii) an organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof; and
(Iii) Fuel selected from biofuel, diesel, marine fuel, heating kerosene, middle distillate oil and heavy oil. (I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof;
(Ii) an organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof; and
(Iii) providing a fuel composition comprising fuel; and
A method of combusting a fuel composition in a combustion system with exhaust, comprising the step of combusting the fuel composition so as to reduce soot and ash in the exhaust. 10. The invention of any one of claims 6 to 9, wherein the fuel composition comprises a sufficient amount of the metal compound (i) to provide at least 0.03 ppm of metal. 11. The invention of any one of claims 6 to 10, wherein the fuel composition comprises an amount of metal compound (i) that provides 2.40 ppm or less of metal. The fuel composition according to any one of claims 6 to 11, wherein the fuel composition contains 70 ppm or less of the organic compound (ii). The invention according to any one of claims 6 to 12, wherein the fuel composition contains at least 1 ppm of the organic compound (ii). 14. The invention of any one of claims 6 to 13, wherein the fuel composition comprises from about 10 ppm to about 60 ppm organic compound (ii). The following uses to reduce soot and ash in the exhaust of fuel combustion systems:
(I) a metal compound selected from iron compounds, manganese compounds, calcium compounds, cerium compounds and mixtures thereof; and
(Ii) An organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantane, propylene carbonate and mixtures thereof. 16. The invention according to any one of claims 1 to 15, wherein the metal compound (i) is selected from iron compounds and mixtures thereof. 17. The invention of claim 16, wherein the iron compound is an iron complex selected from bis-cyclopentadienyl iron, substituted bis-cyclopentadienyl iron, iron tartrate and mixtures thereof. 18. The invention according to claim 1, wherein the metal compound (i) is bis-cyclopentadienyl iron. 17. The iron compound is a substituted bis-cyclopentadienyl iron selected from adamantyl bis-cyclopentadienyl iron, bis (dicyclopentadienyl iron) dicarbonyl, and mixtures thereof. The invention described. The organic compound (ii) is a bicyclic monoterpene or a substituted bicyclic monoterpene selected from camphor, camphene, isobornyl acetate, dipropylene glycol-isobornyl ether and mixtures thereof Item 21. The invention according to any one of Items 1 to 19. 21. The invention according to claim 1, wherein the organic compound (ii) is camphor. The invention according to any one of claims 1 to 15, wherein the metal compound (i) is bis-cyclopentadienyl iron and the organic compound (ii) is camphor. 23. The invention according to any one of claims 1 to 22, wherein the ratio of the metal compound (i) to the organic compound (ii) is 9: 1 to 1: 700. 24. The invention according to any one of claims 1 to 23, wherein the ratio of the metal provided by the metal compound (i) to the organic compound (ii) is 6:10 to 3: 1000. A fuel additive composition substantially as hereinbefore described with reference to any of the Examples. A fuel composition substantially as hereinbefore described with reference to any of the Examples. Use substantially as hereinbefore described with reference to any of the Examples. A method substantially as hereinbefore described with reference to any of the Examples.