Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/228—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
  • C10L1/2286—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen triple bonds, e.g. nitriles
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
  • C10L1/233—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring containing nitrogen and oxygen in the ring, e.g. oxazoles
  • C10L1/2335—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring containing nitrogen and oxygen in the ring, e.g. oxazoles morpholino, and derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16

Definitions

• the present invention relates to the use of oligo- or polyamines which have a number-average molecular weight of from 46 to 70 000 and are free of phenolic hydroxyl groups for increasing the oxidation stability of biofuel oils based on fatty acid esters, or of mixtures of such biofuel oils with middle distillates of fossil origin and/or of vegetable and/or animal origin, which are essentially hydrocarbon mixtures and are free of fatty acid esters.
• the present invention further relates to a mixture of specific representatives of such oligo- or polyamines and biofuel oils based on fatty acid esters.
• the present invention further relates to a fuel which comprises a major proportion of a fuel oil which consists of
• biofuel oils which are usually also referred to as “biodiesel” and usually comprise high proportions of unsaturated fatty acid esters are, owing to their chemical structure, more sensitive to oxidative decomposition by atmospheric oxygen than fuel oils of fossil origin, their oxidation stability in the course of storage is often improved by admixing them with small amounts of antioxidants.
• Antioxidants typically used for this purpose are sterically hindered phenols, for example 2,6-di-tert-butyl-4-methylphenol (“BHT”), 3-tert-butylhydroxyanisole (“BHA”) and tert-butylhydroquinone (“TBHQ”), as described in the literature article by Mittelbach and Schober in JAOCS, Vol. 80, 8 (2003), p. 817-823.
• BHT 2,6-di-tert-butyl-4-methylphenol
• BHA 3-tert-butylhydroxyanisole
• TBHQ tert-butylhydroquinone
• Kerobit® BPD a secondary aromatic amine of the N,N′-di-sec-butyl-p-phenylenediamine structure, is suitable as an antioxidant for gasolines and jet fuels.
• WO 03/095593 recommends succinimides obtainable by reacting C 4 - to C 29 -alkyl- or -alkenylsuccinic anhydride and primary amines, which may also be polyamines, as additives for improving the thermal stability of aviation fuels, and also of biofuels such as vegetable oils and esters of vegetable oils.
• WO 94/19430 describes reaction products of polyamines with acylating agents, especially with fatty acids, as antifoams for mixtures of biofuel oil and middle distillates of fossil origin.
• DE 10 2004 024 532 A1 discloses fuel oils which comprise a major proportion of a mixture of middle distillate fuel oil and biofuel oil, and a minor proportion of oil-soluble oligo- or polyethyleneimines which have been alkoxylated with ethylene oxide or propylene oxide and thus have ether oxygen functions. These alkoxylated oligo- or polyethyl-eneimines, however, act there as demulsifiers for mixtures of fuel and water.
• the stabilizing action of the abovementioned antioxidants, like that of the sterically hindered phenols, in the biofuel oil is, however, generally still insufficient. In particular, the dosages needed are too high. It was therefore an object of the invention to provide more effective antioxidants for biofuel oils.
• oligo- or polyamines which have a number-average molecular weight of from 46 to 70 000 and are free of phenolic hydroxyl groups for increasing the oxidation stability.
• Cationic structures especially ammonium or substituted ammonium compounds, are preferably excluded in the oligo- or polyamines to be used in accordance with the invention.
• the number-average molecular weight of the oligo- or polyamines is from 46 (for diaminomethane as the smallest possible representative) to 70 000, although this upper limit is not critical.
• Preferred ranges for the number-average molecular weight are from 58 (for example for 1,2-ethylenediamine) to 40 000, especially from 116 to 10 000, in particular from 130 to 5000, most preferably from 200 to 2000.
• the oligo- or polyamines mentioned have preferably from 2 to 10, especially from 2 to 6, in particular from 2 to 5 nitrogen atoms in the molecule.
• the present invention relates to the inventive use of oligo- or polyamines of the general formula I
• the R 1 to R 6 radicals are each independently hydrogen, C 1 - to C 30 -alkyl groups, C 5 - to C 8 -cycloalkyl groups, C 1 - to C 29 -alkylcarbonyl groups or C 2 - to C 8 -cyanoalkyl groups, where the R 1 and R 2 and/or R 5 and R 6 radicals may in each case also, together with the nitrogen atom which bears them, form a five- or six-membered, saturated or unsaturated ring which may also have further heteroatoms (typically nitrogen and/or oxygen and/or sulfur) and/or carbonyl carbon atoms and bear additional substituents, or in each case also together be a methylidene moiety which may be substituted by C1- to C 30 -alkyl groups and/or C 6 - to C 12 -aryl groups,
• the bridging members A 1 to A 3 are each independently C 1 - to C 12 -alkylene groups and/or C 6 - to C 12 -arylene groups, where the R 1 and/or R 5 radicals may in each case also, together with the nitrogen atom which bears them and a carbon atom of an alkylene group A 1 or A 3 , form a five- or six-membered, saturated or unsaturated ring which may also have further heteroatoms (typically nitrogen and/or oxygen and/or sulfur and/or carbonyl carbon atoms and bear additional substituents, and
• n and m are each integers from 0 to 30.
• the optional substitutents mentioned on the five- or six-membered, saturated or unsaturated rings may, for example, be relatively long-chain or relatively short-chain hydrocarbyl radicals, especially appropriate linear or branched alkyl radicals.
• Useful radicals here are firstly hydrocarbyl radicals having from 1 to 30, preferably from 1 to 20 carbon atoms, and secondly long-chain hydrocarbyl radicals having from 30 to 200, preferably from 40 to 100 carbon atoms, for example appropriate polyisobutenyl radicals.
• the oligo- or polyamines to be used in the context of the present invention comprise preferably, as R 1 to R 6 radicals, at least one hydrocarbyl radical having from 1 to 30 carbon atoms, especially having from 2 to 30 carbon atoms, more preferably having from 3 to 30 carbon atoms, in particular having from 5 to 30 carbon atoms.
• Such relatively long-chain hydrocarbyl radicals ensure sufficient fuel solubility.
• the present invention therefore relates to a fuel which comprises a minor proportion of an oligo- or polyamine which has at least one such hydrocarbyl radical having from 5 to 30, especially from 10 to 22, in particular from 12 to 18 carbon atoms.
• Examples of such relatively long-chain hydrocarbyl radicals include pure aliphatic linear or branched hydrocarbon radicals which may be of synthetic or natural origin. Examples thereof are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethyl butyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-eth
• Alicyclic hydrocarbyl radicals are also suitable as substituents on the aliphatic oligo- or polyamines in the context of the present invention. Examples thereof are cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl and cyclooctyl.
• Suitable relatively long-chain hydrocarbyl radicals are also linear or branched alkylcarbonyl radicals, especially radicals of corresponding fatty acids having from 5 to 30, especially from 10 to 22, in particular from 12 to 18 carbon atoms. Examples thereof are formyl, acetyl, n-propanoyl, isopropanoyl, n-butanoyl, 2-butanoyl, isobutanoyl, tertbutanoyl, pentanoyl, 1-methylbutanoyl, 2-methylbutanoyl, 3-methylbutanoyl, 2,2-dimethylpropanoyl, 1-ethylpropanoyl, n-hexanoyl, 1,1-dimethylpropanoyl, 1,2-dimethylpropanoyl, 1-methylpentanoyl, 2-methylpentanoyl, 3-methylpentanoyl, 4-methylpentanoyl, 1,1-dimethylbutanoyl
• the natural raw material sources used for the abovementioned relatively long-chain aliphatic hydrocarbon radicals or relatively long-chain alkylcarbonyl radicals are in particular vegetable or animal fats or oils, for example coconut oil, tall oil, palm oil, rapeseed oil, soybean oil or jatropha oil.
• the hydrocarbyl radicals are inevitably present as homologous mixtures and/or as mixtures of saturated and unsaturated chains.
• Oligo- or polyamines substituted by the abovementioned alkylcarbonyl radicals can be prepared in a simple manner familiar to those skilled in the art from the amine substrate and a reactive derivative of the corresponding fatty acid, for example a lower alkyl ester, a halide such as the fatty acid chloride or the anhydride.
• alkylcarbonyl radicals in the aliphatic oligo- or polyamines can be converted, for example by common hydrogenation processes, to the corresponding relatively long-chain aliphatic hydrocarbon radicals having the same carbon number.
• Suitable bridging members A 1 to A 3 are in principle all divalent linear or branched aliphatic and divalent aromatic hydrocarbon structures, but preference is given to polyalkylene groups of the formula —(CH 2 ) m — in which m is from 1 to 12, especially from 2 to 6, in particular from 2 to 4, most preferably 2 or 3. 1,2-Ethylene and 1,3-propylene are thus particularly favorable.
• suitable bridging members as well as the ⁇ , ⁇ -bonding hydrocarbon structures are also nonlinear bridging members such as 1,1-ethylene, 1,1-propylene, 2,2-propylene and 1,2-propylene.
• divalent aromatic bridging members A 1 to A 3 are ortho, meta- and para-phenylene.
• the bridging members A 1 to A 3 may be the same or different.
• n and m are each independently integers from 0 to 30, but this upper limit is not critical.
• n and m are preferably each independently from 0 to 6, especially from 0 to 4, in particular from 0 to 2, most preferably 0 or 1.
• the present invention relates to the use of oligo-or polyamines of the general formula I in which the R 1 to R 6 radicals are each independently hydrogen, to C 1 - to C 22 -alkyl groups, C 5 - or C 6 -cycloalkyl groups or C 1 - to C 21 -alkylcarbonyl groups,
• the bridging members A 1 to A 3 are each independently C 2 - or C 3 -alkylene groups and
• n and m are each 0 or 1
• At least one of the R 1 to R 6 radicals is a C 5 - to C 30 -alkyl group, especially a C 10 - to C 20 -alkyl group, a C 5 - or C 6 -cycloalkyl group or a C 4 - to C 29 -alkylcarbonyl group, especially a C 9 - to C 19 -alkylcarbonyl group.
• Typical individual examples of such oligo- or polyamines with relatively short-chain or relatively long-chain hydrocarbyl radicals which can be used for the present invention are as follows:
• the present invention relates to the use of oligo- or polyamines of the general formula I in which all R 1 to R 6 radicals are hydrogen.
• oligo- or polyamines are in particular unsubstituted oligo- and polyalkyleneamines with linear alkylene bridges. Examples thereof are:
• the present invention also provides a mixture of oligo- or polyamines of the general formula I in which
• the R 1 to R 6 radicals are each independently hydrogen, C 1 - to C 30 -alkyl groups, C 5 - to C 8 -cycloalkyl groups or C 2 - to C 8 -cyanoalkyl groups, where the R 1 and R 2 and/or R 5 and R 6 radicals may in each case also, together with the nitrogen atom which bears them, form a five- or six-membered, saturated or unsaturated ring which may also have further heteroatoms and bear additional substituents, or in each case also together be a methylidene moiety which may be substituted by C 1 - to C 30 -alkyl groups and/or C 6 - to C 12 -aryl groups,
• the bridging members A 1 to A 3 are each independently C 1 - to C 12 -alkylene groups and/or C 6 - to C 12 -arylene groups, where the R 1 and/or R 5 radicals may in each case also, together with the nitrogen atom which bears them and a carbon atom of an alkylene group A 1 or A 3 , form a five- or six-membered, saturated or unsaturated ring which may also have further heteroatoms and/or carbonyl carbon atoms and bear additional substituents, and
• n and m are each integers from 0 to 30 and biofuel oils which are based on fatty acid esters in a weight ratio of from 1:100 000 to 1:100, preferably from 1:50 000 to 1:500, especially from 1:20 000 to 1:1000, in particular from 1:10 000 to 1:2000.
• the present invention also provides a fuel which comprises a major proportion of a fuel oil which consists of
• the R 1 to R 6 radicals are each independently hydrogen, C 1 - to C 30 -alkyl groups, C 5 - to C 8 -cycloalkyl groups or C 2 - to C 8 -cyanoalkyl groups, where the R 1 and R 2 and/or R 5 and R 6 radicals may in each case also, together with the nitrogen atom which bears them, form a five- or six-membered, saturated or unsaturated ring which may also have further heteroatoms and bear additional substituents, or in each case also together be a methylidene moiety which may be substituted by C 1 - to C 30 -alkyl groups and/or C 6 - to C 12 -aryl groups,
• the bridging members A 1 to A 3 are each independently C 1 - to C 12 -alkylene groups and/or C 6 - to C 12 -arylene groups, where the R 1 and/or R 5 radicals may in each case also, together with the nitrogen atom which bears them and a carbon atom of an alkylene group A 1 or A 3 , form a five- or six-membered, saturated or unsaturated ring which may also have further heteroatoms and/or carbonyl carbon atoms and bear additional substituents, and
• n and m are each integers from 0 to 30.
• the fuel component (A) is usually also referred to as “biodiesel”.
• This biofuel oil (A) preferably essentially comprises alkyl esters of fatty acids which derive from vegetable and/or animal oils and/or fats.
• Alkyl esters are typically understood to mean lower alkyl esters, especially C 1 - to C 4 -alkyl esters, which are obtainable by transesterifying the glycerides, especially triglycerides, which occur in vegetable and/or animal oils and/or fats by means of lower alcohols, for example ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol or in particular methanol (“FAME”:fatty acid methyl esters).
• FAME fatty acid methyl esters
• oils which can be converted to corresponding alkyl esters and can thus serve as the basis of biodiesel are castor oil, olive oil, peanut oil, palm kernel oil, coconut oil, mustard oil, cottonseed oil and especially sunflower oil, palm oil, soybean oil and rapeseed oil. Further examples include oils which can be obtained from wheat, jute, sesame and shea tree nut; it is also possible to use arachis oil, jatropha oil and linseed oil. The extraction of these oils and their conversion to the alkyl esters are known from the prior art or can be derived therefrom.
• Vegetable fats can in principle likewise be used as a source for biodiesel, but play a minor role.
• animal fats and oils which are converted to corresponding alkyl esters and can thus serve as the basis of biodiesel are fish oil, bovine tallow, porcine tallow and similar fats and oils obtained as wastes in the slaughter or utilization of farm animals or wild animals.
• the saturated or unsaturated fatty acids which underlie the vegetable and/or animal oils and/or fats mentioned, which usually have from 12 to 22 carbon atoms and may bear additional functional groups such as hydroxyl groups, and occur in the alkyl esters, are in particular lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linolic acid, linolenic acid, elaidic acid, erucic acid and ricinoleic acid, especially in the form of mixtures of such fatty acids.
• Typical lower alkyl esters based on vegetable and/or animal oils and/or fats which find use as biodiesel or biodiesel components, are, for example, sunflower methyl ester, palm oil methyl ester (“PME”), soybean oil methyl ester (“SME”) and in particular rapeseed oil methyl ester (“RME”).
• PME palm oil methyl ester
• SME soybean oil methyl ester
• RME rapeseed oil methyl ester
• the fuel component (B) shall be understood to mean middle distillate fuels boiling in the range from 120 to 450° C.
• middle distillate fuels are used in particular as diesel fuel, heating oil or kerosene, particular preference being given to diesel fuel and heating oil.
• Middle distillate fuels refer to fuels which are obtained by distilling crude oil and boil within the range from 120 to 450° C. Preference is given to using low-sulfur middle distillates, i.e. those which comprise less than 350 ppm of sulfur, especially less than 200 ppm of sulfur, in particular less than 50 ppm of sulfur. In special cases, they comprise less than 10 ppm of sulfur; these middle distillates are also referred to as “sulfur-free”. They are generally crude oil distillates which have been subjected to refining under hydrogenating, conditions and which therefore comprise only small proportions of polyaromatic and polar compounds. They are preferably those middle distillates which have 95% distillation points below 370° C., in particular below 350° C. and in special cases below 330° C.
• Low-sulfur and sulfur-free middle distillates may be obtained from relatively heavy crude oil fractions which cannot be distilled under atmospheric pressure.
• Typical conversion processes for preparing middle distillates from heavy crude oil fractions include: hydrocracking, thermal cracking, catalytic cracking, coking processes and/or visbreaking. Depending on the process, these middle distillates are obtained in low-sulfur or sulfur-free form, or are subjected to refining under hydrogenating conditions.
• the middle distillates preferably have aromatics contents of below 28% by weight, especially below 20% by weight.
• the content of normal paraffins is between 5% by weight and 50% by weight, preferably between 10 and 35% by weight.
• middle distillates referred to as fuel component (B) shall also be understood here to mean middle distillates which can either be derived indirectly from fossil sources such as mineral oil or natural gas, or else can be prepared from biomass via gasification and subsequent hydrogenation.
• a typical example of a middle distillate fuel which is derived indirectly from fossil sources is the GTL (“gas-to-liquid”) diesel fuel obtained by means of Fischer-Tropsch synthesis.
• a middle distillate is prepared from biomass, for example via the BTL (“bio-to-liquid”) process, and can either be used alone or in a mixture with other middle distillates as fuel component (B).
• the middle distillates also include hydrocarbons which are obtained by the hydrogenation of fats and fatty oils. They comprise predominantly n-paraffins. It is common to the middle distillate fuels mentioned that they are essentially hydrocarbon mixtures and are free of fatty acid esters.
• the fuel described usually also comprises the additives customary therefor, such as flow improvers for improving the cold performance, especially cold flow improvers (“middle distillate flow improvers”), nucleators, paraffin dispersants (“wax anti settling additives”) and mixtures thereof, and also conductivity improvers, corrosion protection additives, lubricity additives, antioxidants, metal deactivators, antifoams, demulsifiers, detergents, cetane number improvers, solvents or diluents, dyes or fragrances or mixtures thereof.
• flow improvers for improving the cold performance especially cold flow improvers (“middle distillate flow improvers”), nucleators, paraffin dispersants (“wax anti settling additives”) and mixtures thereof
• conductivity improvers such as corrosion protection additives, lubricity additives, antioxidants, metal deactivators, antifoams, demulsifiers, detergents, cetane number improvers, solvents or diluents, dye
• the biofuel oil is unstable toward atmospheric oxygen and decomposes gradually by oxidation in the course of its storage in pure form and also in a mixture with middle distillates of fuel component (B) when suitable precautionary measures are not taken.
• customary antioxidants such as sterically hindered phenols, for example BHT, BHA or TBHQ, has not been found to be effective enough—even in relatively high dosages.
• the above-described oligo- or polyamines fulfill this objective as improved antioxidants in a satisfactory manner. They generally also have better solubility in the biofuel oil and in the corresponding fuel comprising the biofuel oil.
• a useful method for determining the oxidation stability of biofuel oils such as FAME has been found to be the so-called Rancimat method to European standard 14 112, in which an air stream is passed through the biofuel oil under controlled conditions at relatively high temperature (110° C.), and the volatile acidic addition products formed in the oxidation are collected and analyzed by conductometry.
• Most biofuels have induction times of less than 7 hours as base values.
• the oligo- or polyamines described are dosed in the inventive fuel typically in an amount of from 10 to 10 000 ppm by weight based on the amount of the biofuel (A).
• Preferred dosage ranges are from 20 to 2000 ppm by weight, especially from 50 to 1000 ppm by weight, in particular from 100 to 500 ppm by weight.
• Most of the oligo- or polyamines described meet the requirement for a long induction time in the Ranzimate test even with a dosage of 500 ppm by weight or less.
• a mixture of the oligo- or polyamines described with conventional antioxidants, especially with sterically hindered phenols, for example BHT, BHA, TBHQ, trimethylhydroquinone or bisphenol A, preferably in a weight ratio of from 10:1 to 1:10, in particular from 3:1 to 1:3, can lead to a further increase in the antioxidative and hence stabilizing action in the biofuel oil.
• conventional antioxidants especially with sterically hindered phenols, for example BHT, BHA, TBHQ, trimethylhydroquinone or bisphenol A
• Suitable solvents in this context are in particular alcohols such as n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol or 2-propylheptanol, carboxylic esters or fatty acid esters such as rapeseed oil methyl ester, or amines such as dimethylamine, trimethylamine, piperidine or morpholine.
• alcohols such as n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol or 2-propylheptanol
• carboxylic esters or fatty acid esters such as rapeseed oil methyl ester
• amines such as dimethylamine, trimethylamine, piperidine or morpholine.
• the aliphatic oligo- or polyamines described can be used in sufficiently pure form, i.e. largely free of traces of metals such as iron, sodium or potassium, since especially metal traces in fuels can lead easily to faults in the engine and in any exhaust gas catalytic converter system connected downstream.
• the dosages are each based on the active substance; the additives were metered in as 10% by weight solutions in 2-ethylhexanol.

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• 2007
  • 2007-10-23 BR BRPI0718157-4A patent/BRPI0718157A2/pt not_active IP Right Cessation
  • 2007-10-23 CN CNA2007800398619A patent/CN101528896A/zh active Pending
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  • 2007-10-23 WO PCT/EP2007/061317 patent/WO2008049822A2/de active Application Filing
  • 2007-10-23 EP EP07821681A patent/EP2089494A2/de not_active Withdrawn
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