EP1116781B1 - Additif polyfonctionnel pour huiles combustibles - Google Patents

Additif polyfonctionnel pour huiles combustibles Download PDF

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Publication number
EP1116781B1
EP1116781B1 EP00128083A EP00128083A EP1116781B1 EP 1116781 B1 EP1116781 B1 EP 1116781B1 EP 00128083 A EP00128083 A EP 00128083A EP 00128083 A EP00128083 A EP 00128083A EP 1116781 B1 EP1116781 B1 EP 1116781B1
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und
carbon atoms
alkyl
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additive
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EP1116781A1 (fr
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Mattias Dr. Krull
Werner Dr. Reimann
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clariant Produkte Deutschland GmbH
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Clariant GmbH
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    • 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
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • 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
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1981—Condensation polymers of aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • 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
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium

Definitions

  • the present invention relates to an additive for fuel oils containing Ethylene-vinyl ester / olefin terpolymers and amphiphilic lubricants Additives, as well as its use for the improvement of cold flow and Lubricating properties of the so-additive oils.
  • Mineral oils and mineral oil distillates used as fuel oils generally 0.5 wt .-% and more sulfur, the combustion Formation of sulfur dioxide causes. To the resulting Reducing environmental pollution becomes the sulfur content of fuel oils lowered further and further.
  • These Fuel oils are usually prepared by taking the from the petroleum hydrogenated by distillation obtained fractions. In the Desulfurization will also remove other substances that cause the Give fuel oils a natural lubricating effect. To these substances include polyaromatic and polar compounds.
  • EP-A-0 764 198 discloses additives which improve the lubricity of fuel oils improve, and the polar nitrogen compounds based on alkylamines or Alkyl ammonium salts containing alkyl radicals of 8 to 40 carbon atoms.
  • EP-A-0 743 974 discloses the use of mixtures of lubricity additives (Esters of polyhydric alcohols and carboxylic acids having 10 to 25 carbon atoms or Dicarboxylic acids) and flow improvers of ethylene / unsaturated ester copolymers to synergistically improve the lubricity of highly desulfurized oils.
  • EP-A-0 807 676 discloses the use of a mixture of a Carboxylic acid amide and a cold flow improver and / or an ashless Dispersant for improving the cold flow properties of low sulfur Fuel oil.
  • EP-A-0 680 506 discloses the use of esters of monovalent or polyvalent ones Carboxylic acids with monohydric or polyhydric alcohols as Lubricity-improving additive to fuel oils.
  • EP-A-0 807 642 discloses cold flow improvers based on terpolymers which Contain structural units of ethylene, vinyl acetate and 4-methylpentene-1, EP-A-807 643 based on ethylene, vinyl acetate and norbornene.
  • Object of the present invention was to find additive combinations that in largely from sulfur and aromatic compounds freed middle distillates lead to an improvement of the lubricating effect. At the same time, these additives Also included as a cold flow improver, in the oils mentioned soluble and effective as such, and the effect of the lubricity additive supported, and vice versa.
  • additives in addition to lubricity improving amphiphilic terpolymers of ethylene, vinyl esters and contain certain olefins having the required properties.
  • Another object of the invention are fuel oils, the aforementioned Contain additives.
  • Another object of the invention is the use of additives for Simultaneous improvement of lubricity and cold flow properties of Fuel oils.
  • Preferred proportions of A) and B) are between 10 and 90 wt .-%, in particular 20 to 80 wt .-% and especially 40 to 60 wt .-%.
  • the oil-soluble amphiphile (component A) preferably comprises a radical R 1 having 5 to 40, in particular 12 to 35 carbon atoms.
  • R 1 is particularly preferably linear or branched and contains 1 to 3 double bonds in the case of linear radicals.
  • the radical R 2 preferably has 2 to 8 carbon atoms and may be interrupted by nitrogen and / or oxygen atoms.
  • component A carries from 2 to 5 hydroxyl groups, each carbon atom carrying no more than one hydroxyl group.
  • X in formula 1 has the Meaning oxygen.
  • These are in particular fatty acids and esters between carboxylic acids and di- or polyhydric alcohols.
  • Preferred esters contain at least 10, especially at least 12 carbon atoms.
  • Prefers is also that the esters contain free hydroxyl groups, the esterification of the Polyols with the carboxylic acid is therefore not complete.
  • Suitable polyols are for example, ethylene glycol, propylene glycol, diethylene glycol and higher Alkoxylation products, glycerol, trimethylolpropane, pentaerythritol, diglycerol and higher condensation products of glycerol and sugar derivatives.
  • Heteroatom-containing polyols such as triethanolamine are suitable.
  • X is a nitrogen-containing radical
  • reaction products of ethanolamine, Diethanolamine, hydroxypropylamine, dihydroxypropylamine, n-methylethanolamine, Diglycolamine and 2-amino-2-methylpropanol suitable.
  • the implementation takes place preferably by amidation, whereby the resulting amides free OH groups wear.
  • Examples are fatty acid monoethanolamides, diethanolamides and -N-methylethanolamides called.
  • R 3 preferably represents a hydroxyl-bearing alkyl radical having 3 to 8 carbon atoms, or preferably C 2 - to C 18 -alkyl, in particular C 4 - to C 12 -alkyl.
  • R 43 preferably represents a C 2 - to C 8 -, in particular a C 2 - to C 4 radical.
  • the polyamine from which the structural unit formed from R 41 , R 42 and the nitrogen atom connecting them is derived is preferably ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or a higher homologue of the aziridine such as polyethyleneimine, and mixtures thereof. Parts of the amino group may be alkylated. Also suitable are star amines and dendrimers. This refers to polyamines having generally 2-10 nitrogen atoms which are connected to each other via -CH 2 -CH 2 groups and which are saturated in marginal position with acyl or alkyl radicals.
  • R 44 is preferably hydrogen, an acyl radical or an alkoxy group of the formula - (OCH 2 CH 2 ) n -, where n is an integer between 1 and 10, and mixtures thereof.
  • the amides are generally obtained by condensation of the polyamines with the Carboxylic acids or their derivatives such as esters or anhydrides produced. It are preferably 0.2 to 1.5 mol, in particular 0.3 to 1.2 mol, especially 1 mol Used acid per base equivalent.
  • the condensation is preferably carried out at Temperatures between 20 and 300 ° C, in particular between 50 and 200 ° C below Distilling off the water of reaction.
  • solvents preferably aromatic solvents such as benzene, toluene, xylene, trimethylbenzene and / or commercial solvent mixtures such.
  • Solvent Naphtha, ®Shellsol AB, ® Solvesso 150, ® Solvesso 200 are added to the reaction mixture.
  • the Products according to the invention generally have a titratable Base nitrogen of 0.01-5% and an acid number of less than 20 mg KOH / g, preferably less than 10 mg KOH / g.
  • y preferably assumes the values 1 or 2.
  • Preferred polyols have 2 to 8 carbon atoms. They preferably carry 2, 3, 4 or 5 hydroxyl groups, but not more than they contain carbon atoms.
  • the Carbon chain of the polyols can be straight-chain, branched, saturated or unsaturated and optionally contain heteroatoms. Preferably, it is saturated.
  • Preferred carboxylic acids of which the compounds of formula 1 are derived let or represent the compounds of formula 1 have 5 to 40, in particular 12 to 30 carbon atoms.
  • the carboxylic acid has a or two carboxyl groups.
  • the carbon chain of the carboxylic acids can straight chain, branched, saturated or unsaturated.
  • Examples of preferred carboxylic acids include caprylic acid, Capric, lauric, myristic, palmitic, stearic, oleic, Elaidic acid, linoleic acid, linolenic acid and behenic acid, and carboxylic acids with Heteroatoms such as ricinoleic acid.
  • dimer and trimer fatty acids such as they e.g. are accessible by oligomerization of unsaturated fatty acids, as well as Alkenylsuccinic acids are used.
  • ethers and amines of the formula 2 are used in a preferred embodiment. These are partial ethers of polyols, for example glycerol monooctadecyl ethers or hydroxyl-bearing amines, as obtainable, for example, by alkoxylation of amines of the formula R 1 NH 2 or R 1 R 3 NH with alkylene oxides, preferably ethylene oxide and / or propylene oxide. Preference is given to 1-10, in particular 1-5 mol of alkylene oxide per H atom of the nitrogen used.
  • the vinyl esters contained in the terpolymer of component B) are preferably of monocarboxylic acids having 2 to 16, especially 2 to 12 carbon atoms derived. One or even more vinyl esters may be present at the same time.
  • the vinyl esters are vinyl acetate, Vinyl propionate, vinyl 2-ethylhexanoate, vinyl neodecanoate, Vinyl neononanoate, vinyl neoundecanoate, vinyl pivalate or vinyl laurate, in particular vinyl acetate and / or vinyl propionate.
  • the olefin contained in the terpolymer comprises 5, 6 or 7 carbon atoms. It are, for example, penten-1, hexene-1 or heptene-1. Especially preferred embodiments of the invention are 4-methylpentene-1 or norbomene.
  • the terpolymers contain from 10 to 16 mole percent vinyl ester and from 1 to 3 mole percent olefin.
  • Their degree of branching determined by NMR spectroscopy is between 3 and 15, in particular between 3.5 and 10 CH 3 / 100CH 2 groups, which are not derived from the vinyl ester.
  • Terpolymers according to the invention having an ISO 3219 (B) at 140 ° C. measured melt viscosity of 50 to 5000 mPas, preferably 30 to 1,000 mPas and in particular 50 to 500 mPas.
  • the vinyl ester of an aliphatic linear or branched monocarboxylic acid containing 2 to 20 carbon atoms in the Molecule contains, and olefins one starts from mixtures of the monomers.
  • the copolymerization of the starting materials by known methods (see. for example, e.g. Ullmanns Encyclopadie der Technischen Chemie, 5th edition, Vol. A21, Pages 305 to 413).
  • the polymerization is suitable in solution, in suspension, in the gas phase and the high-pressure mass polymerization.
  • the reaction of the monomers is by radicals forming initiators (radical chain starter) initiated.
  • radicals forming initiators Radical chain starter
  • Oxygen, hydroperoxides, peroxides and azo compounds such as Cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxydicarbonate, t-butyl perpivalate, t-butyl per-maleate, t-butyl perbenzoate, Dicumyl peroxide, t-butyl cumyl peroxide, di (t-butyl) peroxide, 2,2'-azo-bis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
  • the initiators are individually or as a mixture of two or more substances in amounts of from 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture used.
  • the desired melt viscosity of the terpolymers is given Composition of the monomer mixture by variation of the Reaction parameters pressure and temperature and optionally by adding Moderators set.
  • Moderators have become hydrogen, saturated or unsaturated hydrocarbons, e.g. Propane, aldehydes, e.g. propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g. Acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone or alcohols, e.g. Butanol, proven.
  • the moderators in quantities up to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture applied.
  • terpolymers To be suitable for use in the additives of the invention, one uses monomer mixtures which except ethylene and optionally a moderator 5 to 40 wt .-%, preferably 10 to 40 wt .-% Vinyl ester and 1 to 40 wt .-% olefin. With the of the composition of the terpolymer deviating composition of the monomer mixture one bears the different polymerization rate of the monomers Bill. The polymers are obtained as colorless melts, which at Solidify room temperature to waxy solids.
  • the additives according to the invention also together with one or more oil-soluble Co-additives are used, which already by themselves the cold flow properties and / or lubricating action of crude oils, lubricating oils or fuel oils improve.
  • oil-soluble Co-additives are paraffin dispersants, alkylphenol-aldehyde resins and comb polymers.
  • Paraffin dispersants reduce the size of the paraffin crystals and cause The paraffin particles do not settle, but colloidly with significantly reduced Sedimentation tendency, remain dispersed.
  • paraffin dispersants have become oil-soluble polar compounds having ionic or polar groups, e.g. amine salts and / or amides obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic Mono-, di-, tri- or tetracarboxylic acids or their anhydrides are obtained.
  • paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols which can be reacted Reaction products of alkenylspirobislactones with amines and Reaction products of terpolymers based on ⁇ , ⁇ -unsaturated Dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers lower unsaturated alcohols.
  • alkylphenol-formaldehyde resins are as Paraffin dispersants suitable. The following are some suitable ones Paraffin dispersants listed.
  • the additives according to the invention can furthermore be used in a mixture with alkylphenol-formaldehyde resins.
  • these alkylphenol-formaldehyde resins are those of the formula wherein R 51 is C 4 -C 50 alkyl or alkenyl, [OR 52 ] is ethoxy and / or propoxy, n is a number from 5 to 100 and p is a number from 0 to 50.
  • the inventive Additives used together with comb polymers By this one understands Polymers in which hydrocarbon radicals having at least 8, in particular at least 10 carbon atoms are attached to a polymer backbone. Preferably, they are homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. at Copolymers have at least 20%, preferably at least 30% of the monomers Side chains (see Comb-like Polymers-Structure and Properties; N. A. Platé and V. P. Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff).
  • Suitable comb polymers are fumarate / vinyl acetate copolymers (cf., EP 0 153 176 A1), copolymers of a C 6 - to C 24 - ⁇ -olefin and an NC 6 - to C 22 -alkylmaleimide (cf., EP-A- 0 320 766), further esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
  • fumarate / vinyl acetate copolymers cf., EP 0 153 176 A1
  • copolymers of a C 6 - to C 24 - ⁇ -olefin and an NC 6 - to C 22 -alkylmaleimide cf., EP-A- 0 320 766
  • the mixing ratio (in parts by weight) of the additives according to the invention with paraffin dispersants or comb polymers is in each case 1:10 to 20: 1, preferably 1: 1 to 10: 1.
  • the additives according to the invention are suitable for improving the cold flow and lubricating properties of animal, vegetable or mineral oils, alcoholic fuels such as methanol and ethanol, as well as mixtures of alcoholic fuels and mineral oils. They are particularly well suited for use in middle distillates. As middle distillates are in particular those mineral oils which are obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil.
  • the additives according to the invention are preferably used in middle distillates which contain not more than 500 ppm, in particular less than 200 ppm of sulfur and in special cases less than 50 ppm of sulfur. These are generally those middle distillates that have been subjected to a hydrogenating refining, and therefore contain only small amounts of polyaromatic and polar compounds that give them a natural lubricating effect.
  • the additives according to the invention are furthermore preferably used in middle distillates which have 95% distillation points below 370.degree. C., in particular 350.degree. C. and in special cases below 330.degree. The effectiveness of the mixtures is better than would be expected from the individual components and compared to the mixtures according to the prior art.
  • the additive combinations according to the invention are distinguished under cold blending conditions when the temperature of the oil during the additization is low, ie below 40 ° C., in particular below 20 ° C. and especially below 10 ° C.
  • the additive components of the invention may be mineral oils or Mineral oil distillates are added separately or in mixture.
  • Mixtures have solutions or dispersions 10 to 90 wt .-%, preferably from 20 to 80 wt .-%, the additive combination contained proven.
  • suitable Solvent or dispersant are aliphatic and / or aromatic Hydrocarbons or hydrocarbon mixtures, e.g.
  • Petroleum fractions Kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or commercial Solvent mixtures such as Solvent Naphtha, ®Shellsol AB, ® Solvesso 150, ® Solvesso 200, ®Exxsol, ®ISOPAR and ®Shellsol D grades.
  • Solvent Naphtha ®Shellsol AB
  • ® Solvesso 150 ® Solvesso 200
  • ®Exxsol ®ISOPAR
  • ®Shellsol D grades Due to the additives in their lubricating and / or cold-flow properties improved mineral oils or Mineral oil distillates contain from 0.001 to 2, preferably 0.005 to 0.5 wt .-% additive, based on the distillate.
  • the additives may be used alone or together with other additives, for example, with other pour point depressants, dewaxing aids, corrosion inhibitors, antioxidants, conductivity improvers, sludge inhibitors, dehazems, and cloud point depressant additives.
  • pour point depressants dewaxing aids
  • corrosion inhibitors corrosion inhibitors
  • antioxidants antioxidants
  • conductivity improvers corrosion inhibitors
  • sludge inhibitors sludge inhibitors
  • dehazems dehazems
  • cloud point depressant additives for example, with other pour point depressants, dewaxing aids, corrosion inhibitors, antioxidants, conductivity improvers, sludge inhibitors, dehazems, and cloud point depressant additives.
  • the addition of these additives to the oil can be carried out together with the additive components according to the invention or separately.
  • the effectiveness of the additives according to the invention as lubricity enhancers and cold flow improvers is explained in more detail by
  • Test oil 1 Test oil 2 Test oil 3 Test oil 4 Test oil 5 Cloud Point (CP) (° C) + 1 - 9,6 - 3,2 - 4,3 - 26.8 Cold Filter Plugging Point (CFPP) (° C) - 2 - 14 - 6 - 6 - 27 Pour point (PP) (° C) - 3 - 12 - 9 - 12 - 27 n-paraffin content (% by weight) 23 21.5 18.9 18.2 16.8 Initial boiling point (IBP) (° C) 163 172 187.9 186.9 185.8 Boiling range 90% - 20% (K) 104 76.9 99.8 102.2 89.9 FBP-90% (K) 27 18 24.2 19.0 21 Siedeende (FBP) (° C) 332 336 359.6 358.6 320.7 density 0.828 0.831 0.843 0.842 0.819 S content (ppm) 290 35 54.2 478 6 HFRR-WSD ( ⁇ m) 571
  • the boiling characteristics were determined according to ASTM D-86, the determination the CFPP value according to EN 116 and the determination of the cloud point according to ISO 3015.
  • An ADT value ⁇ 15 is taken as an indication that the gas oil is normal cold weather is satisfactorily usable. Products with ADT values> 25 are referred to as non-filterable.
  • the lubricity of the additives was measured using an HFRR device from PCS Instruments performed.
  • the tempered at 22 ° C additives are added to the dosed at 22 ° C tempered oil and shaken vigorously for 30 seconds. To 24 hours storage at + 3 ° C will be the oil according to the conditions of the British Rail test filtered and the filtrate on the lubricating effect determined in the HFRR test.
  • HFRR High Frequency Reciprocating Rig Test
  • the Results are known as friction coefficient (friction) and wear scar (WSD) specified. A low coefficient of friction and a low Wear Scar show a good lubricating effect.
  • the polymers were 50% in kerosene set.
  • the viscosity was determined by means of a rotational viscometer (Haake RV 20) with plate-cone measuring system at 140 ° C, in accordance with ISO 3219 (B).
  • the additives according to the invention also used in admixture with paraffin dispersants become.
  • the employed Wachsdispergator (F) is a mixture of 2 parts of a reaction product of a terpolymer of C 14/16 - ⁇ -olefin, maleic anhydride and 2 equivalents of di-tallow Allylpolyglkol with and a part of nonylphenol-formaldehyde resin.
  • the cold flow improver polymers mentioned and, if appropriate, additionally the said wax dispersant are mixed with the abovementioned amphiphiles.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (10)

  1. Additifs destinés à améliorer les propriétés d'écoulement à froid et de lubrification d'huiles combustibles, composés de
    A) 5% à 95% en poids d'au moins un composé amphiphile oléosoluble de formule
    Figure 00500001
       ou R1 ― X ― R2 dans lesquelles R1 représente un groupe alkyle, alcényle, hydroxyalkyle ou un groupe aromatique contenant 1 à 50 atomes de carbone, X représente NH, NR3, O ou S, y = 1, 2, 3 ou 4, R2 représente un atome d'hydrogène ou un groupe alkyle, portant des groupes hydroxyle, contenant 2 à 10 atomes de carbone et R3 représente un groupe alkyle portant un atome d'azote et/ou un groupe alkyle portant des groupes hydroxyle, contenant 2 à 10 atomes de carbone, ou un groupe alkyle en C1 à C20, et R1 et R2 contiennent ensemble au moins 15 atomes de carbone,
    B) 5% à 95% en poids d'un terpolymère d'éthylène, d'ester vinylique d'un ou de plusieurs acides monocarboxyliques aliphatiques linéaires ou ramifiés, qui contiennent 2 à 20 atomes de carbone dans la molécule, et d'une oléfine en C5 à C7, ayant une proportion de 9% à 18% en moles d'ester vinylique et de 0,5% à 5% en moles d'oléfine (à chaque fois par rapport au terpolymère) présentant une viscosité à l'état fondu, mesurée à 140°C, de 20 à 10 000 mPa.s.
  2. Additifs selon la revendication 1, caractérisés en ce que le composant A) est un ester d'un acide carboxylique avec un polyol contenant 2 à 8 atomes de carbone.
  3. Additifs selon la revendication 1 et/ou 2, caractérisés en ce que le groupe R1 contient 5 à 40 atomes de carbone.
  4. Additifs selon l'une ou plusieurs des revendications 1 à 3, caractérisés en ce que le composant A est une alcanolamine d'acide gras ou un alcanolamide d'acide gras.
  5. Additifs selon l'une ou plusieurs des revendications 1 à 4, caractérisés en ce que les terpolymères du composant B présentent une viscosité à l'état fondu à 140°C de 50 à 5000 mPa.s.
  6. Additifs selon l'une ou plusieurs des revendications 1 à 5, caractérisés en ce que l'oléfine contenue dans le terpolymère du composant B) est le 4-méthylpentène ou le norbonène.
  7. Additifs selon l'une ou plusieurs des revendications 1, 3, 5 et 6, caractérisés en ce que le composant A) est un acide gras contenant 5 à 30 atomes de carbone.
  8. Huiles combustibles, contenant des additifs selon l'une ou plusieurs des revendications 1 à 7.
  9. Utilisation des additifs selon l'une ou plusieurs des revendications 1 à 7 pour améliorer à la fois l'effet lubrifiant et les propriétés d'écoulement à froid d'huiles combustibles.
  10. Mélanges d'additifs selon l'une ou plusieurs des revendications 1 à 7 avec des résines alkylphénolformaldéhyde ou des polymères en peigne de formule
    Figure 00520001
    dans laquelle
    A
    représente R', COOR', OCOR', R"-COOR' ou OR' ;
    D
    représente un atome d'hydrogène, CH3, A ou R";
    E
    représente un atome d'hydrogène ou A ;
    G
    représente un atome d'hydrogène, R", R"-COOR', un groupe aryle ou un groupe hétérocyclique ;
    M
    représente un atome d'hydrogène, COOR", OCOR", OR" ou COOH ;
    N
    représente un atome d'hydrogène, R", COOR", OCOR, COOH ou un groupe aryle ;
    R'
    représente une chaíne hydrocarbonée contenant 8 à 150 atomes de carbone ;
    R"
    représente une chaíne hydrocarbonée contenant 1 à 10 atomes de carbone ;
    m
    est un nombre compris entre 0,4 et 1,0 ; et
    n
    est un nombre compris entre 0 et 0,6,
    et le rapport de mélange de l'additif selon les revendications 1 à 7 au dispersant de paraffine ou au polymère en peigne va de 1:10 à 20:1.
EP00128083A 2000-01-11 2000-12-21 Additif polyfonctionnel pour huiles combustibles Expired - Lifetime EP1116781B1 (fr)

Applications Claiming Priority (2)

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DE10000649A DE10000649C2 (de) 2000-01-11 2000-01-11 Mehrfunktionelles Additiv für Brennstofföle
DE10000649 2000-01-11

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Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2392061A1 (fr) * 1999-11-30 2001-06-07 Terence Cox Formulations d'additifs pour la production de petrole
EP1116780B1 (fr) * 2000-01-11 2005-08-31 Clariant GmbH Additif polyfonctionnel pour huiles combustibles
DE10136828B4 (de) * 2001-07-27 2005-12-15 Clariant Gmbh Schmierverbessernde Additive mit verminderter Emulgierneigung für hochentschwefelte Brennstofföle
DE10155747B4 (de) * 2001-11-14 2008-09-11 Clariant Produkte (Deutschland) Gmbh Additive für schwefelarme Mineralöldestillate, umfassend einen Ester eines alkoxylierten Polyols und ein Alkylphenol-Aldehydharz
ES2464840T3 (es) * 2002-07-09 2014-06-04 Clariant Produkte (Deutschland) Gmbh Uso de líquidos oleosos para mejorar la estabilidad frente a la oxidación de aceites combustibles
JP4484458B2 (ja) * 2002-07-09 2010-06-16 クラリアント・プロドゥクテ・（ドイチュラント）・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 高度に脱硫された燃料油用の酸化安定性潤滑剤添加剤
DE10357880B4 (de) * 2003-12-11 2008-05-29 Clariant Produkte (Deutschland) Gmbh Brennstofföle aus Mitteldestillaten und Ölen pflanzlichen oder tierischen Ursprungs mit verbesserten Kälteeigenschaften
WO2005097953A1 (fr) * 2004-04-06 2005-10-20 Akzo Nobel N.V. Additifs reducteur de la viscosite a faible ecoulement pour des compositions huileuses
EP1674554A1 (fr) * 2004-12-24 2006-06-28 Clariant Produkte (Deutschland) GmbH Additifs pour distillats d'huiles minérales, à faible contenu en soufre, comprenant un copolymère greffé à base de copolymères d'éthylène-acétate de vinyle.
EP1690896B1 (fr) * 2005-02-11 2016-06-08 Infineum International Limited Additifs pour compositions d'huile
US20060191191A1 (en) * 2005-02-11 2006-08-31 Colin Morton Additives for oil compositions
DE102005035277B4 (de) * 2005-07-28 2007-10-11 Clariant Produkte (Deutschland) Gmbh Mineralöle mit verbesserter Leitfähigkeit und Kältefließfähigkeit
DE102006001381A1 (de) * 2006-01-11 2007-07-12 Clariant International Limited Additive für schwefelarme Mineralöldestillate, umfassend Pfropfcopolymere auf Basis von Ethylen-Vinylester-Copolymeren
DE102006001380A1 (de) * 2006-01-11 2007-07-26 Clariant International Limited Additive für schwefelarme Mineralöldestillate, umfassend Pfropfcopolymere auf Basis von Ethylen-Vinylacetat-Copolymeren
DE102006033151B4 (de) * 2006-07-18 2014-11-20 Clariant International Limited Additive zur Verbesserung der Kälteeigenschaften von Brennstoffölen
US20090090047A1 (en) * 2007-10-04 2009-04-09 Baker Hughes Incorporated Additive Useful for Stabilizing Fuel Oils
US20090090655A1 (en) * 2007-10-04 2009-04-09 Baker Hughes Incorporated Additive Useful for Stabilizing Crude Oil
DE102009060389A1 (de) * 2009-12-24 2011-06-30 Clariant International Ltd. Kälteadditive mit verbesserter Fließfähigkeit
WO2011138400A1 (fr) * 2010-05-07 2011-11-10 Basf Se Terpolymère et son utilisation pour améliorer les propriétés d'écoulement à froid de carburants de distillat moyen
US20110271586A1 (en) * 2010-05-07 2011-11-10 Basf Se Terpolymer and use thereof for improving the cold flow properties of middle distillate fuels
US10457884B2 (en) 2013-11-18 2019-10-29 Afton Chemical Corporation Mixed detergent composition for intake valve deposit control
US10273425B2 (en) 2017-03-13 2019-04-30 Afton Chemical Corporation Polyol carrier fluids and fuel compositions including polyol carrier fluids
US11873461B1 (en) 2022-09-22 2024-01-16 Afton Chemical Corporation Extreme pressure additives with improved copper corrosion
US12024686B2 (en) 2022-09-30 2024-07-02 Afton Chemical Corporation Gasoline additive composition for improved engine performance
US11884890B1 (en) 2023-02-07 2024-01-30 Afton Chemical Corporation Gasoline additive composition for improved engine performance
US11795412B1 (en) 2023-03-03 2023-10-24 Afton Chemical Corporation Lubricating composition for industrial gear fluids

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1047493A (fr) * 1963-01-30
US4211534A (en) * 1978-05-25 1980-07-08 Exxon Research & Engineering Co. Combination of ethylene polymer, polymer having alkyl side chains, and nitrogen containing compound to improve cold flow properties of distillate fuel oils
EP0153177B1 (fr) 1984-02-21 1991-11-06 Exxon Research And Engineering Company Compositions de distillat moyen à caractéristiques d'écoulement à froid
DE3742630A1 (de) 1987-12-16 1989-06-29 Hoechst Ag Polymermischungen fuer die verbesserung der fliessfaehigkeit von mineraloeldestillaten in der kaelte
DE3926992A1 (de) 1989-08-16 1991-02-21 Hoechst Ag Verwendung von umsetzungsprodukten von alkenylspirobislactonen und aminen als paraffindispergatoren
ES2110124T3 (es) 1993-01-06 1998-02-01 Clariant Gmbh Termopolimeros a base de anhidridos de acidos carboxilicos alfa,beta-insaturados, de compuestos alfa,beta-insaturados y de polioxialquileneteres de alcoholes inferiores insaturados.
GB9301119D0 (en) 1993-01-21 1993-03-10 Exxon Chemical Patents Inc Fuel composition
GB9411614D0 (en) * 1994-06-09 1994-08-03 Exxon Chemical Patents Inc Fuel oil compositions
DE4422159A1 (de) 1994-06-24 1996-01-04 Hoechst Ag Umsetzungsprodukte von Polyetheraminen mit Polymeren alpha,beta-ungesättigter Dicarbonsäuren
GB9417667D0 (en) * 1994-09-02 1994-10-19 Exxon Chemical Patents Inc Oil additives, compositions and polymers for use therein
EP0743973B2 (fr) 1994-12-13 2013-10-02 Infineum USA L.P. Carburant contenant des polyoxyalkylenes
GB9500460D0 (en) * 1995-01-10 1995-03-01 Exxon Chemical Patents Inc Fuel compositions
GB9610363D0 (en) * 1996-05-17 1996-07-24 Ethyl Petroleum Additives Ltd Fuel additives and compositions
DE19620119C1 (de) * 1996-05-18 1997-10-23 Hoechst Ag Terpolymerisate des Ethylens, ihre Herstellung und ihre Verwendung als Additive für Mineralöldestillate
DE19620118C1 (de) * 1996-05-18 1997-10-23 Hoechst Ag Terpolymerisate des Ethylens, ihre Herstellung und ihre Verwendung als Additive für Mineralöldestillate
SK284524B6 (sk) * 1996-05-31 2005-05-05 The Associated Octel Company Limited Použitie esterifikovaných alkenyljantárových kyselín na zvýšenie lubricity tekutého uhľovodíkového paliva
ATE223953T1 (de) 1997-01-07 2002-09-15 Clariant Gmbh Verbesserung der fliessfähigkeit von mineralölen und mineralöldestillaten unter verwendung von alkylphenol-aldehydharzen
DE19758887A1 (de) * 1997-07-08 2006-10-19 Clariant Gmbh Fließverbesserer für Mineralöle
DE19739271A1 (de) 1997-09-08 1999-03-11 Clariant Gmbh Additiv zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten
DE19757830C2 (de) * 1997-12-24 2003-06-18 Clariant Gmbh Brennstofföle mit verbesserter Schmierwirkung
GB9810994D0 (en) * 1998-05-22 1998-07-22 Exxon Chemical Patents Inc Additives and oil compositions
DE19823565A1 (de) * 1998-05-27 1999-12-02 Clariant Gmbh Mischungen von Copolymeren mit verbesserter Schmierwirkung

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US6475250B2 (en) 2002-11-05
US20010013196A1 (en) 2001-08-16
DE50011065D1 (de) 2005-10-06
DE10000649C2 (de) 2001-11-29
JP2001234180A (ja) 2001-08-28
EP1116781A1 (fr) 2001-07-18
CA2331027C (fr) 2009-09-22
CA2331027A1 (fr) 2001-07-11
DE10000649A1 (de) 2001-07-19

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